ThermoFluid Chemistry Nuclear Physics

DOE-HDBK-1015/2-93
JANUARY 1993
DOE FUNDAMENTALS HANDBOOK

CHEMISTRY
Volume 2 of 2
U.S. Department of Energy
FSC-6910
Washington, D.C. 20585

Distribution Statement A. Approved for public release; distribution is unlimited.
This document has been reproduced directly from the best available copy.
Available to DOE and DOE contractors from the Office of Scientific and
Technical Information. P.O. Box 62, Oak Ridge, TN 37831.
Available to the public from the National Technical Information Services, U.S.
Department of Commerce, 5285 Port Royal., Springfield, VA 22161.
Order No. DE93012222
DOE-HDBK-1015/2-93
CHEMISTRY
ABSTRACT
The Chemistry Handbook was developed to assist nuclear facility operating contractors
in providing operators, maintenance personnel, and the technical staff with the necessary
fundamentals training to ensure a basic understanding of chemistry. The handbook includes
information on the atomic structure of matter; chemical bonding; chemical equations; chemical
interactions involved with corrosion processes; water chemistry control, including the principles
of water treatment; the hazards of chemicals and gases, and basic gaseous diffusion processes.
This information will provide personnel with a foundation for understanding the chemical
properties of materials and the way these properties can impose limitations on the operation of
equipment and systems.
Key Words: Training Material, Atomic Structure of Matter, The Periodic Table of the
Elements, Chemical Bonding, Corrosion, Water Chemistry Control, Water Treatment Principles,
Chemical Hazards, Gaseous Diffusion Processes
Rev. 0
CH
DOE-HDBK-1015/2-93
CHEMISTRY
FOREWORD
The Department of Energy (DOE) Fundamentals Handbooks consist of ten academic
subjects, which include Mathematics; Classical Physics; Thermodynamics, Heat Transfer, and
Fluid Flow; Instrumentation and Control; Electrical Science; Material Science; Mechanical
Science; Chemistry; Engineering Symbology, Prints, and Drawings; and Nuclear Physics and
Reactor Theory. The handbooks are provided as an aid to DOE nuclear facility contractors.
These handbooks were first published as Reactor Operator Fundamentals Manuals in 1985
for use by DOE category A reactors. The subject areas, subject matter content, and level of
detail of the Reactor Operator Fundamentals Manuals were determined from several sources.
DOE Category A reactor training managers determined which materials should be included, and
served as a primary reference in the initial development phase. Training guidelines from the
commercial nuclear power industry, results of job and task analyses, and independent input from
contractors and operations-oriented personnel were all considered and included to some degree
in developing the text material and learning objectives.
The DOE Fundamentals Handbooks represent the needs of various DOE nuclear facilities
fundamental training requirements. To increase their applicability to nonreactor nuclear facilities,
the Reactor Operator Fundamentals Manual learning objectives were distributed to the Nuclear
Facility Training Coordination Program Steering Committee for review and comment. To update
their reactor-specific content, DOE Category A reactor training managers also reviewed and
commented on the content. On the basis of feedback from these sources, information that applied
to two or more DOE nuclear facilities was considered generic and was included. The final draft
of each of the handbooks was then reviewed by these two groups. This approach has resulted
in revised modular handbooks that contain sufficient detail such that each facility may adjust the
content to fit their specific needs.
Each handbook contains an abstract, a foreword, an overview, learning objectives, and text
material, and is divided into modules so that content and order may be modified by individual
DOE contractors to suit their specific training needs. Each handbook is supported by a separate
examination bank with an answer key.
The DOE Fundamentals Handbooks have been prepared for the Assistant Secretary for
Nuclear Energy, Office of Nuclear Safety Policy and Standards, by the DOE Training
Coordination Program. This program is managed by EG&G Idaho, Inc.
Rev. 0
CH
DOE-HDBK-1015/2-93
CHEMISTRY
OVERVIEW
The Department of Energy Fundamentals Handbook entitled Chemistry was prepared as
an information resource for personnel who are responsible for the operation of the Departments
nuclear facilities. An understanding of chemistry will enable contractor personnel to understand
the intent of the chemical concerns within their facility. A basic understanding of chemistry is
necessary for DOE nuclear facility operators, maintenance personnel, and the technical staff to
safely operate and maintain the facility and facility support systems. The information in the
handbook is presented to provide a foundation for applying engineering concepts to the job. This
knowledge will help personnel understand the impact that their actions may have on the safe and
reliable operation of facility components and systems.
The Chemistry handbook consists of five modules that are contained in two volumes. The
following is a brief description of the information presented in each module of the handbook.
Volume 1 of 2
Module 1 - Fundamentals of Chemistry
Introduces concepts on the atomic structure of matter. Discusses the periodic table
and the significance of the information in a periodic table. Explains chemical
bonding, the laws of chemistry, and chemical equations.
Appendix A - Basic Separation Theory
Introduces basic separation theory for the gaseous diffusion process.
Discusses converter construction and basic operating principals.
Module 2 - Corrosion
Supplies basic information on the chemical interaction taking place during the
corrosion process between the environment and the corroding metal.
Rev. 0
CH
DOE-HDBK-1015/2-93
CHEMISTRY
OVERVIEW (Cont.)
Volume 2 of 2
Module 3 - Reactor Water Chemistry
Describes the chemical measures taken to retard the corrosion often found in water
systems. The consequences of radioactivity on facility cooling water systems are
also addressed.
Module 4 - Principles of Water Treatment
Details the principles of ion exchange in the context of water purity. Discusses
typical water treatment methods and the basis for these methods.
Module 5 - Hazards of Chemicals and Gases
Explains why certain chemicals are considered hazardous to facility personnel.
Includes general safety rules on handling and storage.
The information contained in this handbook is by no means all encompassing. An attempt
to present the entire subject of chemistry would be impractical. However, the Chemistry
Handbook does present enough information to provide the reader with a fundamental knowledge
level sufficient to understand the advanced theoretical concepts presented in other subject areas,
and to better understand basic system and equipment operation.
Rev. 0
CH
Department of Energy
Fundamentals Handbook
CHEMISTRY
Module 3
Reactor Water Chemistry
DOE-HDBK-1015/2-93
TABLE OF CONTENTS
TABLE OF CONTENTS
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
iv
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
EFFECTS OF RADIATION
ON WATER CHEMISTRY (SYNTHESIS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Interaction of Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
CHEMISTRY PARAMETERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Specific Parameters . . . . . . . . .
pH . . . . . . . . . . . . . . . . . . . . .
Dissolved Oxygen . . . . . . . . . .
Hydrogen . . . . . . . . . . . . . . . .
Total Gas . . . . . . . . . . . . . . . .
Conductivity . . . . . . . . . . . . . .
Chlorides . . . . . . . . . . . . . . . .
Fluorine . . . . . . . . . . . . . . . . .
Radioactivity . . . . . . . . . . . . . .
Tritium . . . . . . . . . . . . . . . . . .
Abnormal Chemistry Conditions
Injection of Air . . . . . . . . . . . .
Fuel Element Failure . . . . . . . .
Resin Overheating . . . . . . . . . .
Summary . . . . . . . . . . . . . . . .
Rev. 0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Page i
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
12
14
15
16
18
19
21
22
23
23
25
25
28
28
30
CH-03
LIST OF FIGURES
DOE-HDBK-1015/2-93
LIST OF FIGURES
Figure 1 Change in pH, Gas Concentration, and Nitrogen Compounds
With Excess Oxygen Added . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Figure 2 Corrosion Rate vs. pH for Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Figure 3 Pressurizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Figure 4 pH and Conductivity as a Function of NH3 Concentration . . . . . . . . . . . . . . . 19
Figure 5 Theoretical Conductivity as a Function of pH . . . . . . . . . . . . . . . . . . . . . . . . 20
Figure 6 Facility Start-up with Air in Loop . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
CH-03
Page ii
Rev. 0
DOE-HDBK-1015/2-93
LIST OF TABLES
LIST OF TABLES
Table 1 Summary of Reactor Coolant Chemistry Control . . . . . . . . . . . . . . . . . . . . . . 13
Table 2 Hydrogen Isotopes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Rev. 0
Page iii
CH-03
REFERENCES
DOE-HDBK-1015/2-93
REFERENCES
Donald H. Andrews and Richard J. Kokes, Fundamental Chemistry, John Wiley & Sons,
Inc., 1963
Compressed Gas Association, Inc., Handbook of Compressed Gases, 2nd Edition,
Reinhold Publishing Corporation, 1981.
R. A. Day, Jr. and R. C. Johnson, General Chemistry, Prentice Hall, Inc., 1974.
Dickerson, Gray, Darensbourg and Darensbourg, Chemical Principles, 4th Edition, The
Benjamin Cummings Publishing Company, 1984.
Academic Program for Nuclear Plant Personnel, Volume II, Chemistry, Columbia, MD,
General Physics Corporation, Library of Congress Card #A 326517, 1972.
General Physics Corporation, Fundamentals of Chemistry, General Physics Corporation,
1982.
Glasstone and Sesonske, Nuclear Reactor Engineering, 3rd Edition, Van Nostrand
Reinhold Company, 1981.
McElroy, Accident Prevention Manual for Industrial Operations Engineering and
Technology, Volume 2, 8th Edition, National Safety Council, 1980.
Sienko and Plane, Chemical Principles and Properties, 2nd Edition, McGraw and Hill,
1974.
Underwood, Chemistry for Colleges and Schools, 2nd Edition, Edward Arnold, Ltd., 1967.
Norman V. Steere and Associates, CRC Handbook of Laboratory Safety, 2nd Edition,
CRC Press, Inc., 1971.
CH-03
Page iv
Rev. 0
DOE-HDBK-1015/2-93
OBJECTIVES
TERMINAL OBJECTIVE
1.0
Without references, DESCRIBE the effects of radiation on reactor water and methods of
treatment for the products.
ENABLING OBJECTIVES
1.1
DESCRIBE the process of radiolytic decomposition and recombination of water.
1.2
DESCRIBE the process of radiolytic decomposition and recombination of nitric acid and
ammonia.
1.3
STATE the advantage of maintaining excess hydrogen in reactor water.
1.4
STATE the three sources of radioactivity in reactor water and each ones decay product.
1.5
STATE the following for reactor water chemistry.

a.
b.
c.
1.6
Rev. 0
Nine parameters controlled

Reason for controlling each parameter
Method of controlling each parameter
STATE the possible effects of abnormal chemistry on core conditions.
Page v
CH-03
OBJECTIVES
DOE-HDBK-1015/2-93
Intentionally Left Blank
CH-03
Page vi
Rev. 0
DOE-HDBK-1015/2-93
ON WATER CHEMISTRY (SYNTHESIS)
Radiation synthesis is a process that takes place in the reactor coolant system.
This phenomenon is limited to the reactor coolant system because of the high flux
(radiation) levels that exist in the core region and further complicate chemistry
control of the reactor plant.
EO 1.1
DESCRIBE the process of radiolytic decomposition and

recombination of water.
EO 1.2
DESCRIBE the process of radiolytic decomposition and

recombination of nitric acid and ammonia.
EO 1.3
STATE the advantage of maintaining excess hydrogen in

reactor water.
EO 1.4
STATE the three sources of radioactivity in reactor water

and each one's decay product.
Interaction of Radiation
As reactor coolant water passes through the core region of an operating reactor, it is exposed
to intense radiation. The major components of the radiation field are neutrons, protons, gamma
rays, and high energy electrons (beta particles). These types of radiation interact with the
coolant water primarily by an ionization process and have a marked effect on the water itself
and on the chemical reactions between substances dissolved in the water. This section discusses
these effects, and in particular the effects that involve gases dissolved in reactor coolant.
The interaction of radiation with matter produces ion pairs. Usually, the negative member of
the ion pair is a free electron and the positive member is a polyatomic cation, the exact nature
of which depends on the particular substance being irradiated. For example, the interaction of
radiation with water is illustrated by the following reaction.
H2O
Rev. 0
radiation
Page 1
H2O
(3-1)
CH-03
DOE-HDBK-1015/2-93
Both of these species are very reactive chemically, and there are several reaction pathways
available to each. Some of these mechanisms are very complex and are usually of little practical
value to the reactor operator, who is more concerned with the overall, observable effects. In
the case of water, the overall effect of irradiation is shown in the following reaction.
2H2O
radiation
2H2
O2
(3-2)
Because this result is not at all apparent from Reaction (3-1), the following section describes
the intermediate processes in some detail. This discussion is presented only to illustrate the
types of reaction mechanisms that occur in irradiated solutions. Subsequent discussions
primarily involve only the overall effects of these processes.
Reaction (3-1) shows that irradiation of pure water produces an electron and a H2O+ ion. As
stated, both species are highly reactive. The H2O+ ion rapidly reacts with a water molecule as
follows.
H2O
H2O
H3O
OH
(3-3)
The species OH is an uncharged hydroxyl group. Neutral groups such as this, in which all
chemical bonding capacity is not satisfied, are common intermediate species in chemical
reactions and are called radicals or sometimes free radicals.
The electron produced by Reaction (3-1) first forms a species called the hydrated electron,
denoted by eaq-. The hydrated electron may be thought of as resulting from the interaction of
a negative electron with the positive end of a polar water molecule. This is analogous to the
formation of hydronium ions by interaction of a positive proton (H+) with the negative end of
a water molecule. Because the water molecules associated with hydrated electrons do not
participate in subsequent chemical reactions, they are not shown in chemical equations, and the
hydrated electron (eaq-) is used instead.
Hydrated electrons may interact with H3O+ ions in solution or with water molecules. Both
reactions produce another reactive species, atomic hydrogen.
eaq
H3O
H2O
H2O
(3-4)
or
eaq
OH
(3-5)
Reaction (3-4) usually predominates.

CH-03
Page 2
Rev. 0
DOE-HDBK-1015/2-93
Because Reactions (3-4) and (3-5) are slow compared to that in Reaction (3-3), there are three
reactive species present at any one time: hydroxyl radicals (OH), hydrated electrons (eaq-), and
hydrogen atoms (H). These species may undergo any of several possible reactions such as the
following.
OH
OH
H2O2 (hydrogen peroxide)
(3-6)
OH
H2O
(3-7)
H2
(3-8)
H2O
eaq
H2
OH
H2
(3-9)
OH
H2O
(3-10)
Hydrogen peroxide, formed by Reaction (3-6), may also react with the original reactive species,
but at high temperatures H2O2 is unstable, and the predominant reaction is decomposition.
2H2O2
O2
(3-11)
2H2O
To illustrate the overall result of these reactions, let us assume that each of the reactive species
produced by successive steps in the irradiation of water reacts in only one way. That is,
whenever several reactions of a particular substance are possible, assume that one predominates
to such an extent that the others are negligible. The following set of reactions is one possibility.
In some cases, entire reactions are multiplied by a factor to allow cancellation of terms when
the reactions are summed.
4 ( H2O
radiation
H2O )
(3-1)
H2O
H3O
OH )
(3-3)
4 ( H2O
eaq
H3O
2 ( OH
Rev. 0
H
OH
Page 3
H2O
H2O2 )
(3-4)
(3-6)
CH-03
DOE-HDBK-1015/2-93
2 (H
2H2O2
Net reaction:
8 H2O
(3-8)
H2 )
O2
radiation
(3-11)
2H2O
2H2
O2
6H2O
or
2 H2O
radiation
2H2
O2
(3-12)
The net result of these reactions is simply the decomposition of water. If H2 and O2 are allowed
to escape from solution as gases, the reaction continues as written. If, however, the water is
contained in a closed system under pressure (as in a reactor coolant system), H2 and O2 are
confined, and an equilibrium state is reached because radiation also causes the reverse of
Reaction (3-2) to take place. Primarily neutron and gamma radiation induce both the
decomposition of water and the recombination of H2 and O2 to form water. Thus, it is
appropriate to write Reaction (3-2) as a radiation-induced equilibrium reaction.
radiation
2H2O
2H2
O2
(3-12)
radiation
To arrive at the overall effect of radiation on water, the above process involved the assumption
that only one reaction pathway is available to each reactive species. This was done primarily
for convenience because inclusion of every possible reaction in the summation process becomes
rather cumbersome. Even if all the reactions are taken into account, the net result is the same
as Reaction (3-12), which is reasonable because inspection of Reactions (3-3) through (3-11)
shows that the only stable products are H2, O2, and H2O (H3O+ and OH- combine to form water,
and H2O2 decomposes at high temperature). Perhaps not as obvious, more water is consumed
than is produced in these reactions, and the net result is the initial decomposition of water that
proceeds until equilibrium concentrations of H2 and O2 are established.
Before discussing the effects of radiation on other processes, chemical equilibrium in the
presence of ionizing radiation should be mentioned. Equilibrium processes in aqueous solutions
are discussed briefly in Module 1, which states that temperature influences the equilibrium.
Ionizing radiation also influences the equilibrium of these solutions.
CH-03
Page 4
Rev. 0
DOE-HDBK-1015/2-93
Radiation has an effect on the equilibrium in the case of water. In the absence of radiation,
water does not spontaneously decompose at 500 F and the equilibrium lies far to the right.
2H2
O2
2H2O
When irradiated, however, water does decompose, as shown above. Also, H2 and O2 do not
normally react at 500 F because a large activation energy is required to make the reaction
occur. Radiation, in effect, supplies this activation energy, and the reaction takes place readily.
Thus, radiation increases the rates of both forward and reverse reactions, although not by the
same factor.
In general, the effect of radiation on the equilibrium for a given reaction cannot be predicted
quantitatively. The situation is further complicated by the observation that the effect on the
equilibrium may vary with the intensity of the radiation. In nuclear facilities, the effect may vary
with the power level of the facility. In most cases, this complication is not a severe problem
because the direction of the effect is the same; only the degree or magnitude of the effect varies
with the intensity of the radiation.
As noted several times previously, reactor coolant is maintained at a basic pH (in facilities other
than those with aluminum components or those that use chemical shim reactivity control) to
reduce corrosion processes. It is also important to exclude dissolved oxygen from reactor
coolant for the same reason. As shown in the preceding section, however, a natural consequence of exposing pure water to ionizing radiation is production of both hydrogen and oxygen.
The addition of a base to control pH has essentially no effect on this feature.
To prevent the formation of oxygen in reactor coolant, hydrogen is added. Hydrogen
suppresses the formation of oxygen primarily by its effect on the reactions that OH radicals,
produced by Reaction (3-3), undergo. In the presence of excess hydrogen, hydroxyl radicals
react predominantly by Reaction (3-10) rather than as in Reactions (3-6) through (3-8).
H2
OH
H2O
(3-10)
Hydrogen atoms from this equation subsequently react to form H2 and H2O by Reactions (3-7),
(3-8), and (3-9). None of these reactions leads to O2, or H2O2, which decomposes to form O2
and H2O at high temperatures. Thus, the addition of H2 to reactor coolant largely eliminates
production of free oxygen.
Rev. 0
Page 5
CH-03
DOE-HDBK-1015/2-93
Another way of viewing the effect of hydrogen on reactor coolant is through its effect on the
equilibrium of the reaction.
2 H2O
radiation
2H2
O2
(3-12)
By LeChatelier's principle, the addition of excess hydrogen forces the equilibrium to the left,
which requires that O2 be consumed. If the dissolved hydrogen concentration is sufficiently
large, only a very small amount of oxygen will be present at equilibrium. Normally, therefore,
reactor coolant contains excess dissolved hydrogen, and there is no significant net
decomposition of water by radiation.
Reactor coolant makeup water usually contains a small amount of air, which is composed
primarily of nitrogen and oxygen in a volume ratio of 4:1 (80 percent nitrogen, 20 percent
oxygen). These gases undergo radiation-induced reactions. The reactions are the same as those
that occur in certain accident situations and are included in the following discussion.
In addition to the small amount of air normally dissolved in makeup water, there is a small
possibility that air may be accidentally injected directly into the reactor coolant system.
Whenever air enters the reactor coolant system, and the reactor is operating, the most immediate
reaction involves oxygen from the air and hydrogen, which is normally present in the coolant.
2H2
O2
radiation
radiation
2H2O
(3-13)
That is, the addition of O2 disturbs the above equilibrium and causes the equilibrium to shift to
the right, consuming both H2 and O2 . The concentration of hydrogen normally maintained in
reactor coolant is such that small amounts of oxygen will be rapidly consumed before any excess
oxygen can cause severe corrosion problems to occur.
Reaction (3-13) also consumes oxygen added to the reactor coolant as a natural consequence
of air dissolved in makeup water. Other than initial fill of the reactor coolant system, the
situations that require the largest amounts of makeup water are feed and bleed operations to
correct an abnormal chemistry parameter or cooldown after some period of reactor operation.
In this case, gamma radiation from the decay of fission products in the reactor core continues
to induce the H2 - O2 reaction for some period after shutdown. During initial fill and long
shutdown periods, chemicals other than hydrogen (e.g. hydrazine) may be added to reactor
coolant to remove any dissolved oxygen.
CH-03
Page 6
Rev. 0
DOE-HDBK-1015/2-93
After essentially all of the oxygen has been consumed by reaction with hydrogen, the nitrogen
contained in air will remain. For small air additions, some hydrogen will also remain; thus, the
reactor coolant will contain both dissolved hydrogen and dissolved nitrogen. These two gases
do not react in an unirradiated solution at low temperature and pressure. When exposed to
radiation, however, the gases do react by the following reaction.
3H2
radiation
N2
2NH3 (ammonia)
(3-14)
Again, this is an equilibrium reaction, and radiation induces the reaction in both directions.
Ammonia (NH3) produced by this reaction combines with water to form ammonium hydroxide
(NH4OH).
NH3
H2O
NH4
OH
(3-15)
Under the operating conditions of reactor coolant, Reaction (3-14) is far from complete. In
most cases, less than about 10 percent of the nitrogen will be converted to ammonia. If no
additional base were added to reactor coolant, Reaction (3-14) would be sufficient to cause the
coolant to be mildly basic, pH 9. In the presence of added base, however, the reaction has only
a very slight and negligible effect on pH.
If the base NH3 were used to control reactor coolant pH, the reverse of Reaction (3-14) would
be more important. The reverse step of this reaction requires that some of the ammonia added
to the coolant decompose into N2 and H2. Because operating conditions favor this step of the
equilibrium, rather than formation of NH3, it would be expected that most of the ammonia added
would decompose. However, the rate of the ammonia decomposition reaction is slow, and the
pH of reactor coolant can be maintained in the required range. It should also be noted that the
decomposition of NH3 would produce hydrogen gas in significant concentrations in reactor
coolant (sufficient to satisfy normal H2 requirements).
In the event that a large quantity of air is injected into the reactor coolant system, the inventory
of dissolved hydrogen would be rapidly depleted by Reaction (3-13). If the amount of air
injected is sufficiently large, there could be oxygen remaining in the coolant after depletion of
the hydrogen. In this case, another reaction is available to the oxygen and nitrogen in the air.
2 N2
5O2
2 H2O
radiation
4HNO3
(3-16)
Nitric acid (HNO3) produced by this reaction will neutralize any base contained in the coolant,
and if sufficient acid is produced, the coolant will acquire an acidic pH.
Rev. 0
Page 7
CH-03
DOE-HDBK-1015/2-93
Normally, the amount of hydrogen maintained in the reactor coolant, in conjunction with other
precautions employed, greatly reduces the probability that the amount of oxygen entering the
coolant will be sufficient to lead to Reaction (3-16). If a large amount of air were accidentally
added to the reactor coolant, one solution would be to add more hydrogen. The added hydrogen
would react with remaining oxygen, disrupting the equilibrium of Reaction (3-16) causing the
reverse step of that reaction to occur. When all the oxygen has been removed, H2 and N2 could
react by Reaction (3-14) and help reestablish a basic pH. The relationship between these
reactions and pH following the initial oxygen addition, and a subsequent hydrogen addition, is
illustrated in Figure 1.
Figure 1 Change in pH, Gas Concentration, and Nitrogen Compounds

With Excess Oxygen Added
CH-03
Page 8
Rev. 0
DOE-HDBK-1015/2-93
In the preceding discussion, the reactions possible after the addition of air to reactor coolant
containing hydrogen were described. These are Reactions (3-13), (3-14), and (3-16). The
relative rates of these reactions are of considerable importance. Briefly, Reaction (3-13) is much
more rapid than either of the others, and Reaction (3-16) is faster than Reaction (3-14). Thus,
the sequence of reactions is as described in the preceding sections. H2 and O2 react to form
water. If hydrogen remains, it undergoes an incomplete reaction with N2 to form small amounts
of NH3. If O2 remains after all the H2 has been consumed, the O2 - N2 reaction produces nitric
acid.
The flux of neutrons and protons in a nuclear reactor core region leads to several important
nuclear reactions with the constituent atoms of water. Most of these reactions involve oxygen
isotopes and fast neutrons or protons.
In many cases, the absorption of a fast neutron by a nucleus is immediately followed by ejection
of a proton. These reactions are called neutron-proton or n-p reactions and are commonly
written (using the 16O reaction to illustrate) in the following manner.
16
8
O (n, p) 167N (t1/2 = 7.13 seconds)
(3-17)
In this notation, the original isotope that undergoes the reaction is written first, the product
isotope is last, and the two are separated by, in order, the particle absorbed and the particle
emitted. The isotope 167N decays to 168O with a 7.13-second half-life by emitting a beta particle
( -) and a high-energy gamma ray (6 Mev predominantly).
16
7
16
8
O+
Oxygen-17 undergoes a similar reaction.

17
8
O (n, p) 177N (t1/2 = 4.1 seconds)
The isotope
(3-18)
17
7
N decays by emission of a beta particle, a neutron, and a gamma ray.

17
7
16
8
O+
+ 10n +
Reactions (3-17) and (3-18) have no significant chemical effect on reactor coolant because of
the relatively small number of atoms that undergo these reactions. They are of considerable
importance, however, because the radioactive species 167N and 177N are carried outside the core
region by the flow of reactor coolant. The neutrons and high-energy gamma rays emitted by
these isotopes easily penetrate the piping and components that contain the coolant and are
important considerations in the design of shielding for nuclear facilities. Because the half-lives
of these isotopes are very short, they decay to low levels very rapidly after shutdown and are,
therefore, of little concern during such periods.
Rev. 0
Page 9
CH-03
DOE-HDBK-1015/2-93
Two other nuclear reactions with oxygen isotopes are shown below.
18
8
O (p, n) 189F (t1/2 = 112 minutes)
16
8
O (p, ) 137N (t1/2 = 10 minutes)
An ejected alpha particle is indicated by . The protons that cause these reactions result from
inelastic collisions of fast neutrons with hydrogen atoms in water molecules. The radioactivity
levels of these isotopes are much lower than the levels of 167N and 177 N during reactor facility
operation. However, during the period from a few minutes to about five hours after reactor
shutdown or after removing a coolant sample from the system, 137N and 189 F are the principal
sources of radioactivity in the reactor coolant of most reactor facilities.
13
7
18
9
13
6
C + +10
18
8
O + +10
The only significant nuclear reaction that occurs with hydrogen involves deuterium (21H), which
comprises about 0.015 percent of natural hydrogen.
2
1
H (n, ) 31H (t1/2 = 12.3 years)
Tritium (31H) decays by emission of a very weak particle (0.02 Mev) and no gamma rays.
Thus, tritium is not a radiological hazard unless it enters the body in significant amounts.
Tritium can enter the body through inhalation or ingestion. It is also possible to absorb forms
of tritium through the skin.
CH-03
Page 10
Rev. 0
DOE-HDBK-1015/2-93
Summary
The important information in this chapter is summarized below.
Effects of Radiation on Water Chemistry (Synthesis) Summary

The intense radiation inside the core of an operating nuclear reactor produces several
chemical effects on the reactor coolant itself and on substances dissolved in the
coolant. Radiation causes pure water to decompose into H2 and O
2 . The
decomposition is suppressed by adding excess hydrogen.
2H2O
2H2 + O2
Excess hydrogen is added to suppress the decomposition of reactor water. It also

reacts with any oxygen that enters the reactor coolant system, usually as a component
of air in makeup water, provided the amount of oxygen is not excessive. If the
amount of oxygen is more than enough to deplete the hydrogen, the excess oxygen
reacts with nitrogen (also a component of air) and forms nitric acid. In the case of
addition of very large amounts of air, the amount of nitric acid produced may be
more than enough to neutralize the normally basic coolant and cause it to become
acidic.
Radiation induces the combination of N2 and H2 to form ammonia, although the
extent of this reaction is small and usually has a negligible effect on the pH of reactor
coolant. All of the reactions in this chapter are reversible and reach an equilibrium
state under normal operating conditions. Changes in the concentrations of any of the
reactants disturb the equilibrium and causes the reaction to shift in the direction
which restores the equilibrium.
2NH3
N2 + 3H2
Radiation also produces several nuclear reactions in reactor coolant. The products
16
17
7N and 7N, of two of these reactions, contribute radioactivity to the reactor coolant,
adding significantly to the shielding requirements for nuclear reactors. Others, 137N
and 189F, are also major contributors to the radioactivity in reactor coolant.
16
7
16
8
13
7
13
6
N
N
Rev. 0
O+
17
7
C + +10
16
8
18
9
Page 11
+ 01n +
O+
18
8
O + +10
CH-03
CHEMISTRY PARAMETERS
DOE-HDBK-1015/2-93
The reasons for control of selected chemistry parameters, and some of the
more common methods of controlling these parameters will be discussed. No
attempt will be made to identify specific values of any of the parameters
discussed because of the number of different reactor facilities involved, but
an overview concerning the bases and common methods used will be included.
For operating values and specifications, users should refer to local facility
publications. In addition, some information on tritium is provided.
EO 1.5
STATE the following for reactor water chemistry.

a.
b.
c.
EO 1.6
Nine parameters controlled

Reason for controlling each parameter
Method of controlling each parameter
STATE the possible effects of abnormal chemistry on core

conditions.
Specific Parameters
Specific chemical parameters vary from facility to facility but generally include the following:
pH, dissolved oxygen, hydrogen, total gas content, conductivity, chlorides, fluorine, boron,
and radioactivity. For the parameters indicated, control is generally achieved by one or more
of three basic processes.
(1)
Ion exchange in the primary system demineralizer(s) or by supplemental

chemical additions
(2)
Oxygen scavenging by hydrogen or hydrazine addition
(3)
Degassification
Table 1 lists the more common chemistry parameters measured and/or controlled, the reasons
each is measured and/or controlled, and control methods utilized.
CH-03
Page 12
Rev. 0
DOE-HDBK-1015/2-93
TABLE 1
Summary of Reactor Coolant Chemistry Control
Parameter
pH
Reason
To inhibit corrosion
To protect corrosion film
To preclude caustic stress
corrosion
Dissolved Oxygen
Method of Control
Ion exchange
Ammonium hydroxide
addition
Nitric acid addition
Hydrogen addition
To inhibit corrosion
Hydrazine addition
To scavenge oxygen
Hydrogen
To suppress radiolytic
decomposition of water
Hydrogen addition
To scavenge nitrogen
Total Gas Content
Conductivity
To preclude hydrogen
embrittlement
Degassification
To protect pumps
Degassification
To indicate air in leakage
Deaeration of makeup water
To minimize scale formation
Ion exchange
To indicate increased corrosion
Feed and Bleed

Ion exchange
Chlorides
To preclude chloride stress

corrosion
Fluorine
To preclude corrosion of Zr
cladding
Feed and Bleed
To control reactivity
Boric acid addition
To indicate increased corrosion
Ion exchange
Feed and bleed

Ion exchange
Boron
To indicate a crud burst

Radioactivity
To indicate a core fuel defect
Feed and bleed
To monitor effectiveness of
demineralizer
Rev. 0
Page 13
CH-03
DOE-HDBK-1015/2-93
pH
The reason for controlling pH in the reactor coolant system is to minimize and control corrosion.
As discussed in Module 1, the presence of excess H+ ions in solution results in an acidic condition.
In reactor facilities (except those containing aluminum components), acidic conditions are
detrimental to the materials of construction in a number of ways. An acidic condition in the primary
coolant results in processes that are potentially harmful to the system as follows. First, a low pH
promotes rapid corrosion by deteriorating or "stripping off" the protective corrosion film, and
second, corrosion products such as ferrous oxide (Fe3O4), which is predominant in the corrosion
film, are highly soluble in an acidic solution. Figure 2 shows how the corrosion rate increases as
the pH decreases. Thus for facilities not using aluminum components, a neutral or highly basic pH
is less corrosive.
Figure 2 Corrosion Rate vs. pH for Iron
In nuclear facilities that do not use chemical shim to control reactivity, pH is normally maintained
at a relatively high value, such as a pH of about 10. In these facilities the upper limit for pH is set
based on caustic stress corrosion considerations because caustic stress corrosion becomes more
probable as higher pH values are approached.
In facilities that use chemical shim reactivity control (chemical shim involves the addition of boron
in the form of boric acid) the pH is maintained at a much lower value. A low pH is necessary
because of the large amounts of boric acid added to the reactor coolant. Accordingly, pH in these
facilities is maintained as high as possible consistent with the reactivity requirements of the nuclear
facility, with pH range from 5 to 7 being common.
CH-03
Page 14
Rev. 0
DOE-HDBK-1015/2-93
In facilities using aluminum components, pH is maintained on the acidic side of the scale
because of the corrosion characteristics of aluminum discussed in Module 2. In these facilities
pH may be controlled by the addition of a dilute nitric acid (HNO3) solution to the reactor
coolant system in conjunction with an ion exchange system of some type.
Regardless of the pH range maintained, most facilities use an ion exchange process (described
in Module 4) to help control pH. For the high pH facilities, the most common means of control
is the use of a lithium or an ammonium form cation and a hydroxyl form anion. When lithium
is used, it must be 7Li because other lithium isotopes produce tritium, which represents a
significant biological hazard to personnel. In facilities that employ high pH chemistry control
and do not use chemical shim reactivity control, it is sometimes necessary to add a strong base
solution such as ammonium or lithium hydroxide. When chemical additions are used for pH
control, facility design and operating procedures are utilized to preclude overconcentration at
any point in the system, which may lead to caustic stress corrosion conditions. Many reactions
that take place in the reactor coolant system can affect pH; therefore chemistry control must be
considered carefully to preclude upsetting the pH balance provided by the ion exchanger.
Dissolved Oxygen
Control of the dissolved oxygen content in the reactor facility system is of paramount
importance because of its contribution to increased corrosion. The base reactions of concern
regarding high concentrations of dissolved oxygen are the following.
3 Fe
2O2
Fe3O4
(3-19)
4Fe
3 O2
2Fe2O3
(3-20)
They are dependent on both the concentration of oxygen and temperature. Reaction (3-19) is
predominant at high temperatures (>400 F) in the presence of lower oxygen concentrations.
This corrosion film, ferrous oxide, is also known as magnetite and is a black, generally
tightly-adherent film that provides a protective function to surfaces within the facility.
Reaction (3-20) occurs at temperatures below about 400 F in the presence of higher oxygen
concentrations. Ferric oxide (Fe2O 3) is more commonly known as rust and is generally a
reddish color. This corrosion product adheres loosely to surfaces and is therefore easily
removed and transported throughout the system for subsequent deposition and possible
irradiation. In either of the reactions, the corrosion rate is accelerated by increased
concentrations of dissolved O2 and can be aggravated further by the presence of other
substances that may be present in the system.
Rev. 0
Page 15
CH-03
DOE-HDBK-1015/2-93
In addition to the direct contribution to corrosion, oxygen reacts with nitrogen to lower the pH
of the reactor water, which also results in an increased rate of corrosion. Oxygen and nitrogen
react to form nitric acid by the following reaction.
5 O2
2N2
2H2O
radiation
4 HNO3 (nitric acid)
In all the reactions presented, it can be seen that oxygen concentrations promote corrosion. It
follows then that if corrosion is to be minimized, oxygen concentrations must be maintained as
low as possible. In most nuclear facility reactor coolant systems, the limit for dissolved oxygen
concentrations is expressed in ppb (parts per billion). Concentration may be monitored on a
continuous basis by using an in-line analyzing system or periodically by withdrawing a sample
volume and analyzing that sample. Monitoring oxygen levels is done not only to ensure that
no oxygen is available for corrosion, but also to indicate the introduction of air into the system.
Hydrogen
Because the presence of dissolved oxygen contributes to most mechanisms of corrosion, the
concentration of oxygen is controlled and reduced by the addition of scavenging agents in most
facilities. Hydrogen gas (H2) and hydrazine (N2H4) are the scavenging agents normally used to
eliminate dissolved oxygen from the reactor coolant system. These substances scavenge oxygen
by the following reactions.
2H2
N2H4
O2
radiation
radiation
O2
2H2O
2H2O
(3-13)
N2
(3-21)
Because hydrazine decomposes rapidly at temperatures above about 200 F (forming NH3, H2,
and N2), hydrogen gas is used as the scavenging agent during hot operation and hydrazine is
used when the reactor coolant system is cooled below 200oF.
(Heat)
2NH3
N2
2 N2H4
(decomposition of hydrazine)
H2
The decomposition reactions of hydrazine pose additional problems in chemistry control. Even
if sufficient hydrazine were added to overcome the loss due to decomposition, instability of
coolant pH would probably occur by the following reactions.
2N2
3H2
CH-03
5 O2
2H2O
N2
2 H2O
Page 16
4 HNO3 (acid)
2NH4OH (base)
(3-16)
(3-22)
Rev. 0
DOE-HDBK-1015/2-93
The use of hydrogen gas at temperatures above 200 F precludes the generation of the
compounds formed by Reactions (3-16) and (3-22). In addition, hydrogen is compatible with
the high flux levels present in the reactor core. Accordingly, advantage may be taken of the
reversibility of the radiolytic decomposition of water. The following reaction illustrates the
scavenging process utilizing hydrogen.
2H2
O2
radiation
radiation
2H2O
(3-13)
As indicated, the reaction is an equilibrium process and will therefore depend on the relative
concentrations of the reactants and the products. By maintaining an excess of hydrogen (H2),
the reaction is forced to shift to the right and theoretically eliminates any dissolved oxygen that
may be present. As long as an inventory of H2 is present in the coolant, dissolved oxygen will
be eliminated or forced to recombine immediately after radiolytic decomposition, thereby being
unavailable for corrosion reactions.
A boiling water reactor (BWR) facility is susceptible to corrosion, resulting from dissolved
oxygen, in the same reactions as are present in a pressurized water reactor (PWR). However,
because of the design of these facilities the use of chemical additives is prohibited because
continuous concentration would occur in the reactor vessel due to boiling. Boiling would result
in a plating out process, and the irradiation of these concentrated additives or impurities would
create an extreme environment of radiation levels as well as adverse corrosion locations.
By the very nature of operation of a BWR facility, the buildup of high concentrations of
dissolved oxygen is prevented. Because boiling is occurring in the reactor vessel and the steam
generated is used in various processes and subsequently condensed, removal of dissolved gases
is a continual process. As stated, boiling is an effective means of removing gases from a
solution. If we were to compare the oxygen content of the steam and the water in a BWR, we
would find typical concentrations of 100 ppb to 300 ppb in the water and 10,000 ppb to
30,000 ppb in the steam. This concentration process is continuous during operation, and the
dissolved oxygen remains in the gaseous state and is subsequently removed in the condensing
units along with other noncondensible gases. As with PWR facilities, BWR facilities minimize
the introduction of dissolved oxygen by pretreating makeup water by some method. The large
oxygen concentrations measured in the steam system result primarily from the radiolysis of
water according to Reaction (3-12), and as operation is continued, the equilibrium
concentration of 100 ppb to 300 ppb is established. This concentration of oxygen is consistent
with the objective of minimizing corrosion.
Rev. 0
Page 17
CH-03
DOE-HDBK-1015/2-93
Total Gas
Total gas concentration in the reactor coolant
system is another parameter of concern.
Total gas is the sum of all gases contained in
the coolant system and is made up primarily
of hydrogen (H2), nitrogen (N2 ), argon (Ar),
and oxygen (O2). The small amounts of
fission gases (Kr and Xe) normally present in
the system may also contribute to the total gas
concentration; however, under normal
conditions these are essentially undetectable.
Total gas is of concern because high
concentrations can result in the formation of
gas pockets in areas that are high points of the
system where low or stagnant flow conditions
exist. Of particular concern in PWR facilities
are the erosion and corrosion that may occur
on the impellers of the primary coolant
pumps. As the concentration of gas is
increased, the probability of the gas coming
out of solution in significant amounts in areas
of low pressure is also increased. This low
pressure condition exists at the inlet to the
primary coolant pump impeller (where
centrifugal pumps are utilized). As these gas
bubbles are forced back into solution on the
high pressure side of the impeller, erosion can
occur as a result of the gas bubble impinging
on the impeller. In extreme concentrations of
total gas, loss of pump priming and cavitation
can occur with resultant mechanical pump
damage.
Figure 3 Pressurizer
Reduction of total gas concentrations in PWRs is normally accomplished by the venting of a

steam space. In those facilities utilizing a pressurizer, the steam space in the top of the
pressurizer is designed to accomplish this venting operation either continuously or
intermittently. This process of reducing the total gas concentration is generally referred to as
degassification. A typical PWR pressurizer with degassification piping is shown in Figure 3.
Degassification is not normally required in a BWR because of its design. As discussed
previously, the boiling action in the reactor vessel strips dissolved gases from the water, and
they are continuously removed in the condensing phase of the energy cycle.
CH-03
Page 18
Rev. 0
DOE-HDBK-1015/2-93
Conductivity
Conductivity of reactor facility water is measured to provide an indication of dissolved ionic
substances in the coolant. Conductivity measurements provide quantitative rather than
qualitative information because it is possible to determine the total conductivity of the ions
present, but not the specific types of ions present. Because many ions such as iron (Fe+++),
chromium (Cr+++), copper (Cu++) and aluminum (Al+++) are susceptible to forming oxides and
plating out as scale on heat transfer surfaces, reactor coolant conductivity is normally controlled
at a level as low as practicable and consistent with pH. By monitoring conductivity levels in
the reactor facility systems, the operator is able to cross check the chemistry of these systems,
thereby achieving a higher confidence level in the parameters measured.
Regardless of the operating limits specified for a given reactor facility, operating relationships
can be established between pH and conductivity levels of the coolant. Figure 4 shows a typical
relationship of the pH and conductivity of a reactor coolant system using high pH, ammonium
hydroxide chemistry control as a function of the ammonia (NH3) concentration.
Figure 4 pH and Conductivity as a Function of NH3 Concentration
Rev. 0
Page 19
CH-03
DOE-HDBK-1015/2-93
Figure 5 shows the theoretical relationship of pH versus conductivity in a solution containing

pure water. A second curve is added to the graph that illustrates the relationship that exists
when nitric acid (HNO3) is used as a pH control agent (such as may be utilized in facilities with
aluminum components).
Figure 5 Theoretical Conductivity as a Function of pH
In both Figure 4 and Figure 5, a definite relationship exists between pH and conductivity,
assuming no foreign ions are present. A similar graph could be constructed for those facilities
using cation resins of a different base such as lithium or barium.
CH-03
Page 20
Rev. 0
DOE-HDBK-1015/2-93
The key point of this discussion is the realization that a theoretical, or calculated, relationship
does exist, and measurements that vary appreciably from the theoretical values should be
investigated and corrective action taken.
Excessively high conductivity levels are an indication of the presence of undesired ions. This
condition warrants further investigation to locate the source of the impurity because, in addition
to other chemistry problems, it contributes to general corrosion by increasing the reaction rates
of the electrochemical cells. The purity of the makeup water, and any pH control agents added,
should be verified to determine the cause. pH should also be checked because of the
relationship of these parameters. Other chemistry parameters should also be checked, such as
Cl- and F-. After the cause of high conductivity has been determined, appropriate steps should
be taken to return conductivity to its normal value. One method that is often used is a feed and
bleed procedure whereby water is added to and drained from the facility at the same time. If
this method is used, verification of makeup water purity must be ensured to prevent
compounding the problem.
Low conductivity is also an indicator of a potential problem because, in high purity basic
systems, the only possible cause of low conductivity is a low pH. For example, in a system
using high pH ammonium hydroxide control, the introduction of air into the facility could result
in the formation of nitric acid (HNO3) with a reduction in pH by the following reaction.
2N2
5 O2
2H2O
4 HNO3
(3-16)
Conductivity decreases even more than would be expected because of the formation of
NH4NO3. NO3- is not as conductive as OH-, so the NH4NO3 results in a lower conductivity than
NH4OH. This neutralization of NH4OH is shown by the following reaction.
NH4OH
HNO3
NH4NO3
H2O
(3-23)
The water formed is only slightly ionized, so the solution conductivity is lowered even further.
Chlorides
Another parameter that is carefully monitored and controlled in most nuclear facilities is
chloride (Cl-). The reason for maintaining the chloride ion concentration at the minimum level
practicable is that several forms of corrosion are affected by the chloride ion, and the type of
greatest concern is chloride stress corrosion. The mechanics of chloride stress corrosion were
discussed in detail in Module 2 and will therefore not be repeated in this section.
Rev. 0
Page 21
CH-03
DOE-HDBK-1015/2-93
When high levels of Cl- are suspected, or detected, immediate steps must be taken to eliminate
the source and remove Cl- from the system because of the potential consequences. If Cl- is
present in the reactor coolant system, one method of removing it is to initiate a feed and bleed
operation after determining that makeup water supplies are not the source of contamination.
Because of the large volume of water normally contained in the reactor coolant system, cleanup
by this method involves considerable amounts of pure water and a significant amount of time.
Additional problems associated with feed and bleed operations include changes in pH and a loss
of H2 from the reactor coolant system during the cleanup. Changes to either, or both, of these
parameters have the potential to further aggravate the occurrence of chloride stress corrosion
because: pH changes from the optimum operating limits cause increased general corrosion; and
a loss of H2 from the reactor coolant makes the dissolved oxygen that is normally present from
either radiolysis or contained in the makeup water available to interact with the Cl- ions. This
would promote chloride stress corrosion (recalling that Cl-, O2, and tensile stress are all
necessary for chloride stress corrosion to occur).
The fact that a large amount of makeup water is being introduced will result in hydrogen
depletion because even deaerated water contains small amounts of oxygen. H2 will also be lost
because of the draining of coolant from the system. During conditions that require the use of
feed and bleed to correct a chemistry anomaly of any type, increased attention to all parameters
becomes increasingly important.
Another method that may be used to control Cl- concentrations in the reactor coolant is to route
more bypass flow through the ion exchanger system, where installed. Use of this system
precludes the requirements of a large inventory of makeup water as well as the disposal
problems that arise from the bleed (draining) of coolant from the system. Because the ion
exchanger has minimal effect on dissolved gases, depletion of hydrogen does not contribute to
the potential of the problem. Increasing flow through the ion exchanger(s) may cause changes
to the pH of the system, however, and as in the case of feed and bleed, increased vigilance is
necessary to ensure pH, as well as other parameters, are properly controlled and maintained.
Fluorine
Fluorine (F-) is another parameter monitored and controlled in some reactor facilities. High
levels of F- are potentially hazardous for two reasons. First, F- promotes corrosion of zirconium
by a stress corrosion mechanism at the inner surface of the clad (fluorine can be introduced to
this region because of the existence of small defects or "pinholes" that cannot be completely
avoided in the fuel clad). Second, F- is a major contributor to radiation levels of the reactor
coolant. Although some radioactive 18F is produced by a proton, neutron reaction with 18O, the
only significant possible sources are impure makeup water or contamination of chemical agents,
such as NH3 and Li, which are added to the reactor coolant system.
18
O (p,n) 18F (half-life F 112 minutes)
CH-03
Page 22
Rev. 0
DOE-HDBK-1015/2-93
Removal of F- is accomplished in the same manner as the removal of Cl- , that is, by feed and
bleed or increased flow through the ion exchanger system. Removal by ion exchange, however,
is not as effective as for Cl- because of the lower affinity of F- for exchange. As in the case of
Cl- contamination, if feed and bleed is the method selected for cleanup, the purity of the makeup
water must be verified and other chemistry parameters monitored closely to preclude
aggravation of the existing conditions.
Radioactivity
Radioactivity of the reactor coolant system is monitored and controlled because it is a good
indicator of several conditions that may occur in the system. These include increased corrosion,
crud bursts, fuel element defect or failure, and improper operation of the ion exchanger (where
installed). Radioactivity levels in the reactor coolant system are normally kept at nominal values
during normal conditions by the ion exchanger. In facilities that do not use ion exchangers,
other methods that vary from facility to facility are used to control radioactivity. These include
processes such as chemical cleanup followed by feed and bleed with subsequent disposal
procedures and reactor shutdown in severe cases. Reactor coolant gaseous activity is also
monitored, and it provides an indication of cladding failures and the introduction of air during
reactor operation. Gaseous activity levels are normally controlled by degassification. Operating
limits are established in most reactor facilities to operate the reactor safely, to limit radioactive
releases to the environment, and to prevent excessive personnel exposure during operation and
shutdown.
Tritium
This section provides introductory information about tritium and its properties.
Environmental Sources
Tritium occurs naturally in the environment. Reactions between cosmic rays and upper
atmosphere constituents produce tritium. The following are examples of these reactions.
14
7
N + 10n
3
1
2
1
H + 21H
3
1
H +
12
6
H + 11H
Tritium becomes incorporated into water and falls to earth as rain. At an estimated
production rate of 4 x 106 Ci/Yr, a world steady state natural inventory of 70 x 106 Ci
results.
Rev. 0
Page 23
CH-03
DOE-HDBK-1015/2-93
Man-made Sources
Numerous potential and actual sources of tritium production exist in the United States,
the United Kingdom, France, and other countries. They include light-water reactors,
heavy-water reactors, fuel reprocessing facilities, and production reactors. Light-water
reactors produce between 500 and 1000 Ci/yr of tritium in their coolant for every 1000
MW(e) of power. Heavy-water reactors produce approximately 2 x 106 Ci/yr of tritium
in their coolant for every 1,000 MW(e) of power.
Atomic Weight/Hydrogen Isotopes

The atomic weights, symbols, and abundance of the three well-known isotopes of
hydrogen are given in Table 2. 14H and 15H are also known. However, because they decay
in fractions of a single second, they are not extensively studied. Unless otherwise
specified in this chapter, the term hydrogen includes protium, deuterium, and tritium. 11H
will be used to refer to protium; confusion with elemental hydrogen will be eliminated by
spelling out the latter.
TABLE 2
Hydrogen Isotopes
Physical
Symbol
Common
Symbol
Name
Abundance
(%)
Mass
(amu)
1
1
Protium
99.985
1.007825
2
1
Deuterium
0.015
2.01400
3
1
Tritium
emitter*
3.01605
H
H
H
* 12.32-years half-life
Disintegration
Tritium decays by emitting a weak beta particle together with an antineutrino. The
product is helium-3. Helium is a monatomic gas; therefore, the decay of 1 mole of T2
yields 2 moles of helium. This causes a pressure buildup in sealed vessels containing
diatomic tritium gas (or HT or DT gas). The following reaction is tritium disintegration.
3
1
CH-03
3
2
He
Page 24
Rev. 0
DOE-HDBK-1015/2-93
Solubility
Hydrogen gas (including tritium gas) dissolves to some extent in most materials. Tritium
and deuterium behave like protium, except for small isotopic effects. Hydrogen atoms
or diatomic hydrogen molecules and some larger hydrogen-bearing molecules dissolve
interstitially; that is, they diffuse into a structure and locate between atoms or molecular
frameworks. As it dissolves, the hydrogen slightly disrupts the structural networks of the
material and causes expansion. The extent of the disruption, along with the extent of
chemical attractive/repulsive forces between the hydrogen and the material, determines
the ultimate equilibrium state.
Solubility in Polymers, Glasses, and Ceramics

Hydrogen gas dissolves as the molecular hydrogen species in many materials. For these
systems, solubility is generally endothermic and is directly proportional to gaseous
overpressure. The materials in which hydrogen dissolves as the molecular species include
organic polymers and glasses at less than 150 C. Organic polymers generally have
atomic-scale voids in the twisted polymer chain, and the hydrogen molecules seek these
sites. Hydrogen dissolution in glasses is assumed to be similar.
Abnormal Chemistry Conditions

As indicated earlier in this module, there are times when actions taken regarding one specific
chemistry parameter may affect more than that parameter (such as feed and bleed operations).
This may also be the case during many abnormal conditions that the reactor coolant system may
be subjected to.
In this section, we will consider the conditions resulting from injection of air, fuel element
failure, and overheating of resin and discuss the probable changes to other chemistry parameters
that may occur.
Injection of Air
Injection of small and large amounts of air into the reactor coolant system was previously
analyzed. When sufficient oxygen is added to deplete the hydrogen inventory, acidic pH results
in those facilities where high (basic) pH is maintained. This reduction in pH is accompanied by
secondary effects to the coolant. The reduced pH causes a change in solubility of the corrosion
film on facility materials and results in part of this film being released for transport throughout
the coolant system. This release, or crud burst, is detected by an increase in radiation levels of
the coolant, increased conductivity, and lowering of the ion exchanger efficiency. Radiation
levels increase because corrosion products that had been attached to core surfaces and were
highly activated by the neutron flux are transported to other parts of the system.
Rev. 0
Page 25
CH-03
DOE-HDBK-1015/2-93
Conductivity increases because many of the corrosion products are released in an ionic or
radical form and are capable of conducting electricity. In the early stages of the introduction
of air, conductivity may exhibit erratic behavior because of the relationship of conductivity and
pH. As pH begins to fall, conductivity tends to follow, but the presence of suspended corrosion
products offsets the theoretical conductivity. The resultant increase is dependent upon the
concentration of corrosion products. Additionally, should pH fall below about 7, conductivity
increases as pH is further reduced.
Ion exchanger efficiency decreases because the increased crud inventory consists of both
particulate and colloidal products. The ion exchanger is only about 90% effective as a filter,
as compared to approximately 100% effectiveness as an ion exchanger, so effluent radioactivity
levels increase by a greater proportion. Also, crud in the colloidal form has an even lower
probability of being removed by ion exchange or filtration than does particulate crud, and again
the effluent radioactivity is increased.
Hydrogen and total gas react as expected. Because air contains primarily N2 and O2, the gas
inventory in the system increases. Hydrogen levels decrease because of reactions with both O2
40
and N2. Air also contains approximately 1% of 18
Ar by volume. When large amounts of air are
40
added to the reactor coolant system, the 18Ar becomes activated by the neutron flux in the core
region and becomes radioactive in the form of 41
18Ar, causing an increase in the gaseous activity
of the reactor coolant.
Figure 6 illustrates changes to chemistry in an experimental facility that was started up with high
oxygen and nitrogen in the system from the deliberate addition of air. As the power level and
temperature were increased, nitric acid formed and neutralized the ammonium hydroxide
present from previous operation. Conductivity and pH decreased until pH 7 was reached; when
the water became acidic the conductivity showed a corresponding increase. With the formation
of nitric acid (from the nitrogen present), a corresponding increase in chromate ion was
observed (in this case Cr concentrations are directly related to crud inventories and result from
chemical attack on facility materials). The process was reversed by adding hydrogen, which
combined with the oxygen and reduced the nitrate and chromate ions.
It should be noted, however, that in the above experiment the chromate ions were effectively
removed from the coolant by decreasing their solubility. This would not be the case for the
majority of the crud. The vast majority of crud would remain suspended in the coolant until it
was either removed mechanically (filtered) or settled and redeposited at other locations in the
system (including redeposition on the core surfaces).
CH-03
Page 26
Rev. 0
DOE-HDBK-1015/2-93
Figure 6 Facility Start-up With Air in Loop
Rev. 0
Page 27
CH-03
DOE-HDBK-1015/2-93
Fuel Element Failure

During operation of a nuclear reactor facility an equilibrium level of fission products is
established in the reactor coolant. These fission products are the result of trace impurities of
fuel material contained in the cladding surfaces as either natural impurities or a result of the fuel
fabrication process. The mechanism by which the fission products enter the coolant is normally
by fission recoil. Weld porosity is another potential path for the fuel, but generally quality
control prevents this from occurring. During normal facility operation, these fission products
are minor contributors to the overall radioactivity of the reactor coolant system.
If a defect were present or a failure of a fuel element occurred, large amounts of fission
products would potentially have a path to the coolant system. If this happened, significant
changes would occur within the reactor coolant chemistry parameters. Because most facilities
analyze for gross coolant radioactivity either continuously or periodically, the analysis would
be likely to detect all but the most minute failures.
When routine gaseous radioactive levels are monitored, an increase in this parameter's value
would be seen. This is because many of the fission products are gaseous, and these gases are
more mobile than particles of exposed fuel (the exposed fuel generally undergoes a process of
erosion that washes the fuel into the coolant stream). The other parameter that may change is
the ion exchange efficiency (where utilized), because many of the fission products released have
a lower affinity for the exchange sites on the resin beads than the exchange anion or cation.
Accordingly, the ion exchanger would not effectively remove these fission products and effluent
radioactivity levels would increase significantly. Fission gases would also pass on through the
ion exchanger and contribute to effluent activity. In addition, because some of the fission gases
have relatively short half-lives, the amount of time they are held up in the ion exchanger is
sufficient for some of these gases to decay to a radioactive solid.
These solid particles would contribute to effluent samples that may be concentrated prior to
analysis. Some facilities monitor for specific fission product inventories in the reactor coolant
to provide base level information. If a defect or failure were to occur, these levels would
obviously increase to indicate the failure.
Resin Overheating
Because the potential for elevated temperatures exists during most conditions of facility
operation, we will summarize the results from the resin in an ion exchanger overheating.
Module 4 addresses resin in great detail, and the actual resin breakdown will be included there.
Basically the resin of an ion exchanger is an inert polystyrene structure with ion exchange sites
"loosely" attached. The basic structure is stable up to fairly high temperatures (approximately
300 F), but the active exchange sites are not. There are two types of exchange sites: anion and
cation. The anion resin begins to decompose slowly at about 140 F, and the decomposition
CH-03
Page 28
Rev. 0
DOE-HDBK-1015/2-93
becomes rapid above 180 F. The cation resin is stable up to about 250 F. Because these
temperatures are well below normal reactor coolant temperatures, the temperature of the
coolant must be lowered before it passes through the ion exchange resin.
The decomposition of resin produces an alcohol form of the resin, which has no exchange
capability, and trimethylamine (TMA), N(CH3)3. TMA is a weak base, similar to ammonia, that
reacts with water as follows.
N(CH3)3
H2O
NH(CH3)3
OH
If large amounts of TMA are released to the coolant, the pH may increase noticeably. For
example, 1 ppm of TMA in reactor coolant that uses lithium form resin will cause a noticeable
increase in pH. TMA may also interfere with the analysis for chloride ions (which is routinely
performed on reactor coolant) by giving a false indication of high chloride concentration.
Another significant property of TMA is its intense odor of dead fish. Although the presence
of such an odor from reactor coolant is not definitive for TMA, it may give an indication of
resin overheating.
The other product of resin breakdown, [R - CH2N(CH3)2], is an amine with exchange
capabilities considerably less than the original form of the resin. Thus, both reactions lead to
partial (or complete) loss of exchange capability. If the temperature is sufficiently high, or if
a lower temperature (but greater than 180 F) is sustained for a long enough period, the resin
will be unfit for use. If the temperature becomes very high (greater than about 450 F), the
polymeric base structure of the resin will decompose, forming a complex mixture of organic tars
and oils.
The preceding discussion concerned the decomposition of resins in their original forms. It
should be noted that if overheating occurs after the resin has been in operation for some time,
part of the resin will be in a different form due to the exchange process. As a result, some of
the previously removed impurities will be released to the coolant if decomposition occurs.
A number of changes are probable if overheating of resin occurs. Reactor coolant Cl- levels
would probably increase as a result of thermal breakdown and subsequent release. Ion
exchanger effectiveness would be greatly reduced for similar reasons. Radioactivity levels of
the reactor coolant would increase because of the release of impurities collected and later
released from the resin. pH would likely decrease because of the release of H+ ions from the
resin complex and may cause acidic conditions in the reactor coolant if the temperature is
sufficient (>250 F). Because certain types of resin decompose at lower temperatures, pH may
increase as a result of the release of TMA and be accompanied by a dead fish odor. Because
of the consequences of overheated resin, stringent temperature limitations are necessary. If
overheating occurs, the ion exchanger should be taken out of service immediately and the cause
rectified. The resin must be replaced prior to placing the ion exchanger back in service after
overheating.
Rev. 0
Page 29
CH-03
DOE-HDBK-1015/2-93
Summary
Chemistry Parameters Summary

Table 1 provides a summary of the parameters, why they are controlled, and the
methods of control.
The following abnormal chemistry conditions are discussed:
Injection of air will cause the hydrogen inventory to become depleted, which
in turn can lead to a pH swing towards the acidic end. This reduced pH
leads to a loosened corrosion film hence a crud burst. The crud burst causes
higher radiation levels and an increase in conductivity.
Fuel element failure allows large amounts of fission products a possible
release path to the reactor coolant. This could lead to a lowered ion
exchange efficiency.
Resin overheating results in the decomposition of the resin. The products
of the decomposition can seep into the reactor coolant and affect the
chemistry in several ways. A few of the common products and their
resulting influence on the chemistry is discussed.
CH-03
Page 30
Rev. 0
CHEMISTRY
Module 4
Principles of Water Treatment
DOE-HDBK-1015/2-93
TABLE OF CONTENTS
TABLE OF CONTENTS
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
PURPOSE OF WATER TREATMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Water Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
WATER TREATMENT PROCESSES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Principles of Ion Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Specific Ion Exchanger Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
DISSOLVED GASES, SUSPENDED SOLIDS,
AND pH CONTROL . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Removal of Dissolved Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Removal of Suspended Solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
pH Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Resin Bed Malfunctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
15
20
21
22
26
WATER PURITY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Water Purity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Rev. 0
Page i
CH-04
TABLE OF CONTENTS
DOE-HDBK-1015/2-93
LIST OF FIGURES
Figure 1 Polymerization of Cross-Linked Polystyrene Resins . . . . . . . . . . . . . . . . . . . . . . 5
Figure 2 Production of Anion and Cation Forms of Cross-Linked
Polystyrene Ion Exchange Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Figure 3 Schematic Diagram of a Typical Ion Exchanger . . . . . . . . . . . . . . . . . . . . . . . . . 8
Figure 4 Typical History Curve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Figure 5 A Typical Pretreatment System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Figure 6 Behavior of Hydrogen Form Cation Exchange Bed as it
Removes Ammonium Ions From Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
CH-04
Page ii
Rev. 0
DOE-HDBK-1015/2-93
LIST OF TABLES
LIST OF TABLES
Table 1 Typical Ionized Impurities in Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Table 2 Properties of Ion Exchange Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Table 3 Water Purity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Rev. 0
Page iii
CH-04
REFERENCES
DOE-HDBK-1015/2-93
REFERENCES
Inc., 1963
1982.
1974.
Underwood, Chemistry for Colleges and Schools, 2nd Edition, Edward Arnold, Ltd.,
1967.
CH-04
Page iv
Rev. 0
DOE-HDBK-1015/2-93
OBJECTIVES
TERMINAL OBJECTIVE
1.0
Without references, EXPLAIN the concept and application of ion exchange in water
purification.
ENABLING OBJECTIVES
1.1
LIST the three reasons for removing impurities from water prior to use in reactor
systems.
1.2
DEFINE the following terms:

a.
b.
c.
d.
1.3
e.
f.
g.
h.
Polymer
Mixed-bed demineralizer
Affinity
Decontamination factor
DESCRIBE the following:

a.
b.
c.
1.4
Ion exchange
Demineralize
Cation
Anion
Resin bead
Cation resin
Anion resin
DISCUSS the following factors of ion exchange:

a.
b.
Relative affinity
1.5
WRITE the reaction for removal of NaCl and CaSO4 by a mixed-bed ion exchanger such
as one containing HOH resin.
1.6
EXPLAIN the three basic methods used to remove dissolved gases from water.
1.7
LIST five filtration mediums used to remove suspended solids from water.
1.8
EXPLAIN how mixed-bed ion exchangers may be used to control pH.
Rev. 0
Page v
CH-04
OBJECTIVES
DOE-HDBK-1015/2-93
ENABLING OBJECTIVES (Cont.)

1.9
DISCUSS resin malfunctions, including the following:

a.
b.
c.
1.10
CH-04
Channeling
Breakthrough
Exhaustion
LIST the maximum conductivity and approximate concentration of electrolyte for each
level of purity for makeup water.
Page vi
Rev. 0
DOE-HDBK-1015/2-93
PURPOSE OF WATER TREATMENT

Water normally contains many impurities, among which are trace minerals and
chemicals. The need for removing these impurities is discussed in this chapter.
EO 1.1
LIST the three reasons for removing impurities from water

prior to use in reactor systems.
Water Treatment
Water treatment is necessary to remove the impurities that are contained in water as found in
nature. Control or elimination of these impurities is necessary to combat corrosion, scale
formation, and fouling of heat transfer surfaces throughout the reactor facility and support
systems.
The following are three reasons for using very pure water in reactor facility systems.
Rev. 0
1.
To minimize corrosion, which is enhanced by impurities.
2.
To minimize radiation levels in a reactor facility. Some of the natural impurities

and most of the corrosion products become highly radioactive after exposure
to the neutron flux in the core region. If not removed, these soluble and
insoluble substances may be carried to all parts of the system.
3.
To minimize fouling of heat transfer surfaces. Corrosion products and other

impurities may deposit on core surfaces and other heat transfer regions, which
result in decreased heat transfer capabilities by fouling surfaces or blockage of
critical flow channels. Areas of high concentrations of these impurities and
corrosion products may also lead to extreme conditions of the various corrosion
processes with resultant failure of components or systems.
Page 1
CH-04
DOE-HDBK-1015/2-93
There are several processes used in reactor facilities to purify the water in the systems and
water used as makeup. Deaeration is used to strip dissolved gases, filtration is effective in the
removal of insoluble solid impurities, and ion exchange removes undesirable ions and replaces
them with acceptable ions. Typical ionized impurities found in water are shown in Table 1.
TABLE 1
Typical Ionized Impurities in Water
Cations
Anions
Ca++
NO3-
Mg++
OH-
Na+
SO4--
K+
Cl-
Al+++
HCO3-
Fe++
HSiO3-
Cu++
HCrO3-
Summary
Purpose of Water Treatment Summary

There are three general reasons to treat water for its impurities:
CH-04
1.
To minimize corrosion, which is enhanced by impurities
2.
To minimize radiation levels in the reactor facility
3.
To minimize fouling of heat transfer surfaces
Page 2
Rev. 0
DOE-HDBK-1015/2-93
WATER TREATMENT PROCESSES

One of the more common water treatment methods is the use of demineralizers
and ion exchange. This method will be discussed in this chapter.
EO 1.2

a.
b.
c.
d.
EO 1.3
Polymer
Mixed-bed demineralizer
Affinity
Resin bead
Cation resin
Anion resin
DISCUSS the following factors of ion exchange:

a.
b.
EO 1.5
e.
f.
g.
h.
DESCRIBE the following:

a.
b.
c.
EO 1.4
Ion exchange
Demineralize
Cation
Anion
Relative affinity
WRITE the reaction for removal of NaCl and CaSO4 by a

mixed-bed ion exchanger such as one containing HOH resin.
Principles of Ion Exchange

Ion exchange is a process used extensively in nuclear facilities to control the purity and pH of
water by removing undesirable ions and replacing them with acceptable ones. Specifically, it is
the exchange of ions between a solid substance (called a resin) and an aqueous solution (reactor
coolant or makeup water). Depending on the identity of the ions that a resin releases to the
water, the process may result in purification of water or in control of the concentration of a
particular ion in a solution. An ion exchange is the reversible exchange of ions between a liquid
and a solid. This process is generally used to remove undesirable ions from a liquid and
substitute acceptable ions from the solid (resin).
The devices in which ion exchange occurs are commonly called demineralizers. This name is
derived from the term demineralize, which means the process whereby impurities present in the
incoming fluid (water) are removed by exchanging impure ions with H+ and OH- ions, resulting
in the formation of pure water. H+ and OH- are present on the sites of resin beads contained in
the demineralizer tank or column.
Rev. 0
Page 3
CH-04
DOE-HDBK-1015/2-93
There are two general types of ion exchange resins: those that exchange positive ions, called
cation resins, and those that exchange negative ions, called anion resins. A cation is an ion with
a positive charge. Common cations include Ca++, Mg++, Fe++, and H+. A cation resin is one that
exchanges positive ions. An anion is an ion with a negative charge. Common anions include
Cl-, SO4--, and OH-. An anion resin is one that exchanges negative ions. Chemically, both types
are similar and belong to a group of compounds called polymers, which are extremely large
molecules that are formed by the combination of many molecules of one or two compounds in
a repeating structure that produces long chains.
A mixed-bed demineralizer is a vessel, usually with a volume of several cubic feet, that contains
the resin. Physically, ion exchange resins are formed in the shape of very small beads, called
resin beads, with an average diameter of about 0.005 millimeters. Wet resin has the appearance
of damp, transparent, amber sand and is insoluble in water, acids, and bases. Retention elements
or other suitable devices in the top and bottom have openings smaller than the diameter of the
resin beads. The resin itself is a uniform mixture of cation and anion resins in a specific volume
ratio depending on their specific gravities. The ratio is normally 2 parts cation resin to 3 parts
anion resin.
In some cases, there may be chemical bonds formed between individual chain molecules at
various points along the chain. Such polymers are said to be cross-linked. This type of polymer
constitutes the basic structure of ion exchange resins. In particular, cross-linked polystyrene is
the polymer commonly used in ion exchange resins. However, chemical treatment of polystyrene
is required to give it ion exchange capability, and this treatment varies depending on whether the
final product is to be an anion resin or a cation resin.
The chemical processes involved in producing anion and cation resins are outlined in Figure 1
and Figure 2, beginning with the formation of cross-linked polystyrene. The polymer itself is a
covalent compound. By the chemical reactions indicated in Figure 2, hydrogen atoms covalently
bonded to the original polymer at certain sites are replaced by functional groups (called radicals)
such as SO3H (sulfonic acid) and CH2N(CH3)3Cl (quaternary ammonium). Each such group is
covalently bonded to the polymer, but each also contains an atom that is bonded to the radical
group by a predominantly ionic bond. In the two examples above, H in SO3H and Cl in
CH2 N(CH3)3Cl are the ionically-bonded atoms. Sometimes these are written as SO3 - H+ and
CH2N(CH3)3+Cl- to emphasize their ionic characters. These ions (H+and Cl-) are replaceable by
other ions. That is, H+ will exchange with other cations in a solution, and Cl- will exchange with
other anions.
In its final form, an ion exchange resin contains a huge, but finite, number of sites occupied by
an exchangeable ion. All of the resin, except the exchangeable ion, is inert in the exchange
process. Thus, it is customary to use a notation such as R-Cl or H-R for ion exchange resins.
R indicates the inert polymeric base structure and the part of the substituted radical that does not
participate in exchange reactions. The term R is inexact because it is used to represent the inert
portion of both cation and anion resins, which are slightly different. Also, the structure
represented by R contains many sites of exchange, although only one is shown by the notation,
such as R-Cl. Despite these drawbacks, the term R is used for simplicity.
CH-04
Page 4
Rev. 0
DOE-HDBK-1015/2-93
Page 5
CH-04
Figure 1 Polymerization of Cross-Linked Polystyrene Resins
Rev. 0
DOE-HDBK-1015/2-93
Page 6
Rev. 0
Figure 2 Production of Anion and Cation Forms of Cross-Linked

Polystyrene Ion Exchange Resins
CH-04
DOE-HDBK-1015/2-93
A particular resin may be prepared in different forms according to the identity of the
exchangeable ion attached. It is usually named according to the ion present on the active sites.
For example, the resin represented by R-Cl is said to be the chloride form of the anion resin, or
simply the chloride form resin. Other common forms are the ammonium form (NH4-R), hydroxyl
form (R-OH), lithium form (Li-R), and hydrogen form (H-R).
The mechanics of the ion exchange process are somewhat complicated, but the essential features
can be understood on the basis of equilibrium concepts discussed in Module 1 and recognition
that the strength of the ionic bond between the resin and an ion varies with the particular ion.
That is, for a particular resin, different ions experience different attractions to the resin. The
term affinity is often used to describe the attraction between a resin and a given ion. This affinity
can be described quantitatively by experimental determination of a parameter called the relative
affinity coefficient. For a qualitative discussion, it suffices to note the relative affinities between
a resin and different ions.
In order of decreasing strength, the relative affinities between a cation resin and various cations
are as follows.
Ba+2 > Sr+2 > Ca+2 > Co+2 > Ni+2 > Cu+2 > Mg+2 > Be+2
Ag+ > Cs+ > Rb+ > K+
NH+ > Na+ > H+ > Li+
Similarly, the relative affinities between an anion resin and various anions are as follows.
SO4-2 > I- > NO3- > Br- > HSO3- > Cl- > OH- > HCO3- > FThe physical arrangement of one type of ion exchange vessel for purifying water is shown in
Figure 3. The ion exchange resin is contained in a vessel with a volume of several cubic feet.
Retention elements at the top and bottom consist of screens, slotted cylinders, or other suitable
devices with openings smaller than the resin beads to prevent the resin from escaping from the
vessel. The resin bed is a uniform mixture of cation and anion resins in a volume ratio of 2 parts
cation resin to 3 parts anion resin. This arrangement is called a mixed-bed resin, as opposed to
an arrangement of cation and anion resins in discrete layers or separate vessels. The use of
different volumes of the two types of resins is due to the difference in exchange capacity between
cation and anion resins. Exchange capacity is the amount of impurity that a given amount of
resin is capable of removing, and it has units of moles/ml, equivalents/ml, or moles/gm. The
anion resin is less dense than the cation resin; thus, it has a smaller exchange capacity, and a
larger volume is needed for anion resins than for the cation resins to obtain equal total exchange
capabilities.
Rev. 0
Page 7
CH-04
DOE-HDBK-1015/2-93
Figure 3 Schematic Diagram of a Typical Ion Exchanger
CH-04
Page 8
Rev. 0
DOE-HDBK-1015/2-93
Because of the different densities of anion and cation resins, the flow of solution (impure water)
is from top to bottom. If the flow were reversed, the lighter anion resin would gradually rise
to the top by a process called classification, resulting in a layer of anion resin on top of the
cation resin, as shown in Figure 3. In the example shown, the layering results from regeneration
and/or backwash. In systems not using a backwash, the anion and cation resin beads are
uniformly mixed. Many systems use a backwash procedure, if the resins are regenerated, to
remove solids collected by filtration and to separate the resins for regeneration. They are
remixed after regeneration.
For fixed amounts of anion and cation resins, the efficiency for removal of impurities is greater
in a mixed-bed resin than a layered arrangement. The main reason is that for layered resins
there may be large pH gradients within the column of resin. If, for example, the hydroxyl form
resin is on top, as solution passes through it anionic impurities are removed and replaced by
OH- ions; thus, the pH increases. This increase in pH may decrease the efficiency in lower
portions of the resin bed for removing impurities. It may also cause some impurities to
precipitate because solubility changes with pH. The resin column will filter some undissolved
material, but the efficiency for filtration is usually significantly less than that for removal by ion
exchange. Thus, the overall efficiency is less than in a mixed-bed resin.
The capacity of ion exchange resins to remove impurity ions is given in Table 2 along with other
information on resins. For instance, each cubic foot of a mixed-bed resin is capable of
exchanging with 19.8 moles each of monovalent cations and anions. Mixed-bed resins are
available commercially and in practical applications several cubic feet are used in a purification
system.
TABLE 2
Properties of Ion Exchange Resins
Properties
Cation Resin
Anion Resin
Ion exchange capacity,

moles of single ion/ml
1.75 x 10-3
1.20 x 10-3
0.7 x 10-3 anion & cation
Ion exchange capacity,

moles of single ion/ft3
49.5
34.0
19.8 anion & cation
Density of wet resin

particles, grams/ml
1.27
1.10
--
Bulk density of loaded bed

(including voids), grams/ml
0.80
0.62
0.70
--
--
60% anion & 40% cation
Volume fraction
Rev. 0
Page 9
Mixed-Bed Resin
CH-04
DOE-HDBK-1015/2-93
The ion exchange process is reversible. If too much solution is passed through the ion
exchanger (that is, the capacity of the resin has been exceeded) the exchange may reverse, and
undesirable ions or other substances that were previously removed, will be returned to the
solution at the effluent. Therefore, it is necessary to periodically monitor the performance of
the ion exchanger and either replace or regenerate the resin when indicated. Ion exchanger
performance is measured by comparing the solution concentration, conductivity, or radioactivity
at the influent and effluent. The parameter measured depends upon the purpose of the ion
exchanger. The term normally applied to ion exchanger effectiveness is decontamination factor
(DF), which is defined as a ratio of the concentration (or activity) of the fluid at the inlet
compared to the concentration (or activity) at the effluent, which expresses the effectiveness
of an ion exchange process.
DF
Influent concentration, conductivity, or radioactivity

Effluent concentration, conductivity, or radioactivity
Example 1:
An ion exchanger influent contains 15 ppm chloride (Cl). Effluent chloride is measured
at 0.1 ppm. What is the DF of this ion exchanger?
Solution:
DF
Influent concentration
Effluent concentration
DF
15 ppm Cl
0.1 ppm Cl
DF
150
Example 2:
Reactor coolant activity entering the purification ion exchanger equals 2.8 x 10-2 Ci/ml
gross activity. Ion exchanger effluent activity taken at the same time and conditions is
measured at 1.0 x 10-4 Ci/ml. What is the DF?
Solution:
CH-04
DF
Influent radioactivity
Effluent radioactivity
DF
2.8 10
1.0 10
DF
280
2
4
Page 10
Ci/ml
Ci/ml
Rev. 0
DOE-HDBK-1015/2-93
Resin performance may be monitored using a history curve that plots DF with respect to time.
A typical history curve is shown in Figure 4, with the resin considered "exhausted" at point X.
Figure 4 Typical History Curve
Specific Ion Exchanger Reactions

Suppose a solution containing Na+ ions is passed through hydrogen resin. From the relative
affinities given earlier, Na+ ions are attracted to the resin more strongly than H+ ions. Thus, Na+
ions will displace H+ ions from the resin or, in other words, Na+ ions and H+ ions exchange
place between resin and solution. The process can be described by the following equilibrium
reaction.
H R
Na
Na R
(4-1)
In most practical situations, a solution containing impurities at low concentrations is passed

through a large amount of resin. By LeChatelier's Principle, the equilibrium of Reaction (4-1)
is forced far to the right. The equilibrium is displaced so far that, for practical purposes, all Na+
ions are removed from solution and replaced by H+ ions. As a result, the solution will be acidic
because of the excess of H+ ions.
If a solution containing Cl- ions is passed through hydroxyl resin, the Cl- ions will be removed
according to the following reaction.
R OH
Cl
R Cl
OH
(4-2)
Again, for a dilute solution and a large amount of resin, the removal of Cl- ions is essentially
100 percent complete. In this case, the final solution will be basic because of the excess of
OH- ions.
Rev. 0
Page 11
CH-04
DOE-HDBK-1015/2-93
Consider a situation in which the entering impurities are calcium sulfate (CaSO4) and sodium
chloride (NaCl), and the ion exchanger is a mixture of both hydrogen and hydroxyl resins
(mixed-bed).
H R
H R
R OH
R OH
Ca
Na
SO4
Ca R
Cl
Na R
R SO4
R Cl
H
H
OH
OH
(4-3)
(4-4)
In the reaction with NaCl, both Na+ and Cl- ions are removed from solution and replaced by H+
and OH- ions, respectively (the CaSO4 reaction has the same result). If the initial solution
contained only NaCl, then the concentrations of Na+ and Cl- ions were equal. Because both are
removed with 100 percent efficiency, the concentrations of H+ and OH- ions added to the
solution are equal; thus, the solution is neutral. In solution, H+ and OH- ions must obey the
relationship for the ionization of water (refer to Module 1).
Kw = 10-14 = [H+] [OH-]
Because of the very small value of the dissociation constant Kw, the great majority of H+ and
OH- ions supplied by the resin must combine to form water by the following reaction.
H+ + OH-
H2O
(4-5)
By this process, the original NaCl solution becomes pure water.

The preceding examples involve hydrogen and hydroxyl resins. The use of other resins,
especially cation resins, is very common. For instance, suppose a solution containing Na+ ions
is passed through a lithium resin. Again referring to the relative affinities, Na+ is attracted to
the resin more strongly than is Li+; thus, Na+ ions will displace Li+ from the resin.
CH-04
Page 12
Rev. 0
DOE-HDBK-1015/2-93
Summary
Ion Exchange Summary

Demineralize is defined as the process whereby impurities present in the
incoming fluid (water) are removed by exchanging impure ions with H+ and
OH- ions resulting in the formation of pure water.
Ion exchange is a process used extensively in nuclear facilities to control
the purity and pH of water by removing undesirable ions and replacing
them with acceptable ones.
Mixed-bed demineralizer is a vessel containing resin that is a uniform
mixture of cation and anion resins in a specific volume ratio depending on
their specific gravities. Normally the ratio is 2 parts cation resin to 3 parts
anion resin.
Cation is an ion with a positive charge. Common cations include Ca++,
Mg++, Fe++, and H+. A cation resin is one that exchanges positive ions.
Anion is an ion with a negative charge. Common anions include Cl-, SO4-2,
and OH-. An anion resin is one that exchanges negative ions.
Decontamination factor (DF) is a ratio of the concentration (or activity) of
the fluid at the inlet compared to the concentration (or activity) at the
effluent, which defines the effectiveness of the ion exchange process.
Mathematically it is:
DF
Influent concentration, conductivity, or radioactivity

Effluent concentration, conductivity, or radioactivity
Polymers are extremely large molecules that are formed by the combination
of many molecules of one or two compounds in a repeating structure that
produces long chains.
Affinity is often used to describe the attraction between a resin and a given
ion. This affinity can be described quantitatively by experimental
determination of a parameter called the relative affinity coefficient.
Rev. 0
Page 13
CH-04
DOE-HDBK-1015/2-93
Ion Exchange Summary (Cont.)

Resin beads are long-chain cross-linked polymers that contain sites
occupied by exchangeable ions. The general order of affinity serves as a
useful guide in understanding many ion exchange processes. Cation and
anion resins are named according to the identity of the ion occupying the
exchange sites, such as hydrogen, hydroxyl, and chloride. Mixed-bed
resins are used to remove both cations and anions.
The effectiveness of any ion exchanger is directly related to the relative
affinities between a resin and different ions. In order of decreasing
strength, the relative affinities between a cation resin and various cations
are:
Ba+2 > Sr+2 > Ca+2 > Co+2 > Ni+2 > Cu+2 > Mg+2 > Be+2
Ag+ > Cs+ > Rb+ > K+
NH+ > Na+ > H+ > Li+
Similarly, the relative affinities of the anion resin for various anions are:
SO4-2 > I- > NO3- > Br- > HSO3- > Cl- > OH- > HCO3- > FThe higher the relative affinity the more effective the ion exchanger. This
effectiveness is expressed by the Decontamination Factor.
The reaction for removal of NaCl and CaSO4 by a mixed-bed ion
exchanger such as one containing HOH resin is as follows:
H R
R OH
Ca
SO4
H R
R OH
Na
Cl
CH-04
Ca R
Na R
Page 14
R SO4
R Cl
H
H
OH
OH
Rev. 0
DOE-HDBK-1015/2-93
DISSOLVED GASES, SUSPENDED SOLIDS, AND pH CONTROL
DISSOLVED GASES, SUSPENDED SOLIDS,

AND pH CONTROL
The presence of dissolved gases, suspended solids, and incorrect pH can be
detrimental to the water systems associated with a reactor facility. Therefore,
these conditions must be minimized or eliminated to reduce corrosion in the
systems of the facility. The way these conditions are controlled and the
difficulties in controlling them are discussed in this chapter.
EO 1.6
EXPLAIN the three basic methods used to remove dissolved

gases from water.
EO 1.7
LIST five filtration mediums used to remove suspended

solids from water.
EO 1.8
EXPLAIN how mixed-bed ion exchangers may be used to

control pH.
EO 1.9
DISCUSS resin malfunctions, including the following:

a.
b.
c.
Channeling
Breakthrough
Exhaustion
Removal of Dissolved Gases

Dissolved gases result from different sources depending upon which system we examine. In the
following discussion, we will address makeup water, reactor coolant systems, secondary facility
water systems, the sources of dissolved gases, and methods used to reduce their concentrations
to acceptable levels.
Many facilities use raw water as a source for makeup water systems. Pretreatment of this water
is accomplished in various ways from distillation to a series of distinct processes as shown in
Figure 5. In a pretreatment system similar to that shown in Figure 5, a resin column containing
a cation resin (hydrogen form) is used to remove cations. The water entering the cation
exchanger contains numerous ions including sodium (Na+), bicarbonate (HCO3- ), and others
+
(HCO3- is one of the major impurities in many raw water systems). Na
ions result from the
water softener located upstream in the pretreatment system. In addition to the HCO3- ions, raw
water contains large amounts of magnesium (Mg++) and calcium (Ca++), as well as small amounts
of other ionic impurities.
Rev. 0
Page 15
CH-04
DOE-HDBK-1015/2-93
Figure 6 A Typical Pretreatment System
The reactions that occur in the water softener include the removal of both Mg++ and Ca++ ions.
The water softener contains resin in which the insoluble exchange site is the SO3- molecule, and
the soluble ions attached to the exchange site are Na+ ions. When water containing Mg++, Ca++,
and HCO3- ions is passed over the resin in the softener, the ions are exchanged by the following
reaction (Mg++ removal is similar).
2R SO3 Na
(resin complex)
Ca
HCO3
2R SO3Ca
2Na
HCO3
(4-6)
(resin complex)
Note that electrical neutrality is maintained before and after the exchange reaction. One calcium
ion with two positive charges is attached to two exchange sites that release two sodium ions with
one positive charge each. The HCO3- ion is not affected by the reaction and passes through the
resin of the softener.
To obtain pure water, it is necessary to demineralize the water completely, which is accomplished
using a cation exchanger, an aerator, and an anion exchanger.
CH-04
Page 16
Rev. 0
DOE-HDBK-1015/2-93
The cation exchanger contains resin in the hydrogen form. In this treatment step, essentially all
cations entering the ion exchanger will be held at the exchange site, and H+ will be released as
shown in the following typical reaction (the anions, specifically the HCO3- ions, are unaffected
by the cation exchanger).
Na
HCO3
R SO3 H
R SO3 Na
HCO3
(4-7)
The water leaving the resin is somewhat acidic (depending on the incoming ion concentration)
because it contains H+ ions and whatever anion was associated with the incoming cation. After
passing through the cation resin, the HCO3- ions combine with the H+ ions to form carbonic acid
(H2CO3). Carbonic acid is a weak acid that will decompose to water and CO2 by the following
reaction.
H2CO3
H2O
CO2
(4-8)
Because the carbonic acid readily dissociates, the aerator is used to remove the CO2 from the
makeup water at this point in the system. If we aerate the water by some means, such as spraying
it through a tower or blowing air through the water, the CO2 is "stripped" from the water and
vented to the atmosphere. The removal of CO2 forces Reaction (4-8) to shift to the right, which
converts more H2CO3 to CO2 . With sufficient aeration, all bicarbonate (HCO3 -), and therefore
CO2, can be removed.
Similar reactions occur in the anion exchanger. For example, anion resin, which has hydroxide
ions at the exchange sites, will react as indicated in the following typical reaction.
H
Cl
R N(CH3)3 OH
R N(CH3)3 Cl
HOH
(4-9)
In this pretreatment system, the anion resin is downstream of the cation resin, and the only cations
present are hydrogen ions. When the hydroxyl ions are released from the anion exchange sites,
they combine with the hydrogen ions to form water. As a result, pure water appears at the
effluent (this is somewhat overstated because a very small amount of other cations and anions
pass unaffected through the resin columns in actual practice).
Another method sometimes used to remove dissolved gases from water is deaeration. In this
process, the water is stored in vented tanks containing electric heaters or steam coils. The water
is heated to a temperature sufficient for slow boiling to occur. This boiling strips dissolved gases
from the stored water, and these gases are then vented to the atmosphere. Usually, the vented
gases are directed through a small condenser to limit the loss of water vapor that would escape
as steam along with the gases. This method is particularly effective in removing dissolved oxygen
as well as other entrained gases (CO2, N2, and Ar).
Rev. 0
Page 17
CH-04
DOE-HDBK-1015/2-93
Removal of dissolved gases from the reactor coolant system is usually accomplished by venting
a steam space or high point in the system. In pressurized water reactors (PWR), this is normally
accomplished in the pressurizer. The steam space is the high point of the system, and the boiling
and condensing action causes a constant stripping of dissolved gases to occur. The steam space
is vented either intermittently or constantly, and the gases are carried off in the process.
In addition to the mechanical means mentioned above, the use of scavengers in a PWR prevents
the presence of dissolved oxygen. Two methods are normally used in this regard. When facility
temperature is above approximately 200 F, gaseous hydrogen is added and maintained in the
primary coolant to scavenge oxygen by the following reaction.
2H2
O2
2 H2O
(4-10)
The other scavenger is hydrazine (N2H4). Hydrazine is thermally unstable and decomposes at
temperatures above 200 F to form ammonia (NH3), nitrogen (N
2 ), and hydrogen 2 (H ).
Consequently, the use of hydrazine as an oxygen scavenger is limited to temperatures below
200 F. Hydrazine scavenges oxygen by the following reaction.
N2H4
O2
2H2O
N2
(4-11)
The presence of dissolved gases in the steam facility of a PWR is as detrimental as the presence
of these gases is in the reactor coolant systems. Because steam facility systems contain metals
other than stainless steel, they are even more susceptible to certain types of corrosion in the
presence of oxygen and carbon dioxide. Removal of dissolved gases from the steam system is
accomplished in two ways: by mechanical means such as air ejectors or mechanical pumps; and
by using chemicals that scavenge oxygen.
Because boiling occurs in the steam generators, any dissolved gases entrained in the feedwater
will be stripped out during the boiling process. These gases are carried with the steam through
the turbines and auxiliary systems and ultimately end up in the condensers. The design of the
condensers is such that noncondensible gases (for example, O2, CO2) are collected and routed to
the air removal system (which consists of air ejectors or mechanical pumps), where they are
subsequently discharged to the atmosphere.
Scavenging involves the use of solid additives and volatile chemicals. One commonly-used solid
chemical additive is sodium sulfite (Na2SO3). Scavenging of oxygen occurs by the following
reaction.
2Na2SO3
O2
2 Na2SO4
(4-12)
As can be seen by Reaction (4-12), oxygen is consumed in the reaction resulting in the formation
of sodium sulfate, Na2SO4 (a soft sludge). Addition of this scavenging agent is limited to drumtype steam generators. Once Thru Steam Generators (OTSG) do not use this method, but instead
use controls that keep all scale-forming chemicals out of the steam generators.
CH-04
Page 18
Rev. 0
DOE-HDBK-1015/2-93
Sodium sulfite reacts rapidly with oxygen and is a very efficient scavenger. However, being a
solid and the source of another solid (Na2SO4) that is produced during the reaction, sodium
sulfite has the potential of fouling heat transfer surfaces. An additional problem associated with
the use of sodium sulfite is corrosion of secondary system components resulting from its
decomposition products. At the temperatures present in the steam generators, sodium sulfite
can decompose as follows.
H2O
Na2SO3
2NaOH
SO2
(4-13)
Sulfur dioxide (SO2) is a gas and is carried over to the remainder of the steam facility. With
water (in the steam or in the feed/condensate system), the SO2 reacts in the following manner.
H2O
SO2
H2SO3
(acidic)
(4-14)
This acidic condition is corrosive to all components in the secondary system.

Because of the problems associated with sodium sulfites, many facilities use volatile chemistry
control of the secondary steam system to control dissolved gases in conjunction with air
removal systems. This control utilizes hydrazine (Reaction 4-11) and morpholine (Reaction 415) to eliminate oxygen and carbon dioxide, respectively.
2 C4H9NO
N2H4
O2
H2O
CO2
2H2O
N2
(oxygen consumed)
C4H9NO C4H9COOH
HNO3
H2
(carbon dioxide consumed)
(4-11)
(4-15)
As can be seen by Reaction (4-11), no solids are formed; thus, the tendency of fouling heat
transfer surfaces is reduced. An additional benefit results from the decomposition of hydrazine
by the following reactions.
2N2H4
NH3
2 NH3
H2O
N2
NH4OH
H2
(4-16)
(4-17)
These reactions result in an alkaline pH condition that decreases corrosion in the steam facility.
As can be seen in Reaction (4-15), the consumption of CO2 takes place. Two benefits result
from this reaction; 1) the inventory of dissolved gases in the steam facility is reduced, and 2)
is the reaction contributes to maintaining a higher pH by eliminating carbonic acid (H2CO3),
thus reducing corrosion.
Rev. 0
Page 19
CH-04
DOE-HDBK-1015/2-93
Removal of Suspended Solids

Referring back to Figure 5 and examining the effluent of the softener, we find that both sodium
salts and precipitates are present. These substances result from reactions that typically occur
based on the presence of Ca++ and Mg++ salts. The chemicals most commonly used for
softening are soda ash or sodium carbonate (Na2CO3) and hydrated lime (Ca(OH)2 ). Hard
water (water containing Ca++ and Mg++ salts) contains calcium and magnesium bicarbonates
(Ca(HCO3)2) and (Mg(HCO3 )2 ), as well as calcium sulfate (CaSO4 ) and magnesium chloride
(MgCl2). These impurities produce the following reactions.
Ca(HCO3)2
Mg(HCO3)2
Ca(OH)2
2Ca(OH)2
2CaCO3
Mg(OH)2
MgSO4
Ca(OH)2
Mg(OH)2
CaSO4
Na2CO3
CaCO3
MgCl2
Ca(OH)2
Mg(OH)2
CaCl2
Na2CO3
CaCO3
2 H2O
2CaCO3
CaSO4
(4-18)
2 H2O
(4-19)
(4-20)
Na2SO4
(4-21)
CaCl2
(4-22)
2NaCl
(4-23)
As evident from the above reactions, although Ca++ and Mg++ ions can be removed from
solution, soluble sodium salts are formed. Consequently the total dissolved solid content is
essentially unchanged. CaCO3 and Mg(OH)2 are in precipitate form and must also be removed
from the solution. One method of doing this is by filtration. Filtration is the process in which
insoluble solids are removed from the water by passing them through a filter medium consisting
of some type of porous material. This process will remove suspended solids and precipitates,
but has no effect on dissolved solids. Numerous materials are used as filter media and include
sand, activated charcoal, anthracite, diatomaceous earth, and to some extent resin in an ion
exchanger. Sand is not normally used in nuclear applications because of the silicate ion (SiO3=)
associated. Silicate ions are undesirable because they hydrolyze in water and form a weak acid,
which tends to increase corrosion. Activated charcoal is often used following a chlorinator in
a water treatment system because it removes excess residual chlorine as well as suspended
matter.
There are two types of mechanical filters in use, gravity and pressure. Pressure filters are the
most widely used because they can be installed in a pressurized system, thereby eliminating the
need for additional pumps (gravity filters require pumps to provide a motive force). In addition,
in a pressurized filter system, flow rate and other associated parameters can be better controlled.
CH-04
Page 20
Rev. 0
DOE-HDBK-1015/2-93
Another method used for the removal of suspended corrosion products in facility fluid systems
is the electromagnetic filter. These are gaining popularity in PWR feed and condensate systems
where they have proven effective in reducing the crud loading of these systems, thereby reducing
the inventory of corrosion products in steam generators.
Ion exchangers also function as filtration units by virtue of the size of the resin beads and the
torturous path the water must follow in passing through the resin. The filtration efficiency,
however, is significantly less than the ion exchange efficiency (90% or less for filtration versus
approximately 100% for most ion exchange reactions). Filtration efficiency depends largely on
the size of the suspended materials, with greater efficiency for the larger particles. Adverse
effects of this filtration process are similar to those occurring in other types of filters. In a
radioactive system, the buildup of filtered particles (crud) can increase the radiation to
prohibitive levels or cause flow reductions that may necessitate removal or backwash of the
resin.
pH Control
As discussed in Module 2, in reactor facilities other than those containing aluminum components
or using chemical shim, reactor coolant is maintained in an alkaline condition to control
corrosion in the system. In practice, if the desired alkaline condition is established, and no other
action is taken, the pH gradually decreases during operation of the facility. This is due to factors
such as dilution from makeup water additions to compensate for coolant losses caused by
sampling, leakage, volume changes on facility cooldown, and reaction of hydroxyl ions (OH-)
with metals and corrosion products. Thus, hydroxyl ions must be added to the coolant to
maintain a basic pH. The ion exchange process provides a convenient means of helping to
control the pH of reactor coolant by adding OH- ions from the exchange reactions of the resin.
A hydroxyl form anion resin, and a cation resin in some form other than the hydrogen form, may
be used for this purpose as in a mixed-bed arrangement, similar to that shown in Figure 3, or
in separate cation and anion units where flow is individually controlled. Usually, a portion of
the reactor coolant is diverted from its normal path, passes through the ion exchange resin, and
then is returned to the main coolant path. In this way, part of the coolant is constantly purified,
and in the process hydroxyl ions are released to the coolant. These hydroxyl ions tend to
increase the pH (or limit the decrease), thereby offsetting the effects mentioned in the preceding
paragraph.
Suppose that the cation resin is in the ammonium form. As reactor coolant passes through the
ion exchange system, ionic impurities will be removed and NH4+ and OH- will be added. Thus,
the resin serves both to purify the coolant and to help maintain the pH of the coolant by
releasing NH4OH.
Rev. 0
Page 21
CH-04
DOE-HDBK-1015/2-93
The major sources of ionic impurities in reactor coolant are impurities in makeup water and
corrosion products. The amount of these impurities in reactor coolant is normally very small;
thus, the base added to the coolant by the ion exchange resin is usually not sufficient to entirely
compensate for the losses described above. For this reason, the pH of reactor coolant is
measured regularly, and additional base is added as needed. The frequency of addition varies
considerably with the type of base used.
Resin Bed Malfunctions

The resin beds of ion exchangers are susceptible to malfunction from a number of causes.
These causes include channeling, breakthrough, exhaustion, and overheating.
Channeling
Channeling is a condition in which the resin allows a direct flow of water through the
ion exchanger. Flow channels are established from the inlet to the outlet of the ion
exchanger, which allows water to flow essentially unrestricted through the resin via
these paths. If channeling occurs, the water flowing through the resin bed has
insufficient contact with the resin beads and results in a decrease in effectiveness of the
ion exchanger.
Channeling most often results from improper filling of the ion exchanger with resin. If
insufficient water is mixed with the resin when it is added, the resin column may contain
pockets, or voids. These voids may then set up flow paths for channeling to occur.
Improper design or malfunction of the water inlet connection (flow diffuser) can also
lead to channeling.
Breakthrough and Exhaustion

To gain further insight into the processes that occur in a column of mixed bed resin as
it removes an impurity, it is worthwhile to construct a series of curves such as those
shown in Figure 6. These curves illustrate the behavior of hydrogen form resin as it
removes NH4+ ions from solution (the behavior of an anion resin is analogous). The
two rows of curves schematically represent the concentrations of H+ and NH4+ on the
resin and in the effluent (exiting solution).
In the bottom row, concentration is plotted against volume of solution that has passed
through the column. That is, the plots represent the concentration of the indicated ion
in the effluent solution after a volume of solution has passed through the resin. It is
assumed that the concentration of NH4+ in the influent is constant. NH4+ ions are more
strongly attracted to the resin than are H+ ions. Thus, NH4+ ions readily exchange for
H+ ions on the resin.
CH-04
Page 22
Rev. 0
CH-04
DOE-HDBK-1015/2-93
Page 23
Figure 6 Behavior of Hydrogen Form Cation Exchange Bed as it

Removes Ammonium Ions From Solution
Rev. 0
DOE-HDBK-1015/2-93
As solution passes through the resin column, the relative amounts of ammonium and
hydrogen ions on the resin change. The actual exchange process occurs primarily in a
relatively narrow band of the column rather than over the entire length. This band is
called the exchange zone. Assuming the column is vertical and that solution flows from
top to bottom, the resin above the exchange zone is depleted; that is, practically all the
exchange capacity has been used. Below the exchange zone, essentially none of the
resin's exchange capacity has been used. As more and more solution flows through the
column, the exchange zone gradually moves downward as more of the resin is depleted.
Eventually, as the exchange zone approaches the end of the column, small amounts of
NH4 + begin to appear in the effluent. The point at which this occurs is called
breakthrough. If more solution passes through the resin, the concentration of NH4+ in
the effluent increases until it is the same as the concentration in the influent. This
condition is called exhaustion and indicates that essentially all the exchange capacity of
the resin has been used. (Because of the equilibrium nature of the exchange process,
a small amount of the resin may remain in the hydrogen form, but not enough to remove
any more ionic impurities.) Note that because the exchange zone in this case was
narrow, a relatively small volume of solution takes the resin from breakthrough to
exhaustion.
Resin Overheating
The potential for elevated temperatures exists during most conditions of facility
operation, we will examine in detail the processes that occur if the resin in an ion
exchanger is overheated. Although the inert polystyrene basic structure of resin is
stable up to fairly high temperatures (approximately 300 F), the active exchange sites
are not. The anion resin begins to decompose slowly at about 140 F, and the
decomposition becomes rapid above 180 F. The cation resin is stable up to about
250 F. Because these temperatures are well below normal reactor coolant
temperatures, the temperature of the coolant must be lowered before it passes through
the ion exchange resin.
The anion resin (hydroxyl form) decomposes by either of two mechanisms with
approximately equal probability.
R CH2N(CH3)3 OH
heat
R CH2OH
N(CH3)3
(4-24)
or
R CH2N(CH3)3 OH
CH-04
heat
R CH2N(CH3)2
Page 24
CH3OH
(4-25)
Rev. 0
DOE-HDBK-1015/2-93
Reaction (4-24) produces an alcohol form of the resin, which has no exchange
capability, and trimethylamine (TMA), N(CH3) 3. TMA is a weak base, similar to
ammonia, that reacts with water as follows.
N(CH3)3
H2O
NH(CH3)3
OH
If large amounts of TMA are released to the coolant, the pH may increase noticeably.
For example, 1 ppm of TMA in reactor coolant that uses lithium resin will cause a
noticeable increase in pH. TMA may also interfere with the analysis for chloride ions
(which is routinely performed on reactor coolant) by giving a false indication of high
chloride concentration. Another significant property of TMA is its intense odor of dead
fish. Although the presence of such an odor from reactor coolant is not definitive for
TMA, it may give an indication of resin overheating.
The methyl alcohol (CH3OH) produced by Reaction (4-25) is not expected to have a
harmful effect on the reactor coolant system. The other product of this reaction
[R - CH2N(CH3)2] is an amine with exchange capabilities considerably less than the
original form of the resin. Thus, both reactions lead to partial (or complete) loss of
exchange capability. If the temperature is sufficiently high, or if a lower temperature
(greater than 180 F) is sustained for a long enough period, the resin will be unfit for use.
Cation exchange resin begins to undergo thermal decomposition at temperatures above
about 250 F by the following reaction.
R SO3H
H2O
heat
R H
2H
SO4
(4-26)
This reaction destroys all exchange capacity of the cation resin and also produces an
acid. The Reactions (4-24) through (4-26) are the initial reactions when resin is
overheated. If the temperature becomes very high (greater than about 450 F), the
polymeric base structure of the resin will decompose, forming a complex mixture of
organic tars and oils.
The preceding discussion concerned the decomposition of resins in their original forms.
It should be noted that if overheating occurs after the resin has been in operation for
some time, part of the resin will be in a different form due to the exchange process. As
a result, some of the previously-removed impurities will be released to the coolant if
decomposition occurs. For example, the chloride form of the anion resin will form
CH3Cl by the reaction corresponding to Reaction (4-25).
R CH2N(CH3)3 Cl
Rev. 0
heat
R CH2N(CH3)2
Page 25
CH3Cl
CH-04
DOE-HDBK-1015/2-93
The CH3Cl (chloromethane) will be released to the coolant and will decompose in the
radiation field of the reactor core, producing Cl- ions. Similarly, the sodium form of the
cation resin will release Na+ ions by the following reactions.
R SO3Na
H2O
heat
R H
Na
SO4
A number of changes are probable if overheating of resin occurs. Reactor coolant Cllevels would probably increase as a result of thermal breakdown and subsequent release.
Ion exchanger effectiveness would be greatly reduced for similar reasons. Radioactivity
levels of the reactor coolant would increase because of the release of impurities collected
and later released from the resin. pH would likely decrease because of the release of H+
ions from the cation resin complex and may cause acidic conditions of the reactor
coolant if the temperature were sufficient (>250 F). Because the anion resin
decomposes at lower temperatures, pH may increase as a result of the release of TMA
and be accompanied by a dead fish odor. Because of the consequences of overheated
resin, stringent temperature limitations are necessary. If overheating occurs, the ion
exchanger should be taken out of service immediately and the cause rectified. The resin
must be replaced prior to placing the ion exchanger back in service after overheating.
Summary
Dissolved Gases, Suspended Solids

And pH Control Summary
Because of the presence of impurities, raw water sources undergo treatment prior
to use as makeup water in reactor facility systems. These systems normally utilize
several distinct processes that remove solids, ionic impurities, and gases.
Pretreatment of makeup water is necessary to reduce corrosion, minimize
radiation, and limit fouling of heat transfer surfaces.
If the hydrogen and hydroxyl forms of resin are used, the result is pure, neutral
water. Other forms may be used to remove unwanted impurities from solution
and substitute another substance, such as a base, to help control pH. Resins also
filter solids suspended in a solution, but the efficiency for this is usually less than
the efficiency for removal by ion exchange.
CH-04
Page 26
Rev. 0
DOE-HDBK-1015/2-93
Dissolved Gases, Suspended Solids

And pH Control Summary (Cont.)
Dissolved gases are removed from reactor facility systems to limit corrosion by
any one of the following methods or combinations of methods:
Aeration - The spraying of the water to physically release the entrained
gasses, then venting the gas.
Deaeration - The heating of the water to a slow boil, then vents the gas
usually to a condenser so the moisture is not lost.
Addition of scavengers - Examples are hydrogen, hydrazine, and
morpholine, the scavenger combines with the gas and removes it
chemically.
Channeling in an ion exchanger occurs when there is a direct flowpath for the
water that decreases the resin-water contact. Channeling may occur in the resin
bed as a result of improper filling or malfunction of the inlet connection.
Resins are susceptible to damage by overheating. Although a resin contains a very
large number of exchange sites, the number is finite and the resin exchange
capability is eventually depleted. The first indication of depletion is breakthrough,
which occurs when impurity ions begin to appear in the solution after it has passed
through the resin.
When the concentration of impurities is the same before and after the solution
passes through the resin, the resin has reached a state of exhaustion.
Suspended solids are removed by the use of mechanical filters. The two basic
categories of mechanical filters are gravity flow and pressure flow filters. The
pressure flow filters are more likely to be used because there are better control
capabilities. Numerous materials are used as filter media and include sand,
activated charcoal, anthracite, diatomaceous earth, and to some extent the resin
in an ion exchanger
Rev. 0
Page 27
CH-04
WATER PURITY
DOE-HDBK-1015/2-93
WATER PURITY
The fewer the contaminants in water, the less corrosion takes place. The methods
of water treatment have been explored previously. This chapter discusses how
water purity is quantified. Measuring the purity helps to keep treatment effective.
EO 1.10
LIST the maximum conductivity and approximate

concentration of electrolyte for each level of purity for
makeup water.
Water Purity
The water used in a nuclear facility must be of a purity level that is consistent with the overall
objectives of chemistry control in the facility.
There are a number of ways in which pure water is obtained, including distillation systems and
pretreatment systems similar to those mentioned earlier in this module. Regardless of the
method employed, the required purity must be achieved.
Water purity has been defined in many different ways, but one generally accepted definition
states that high purity water is water that has been distilled and/or de-ionized so that it will
have a specific resistance of 500,000 ohms (2.0 micromhos conductivity) or greater. This
definition is satisfactory as a base to work from, but for more critical requirements, the
breakdown shown in Table 3 has been suggested to express degrees of purity.
TABLE 3
Water Purity
Degree of Purity
Pure
Maximum Conductivity
(mhos/cm)
Approximate Concentration
of Electrolyte, mg/1
10
2-5
Very Pure
0.2 - 0.5
Ultrapure
0.1
Theoretically Pure
0.054
CH-04
0.01 - 0.02
Page 28
0.00
Rev. 0
DOE-HDBK-1015/2-93
WATER PURITY
Conductivity is a measure of the ease with which electricity can be passed through a substance.
The presence of ions greatly facilitates the passage of an electric current. Pure water is only
slightly ionized by the dissociation of water: H2O H+ + OH-. At 25 C, the concentration
of the hydrogen and hydroxyl ions is 10-7 moles/liter.
The equivalent conductance of hydrogen (H) is
350
mhos cm 2
equivalent
and the equivalent conductance of OH is

192
mhos cm 2
equivalent.
A mho is a measure of the ease with which electric current will pass and is the inverse of an
ohm, the measure of resistance to the passage of electric current. Conductance and
conductivity are similar qualities (conductivity is measured in mhos/cm , so conductance must
be converted to conductivity). A mho is one millionth of a mho. The total conductivity of
pure water can be calculated by adding the equivalent conductances of H and OH, multiplying
by the normality (see Module 1 for definition), and then multiplying by 10 3 l/cm 3 and
106 mhos/mho . For theoretically pure water this becomes the following.
(350 192)
mhos cm 2
10
equiv
equiv
10
liter
liters
cm
106
mhos
mho
.054
mho
cm
The conductivity limit for demineralized water is 1 mho/cm .

Conductivity will very quickly indicate the presence of any ionic impurities, even if the impurity
concentration is extremely small. As an example, suppose 1.0 mg of NaCl impurity were
deposited in 1 liter of demineralized water. The normality of this solution would be as follows.
1 10
Rev. 0
gm
1 equivalent
liter
58 gm
1
10
58
Page 29
equivalent
liter
1.7 10
equivalent
liter
CH-04
WATER PURITY
DOE-HDBK-1015/2-93
mhos cm 2
, while the equivalent conductance of
equivalent
The equivalent conductance of Na+ is 51

Cl- is 75
mhos cm 2
. The conductivity of the solution is
equivalent
(51 75)
mhos cm 2
1.7 10
equivalent
equivalent
10
liter
liter
mho
106
cm
mho
2.2
mho
,
cm
which is well above the limit. Even extremely low concentrations of ionic impurities can easily
be detected. The most probable cause is a depleted or damaged resin bed that is no longer
capable of removing ionic contaminants. The depleted bed should be removed from service,
and a fresh resin bed placed in service.
For most applications in nuclear facilities, the specification that is identified as Very Pure
(1.0 mho/cm maximum conductivity) is used. Ultra Pure demineralized water is normally only
required in laboratory situations and is mentioned for information purposes only.
Summary
Water Purity Summary

Water Purity is clarified below.
Degree of Purity
Maximum Conductivity(mhos/cm)
Approximate
Concentration of
Electrolyte, mg/1
Pure
10
2-5
Very Pure
0.2 - 0.5
Ultrapure
0.1
0.01 - 0.02
Theoretically Pure
0.054
0.00
CH-04
Page 30
Rev. 0
CHEMISTRY
Module 5
Hazards of Chemicals and Gases
DOE-HDBK-1015/2-93
TABLE OF CONTENTS
TABLE OF CONTENTS
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
CORROSIVES (ACIDS AND ALKALIES) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Alkalies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
General Safety Precautions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
2
2
6
TOXIC COMPOUND . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Toxic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
COMPRESSED GASES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Compressed Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Basic Safety Precautions Regarding Compressed Gases . . . . . . . . . . . . . . . . . . .
Cryogenic Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Treating Cold-Contact Burns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Specific Properties of Selected Industrial Gases . . . . . . . . . . . . . . . . . . . . . . . . .
Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sources of Ignition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
16
19
20
23
24
25
25
26
26
27
FLAMMABLE AND COMBUSTIBLE LIQUIDS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

Flammable and Combustible Liquids Definitions . . . . . . . . . . . . . . . . . . . . . . . . .
Safety Precautions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Rev. 0
Page i
30
33
39
42
CH-05
LIST OF FIGURES
DOE-HDBK-1015/2-93
LIST OF FIGURES
Figure 1 Excerpt of Toxic Substance List . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Figure 2 Typical Material Safety Data Sheet (Sections I-IV) . . . . . . . . . . . . . . . . . . . . . . 13
Figure 3 Typical Material Safety Data Sheet (Sections V-VIII) . . . . . . . . . . . . . . . . . . . . 14
Figure 4 DOT Flammable Liquid Labels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Figure 5 Typical Static-Producing Situations, Including Charge Separation In Pipe . . . . . 34
Figure 6 Bonding and Grounding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Figure 7 Grounding Above-Ground Storage Tanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Figure 8 Bonding During Container Filling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Figure 9 Storage Container With Spring-Loaded Cover . . . . . . . . . . . . . . . . . . . . . . . . . 39
Figure 10 A Flammable Liquids Mixing and Storage Room . . . . . . . . . . . . . . . . . . . . . . . 40
CH-05
Page ii
Rev. 0
DOE-HDBK-1015/2-93
LIST OF TABLES
LIST OF TABLES
Table 1 Safety Properties of Cryogenic Fluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Table 2 Emergency Measures for Treating Cold-Contact Burns . . . . . . . . . . . . . . . . . . . 23
Rev. 0
Page iii
CH-05
REFERENCES
DOE-HDBK-1015/2-93
REFERENCES
Inc., 1963
1982.
1974.
1967.
CH-05
Page iv
Rev. 0
DOE-HDBK-1015/2-93
OBJECTIVES
TERMINAL OBJECTIVE
1.0
Without references, DISCUSS the hazards associated with chemicals (liquid and gas)
found in a nuclear plant.
ENABLING OBJECTIVES
1.1
STATE the hazards associated with the use of corrosives.
1.2
STATE the general safety precautions necessary for the handling, storage, and disposal
of corrosives.
1.3
LIST the general safety precautions regarding toxic compounds.
1.4
LIST the criteria used to determine if a compound is a health hazard.
1.5
STATE the methods by which toxic compounds may enter the body.
1.6
SUMMARIZE the purpose and general contents of the following:

a.
b.
1.7
Material Safety Data Sheets (MSDS)

Toxic Substance List

a.
b.
Compressed gas
Non-liquified gases
c.
d.
Liquified gases
Dissolved gases
1.8
STATE the five major families of gases.
1.9
STATE the general safety precautions regarding the use, handling, and storage of gases.
1.10
STATE the safety precautions for working with cryogenic liquids.
1.11
LIST the physical properties and special precautions for the following gases:
a.
b.
c.
Rev. 0
Hydrogen
Oxygen
Nitrogen
Page v
CH-05
OBJECTIVES
DOE-HDBK-1015/2-93

1.12

a.
b.
Flammable liquid
Combustible liquid
1.13
STATE general safety precautions regarding the use, handling, and storage of flammable
and combustible liquids.
1.14
STATE the reasons for and techniques used in bonding and grounding of flammable
liquid containers.
1.15
LIST four sources of ignition of flammable liquids.
1.16
STATE the health hazards associated with flammable and/or combustible liquids.
CH-05
Page vi
Rev. 0
DOE-HDBK-1015/2-93 CORROSIVES (ACIDS AND ALKALIES)
CORROSIVES (ACIDS AND ALKALIES)

There are two basic groups of corrosives: acids and alkalies. These
chemicals require precautions for safe handling. These precautions will be
discussed in this chapter.
EO 1.1
STATE the hazards associated with the use of corrosives.
EO 1.2
STATE the general safety precautions necessary for the

handling, storage, and disposal of corrosives.
Acids
Acids are compounds of hydrogen and one or more other elements (with the exception of
carbon) that dissociate or break down to produce hydrogen ions (H+) when dissolved in water
or certain other solvents.
Acids are corrosive in any form, and in high concentrations destroy body tissue and cause severe
burns on contact with the skin. The eyes are very susceptible, and permanent damage or loss
of sight may result from contact with acids. The inhalation of excessive concentrations of vapor
or mist is extremely irritating to the respiratory system and to mucous membranes in particular.
Accidental swallowing of concentrated acids may result in severe irritation of, and damage to,
the throat and stomach which, in some cases, may prove fatal. Some of these materials are
specifically poisonous as well as irritating. In lower concentrations, repeated skin contact may
result in inflammation.
Concentrated aqueous solutions of acids are not in themselves flammable. The potential hazard
is the danger of their mixture with other chemicals or combustible materials which may result
in fire or explosion. Acids also react with many metals resulting in the liberation of hydrogen,
a highly flammable gas, which upon ignition in air may cause an explosion. Some of the acids
are strong oxidizing agents and can react destructively and violently when in contact with
organic or other oxidizable materials.
Personnel exposure requiring immediate action usually involves direct contact of the acid with
the body or eyes of the individual, inhalation of acid vapors or decomposition products, and
ingestion of acid. The initial treatment in all cases of local contact is immediate removal of the
acid with a large amount of water. This treatment must be prolonged until all traces of acid have
been removed, usually a minimum washing time of 15 minutes.
Rev. 0
Page 1
CH-05
DOE-HDBK-1015/2-93
Alkalies
Alkalies (bases) are corrosive caustic substances that dissociate in water and yield hydroxyl ions
(OH - ). Alkalies include: ammonia, ammonium hydroxide; calcium hydroxide and oxide;
potassium, potassium hydroxide and carbonate; sodium, sodium hydroxide; carbonate, peroxide
and silicate; and trisodium phosphate.
The alkalies, whether in solid form or concentrated liquid solution, are more destructive to tissue
than most acids. Alkali dusts, mists, and sprays may cause irritation of the eyes and respiratory
tract and lesions of the nasal septum. Strong alkalies combine with tissue, causing severe burns,
frequently deep ulceration, and ultimate scarring. Severe burns result not only from contact with
solid alkalies, but also from solutions of these compounds. Potassium and sodium hydroxide are
the most active materials in this group. Even dilute solutions of the stronger alkalies tend to
soften the epidermis (skin) and emulsify or dissolve the skin fats. Exposure to atmospheres
contaminated with alkalies may result in damage to the upper respiratory tract and to lung tissue,
depending upon the severity of the exposure. The effects of inhalation may vary from mild
irritation of the nasal mucous membranes to severe inflammation of the lungs.
Ingestion causes severe damage to mucous membranes or deeper tissues with which contact is
made. Perforation of these tissues may follow, or there may be severe and extensive scar
formation. Death may result if penetration into vital areas occurs.
Even though alkalies are not flammable and will not support combustion, much heat is evolved
when the solid material is dissolved in water. Therefore, cold water must be used to dissolve
solid alkalies, otherwise the solution may boil, and splatter corrosive liquid over a wide area.
General Safety Precautions

Corrosives are available in numerous forms and varying concentrations. Some forms and
concentrations are more hazardous than others, but the potential for serious accidents exists
regardless of the substance in question.
Many of the safety precautions necessary for safe handling and storage are equally applicable to
acids and alkalies. Some of the more common precautions are contained in this section. These
precautions are not all inclusive, nor are they meant to be. Specific corrosives may require
specific precautions, and Material Safety Data Sheets (MSDS) must be consulted in all cases.
The MSDS will be discussed later in this module.
Safety in handling hazardous chemicals depends to a great extent upon effective employee
education, proper safety practices, intelligent supervision, and the use of safe equipment.
Workers should be thoroughly informed of the hazards that may result from improper handling.
Each employee should know what to do in an emergency and should be fully informed about
proper first-aid measures. Hazards from spills and leaks should be minimized by an adequate
supply of water for washing-down. Drainage of hard-surfaced or diked areas should be directed
to minimize the exposure of personnel and equipment. Adequate ventilation should be provided
in areas where chemical mist or dust is present.
CH-05
Page 2
Rev. 0
Alkalies are much more injurious to the eyes than acids because strong acids tend to precipitate
a protein barrier, which prevents further penetration into the tissue. The alkalies do not do this.
They continue to soak into the tissue as long as they are allowed to remain in contact with the
eye. The end result of a corrosive burn to the eye (alkali or acid) is usually a scar on the cornea
and possible permanent damage.
Speed in removing corrosives is of primary importance. If the chemical enters the eyes, they
should be copiously irrigated with water for at least 15 minutes, and a physician should be
consulted immediately. In case of contact with skin or mucous membranes, the safety shower
should be used immediately. Clothing can be removed under the shower. Contaminated skin
areas should be washed with very large quantities of water for 1 to 2 hours, or until medical help
arrives. The ready availability of water, particularly safety showers and eye-washing baths,
greatly minimizes the possibility of severe, extensive damage. Contaminated clothing and shoes
should be thoroughly washed and decontaminated before re-use.
The use of personal protective equipment is not intended as a substitute for adequate control
measures, but because corrosives can cause extensive damage to the body this equipment must
be available as needed. During handling operations where spills or splashes are possible, whole
body protection (eyes, head, body, hands, and feet) may be necessary. All personal protective
equipment should be carefully cleaned and stored following use, and any equipment that cannot
be decontaminated should be discarded.
For the protection of the eyes, chemical safety goggles should be worn. Face shields should be
worn if complete face protection is necessary. Eyewash fountains and safety showers must be
available at any location where eye and/or skin contact may occur. Protection against mist or
dust can be provided by proper respiratory protective equipment. The wearing of protective
clothing is also advisable to avoid skin contact. This may consist of rubber gloves, aprons, shoes
or boots, and cotton coveralls which fit snugly. Safety shoes or boots made of rubber,
chlorobutadiene, or other chemical-resistant materials with built-in steel toecaps are
recommended for workers handling drums or in process areas where leakage may occur.
Containers should be stored in rooms with trapped floor drains. Curbs or a drained gutter,
covered with an appropriate grill, should be constructed at door openings where floor drains are
not provided.
Tanks should be entered for cleaning or repairing only after these have been drained, flushed
thoroughly with water, ventilated, and sampled. Workers entering tanks should be monitored
by someone on the outside of the tank. A supplied-air respirator or self-contained breathing
apparatus, together with rescue harness and lifeline, should be on hand for rescue purposes.
Removal from exposure is the primary, and most important, step where exposure by inhalation
is involved. The individual should be made as warm and comfortable as possible, and a physician
should be called immediately.
Rev. 0
Page 3
CH-05
DOE-HDBK-1015/2-93
Ingestion, the least common mode of contamination, requires immediate medical attention. Any
attempt at first aid beyond drinking large quantities of water should be made only upon the
advice of a physician.
If body burns are severe or extensive, or if the eyes are in any way involved, a physician should
be consulted as soon as possible after first aid is rendered. No attempt should be made to
neutralize the corrosive prior to treatment with water. Any treatment, in addition to the use of
water, should be undertaken only with the advice of the physician.
When corrosives are shipped in small containers such as glass or polyethylene bottles, they
should be well protected, whether individually packaged or several are packaged in a single case.
After careful inspection, the corrosives may be stored in these containers if the containers are
maintained in an upright position and under cover. The containers should be kept off the floor
on materials that are corrosive resistant, or protected with corrosive-resistant coverings, to
facilitate flushing and other cleanup procedures in the event of leakage or spills.
All drums should be stored on individual racks or securely blocked on skids, with the closure
(plug) up to prevent leakage. Drums containing corrosives in liquid form should be vented when
received, and at least weekly thereafter, to relieve accumulated internal pressure.
Cylinders should be stored in an upright position, preferably in individual racks and with the
valve protective cap in place. In all cases, to avoid error, empty and full containers should be
stored in different locations.
Under no circumstance should corrosives be transferred from the original labeled container to
an unmarked container. All containers must be labeled clearly, concisely, and in simple, easily
understood terms. Inspection of containers before handling will disclose conditions such as
breakage, leakage, and improperly positioned closures which could readily cause a leak or spill.
In handling bottles, barrels, or drums containing corrosives, the following guidelines must be
followed.
CH-05
1.
Carefully inspect containers prior to handling.
2.
Use personal protective equipment.
3.
Use equipment specifically designed for the purpose of transporting and

dispensing the chemical in question.
4.
Label all containers into which the chemical is transferred.
Page 4
Rev. 0
Properties of corrosives make several considerations mandatory in the selection of a storage site.
1.
The building, or area within the building selected, should be of fire-resistant

construction.
2.
The floors should be composed of chemical-resistant brick or treated concrete,

be washable, and be provided with adequate drainage.
3.
A well-lit and ventilated area in which there are adequate outlets for water should
be provided.
4.
A relatively cool and dry environment should be maintained, preventing extremes

of temperature and humidity.
5.
Electrical fixtures should be protected against corrosive mists, and wiring should
be enclosed and covered with corrosive-resistant material.
The nature of the corrosive will determine the manner in which it is stored. Most acids should,
to some extent, be isolated, some from all other chemicals, some from certain other acids and
oxidizable materials such as oil and grease, and some from combustible materials.
Generally, adequate natural ventilation is sufficient in areas where corrosives are stored, that is,
where the containers remain unopened. Where acid is used in work areas where dust or mists
may arise (such as in processing equipment or tanks), some form of mechanical exhaust system
must be provided.
Transporting containers within the plant and dispensing at various points throughout the plant
are two high-risk procedures that may cause an accident. Proper equipment can be readily
obtained, which precludes the necessity of using makeshift or otherwise dangerous methods of
transportation.
Handtrucks or power trucks used for transporting containers should have lifting parts, or clamps
specially designed for that purpose. If bottles must be transported in the plant or laboratory,
they should be enclosed in safety bottle carriers that prevent breakage if the bottle is struck or
dropped. All containers (especially acid) must be opened slowly and cautiously because of the
possible buildup of pressure within the container. Corrosives may be dispensed from drums by
means of siphons, drum transfer pumps, or by gravity with the use of a special fitting, such as
a self-closing faucet. Under no circumstances should bottles or drums be subjected to air
pressure to expel the contents.
Rev. 0
Page 5
CH-05
DOE-HDBK-1015/2-93
One final, and extremely important, consideration is the type of container or receptacle into
which corrosives are to be dispensed. The use of an inappropriate or makeshift receptacle can
negate the value of all precautionary measures.
These receptacles may be used for temporary storage or merely as a means of transporting from
storage area to place of use. In any event, an appropriate receptacle meets several conditions.
1.
It is designed for the application.
2.
It is used for no other purpose than that for which it is intended.
3.
It is maintained in a safe, clean, and dry condition.
Summary
Corrosives Summary
The hazards of acids:
High concentrations can destroy body tissue, eyes being especially
susceptible with permanent damage or loss of sight.
Inhalation of acidic vapors can irritate the respiratory system.
Ingestion can destroy the stomach and throat lining, and if the
concentration is strong enough, ingestion can be fatal.
Aqueous solutions can become explosive if combined with other
chemicals or combustible materials
If reacting with metal, hydrogen gas may be a byproduct, which is
very explosive.
CH-05
Page 6
Rev. 0
Corrosives Summary (Cont.)

The hazards of alkalies:
Alkalies are more destructive than the acids.
Alkali dusts, mists, and sprays can cause irritation of nasal passages,
eyes, and respiratory tract.
When in contact with the tissue, strong alkalies will cause ulcers, severe
burns, and eventual scarring.
Ingestion causes perforations of the mucous membrane and deeper
tissues; death may result if penetration is in vital areas.
Precautions when using corrosives:
An adequate supply of washdown water must be available.
Proper ventilation in corrosive work area must be provided.
Proper drainage must be provided such that exposure is limited.
Face shields and safety glasses that protect the eyes from splashes and
extensive vapor should be worn.
Proper personnel safety equipment should be worn when appropriate
(chemical gloves, respirators, coveralls, etc.)
Precautions when storing corrosives:
The building, or area within the building selected, should be of fireresistant construction.
The floors should be composed of chemical-resistant brick or treated
concrete, be washable, and be provided with adequate drainage.
A well-lit and ventilated area in which there are adequate outlets for
water should be provided.
A relatively cool and dry environment should be maintained, preventing
extremes of temperature and humidity.
Electrical fixtures should be protected against corrosive mists, and wiring
should be enclosed and covered with corrosive-resistant material.
Rev. 0
Page 7
CH-05
TOXIC COMPOUNDS
DOE-HDBK-1015/2-93
TOXIC COMPOUNDS
The various chemicals found in industry as well as the home are useful when
properly applied. If the user is uninformed about correct applications,
storage, and potential hazards, these chemicals become threats to safety.
This chapter gives an overview of handling chemicals and resources of
information about these chemicals.
EO 1.3
LIST the general safety precautions regarding toxic

compounds.
EO 1.4
LIST the criteria used to determine if a compound

is a health hazard.
EO 1.5
STATE the methods by which toxic compounds may

enter the body.
EO 1.6
SUMMARIZE the purpose and general contents of

the following:
a.
b.
Material Safety Data Sheets (MSDS)

Toxic Substance List
Toxic Compounds
Because the types of toxic compounds found in industry number in the thousands, and because
specific hazards, controls, and corrective measures may vary with the substance, no attempt will
be made in this section to address specific compounds. Instead, information of a general nature
will be presented on toxic materials. Material Safety Data Sheets (MSDS) are required for all
potentially hazardous and toxic materials and should be consulted for specific descriptions and
precautions concerning the substance in question.
There are some general precautions that should be universally employed regarding toxic
compounds. Many of these precautions are consistent with those already mentioned concerning
corrosives. Proper ventilation, appropriate hygienic practices, housekeeping, protective
clothing, and training for safe handling and storage will diminish many of the hazards that exist.
The toxicity of a material is not synonymous with its health hazard. Toxicity is the capacity of
a material to produce injury or harm to a living organism.
CH-05
Page 8
Rev. 0
DOE-HDBK-1015/2-93
TOXIC COMPOUNDS
Hazard is the possibility that a material will cause injury when a specific quantity is used under
specific conditions. Several key elements are considered when evaluating a health hazard.
Toxicity of the materials used
Physical properties of these materials
Absorption probabilities of these materials by individuals
Extent and intensity of exposure to these materials
Control measures used
Toxicity is relative. It refers to a harmful effect on some biologic mechanism. The term toxicity
is commonly used in comparing one chemical agent with another, but such comparison is
meaningless if the biologic mechanism, and the conditions under which the harmful effects
occur, are not specified.
Although the toxic effects of many chemical agents used in industry are well known, the toxic
effects of many other commonly used chemical agents are not as well defined. The toxicity of
a material is not a physical constant (such as boiling point, melting point, or temperature);
therefore, only a general statement can be made concerning the harmful nature of a given
chemical agent.
Many chemical agents are nonselective in their action on tissue or cells; they may exert a
harmful effect on all living matter. Other chemical agents may act only on specific cells.
Another agent may be harmful only to certain species; other species may have built-in protective
devices.
The degree to which a substance will affect living cells can be measured only after recognizable
changes have occurred following absorption. Some changes (impaired judgment, delayed
reaction time) may be produced at levels too low to cause actual cell damage. Toxicity is
dependent upon the dose, rate, method, and site of absorption, and many other factors including
general state of health, individual differences, tolerance, diet, and temperature.
In general, industrial poisonings usually result from inhalation, ingestion, and absorption.
The inhalation and absorption of toxic agents by the lungs is dependent upon the
solubility in body fluids, the diffusion through the lungs, the volume of
inhalation, the volume of blood in the lungs, and the concentration gradient of
vapors between the inhaled air and the blood.
Ingestion of the toxic agent can occur to some extent; however, there would
generally be considerable inhalation of the material where such conditions exist.
Rev. 0
Page 9
CH-05
TOXIC COMPOUNDS
DOE-HDBK-1015/2-93
Absorption through the skin can occur upon exposure to some toxic agents.
Some liquids and vapors are known to pass through the skin in concentrations
high enough such that respiratory protection is not adequate. For example,
hydrogen cyanide (HCN) is known to pass through the unbroken skin.
Consideration should be given to the type of work clothes being worn; if they
become saturated with solvents, they will act as a reservoir to bathe the body
continually with the harmful material.
Most volatile (easily vaporized) organic compounds are eliminated from the body in a matter
of hours or, at most, days. Many of the poisonous elements, however, can be stored for long
periods of time in various parts of the body. Chronic (long term) toxicity damage is unlikely
to have an even distribution throughout the body. In toxicity studies with radioactive isotopes,
the organ which suffers the most severe damage and appears to contribute most to the toxic
effect on the body as a whole, is called the critical organ. The particular organ that shows the
largest amount of damage is the one that is chosen for estimating the effect.
Industrial poisoning may be classified as either acute or chronic. The classification is based on
the rate of intake of harmful materials, rate of onset of symptoms, and the duration of
symptoms.
Acute poisoning is characterized by rapid absorption of the material and sudden, severe
exposure. For example, inhaling high levels of carbon monoxide or swallowing a large quantity
of cyanide compound will produce acute poisoning. Generally, acute poisoning results from
a single dose which is rapidly absorbed and damages one or more of the vital physiological
processes. The development of cancer long after recovery from acute radiation damage is
called a delayed acute effect.
Chronic poisoning is characterized by absorption of a harmful material in small doses over a
long period of time; each dose, if taken alone, would barely be effective. In chronic poisoning,
the harmful materials remain in the tissues, continually injuring a body process. The symptoms
in chronic poisoning are usually different from the symptoms seen in acute poisoning by the
same toxic agent.
The Occupational Safety and Health Act of 1970 requires that the Health and Human Services
publish at least annually, a list of all known toxic substances by generic family, or other useful
grouping, and the concentrations at which such toxicity is known to occur. Under the OSHA
Act, the Secretary of Labor must issue regulations requiring employers to monitor employee
exposure to toxic materials and to keep records of any such exposure.
The purpose of The Toxic Substances List is to identify "all known toxic substances" in
accordance with definitions that may be used by all sections of our society to describe toxicity.
An excerpt of this list is illustrated in Figure 1. It must be emphatically stated that the presence
of a substance on the list does not automatically mean that it is to be avoided. A listing does
mean, however, that the substance has the documented potential of being hazardous if misused,
and, therefore, care must be exercised to prevent tragic consequences.
CH-05
Page 10
Rev. 0
DOE-HDBK-1015/2-93
TOXIC COMPOUNDS
Figure 1 Excerpt of Toxic Substance List
Rev. 0
Page 11
CH-05
TOXIC COMPOUNDS
DOE-HDBK-1015/2-93
The absence of a substance from the list does not necessarily indicate that a substance is not
toxic. Some hazardous substances may not qualify for the list because the dose that causes the
toxic effect is not known.
Other chemicals associated with skin sensitization and carcinogenicity (ability to cause cancer)
may be omitted from the list, because these effects have not been reproduced in experimental
animals or because the human data is not definitive.
It is not the purpose of the list to quantify the hazard by way of the toxic concentration or dose
that is presented with each of the substances listed. Hazard evaluation involves far more than
the recognition of a toxic substance and a knowledge of its relative toxic potency. It involves
a measurement of the quantity that is available for absorption by the user, the amount of time
that is available for absorption, the frequency with which the exposure occurs, the physical form
of the substances, and the presence of other substances, additives, or contaminants (toxic or
non-toxic).
The purpose of the Material Safety Data Sheet (MSDS) is to ensure the individuals working
with chemicals and in the vicinity of chemicals have specific information on these chemicals.
This form identifies the chemical by its technical and common name and lists the
physical/chemical characteristics and fire, explosion, and reactivity hazards. The second page
specifies health hazards and recommends first aid procedures. The safe handling and control
measures are also supplied. The MSDS is a very helpful document, and personnel working
around chemicals should make it a practice to review these sheets frequently for their own
safety. Figures 2 and 3 are copies of the MSDS.
The Code of Federal Regulations recommends that the hazards of all chemicals produced and
imported be evaluated and the information concerning the hazards be transmitted to the
employers and employees. The MSDS, labels on containers, and employee training should be
part of a comprehensive hazards communication program.
CH-05
Page 12
Rev. 0
DOE-HDBK-1015/2-93
TOXIC COMPOUNDS
Figure 2 Typical Material Safety Data Sheet (Sections I-IV)
Rev. 0
Page 13
CH-05
TOXIC COMPOUNDS
DOE-HDBK-1015/2-93
Figure 3 Typical Material Safety Data Sheet (Sections V-VIII)
CH-05
Page 14
Rev. 0
DOE-HDBK-1015/2-93
TOXIC COMPOUNDS
Summary
Toxic Compounds Summary

The general safety precautions regarding toxic compounds:
Proper ventilation
Appropriate hygienic practices
Housekeeping
Protective clothing
Training
The criteria used to determine if a compound is a health hazard:
Toxicity of the materials used
The physical properties
The absorption probabilities of these materials by individuals
The extent and intensity of exposure to these materials
The control measures used
The methods by which toxic compounds may enter the body:
Ingestion
Inhalation
Absorption
The purpose and general contents of the Material Safety Data Sheets (MSDS) is to
ensure the individuals working with and in the vicinity of chemicals have specific
information of these chemicals. This form identifies the chemical, by technical and
common name, lists the physical/chemical characteristics, any fire or explosion
hazard as well as reactivity hazards. The second page will specify health hazards
and recommend first aid procedures. The safe handling and control measures are
also supplied.
The purpose and general contents of the Toxic Substance List is to identify "all
known toxic substances" in accordance with definitions that may be used by all
sections of our society to describe toxicity. This form identifies known toxic
chemicals which have been proven in lab tests or have definite human data. It lists
the chemical name, level of concentration at which it is hazardous, concentration
limits for set time exposures both weighted averages and ceiling limits.
Rev. 0
Page 15
CH-05
COMPRESSED GASES
DOE-HDBK-1015/2-93
COMPRESSED GASES
Gases are commonly used throughout industry. These gases come in several
forms and are often as dangerous as they are useful. This chapter provides
background knowledge of these gases.
EO 1.7

a.
b.
Compressed gas
Non-liquified gases
c.
d.
Liquified gases
Dissolved gases
EO 1.8
STATE the five major families of gases.
EO 1.9
STATE the general safety precautions regarding

the use, handling, and storage of gases.
EO 1.10
STATE the safety precautions for working with

cryogenic liquids.
EO 1.11
LIST the physical properties and special

precautions for the following gases:
a.
b.
c.
Hydrogen
Oxygen
Nitrogen
Compressed Gases
Gases in compressed form serve countless indispensable roles in modern technology. Oxygen
is used extensively to produce stronger and cheaper steels. Acetylene welding and brazing of
certain metals has been common for many years. Other compressed, flammable gases such as
hydrogen are equally necessary for the welding of certain metals. Some metals and alloys (such
as stainless steel, titanium, and zirconium) can be welded only under an inert gas atmosphere.
Carbon dioxide is used extensively in fire extinguishers for chemical and electrical fires. In the
nuclear industry, uses of compressed gases range from the addition of nuclear grade hydrogen
to reactor plant systems to propane and butane for heating components or spaces.
Gases are compressed for practical reasons of transportation, storage and use. The definition
of compressed gas by the Interstate Commerce Commission (ICC) reads: "... any material or
mixture having in the container an absolute pressure exceeding 40 psi (pounds per square inch)
at 70 F, or regardless of the pressure at 70 F, having an absolute pressure exceeding 140 psi
at 130 F; or any flammable material having a vapor pressure exceeding 40 psi at 100 F."
CH-05
Page 16
Rev. 0
DOE-HDBK-1015/2-93
COMPRESSED GASES
Because we often deal in gage pressures, and absolute pressure is equal to atmospheric pressure
(14.7 psi at sea level) plus the pressure that would be read on an ordinary gage, we can simplify
the above definition. Accordingly, a compressed gas is one that gives a pressure reading of:
1.
either 25 psig (pounds per square inch gage) at 70 F; or 125 psig at 130 F; or
2.
if the contained substance is flammable, 25 psig at 100 F.
This simplified definition and the range of boiling points among gases classify gases into two
major groups that differ in physical state when contained.
1.
Non-liquified gases, which are gases that do not liquify in containers at ambient
temperatures and under pressures attained in commercially used containers that
range to 2000 to 2500 psig.
2.
Liquified gases, which are gases that do become liquids to a very large extent in
containers at ordinary ambient temperatures and at pressures from 25 to
2500 psig.
The first group, commonly called non-liquified gases, have relatively low boiling points,
approximately -150 F or lower.
Non-liquified gases do, however, become liquids if cooled to temperatures below their boiling
points. Those that liquify at "cryogenic" temperatures (from absolute zero [-459.7 F] to around
-240 F) are known as cryogenic fluids.
The second group, or liquified gases, have boiling points relatively near atmospheric
temperatures (from about -130 F to 30 F). The liquified gases solidify at cryogenic
temperatures.
Oxygen, helium and nitrogen are examples of gases in wide use both as non-liquified gases and
cryogenic fluids. With respective boiling points of -297 F, -425 F, and -320 F, they are
charged into high pressure steel cylinders at more than 2000 psig at 70 F for shipment and use
as non-liquified gases. However, when shipped as cryogenic fluids, they are cooled down to
liquid form and charged into special insulated containers that keep them below their boiling
points and are contained at pressures normally less than 75 psig.
A third physical state in the container is represented by only one widely used gas, acetylene.
Acetylene is sometimes referred to as a dissolved gas. A dissolved gas is defined as a gas that
is dissolved into a solution.
Rev. 0
Page 17
CH-05
COMPRESSED GASES
DOE-HDBK-1015/2-93
The industry recommends that free acetylene should not ordinarily be handled at pressures
greater than 15 psig because, if handled at higher pressures without special equipment, it can
decompose with explosive violence. Consequently, acetylene cylinders are packed with an inert
porous material that is saturated with acetone. Acetylene charged into the cylinder dissolves in
the acetone and in solution will not decompose at or below the maximum authorized shipping
pressure of 250 psig at 70 F.
Compressed or liquified gases are also often described according to loosely-knit families to
which they belong through common origins, properties, or uses. The major families of gases are
atmospheric gases, fuel gases, refrigerant gases, aerosol gases, and poison gases.
Atmospheric gases comprise one family. Its most abundant member is nitrogen, constituting
78 percent of air by volume; oxygen, constituting 21 percent of air by volume, is its second most
abundant member. Most of the remaining 1 percent of the atmosphere consists of a sub-family
of gases, the inert gases, that share the property of chemical inertness. Inert gases are chiefly
argon, with minute quantities of helium, neon, krypton, xenon and radon. The last four are
frequently called the rare gases due to their scarcity. Hydrogen also occurs minutely in the
atmosphere, as do a large variety of trace constituents, small amounts of carbon dioxide, and
large amounts of water vapor.
Another family of gases are the fuel gases. Fuel gases burned in air or with oxygen to produce
heat make up a large family related through their major use. Its members are notably the
hydrocarbons including liquefied petroleum (LP) gases, propane, butane, methane, and welding
gases such as acetylene and hydrogen.
An opposite application relates members of another large family, the refrigerant gases. A
refrigerant gas liquifies easily under pressure and works by being compressed to a liquid which
then absorbs large amounts of heat as it circulates through coils where it vaporizes back into
gaseous form. Examples of refrigerant gases include ammonia and the fluorocarbons (freon).
Aerosol propellant gases make up a family also related by use through the introduction of
pressure-packaged products used in the form of a spray or a foam. Propellant gases have
moderate vapor pressures at room temperatures (70 psig down to 35 psig, and even lower in
some cases). It is usually agreed that a good propellant should also be nontoxic, chemically
stable, noncorrosive, and inexpensive. The fluorocarbons (freon) and nitrous oxide are the most
commonly used propellant gases.
Gases considered to be members of the poison gas family are generally those that the ICC has
classified as poison gases to ensure public safety in interstate shipments. Two examples of these
gases are hydrogen cyanide and phosgene.
CH-05
Page 18
Rev. 0
DOE-HDBK-1015/2-93
COMPRESSED GASES
Basic Safety Precautions Regarding Compressed Gases

Compressed and liquified gases are widely useful due to properties including high heat output
in combustion for some gases, high reactivity in chemical processing with other gases, extremely
low temperatures available from some gases, and the economy of handling them all in compact
form at high pressure or low temperature. These same properties, however, also represent
hazards if the gases are not handled with full knowledge and care.
Practically all gases can act as simple asphyxiants by displacing the oxygen in air. The chief
precaution taken against this potential hazard is adequate ventilation of all enclosed areas in
which unsafe concentrations may build up. A second precaution is to avoid entering unventilated
areas that might contain high concentrations of gas without first putting on breathing apparatus
with a self-contained or hose-line air supply. A number of gases have characteristic odors which
can warn of their presence in air. Others, however, like the atmospheric gases, have no odor or
color. Warning labels are required for compressed and liquified gas shipping containers. Similar
warning signs are placed at the approaches to areas in which the gases are regularly stored and
used.
Some gases can also have a toxic effect on the human system, either inhalation, through high
vapor concentrations, or by liquified gas coming in contact with the skin or the eyes. Adequate
ventilation of enclosed areas serves as the chief precaution against high concentrations of gas.
In addition, for unusually toxic gases, automatic devices can be purchased or built to monitor
the gas concentration constantly and set off alarms if the concentration approaches a danger
point. Precautions against skin or eye contact with liquified gases that are toxic or very cold,
or both, include thorough knowledge and training for all personnel handling such gases, the
development of proper procedures and equipment for handling them, and special protective
clothing and equipment (for example, protective garments, gloves, and face shields).
With flammable gases, it is necessary to guard against the possibility of fire or explosion.
Ventilation, in addition to safe procedures and equipment to detect possible leaks, represents a
primary precaution against these hazards. If fire breaks out, suitable fire extinguishing apparatus
and preparation will limit damage. Care must also taken to keep any flammable gas from
reaching any source of ignition or heat (such as sparking electrical equipment, sparks struck by
ordinary tools, boiler rooms, or open flames).
Oxygen poses a combustible hazard of a special kind. Although oxygen does not ignite, it
lowers the ignition point of flammable substances and greatly accelerates combustion. It should
not be allowed closer than 10 feet to any flammable substance, including grease and oil, and
should be stored no closer than 10 feet to cylinders or tanks containing flammable gases.
Rev. 0
Page 19
CH-05
COMPRESSED GASES
DOE-HDBK-1015/2-93
Proper storage and handling of containers avoids many possible incidents. Hazards resulting
from the rupture of a cylinder or other vessel containing gas at high pressure are protected
against by careful and secure handling of containers at all times. For example, cylinders should
never be struck nor allowed to fall, because if the cylinder is charged to a high pressure and the
cylinder valve is broken off, it could become a projectile. Cylinders should not be dragged or
rolled across the floor; they should be moved by a hand truck. Also, when they are upright on
a hand truck, floor, or vehicle, they should be chained securely to keep them from falling over.
Moreover, cylinders should not be heated to the point at which any part of their outside surface
exceeds a temperature of 125 F, and they should never be heated with a torch or other open
flame. Similar precautions are taken with larger shipping and storage containers. Initial
protection against the possibility of vessel rupture is provided by the demanding requirements
and recommendations that compressed gas containers fulfill in their construction, testing and
retesting.
Cryogenic Liquids
Most cryogenic liquids are colorless, odorless, and tasteless when vaporized to a gas. As liquids,
most have no color (except liquid oxygen which is light blue). However, whenever the cold
liquid and vapor are exposed to the atmosphere a warning appears. As the boil-off gases
condense moisture in the air, a fog forms that extends over an area larger than the vaporizing
gas. Many cryogenic liquids are inert gases, and may inert an enclosed space. Inert gases will
not support life.
Both the liquid and its boil-off vapor can rapidly freeze human tissue and can cause many
common materials such as carbon steel, plastic, and rubber to become brittle or fracture under
stress. Liquids in containers and piping at temperatures at or below the boiling point of liquified
air (-318 F) can cause the surrounding air to condense to a liquid.
Extremely cold liquified gases (helium, hydrogen, and neon) can even solidify air or other gases
to which they are directly exposed. In some cases, plugs of ice or foreign material will develop
in cryogenic container vents and openings and cause the vessel to rupture. If a plug forms,
contact the supplier immediately. Do not attempt to remove the plug; move the vessel to a
remote location.
All cryogenic liquids produce large volumes of gas when they vaporize. For example, 1 volume
of saturated liquid nitrogen at 1 atmosphere vaporizes to 696.5 volumes of nitrogen gas at room
temperature at 1 atmosphere.
When vaporized in a sealed container, cryogenic liquids produce enormous pressures. If 1
volume of liquid helium at 1 atmosphere is warmed to room temperature and vaporized in a
totally enclosed container, it has the potential to generate a pressure of more than 14,500 psig.
Because of this high pressure, cryogenic containers are usually protected with two pressure-relief
devices, a pressure-relief valve and a frangible (easily broken) disk.
CH-05
Page 20
Rev. 0
DOE-HDBK-1015/2-93
COMPRESSED GASES
Many safety precautions that must be taken with compressed gases also apply to liquified gases.
However, some additional precautions are necessary because of the special properties exhibited
by fluids at cryogenic temperatures.
The properties of cryogenic liquids affect their safe handling and use. Table 1 presents
information to help determine safe handling procedures. None of the gases listed are corrosive
at ambient temperatures, and only carbon monoxide is toxic.
Always handle cryogenic liquids carefully. They can cause frostbite on skin and
exposed eye tissue. When spilled, they tend to spread, covering a surface
completely and cooling a large area. The vapors emitted by these liquids are also
extremely cold and can damage tissues. The vapor boil-off may inert the
immediate vicinity.
Stand clear of boiling or splashing liquid and its vapors. Boiling and splashing
occurs when a warm container is charged or when warm objects are inserted into
a liquid. These operations should always be performed slowly to minimize
boiling and splashing. If cold liquid or vapor comes in contact with the skin or
eyes, first aid should be given immediately.
Never allow an unprotected part of the body to touch uninsulated pipes or
vessels that contain cryogenic fluids. The extremely cold metal will cause the
flesh to stick fast to the surface and tear when withdrawn. Touching even
nonmetallic materials at low temperatures is dangerous.
Tongs, or a similar device, should be used to withdraw objects immersed in a cryogenic liquid.
Materials that are soft and pliable at room temperature become hard and brittle at extremely low
temperatures and will break easily.
Workers handling cryogenic liquids should use eye and hand protection to protect against
splashing and cold-contact burns. Safety glasses are also recommended. If severe spraying or
splashing is likely, a face shield or chemical goggles should be worn. Protective gloves should
always be worn when anything that comes in contact with cold liquids and their vapors is being
handled. Gloves should be loose fitting so that they can be removed quickly if liquids are spilled
into them. Trousers should remain outside of boots or work shoes.
Rev. 0
Page 21
CH-05
COMPRESSED GASES
CH-05
TABLE 1
Safety Properties of Cryogenic Fluids
Methane
(CH4)
Oxygen
(O2)
Argon
(Ar)
Carbon
Nitrogen Neon
Monoxide
(N2)
(Ne)
(CO)
Hydrogen
(H2)
Helium
(He)
Boiling Point, 1 atm

o
F
o
C
-163
-108
-244
-153
-259
-161
-297
-183
-303
-186
-313
-192
-321
-196
-411
-246
-423
-253
-425
-268
Melting Point, 1 atm

o
F
o
C
-169
-112
-251
-157
-296
-182
-362
-219
-309
-189
-341
-207
-346
-210
-416
-249
-435
-259
N/A
Density, boiling point,

1 atm lb/cu ft
191
151
26
71
87
49
50
75
4.4
7.8
Heat of vaporization
boiling point Btu/lb
41
46
219
92
70
98
85
37
193
10
Volume expansion
ratio, liquid at 1 atm
boiling point to gas at
60o F, 1 atm
559
693
625
881
841
N/A
697
1447
850
754
Flammable
No
No
Yes
N/A
No
Yes
No
No
Yes
No
Rev. 0
Krypton
(Kr)
DOE-HDBK-1015/2-93
Page 22
Xenon
(Xe)
DOE-HDBK-1015/2-93
COMPRESSED GASES
Treating Cold-Contact Burns

Workers will rarely come in contact with a cryogenic liquid if proper handling procedures are
used. In the unlikely event of contact with a liquid or cold gas, a cold-contact "burn" may occur.
Actually, the skin or tissue freezes. Medical assistance should be obtained as soon as possible.
In the interim, the emergency measures presented in Table 2 are recommended.
TABLE 2
Emergency Measures for Treating Cold-Contact Burns
Remove any clothing that may restrict circulation to the frozen area. Do not rub
frozen parts, as tissue damage may result.
As soon as practical, immerse the effected part in warm water (not less than
105 F or more than 115 F, or 40 C to 46 C). Never use dry heat. The victim
should be in a warm room, if possible.
If the exposure has been massive and the general body temperature is depressed,
the patient should be totally immersed in a warm-water bath. Treatment for shock
should be provided.
Frozen tissues are painless and appear waxy and yellow. They will swell and be
painful and prone to infection when thawed. Do not rewarm rapidly. Thawing
may require 15 to 60 minutes and should continue until the pale blue tint of the
skin turns pink or red. Morphine or tranquilizers may be required to control the
pain during thawing and should be administered under professional medical
supervision.
If the frozen part of the body thaws before the doctor arrives, cover the area with
dry sterile dressings and a large, bulky protective covering.
Alcoholic beverages and smoking decrease blood flow to the frozen tissues and
should be prohibited. Warm drinks and food may be administered.
Some liquified gases require special precautions. For example, when liquid oxygen is handled,
all combustible materials, especially oil or gases, should be kept away. Smoking or open flames
should never be permitted where liquid oxygen is stored or handled. NO SMOKING signs
should be posted conspicuously in such areas.
Rev. 0
Page 23
CH-05
COMPRESSED GASES
DOE-HDBK-1015/2-93
Liquid oxygen, or oxygen-rich air atmospheres, should not come in contact with organic
materials or flammable substances. Some organic materials (oil, asphalt, kerosene, cloth, or dirt
containing oil or grease) react violently with oxygen, and may be ignited by a hot spark. Liquid
oxygen may form mixtures that are shock sensitive with fuels, oils, or grease. If liquid oxygen
spills on asphalt, or on another surface contaminated with combustibles (for example, oil-soaked
concrete or gravel), no one should walk on, and no equipment should pass over, the area for at
least 30 minutes after all frost or fog has disappeared.
Any clothing that has been splashed or soaked with liquid oxygen, or exposed to a high
gaseous-oxygen atmosphere, should be changed immediately. The contaminated systems should
be aired for at least an hour so that they are completely free of excess oxygen. Workers exposed
to high-oxygen atmospheres should leave the area and avoid all sources of ignition until the
clothing and the exposed area have been completely ventilated. Clothing saturated with oxygen
is readily ignitable and will burn vigorously.
Specific Properties of Selected Industrial Gases

Anyone who uses gases must have a thorough knowledge of their chemical properties to
maintain a controlled operation. If the gas is flammable, its flammable range and ignition
temperature must be known.
The lower flammable limit is the smallest percent of the gas in air which can ignite when exposed
to the ignition temperature. The upper flammable limit is the point above which the mixture is
too rich in fuel to ignite. The range between these two limits is the flammable, or explosive,
range. The most violent explosion will occur at concentrations about the middle of the
flammable range. Sources of heat that may cause temperatures that exceed the ignition
temperature must be avoided, as well as gas-air mixtures that are within the flammable range.
The physiological effects of the gas must be known, not only types of reactions, but also severity
of reactions. All employees who handle gas should be familiar with its effects, and recommended
control measures.
The chemical reactivity of the gas must be known. This includes a knowledge of the materials
that are resistant to its chemical effects, the materials with which it reacts, and how it reacts with
such materials. Some gases become unstable at high pressures, and others become more
corrosive at high temperatures.
The term Threshold Limit Value (TLV) is sometimes used and is defined as: The highest
time-weighted average concentration of an air contaminant which if breathed for a normal
working day is unlikely to result in health injury to the average person, either at the time, or after
years of exposure.
CH-05
Page 24
Rev. 0
DOE-HDBK-1015/2-93
COMPRESSED GASES
The following discussion addresses some of the more commonly used gases, and describes the
specific chemical properties and characteristics that are important for accident prevention.
Hydrogen
Hydrogen (H2) is the lightest of all elements. Its presence cannot be detected by any of the
senses. It is flammable in oxygen or air, and has a flammable range of from 4.1 percent to
74.2 percent by volume in air. A mixture of 10 to 65 percent hydrogen by volume in air will
explode if ignited. Pure hydrogen burns quietly in air with an almost invisible flame, and when
burned with pure oxygen, a very high temperature may be reached. Hydrogen will burn readily
in chlorine gas, and under proper conditions, will combine with nitrogen, forming ammonia.
Some chemical reactions produce hydrogen as a byproduct. A lead-acid battery will produce
hydrogen when it is being charged. Metallic sodium and potassium are examples of some
chemicals that react violently when exposed to water, producing hydrogen, which may flame
spontaneously due to the heat of the reaction. Many electroplating processes produce hydrogen.
Some chemicals used to remove scale from the water side of boilers give off hydrogen.
Whatever the operation, it is important to know whether hydrogen will be produced, and if so,
precautions must be taken to prevent its accumulation and ignition. The precautions to take
include adequate ventilation to prevent its accumulation and the elimination of possible sources
of ignition. Hydrogen is classified as an asphyxiant.
Nitrogen
Nitrogen (N2) makes up more than 78 percent of the earth's atmosphere. It will not burn or
support combustion. It cannot be detected by any of the senses and it is not toxic. Although it
is often referred to as an inert gas because it does not oxidize readily, it nevertheless forms many
compounds. It is frequently used to inert systems that contain, or have contained, flammable
liquids or gases. Inerting a system means replacing the oxygen with an inert gas in order to
reduce the possibility of fire or explosion.
Nitrogen is fairly soluble in the blood, and a considerable amount will dissolve in the blood of
a person when the air pressure is increased, as in diving, caisson, and some tunnel work. If these
employees are not properly decompressed, the dissolved nitrogen escapes from the blood in the
form of small bubbles in the bloodstream causing intense pain and is often fatal. This disorder
is commonly known as the bends.
If a large amount of nitrogen were released into the air of an enclosed space, it could cause a
serious oxygen deficiency. Nitrogen is an asphyxiant.
Rev. 0
Page 25
CH-05
COMPRESSED GASES
DOE-HDBK-1015/2-93
Oxygen
Oxygen (O2) supports combustion, but does not burn. Even so, it must be considered a
potentially hazardous element from a fire hazard standpoint. The results of an enriched oxygen
atmosphere include a lowered ignition temperature, an increased flammable range, and an
acceleration of the burning rate. Oxygen readily combines with other elements and compounds,
with spontaneous ignition in some cases. When oxygen comes in contact with oil, grease, or fuel
oils, it may ignite violently. Every possible precaution must be taken to prevent this
combination.
Oxygen sustains life, but if pure oxygen were inhaled continuously for extended periods, the
reactions in the body would be too rapid and would cause harmful effects. Oxygen should
always be referred to as oxygen, and not air, to prevent confusion. It should never be used to
run pneumatic equipment because of the possibility of coming in contact with oil that may be
inside the equipment. Finally, oxygen valves should be operated slowly. Abruptly starting and
stopping oxygen flow may ignite contaminants in the system.
Sources of Ignition
All known sources of ignition must be eliminated in areas that contain, or may contain,
flammable gases. This includes areas where gases are being manufactured or used in some
process and in areas where they are stored.
One potential source of ignition is electrical equipment. When used or installed in hazardous
locations, this equipment must be explosion-proof and properly installed.
Electrical equipment includes not only the more obvious equipment such as motors, generators,
motor controls, switches, and lighting fixtures, but also the not so obvious equipment such as
alarm systems, remote controls, telephones and other communication systems.
The use of unapproved portable electric tools and equipment should be strictly prohibited in
hazardous locations. When temporary lighting is used, it must be an approved type and in
excellent repair.
All possible sources of static electricity should be anticipated to prevent its buildup and
discharge. Several methods of control may be used. It is necessary that conductive parts of a
system be bonded (described in the following chapter) together to eliminate the difference in
potential between the parts, and the whole system grounded to eliminate the difference in
potential between the system and ground.
CH-05
Page 26
Rev. 0
DOE-HDBK-1015/2-93
COMPRESSED GASES
When some gases come in contact with certain other substances, spontaneous ignition may
occur. One of the better known of these reactions is that of oxygen with oil. Another reaction
is the possible ignition of hydrogen due to the heat of the reaction which liberated it, such as
sodium in water. Additional sources of ignition are as follows.
The spontaneous ignition that may occur in oily rags and other materials.
Smoking is a principal cause of fire, and calls for strict prohibition in hazardous
areas.
Other sources of ignition include sparks or flame-producing operations such as
grinding or welding, and equipment such as heaters or boilers.
Ferrous handtools can produce a spark when struck against, or by a suitable
object, and may cause ignition of some gas-air mixtures.
Other possible sources of ignition are internal combustion engines and batterypowered electric vehicles.
The most disastrous accidents involving industrial gases have been caused by ignition of gas-air
mixtures. Fires cannot occur without three essential factors being present in the right quantity,
at one place, and at the same time. These factors are fuel, heat, and oxygen (which is normally
supplied by air). When they are present in the same place, in the right amounts, and at the same
time, there will be a fire. To prevent a fire, it is necessary to keep only one of these factors away
from the other two. Air is necessary for life and cannot normally be eliminated, but the fuel and
heat can be kept separated. Proper operational and maintenance procedures will help prevent
a flammable gas from escaping into the air, but because this is always a possibility, it is most
important to eliminate the source of ignition.
Summary
Compressed Gases Summary

The following terms are defined:
Compressed gas is defined as any material or mixture having in the container an
absolute pressure exceeding 40 psi (pounds per square inch) at 70 F, or
regardless of the pressure at 70 F, having an absolute pressure exceeding 140 psi
at 130 F; or any flammable material having a vapor pressure exceeding 40 psi at
100 F.
Rev. 0
Page 27
CH-05
COMPRESSED GASES
DOE-HDBK-1015/2-93
Compressed Gases Summary (Cont.)

Non-liquified gases are gases that do not liquify in containers at ambient
temperatures and under pressures attained in commercially used containers that
range to 2000 to 2500 psig.
Liquified gases are gases which do become liquids to a very large extent in
containers at ordinary ambient temperatures, and at pressures from 25 to
2500 psig.
Dissolved gases are gases dissolved into a solution.
The major families of gases are:
atmospheric gases
fuel gases
refrigerant gases
aerosol gases
poison gases
The general safety precautions for gases:

Ensure there is adequate ventilation of enclosed areas.
Avoid entering unventilated areas that might contain high concentrations of gas
without first putting on breathing apparatus with a self-contained or hose-line air
supply.
Take precautions against skin or eye contact with liquified gases that are toxic or
very cold, or both.
The proper storage and handling of containers avoids many possible incidents.
The safety precautions for working with cryogenic liquids are:
Stand clear of boiling or splashing liquid and its vapors.
Never allow an unprotected part of the body to touch uninsulated pipes or vessels
that contain cryogenic fluids.
Use tongs, or a similar device, to withdraw objects immersed in a cryogenic liquid.
Use appropriate eye and hand protection.
CH-05
Page 28
Rev. 0
DOE-HDBK-1015/2-93
COMPRESSED GASES
Compressed Gases Summary (Cont.)

The physical properties and special precautions for hydrogen include the following:
It is the lightest of all elements
It cannot be detected by any of the senses
It has a flammable range of from 4.1 percent to 74.2 percent by volume in air
It burns with an almost invisible flame
Hydrogen is classified as an asphyxiant, and special precautions, such as adequate
ventilation and the elimination of possible sources of ignition, should be taken to
prevent hydrogen accumulation.
The physical properties and special precautions for nitrogen include the following:
It makes up more than 78 percent of the earth's atmosphere
It will not burn or support combustion
It cannot be detected by any of the senses
It is used to inert systems that contain, or have contained, flammable liquids or
gases
It is fairly soluble in the blood and if the dissolved nitrogen escapes from the
blood in the form of small bubbles in the bloodstream, intense pain occurs and
effects are often fatal
Nitrogen is an asphyxiant and it could cause a serious oxygen deficiency. Special
precautions, such as adequate ventilation, should be taken to prevent nitrogen
accumulation.
The physical properties and special precautions for oxygen include the following:
It supports combustion, but does not burn
Ignition temperature of a combustible material is lower in enriched oxygen
It readily combines with other elements and compounds, with spontaneous
ignition in some cases
When oxygen comes in contact with oil, grease, or fuel oils, it may ignite violently.
Every possible precaution must be taken to prevent this combination. If pure
oxygen were inhaled continuously for extended periods the reactions in the body
would be too rapid and cause harmful effects. Finally, oxygen valves should be
operated slowly. Abruptly starting and stopping oxygen flow may ignite
contaminants in the system.
Rev. 0
Page 29
CH-05
DOE-HDBK-1015/2-93
FLAMMABLE AND COMBUSTIBLE LIQUIDS

One of the most devastating industrial accidents is an explosion resulting in fire.
Carelessness is often the root cause. Improper handling and storage can also
lead to disastrous results. This chapter introduces precautions taken to avoid
accidents with flammable and combustible liquids.
EO 1.12

a.
b.
Flammable liquid
Combustible liquid
EO 1.13
STATE general safety precautions regarding the use,

handling, and storage of flammable and combustible liquids.
EO 1.14
STATE the reasons for and techniques used in bonding and

grounding of flammable liquid containers.
EO 1.15
LIST four sources of ignition of flammable liquids.
EO 1.16
STATE the health hazards associated with flammable and/or

combustible liquids.
Flammable And Combustible Liquids Definitions

As defined by OSHA, DOT, and the National Fire Protection Association Standard, Flammable
and Combustible Liquids Code, NFPA 30, a flammable liquid is one having a flash point below
100 F, and having a vapor pressure not exceeding 40 psia at 100 F. Combustible liquids are
those with flash points at or above 100 F, but below 200 F. Although combustible liquids do
not ignite as easily as flammable liquids, they must be handled with caution because of their
ability to ignite under certain conditions. Flammable and combustible liquids are further
subdivided by NFPA 30 into classes as follows.
Class I
- Those liquids having flash points below 100 F.
IA - Those liquids having flash points below 73 F and having a boiling point
below 100 F.
IB
CH-05
- Those liquids having flash points below 73 F and having a boiling point at
or above 100 F.
Page 30
Rev. 0
IC
DOE-HDBK-1015/2-93
- Those liquids having flash points at or above 73 F and below 100 F.
Class II - Those liquids having flash points at or above 100 F and below 140 F.
Class III - Those liquids having flash points above 140 F.
IIIA - Those liquids having flash points at or above 140 F and below 200 F.
IIIB - Those liquids having flash points above 200 F.
Flammable and combustible liquids vaporize to form flammable mixtures when they are stored
in open containers, when they leak or are spilled, or when heated. The hazard that exists from
these mixtures is largely dependent upon the flash point of the liquid, the concentration of the
mixture, and the potential of a source of ignition at a temperature sufficient to cause the mixture
to burst into flame.
Since it is the vapor-air mixture formed from the evaporation of the liquid that poses the hazard,
exposures of large liquid surface areas and sources of heat should be avoided or prevented
during handling or storage of these liquids.
Some of the commonly used terms associated with flammable and combustible liquids are
provided below.
Auto-Ignition Temperature The minimum temperature at which a flammable mixture will ignite from its own
heat source or contact with a heated surface without necessity of a spark or flame.
Flash Point The minimum temperature at which a liquid gives off vapor in sufficient
concentration to form an ignitible mixture with air near the surface of the liquid
(under controlled test conditions).
Flammable Limits The minimum concentration of vapor in air below which propagation of flame does
not occur on contact with a source of ignition. This is known as the lower
flammable limit (LFL). There is also a maximum concentration of vapor or gas in
air above which propagation of flame will not occur. This is called the upper
flammable limit (UFL).
Flammable Range The difference between the lower and upper flammable limits, expressed in
percentage of vapor or gas in air by volume. Also known as the explosive range.
Propagation of Flame The spread of flame through the entire volume of the flammable mixture from a
single source of ignition.
Rev. 0
Page 31
CH-05
DOE-HDBK-1015/2-93
Volatility The tendency or ability of a liquid to vaporize.

Oxygen Limits The concentration of oxygen below which a normally flammable vapor mixture will
not ignite (normally 12 to 14 percent oxygen). An increase of pressure or
temperature will reduce the required lower oxygen limit, however.
Rate of Diffusion The tendency of one gas or vapor to disperse into or mix with another gas or
vapor. Dependent upon the density of the vapor or gas as compared to air.
Vapor Pressure The pressure exerted by a volatile liquid under any of the conditions of equilibrium
that may exist between the vapors and the liquid.
Oxygen Deficiency The designation given to an atmosphere containing less than the percentage of
oxygen normally found in air (<21%).
The volatility of liquids will increase as heat is applied to them. Accordingly, combustible
liquids should be treated as flammable when they are heated even though the liquid, when not
heated, is outside the flammable range.
The Department of Transportation (DOT) has modified the definition of flammable liquids in
its Hazardous Materials Regulation, 49 CFR parts 170 to 179. They are defined as any liquid
that gives off flammable vapors at or below a temperature of 80 F. This definition is important
because the DOT Flammable Liquid Label, illustrated in Figure 4, is one means by which
containers of flammable liquids can be identified for shipping, receiving, and transportation.
Figure 4 DOT Flammable Liquid Labels
CH-05
Page 32
Rev. 0
DOE-HDBK-1015/2-93
Safety Precautions
Avoid accidental mixture of flammable and combustible liquids. A small amount of a highly
volatile substance may lower the flash point of a less volatile substance and form a more
flammable mixture. In addition, the lower flash point liquid can act as a fuse to ignite the higher
flash point material in the same manner as if it were a flammable mixture.
Fill and discharge lines and openings, as well as control valves associated with flammable and
combustible systems, shall be identified by labels, color coding, or both, to prevent mixing
different substances. All storage tanks shall be clearly labeled with the name of its contents, and
products stored within shall not be intermixed. Transfer lines from different types and classes
of flammable products should be kept separate, and preferably, different pumps should be
provided for individual products.
For handling quantities of flammable liquids up to five gallons, a portable FM (Factory Mutual
Engineering Corp.) or UL (Underwriters Laboratory) approved container should be used. The
container should be clearly identified by lettering or color code.
Smoking, the carrying of strike-anywhere matches, lighters, and other spark-producing devices
should not be permitted in a building or area where flammable liquids are stored, handled, or
used. The extent of the restricted area will depend on the type of products handled, the design
of the building, local codes, and local conditions.
Suitable NO SMOKING signs should be posted conspicuously in those buildings and areas
where smoking is prohibited.
Static electricity is generated by the contact and separation of dissimilar material. For example,
static electricity is generated when a fluid flows through a pipe or from an orifice into a tank.
Examples of several methods of generating static electricity are shown in Figure 5. The principal
hazards created by static electricity are fire and explosion, which are caused by spark discharges.
A point of great danger from a static spark is where a flammable vapor is present in the air, such
as the outlet of a flammable liquid fill pipe, at a delivery hose nozzle, near an open flammable
liquid container, and around a tank truck fill opening. In the presence of a mechanism for
generating a static charge, a spark between two bodies occurs when there is a poor electrical
conductive path between them. Hence, grounding or bonding of flammable liquid containers
is necessary to prevent static electricity from causing a spark.
Rev. 0
Page 33
CH-05
DOE-HDBK-1015/2-93
Figure 5 Typical Static-producing Situations, Including Charge Separation in Pipe
The terms bonding and grounding have sometimes been used interchangeably because of a poor
understanding of the terms. As illustrated in Figure 6, bonding eliminates a difference in
potential between objects. Grounding eliminates a difference in potential between an object and
ground. Bonding and grounding are effective only when the bonded objects are conductive.
When two objects are bonded, the charges flow freely between the bodies, and there is no
difference in their charge. Therefore, the likelihood of sparking between them is eliminated.
Although bonding eliminates a difference in potential between the objects that are bonded, it
does not eliminate a difference in potential between these objects and the earth unless one of the
objects possesses an adequate conductive path to earth. Therefore, bonding will not eliminate
the static charge, but will equalize the potential between the objects bonded so that a spark will
not occur between them.
An adequate ground will discharge a charged conductive body continuously and is recommended
as a safety measure whenever any doubt exists concerning a situation.
CH-05
Page 34
Rev. 0
DOE-HDBK-1015/2-93
Figure 6 Bonding and Grounding
Rev. 0
Page 35
CH-05
DOE-HDBK-1015/2-93
To avoid a spark from discharge of static electricity during flammable liquid filling operations,
a wire bond should be provided between the storage container and the container being filled,
unless a metallic path between the container is otherwise present.
Above-ground tanks used for storage of flammable liquids do not have to be grounded unless
they are on concrete or on nonconductive supports. Ground wires should be uninsulated so they
may be easily inspected for mechanical damage and should never be painted. Figure 7 illustrates
grounding above-ground storage tanks.
Figure 7 Grounding Above-Ground Storage Tanks
CH-05
Page 36
Rev. 0
DOE-HDBK-1015/2-93
Petroleum liquids are capable of building up electrical charges when they (a) flow through
piping, (b) are agitated in a tank or a container, or (c) are subjected to vigorous mechanical
movement such as spraying or splashing. Proper bonding or grounding of the transfer system
usually dissipates this static charge to ground as it is generated. However, rapid flow rates in
transfer lines can cause very high electrical potentials on the surface of liquids regardless of
vessel grounding. Also, some petroleum liquids are poor conductors of electricity, particularly
the pure, refined products, and even though the transfer system is properly grounded, a static
charge may build up on the surface of the liquid in the receiving container. The charge
accumulates because static electricity cannot flow through the liquid to the grounded metal
container as fast as it is being generated. If this accumulated charge builds up high enough, a
static spark with sufficient energy to ignite a flammable air-vapor mixture can occur when the
liquid level approaches a grounded probe or when a probe is lowered into a tank for sampling
or gaging.
This high static charge is usually controlled by reducing the flow rates, avoiding violent splashing
with side-flow fill lines, and using relaxation time, which allows time for the static charge to
discharge.
When flammable liquids are transferred from one container to another, a means of bonding
should be provided between the two conductive containers prior to pouring, as shown in
Figure 8.
In areas where flammable liquids are stored or used, hose nozzles on steam lines used for
cleaning should be bonded to the surface of the vessel or object being cleaned. Also, there
should be no insulated conductive objects on which the steam could impinge and induce a static
charge accumulation.
Nonconductive materials, such as fabric, rubber, or plastic sheeting, passing through or over rolls
will also create charges of static electricity. Static from these materials, as well as static from
the belts, can be discharged with grounded metal combs or tinsel collectors. Radioactive
substances and static neutralizers using electrical discharges are also employed for this purpose.
Bonding and grounding systems should be checked regularly for electrical continuity. Preferably
before each fill, the exposed part of the bonding and ground system should be inspected for parts
that have deteriorated because of corrosion or that have otherwise been damaged. Many
companies specify that bonds and grounds be constructed of bare-braided flexible wire because
it facilitates inspection and prevents broken wires from being concealed.
Electricity becomes a source of ignition where flammable vapors exist if the proper type of
electrical equipment for these atmospheres either has not been installed or has not been
maintained.
Rev. 0
Page 37
CH-05
DOE-HDBK-1015/2-93
Figure 8 Bonding During Container Filling
CH-05
Page 38
Rev. 0
DOE-HDBK-1015/2-93
A summary of reports of experimental evidence and practical experience in the petroleum

industry shows that no significant increase in fire safety is gained by the use of spark-resistant
hand tools in the presence of gasoline and similar hydrocarbon vapors. However, some materials
such as carbon disulfide, acetylene, and ethyl ether have very low ignition energy requirements.
For these and similar materials, the use of special tools designed to minimize the danger of
sparks in hazardous locations can be recognized as a conservative safety measure.
Leather-faced, plastic, and wood tools are free from the friction-spark hazard, although metallic
particles may possibly become embedded in them.
Flammable and combustible liquids and their vapors may create health hazards from both skin
contact and inhalation of toxic vapors. Irritation results from the solvent action of many
flammable liquids on the natural skin oils and tissue. A toxic hazard of varying degree exists in
practically all cases, depending on the concentration of the vapor.
Most vapors from flammable and combustible
liquids are heavier than air and will flow into
pits, tank openings, confined areas, and low
places in which they contaminate the normal
air, and cause a toxic as well as explosive
atmosphere. Oxygen deficiency occurs in
closed containers, such as a tank which has
been closed for a long time, and in which
rusting has consumed the oxygen.
All
containers should be aired and tested for toxic
and flammable atmosphere as well as the
oxygen level before entry.
Storage
Class I and Class II liquids should not be kept
or stored in a building except in approved
containers, as illustrated in Figure 9, within
either a storage cabinet or a storage room that
does not have an opening that communicates
with the public portion of the building. The
Figure 9 Storage Container With
spring-loaded cover is designed to open in
Spring-loaded Cover
order to relieve internal vapor pressure.
Quantities stored in such locations should be
limited. They should not be stored so as to limit use of exits, stairways, or areas normally used
for the safe egress of people. Neither should they be stored close to stoves or heated pipes, nor
exposed to the rays of the sun or other sources of heat.
Rev. 0
Page 39
CH-05
DOE-HDBK-1015/2-93
Losses by evaporation of liquid stored in safety cans at ordinary temperatures are negligible.
Storage of flammable and combustible liquids in open containers should not be permitted.
Approved containers for flammable liquids should be closed after each use and when empty.
Warning labels should be removed from flammable liquid containers when empty (vapor free).
Bulk Class I liquids should be stored in an underground (buried) tank or outside a building. No
outlet from the tank should be inside a building unless it terminates in a special room, as
Figure 10 A Flammable Liquids Mixing and Storage Room
Vehicles used on plant property to transport flammable and combustible liquids in sealed
containers should be designed to minimize damage to the containers.
When employees are filling tanks and other containers, they should be sure to allow sufficient
vapor space (outage) above the liquid level in order to permit expansion of the liquid with
changing temperatures. For example, gasoline expands at the rate of about one percent for each
CH-05
Page 40
Rev. 0
DOE-HDBK-1015/2-93
14 F rise in temperature. Outage space for gasoline of two percent of the capacity of the tank
or compartment is recommended, and permanent high-level markings should be installed.
Storage tanks should be provided with vents. Vent pipes of underground tanks storing Class I
flammable liquids should terminate outside buildings, higher than the fill pipe opening, and not
less than 12 feet above the adjacent ground level. They should discharge vertically upward, and
be located so that flammable vapors cannot enter building openings or be trapped under eaves
or other obstructions. Vent pipes from underground tanks storing Class II or Class III liquids
should terminate outside buildings and higher than the fill pipe opening. Vent outlets should be
above normal snow level.
Additional information concerning installation, protection, and spacing of storage tanks located
above ground, underground, or in areas subject to flooding is beyond the scope of this course.
If this information is desired, it may be found in the National Fire Protection Association
Standards.
Flammable or combustible liquids in sealed containers represent a potential hazard rather than
an active hazard -- the possibility of fire from without. By the same reasoning, inside storage
rooms are undesirable. If they must be used, they should be isolated as much as possible, and
located at or above ground level. They should not be located over basements and should
preferably be along an exterior wall.
Every inside storage room shall be provided with either a gravity (low level intake) or a
continuous mechanical exhaust ventilation system. Mechanical ventilation must be used if
Class I liquids are contained or dispensed inside the room.
Storage cabinets have specific limits on the amount and class of flammable or combustible liquids
that may be stored in them. They must be constructed and sealed so as to be fire resistant.
Cabinets shall be labeled conspicuously -- FLAMMABLE-KEEP FIRE AWAY.
The most advisable storage facility is a separate building set some distance from normally
occupied plant areas. The construction can be similar to that specified for inside storage rooms.
The types and classes of flammable and combustible liquids stored will determine the best design
to be used.
Rev. 0
Page 41
CH-05
DOE-HDBK-1015/2-93
Summary
The important information from this chapter is summarized below.
Flammable and Combustible Liquids Summary

Flammable liquid is one having a flash point below 100 F, and having a vapor
pressure not exceeding 40 psia at 100 F.
Combustible liquids are liquids with flash points at or above 100 F, but below
200 F.
General safety precautions regarding the use, handling, and storage of flammable and
combustible liquids include the following:
The vapor-air mixture formed from the evaporation of the liquid poses a hazard;
therefore, exposures of large liquid surface areas and sources of heat shall be
avoided or prevented during handling or storage of these liquids.
Accidental mixture of flammable and combustible liquids shall be avoided.
Fill and discharge lines and openings, as well as control valves associated with
flammable and combustible systems, shall be identified by labels, color coding, or
both to prevent mixing different substances.
All storage tanks shall be clearly labeled with the name of contents.
Transfer lines from different types and classes of flammable products should be
kept separate, and preferably, different pumps should be provided for individual
products.
When handling quantities of flammable liquids up to five gallons, a portable FM
(Factory Mutual Engineering Corp.) or UL (Underwriters Laboratory) approved
container should be used. The container should be clearly labeled.
Smoking, the carrying of strike-anywhere matches, lighters, and other
spark-producing devices should not be permitted in a building or area where
flammable liquids are stored, handled, or used.
CH-05
Page 42
Rev. 0
DOE-HDBK-1015/2-93
Flammable and Combustible Liquids Summary (Cont.)

The reasons for and techniques used in bonding and grounding of flammable liquid
containers are:
Static electricity is generated by the contact and separation of dissimilar material.
The principal hazards created by static electricity are those of fire and explosion,
which are caused by spark discharges. A spark between two bodies occurs when
there is a poor electrical conductive path between them. Bonding is done to
eliminate a difference in potential between objects. Grounding is done to eliminate
a difference in potential between an object and ground.
Four sources of ignition concerning flammable liquids include the following:
All sources of static electricity (induce sparks)
Improper type of electrical equipment for these atmospheres or poorly maintained
electrical equipment
Flame-producing operations (smoking, grinding or welding)
Improper hand tools that cause sparks
The health hazards associated with flammable and/or combustible liquids are:
Fire and explosions
Skin irritation from the solvent action of many flammable liquids
Vapors gather in low points or enclosed areas and cause a toxic environment
Rev. 0
Page 43
CH-05
DOE-HDBK-1015/2-93
end of text.
CONCLUDING MATERIAL
Review activities:
Preparing activity:
DOE - ANL-W, BNL, EG&G Idaho,

EG&G Mound, EG&G Rocky Flats,
LLNL, LANL, MMES, ORAU, REECo,
WHC, WINCO, WEMCO, and WSRC.
DOE - NE-73
Project Number 6910-0021
CH-05
Page 44
Rev. 0
DOE-HDBK-1015/1-93
JANUARY 1993

CHEMISTRY
Volume 1 of 2
FSC-6910

Technical Information. P.O. Box 62, Oak Ridge, TN 37831; prices available
from (615) 576-8401.
DOE-HDBK-1015/1-93
CHEMISTRY
ABSTRACT
The Chemistry Handbook was developed to assist nuclear facility operating contractors
in providing operators, maintenance personnel, and the technical staff with the necessary
fundamentals training to ensure a basic understanding of chemistry. The handbook includes
information on the atomic structure of matter; chemical bonding; chemical equations; chemical
interactions involved with corrosion processes; water chemistry control, including the principles
of water treatment; the hazards of chemicals and gases, and basic gaseous diffusion processes.
This information will provide personnel with a foundation for understanding the chemical
properties of materials and the way these properties can impose limitations on the operation of
equipment and systems.
Key Words: Training Material, Atomic Structure of Matter, The Periodic Table of the
Elements, Chemical Bonding, Corrosion, Water Chemistry Control, Water Treatment Principles,
Chemical Hazards, Gaseous Diffusion Processes
Rev. 0
CH
DOE-HDBK-1015/1-93
CHEMISTRY
FOREWORD
The DOE Fundamentals Handbooks represent the needs of various DOE nuclear facilities
Rev. 0
CH
DOE-HDBK-1015/1-93
CHEMISTRY
OVERVIEW
The Department of Energy Fundamentals Handbook entitled Chemistry was prepared as
an information resource for personnel who are responsible for the operation of the Departments
nuclear facilities. An understanding of chemistry will enable contractor personnel to understand
the intent of the chemical concerns within their facility. A basic understanding of chemistry is
necessary for DOE nuclear facility operators, maintenance personnel, and the technical staff to
safely operate and maintain the facility and facility support systems. The information in the
handbook is presented to provide a foundation for applying engineering concepts to the job. This
knowledge will help personnel understand the impact that their actions may have on the safe and
reliable operation of facility components and systems.
The Chemistry handbook consists of five modules that are contained in two volumes. The
following is a brief description of the information presented in each module of the handbook.
Volume 1 of 2
Module 1 - Fundamentals of Chemistry
Introduces concepts on the atomic structure of matter. Discusses the periodic table
and the significance of the information in a periodic table. Explains chemical
bonding, the laws of chemistry, and chemical equations.
Appendix A - Basic Separation Theory
Introduces basic separation theory for the gaseous diffusion process.
Discusses converter construction and basic operating principals.
Module 2 - Corrosion
Supplies basic information on the chemical interaction taking place during the
corrosion process between the environment and the corroding metal.
Rev. 0
CH
DOE-HDBK-1015/1-93
CHEMISTRY
OVERVIEW (Cont.)
Volume 2 of 2
Module 3 - Reactor Water Chemistry
Describes the chemical measures taken to retard the corrosion often found in water
systems. The consequences of radioactivity on facility cooling water systems are
also addressed.
Module 4 - Principles of Water Treatment
Details the principles of ion exchange in the context of water purity. Discusses
typical water treatment methods and the basis for these methods.
Module 5 - Hazards of Chemicals and Gases
Explains why certain chemicals are considered hazardous to facility personnel.
Includes general safety rules on handling and storage.
The information contained in this handbook is by no means all encompassing. An attempt
to present the entire subject of chemistry would be impractical. However, the Chemistry
Handbook does present enough information to provide the reader with a fundamental knowledge
level sufficient to understand the advanced theoretical concepts presented in other subject areas,
and to better understand basic system and equipment operation.
Rev. 0
CH
CHEMISTRY
Module 1
Fundamentals of Chemistry
DOE-HDBK-1015/1-93
TABLE OF CONTENTS
TABLE OF CONTENTS
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
vi
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
CHARACTERISTICS OF ATOMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Characteristics of Matter
The Atom Structure . . .
Chemical Elements . . .
Molecules . . . . . . . . . .
Avogadros Number . . .
The Mole . . . . . . . . . .
Mole of Molecules . . . .
Summary . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 1
. 2
. 3
. 7
. 8
. 9
. 10
. 11
THE PERIODIC TABLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

Periodic Table . . . . . . . . . . .
Classes of the Periodic Table
Group Characteristics . . . . . .
Atomic Structure of Electrons
Summary . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
12
16
18
19
22
CHEMICAL BONDING . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
Chemical Bonding . . .
Ionic Bonds . . . . . . .
Covalent Bonds . . . . .
Metallic Bonds . . . . .
Van der Waals Forces
Organic Chemistry . . .
Alkanes . . . . . . . . . .
Alkenes . . . . . . . . . .
Alkynes . . . . . . . . . .
Rev. 0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Page i
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
23
24
25
27
27
28
28
29
30
CH-01
TABLE OF CONTENTS
DOE-HDBK-1015/1-93
TABLE OF CONTENTS (Cont.)

Aromatics . . . . . . . . . . . . . . .
Alcohols . . . . . . . . . . . . . . . .
Aldehydes . . . . . . . . . . . . . .
Basic Chemical Laws . . . . . . .
Forming Chemical Compounds
Combining Elements . . . . . . .
Summary . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
30
30
31
31
32
33
34
CHEMICAL EQUATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Le Chateliers Principle . . . . .
Density . . . . . . . . . . . . . . . .
Molarity . . . . . . . . . . . . . . . .
Normality . . . . . . . . . . . . . . .
Parts per Million . . . . . . . . . .
Chemical Equations . . . . . . . .
Balancing Chemical Equations
Summary . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
36
37
37
38
39
40
40
45
ACIDS, BASES, SALTS, AND pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

Acids . . . . . . . . . . .
Bases . . . . . . . . . . .
Salts . . . . . . . . . . .
pH . . . . . . . . . . . . .
pOH . . . . . . . . . . .
Dissociation Constant
Summary . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
46
47
48
48
49
50
53
APPENDIX A BASIC SEPARATION THEORY . . . . . . . . . . . . . . . . . . . . . . . . . . . A-1

Introduction . . . . . . .
Isotopic Separation . .
Separation Factor . . . .
Stage Separation . . . .
Barrier Measurements
Cascade Theory . . . . .
Circuit Balance . . . . .
CH-01
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Page ii
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
A-1
A-1
. A-2
A-2
. A-5
A-6
. A-7
Rev. 0
DOE-HDBK-1015/1-93
TABLE OF CONTENTS

CONVERTERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Converters . . . . . . . .
Converter Construction
The Gas Cooler . . . . .
Barrier Tubing . . . . .
Process Gas Flow . . .
Diffusion . . . . . . . . .
Rev. 0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Page iii
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
A-10
. A-10
. A-10
. . A-12
. A-12
. . A-12
. A-13
CH-01
LIST OF FIGURES
DOE-HDBK-1015/1-93
LIST OF FIGURES
Figure 1 Schematic of a Simple Atom (Helium) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Figure 2 A Mole of Gold Compared to a Mole of Copper . . . . . . . . . . . . . . . . . . . . . . . 9
Figure 3 Periodic Table of the Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Figure 4 Regional Schematic of Periodic Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Figure 5 Electron Shells of Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Figure 6 Ionic Bond, Sodium Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Figure 7 Covalent Bond, Methane CH4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Figure 8 Formation of the Carbon Dioxide Molecule . . . . . . . . . . . . . . . . . . . . . . . . . 26
Figure 9 Coordinate Covalent Bond, Chlorate Ion ClO3 . . . . . . . . . . . . . . . . . . . . . . . . 26
Figure 10 Van der Waals Forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Figure 11 Alkane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Figure 12 Alkene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Figure 13 Alkyne . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Figure 14 Aromatic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Figure 15 Alcohol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Figure 16 Aldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Figure 17 Ion Product Constant for Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Figure A-1 "R" Stage Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-3
Figure A-2 Variation of Permeability with the Slope Factor and Change in Pressure . . . . A-6
Figure A-3 Pressures, Temperatures, and Flows in a Typical V-31 Stage . . . . . . . . . . . . A-8
Figure A-4 Typical Converter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-11
CH-01
Page iv
Rev. 0
DOE-HDBK-1015/1-93
LIST OF TABLES
LIST OF TABLES
Table 1 Properties of the Atom and its Fundamental Particles . . . . . . . . . . . . . . . . . . .
Table 2 Table of Elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Table 3 Description of the Properties of the First Twenty Elements . . . . . . . . . . . . . . . 12

Table 4 Electrons, Orbital, and Shell Relationships in Atomic Structure . . . . . . . . . . . . 20
Table 5 Ion Product Constant and Neutral pH for Water at Various Temperatures . . . . . 51
Table A-1 Converter Stage Size vs. Location . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
A-10
Rev. 0
CH-01
Page v
REFERENCES
DOE-HDBK-1015/1-93
REFERENCES
Inc., 1963
1982.
1974.
Underwood, Chemistry for Colleges and Schools, 2nd Edition, Edward Arnold, Ltd., 1967.
CH-01
Page vi
Rev. 0
DOE-HDBK-1015/1-93
OBJECTIVES
TERMINAL OBJECTIVE
1.0
Without references, DESCRIBE the characteristics of an atom.
ENABLING OBJECTIVES
1.1

a.
b.
c.
States of matter
Atomic weight
Molecular weight
d.
e.
f.
Mole
Gram atomic weight
Gram molecular weight
1.2
LIST the components of an atom, their relative sizes, and charges.
1.3
STATE the criterion used to classify an atom chemically.
1.4
DEFINE the following subdivisions of the periodic table:

a.
b.
c.
1.5
Periods of the periodic table

Groups of the periodic table
Classes of the periodic table
Given a periodic table, IDENTIFY the following subdivisions:

a.
b.
c.

1.6
LIST the characteristics that elements in the same group on the periodic table share.
1.7
DEFINE the term valence.
Rev. 0
Page vii
CH-01
OBJECTIVES
DOE-HDBK-1015/1-93
TERMINAL OBJECTIVE
2.0
Given an incomplete chemical equation, BALANCE the equation by the method

presented.
ENABLING OBJECTIVES
2.1

a.
b.
Ionic bonds
Van der Waals forces
c.
d.
Covalent bonds
Metallic bonds
2.2
DESCRIBE the physical arrangement and bonding of a polar molecule.
2.3
DESCRIBE the three basic laws of chemical reactions.
2.4
STATE how elements combine to form chemical compounds.
2.5
EXPLAIN the probability of any two elements combining to form a compound.
2.6

a.
b.
Mixture
Solvent
c.
d.
2.7
STATE Le Chateliers principle.
2.8

a.
b.
2.9
CH-01
ppm
Molarity
c.
d.
Solubility
Solute
e.
f.
Solution
Equilibrium
Density
Normality
BALANCE chemical equations that combine elements and/or compounds.
Page viii
Rev. 0
DOE-HDBK-1015/1-93
OBJECTIVES
TERMINAL OBJECTIVE
3.0
Given sufficient information about a solution, CALCULATE the pH and pOH of the
solution.
ENABLING OBJECTIVES
3.1

a.
b.
c.
d.
Acid
Salt
pOH
Alkalies
e.
f.
g.
Base
pH
Dissociation constant of water
3.2
STATE the formula for pH.
3.3
STATE the formula for pOH.
3.4
CALCULATE the pH of a specified solution.
Rev. 0
Page ix
CH-01
OBJECTIVES
DOE-HDBK-1015/1-93
CH-01
Page x
Rev. 0
DOE-HDBK-1015/1-93
CHARACTERISTICS OF ATOMS
Chemistry is defined as the systematic investigation of the properties,
structure, and behavior of matter and the changes matter undergoes. This
general definition raises many questions. These questions are answered in
the study of chemistry. Terms and basic concepts that help in understanding
chemistry will be discussed in this chapter.
EO 1.1

a.
b.
c.
States of matter
Atomic weight
Molecular weight
d.
e.
f.
Mole
Gram atomic weight
Gram molecular weight
EO 1.2
LIST the components of an atom, their relative sizes, and

charges.
EO 1.3
STATE the criterion used to classify an atom chemically.
Characteristics of Matter
The term states of matter refers to the physical forms in which matter exists: solid, liquid, and
gas. Solids are characterized as having both a definite shape and a definite volume. In a solid,
the forces that keep the molecules or atoms together are strong. Therefore, a solid does not
require outside support to maintain its shape.
Liquids have definite volumes but indefinite shapes and are slightly compressible. Liquids take
the shape of their containers. The forces that keep a liquid's molecules or atoms together are
weaker than in the solids.
Gases are readily compressible and capable of infinite expansion. They have indefinite shape and
indefinite volume. Of the three states, gases have the weakest forces holding their molecules or
atoms together.
The different states of matter have one thing in common; they can all be broken down into
fundamental units called atoms.
Rev. 0
Page 1
CH-01
DOE-HDBK-1015/1-93
The Atom Structure

All matter is composed of atoms, existing individually or in combination with each other. An
atom is an extremely small electrically-neutral particle. It is the smallest unit involved in the
chemical change of matter. Atoms can be treated as distinct particles because they behave as
such chemically, but atoms themselves are composed of even smaller subparts. Understanding
these atomic subparticles is important in understanding chemistry.
An atom is composed of a positively-charged nucleus orbited by one or more negatively-charged
particles called electrons. A simplified schematic representation of this arrangement is illustrated
in Figure 1. The nucleus is the core of an atom. It has a positive charge because it usually
consists of two particles, the neutron and the proton (hydrogen is the exception with only a
proton in the nucleus). The neutrons are electrically neutral, and the protons are electrically
positive. A nucleus with one proton has a charge of +1 (or simply 1), and a nucleus with two
protons has a +2 charge. Together the neutrons and protons give the nucleus its mass, but the
proton alone gives the nucleus its positive charge.
Neutrons and protons are relatively massive and are essentially equal in mass.
Figure 1 Schematic of a Simple Atom (Helium)
CH-01
Page 2
Rev. 0
DOE-HDBK-1015/1-93
The particles that orbit the nucleus are electrons. They are very small, with a mass only 1/1835
the mass of a proton or neutron. Each electron is negatively charged, and the charge of one
electron is equal in magnitude (but opposite in sign) to the charge of one proton. The number
of electrons orbiting a nucleus is exactly equal to the number of protons contained in that
nucleus. The equal and opposite charges cancel each other, and the atom as a whole is neutral.
The electrons are bound in the atom by electrostatic attraction. The atom remains neutral unless
some external force causes a change in the number of electrons.
The diameter of the atom is determined by the range of the electrons in their travels around the
nucleus and is approximately 10-8 cm. The diameter of the nucleus is roughly 10,000 times
smaller, approximately 10-13 to 10-12 cm. Because the nucleus is composed of neutrons and
protons that are about 1835 times heavier than an electron, the nucleus contains practically all
the mass of the atom, but constitutes a very small fraction of the volume. Although electrons
are individually very small, the space in which they orbit the nucleus constitutes the largest part
of the atomic volume.
Figure 1 illustrates these size relationships, but not to scale. If the nucleus were the size shown,
the electrons would be several hundred feet away.
Some of the properties of the atom and its component parts are summarized in Table 1. The
masses listed in Table 1 are measured in atomic mass units (amu), which is a relative scale in
which the mass of a proton is about 1.0.
TABLE 1
Properties of the Atom and its Fundamental Particles
Particle Name
Relative Mass
(amu)
Relative Charge
(based on charge of proton)
Electron
0.00055 or 1/1835
-1
Proton
1.0
Neutron
1.0
Chemical Elements
An atom is classified chemically by the number of protons in its nucleus. Atoms that have the
same number of protons in their nuclei have the same chemical behavior. Atoms that have the
same number of protons are grouped together and constitute a chemical element.
Rev. 0
Page 3
CH-01
DOE-HDBK-1015/1-93
Chemical Symbols
At one time chemists used various symbols, similar to shorthand, for the atoms of the
different elements. These symbols were very cumbersome and were replaced by
abbreviations of the names of the elements. Each element has been assigned a specific
one or two letter symbol based on the first letter of its chemical name. Because there are
several elements with the same first letter, it is often necessary to add the second letter
to the symbol. In some cases the symbol comes from an abbreviation for the old latin
name of the element. For example, Fe stands for iron (ferrum) and Cu for copper
(cuprum). The first letter of the chemical symbol is always capitalized. If the symbol
has two letters, the second letter is always lowercase.
Atomic Number
The number of protons in the nucleus plays such an important role in identifying the
atom that it is given a special name, the atomic number. The symbol Z is often used for
atomic number (or number of protons). Hydrogen has an atomic number of 1 and
lawrencium has an atomic number of 103. The atomic number is also equal to the
number of electrons.
Atomic Mass Number

The sum of the total number of protons, Z, and the total number of neutrons, N, is called
the atomic mass number. The symbol is A. Not all atoms of the same element have the
same atomic mass number, because, although the Z is the same, the N and thus the A are
different. Atoms of the same element with different atomic mass numbers are called
isotopes.
Atomic Weight
In Table 1, the masses of atomic particles are given in atomic mass units (amu). These
units represent a relative scale in which the mass of the isotope carbon-12 is used as the
standard and all others are related to it. Specifically, 1 amu is defined as 1/12 the mass
of the carbon-12 atom. Since the mass of a proton or a neutron is approximately 1 amu,
the mass of a particular atom will be approximately equal to its atomic mass number, Z.
The atomic weight of an element is generally more useful than isotopic masses. The
atomic weight of an element is defined as the weighted average of the masses of all of
its natural occurring isotopes. The atomic weight of the elements are listed in Table 2.
The elements that have their atomic weights in parentheses are unstable. For these
elements, the atomic weight of the longest living isotope is used rather than the average
of the masses of all occurring isotopes.
CH-01
Page 4
Rev. 0
DOE-HDBK-1015/1-93
TABLE 2
Table of Elements
Name and Symbol
Atomic
Number
Atomic
Weight
(amu)
Actinium
Ac
89
(227)
Aluminum
Al
13
Americium
Am
Antimony
Name
Atomic
Number
Atomic
Weight
(amu)
Curium
Cm
96
(247)
26.981
Dysprosium
Dy
66
162.50
95
(243)
Einsteinium
Es
99
(252)
Sb
51
121.75
Erbium
Er
68
167.26
Argon
Ar
18
39.948
Europium
Eu
63
151.96
Arsenic
As
33
74.921
Fermium
Fm
100
(257)
Astatine
At
85
(210)
Fluorine
18.998
Barium
Ba
56
137.34
Francium
Fr
87
(223)
Berkelium
Bk
97
(247)
Gadolinium
Gd
64
157.25
Beryllium
Be
9.012
Gallium
Ga
31
69.72
Bismuth
Bi
83
208.980
Germanium
Ge
32
72.59
Boron
10.811
Gold
Au
79
196.967
Bromine
Br
35
79.909
Hafnium
Hf
72
178.49
Cadmium
Cd
48
112.40
Helium
He
4.0026
Calcium
Ca
20
40.08
Holmium
Ho
67
164.930
Californium
Cf
98
(251)
Hydrogen
1.0079
Carbon
12.011
Indium
In
49
114.82
Cerium
Ce
58
140.12
Iodine
53
126.904
Cesium
Cs
55
132.905
Iridium
Ir
77
192.2
Chlorine
Cl
17
35.453
Iron
Fe
26
55.874
Chromium
Cr
24
51.996
Krypton
Kr
36
83.80
Cobalt
Co
27
58.933
Lanthanum
La
57
138.91
Copper
Cu
29
63.546
Lawrencium
Lw
103
(260)
Rev. 0
Page 5
CH-01
DOE-HDBK-1015/1-93
TABLE 2 (Cont.)
Table of Elements
Name and Symbol
Atomic
Number
Atomic
Weight
(amu)
Name
Atomic
Number
Atomic
Weight
(amu)
Lead
Pb
82
207.19
Potassium
19
39.102
Lithium
Li
6.939
Praseodymium
Pr
59
140.90
Lutetium
Lu
71
174.97
Protactinium
Pa
91
231.03
Magnesium
Mg
12
24.312
Promethium
Pm
61
(145)
Manganese
Mn
25
54.938
Radium
Ra
88
226.02
Mendelevium
Md
101
(258)
Radon
Rn
86
(222)
Mercury
Hg
80
200.59
Rhenium
Re
75
186.2
Molybdenum
Mo
42
95.94
Rhodium
Rh
45
102.90
Neodymium
Nd
60
144.24
Rubidium
Rb
37
85.47
Neon
Ne
10
20.183
Ruthenium
Ru
44
101.07
Neptunium
Np
93
237.05
Samarium
Sm
62
150.35
Nickel
Ni
28
58.71
Scandium
Sc
21
44.956
Niobium
Nb
41
92.906
Selenium
Se
34
78.96
Nitrogen
14.006
Silicon
Si
34
78.96
Nobelium
No
102
(259)
Silver
Ag
47
107.87
Osmium
Os
76
190.2
Sodium
Na
11
22.989
Oxygen
15.999
Strontium
Sr
38
87.62
Palladium
Pd
46
106.41
Sulfur
16
32.064
Phosphorus
15
30.973
Tantalum
Ta
73
180.94
Platinum
Pt
78
195.09
Technetium
Tc
43
(98)
Plutonium
Pu
94
(244)
Tellurium
Te
52
127.60
Polonium
Po
84
(209)
Terbium
Tb
65
158.92
CH-01
Page 6
Rev. 0
DOE-HDBK-1015/1-93
TABLE 2 (Cont.)
Table of Elements
Name and Symbol
Atomic
Number
Atomic
Weight
(amu)
Name
Atomic
Number
Atomic
Weight
(amu)
Thallium
Tl
81
204.37
Vanadium
23
50.942
Thorium
Th
90
232.03
Xenon
Xe
54
131.30
Thulium
Tm
69
168.93
Ytterbium
Yb
70
173.04
Tin
Sn
50
118.69
Yttrium
39
88.905
Titanium
Ti
22
47.90
Zinc
Zn
30
65.37
Tungsten
74
183.85
Zirconium
Zr
40
91.22
Uranium
92
238.03
Molecules
Molecules are groups or clusters of atoms held together by means of chemical bonding. There
are two types of molecule; molecules of an element and molecules of a compound.
Molecules of an Element
In certain cases, two single atoms of an element can be attracted to one another by a
bond to form a molecule. Examples of this are hydrogen, oxygen, and bromine. The
molecular formulas for these are H2, O2 , and Br2 . Most gaseous elements exist as
molecules of two atoms.
Molecules of a Compound
Two atoms of different elements held together by a bond form a compound. The
molecule is the primary particle of a chemical compound. Some examples of this type of
molecule include hydrogen chloride (HCl), water (H2O), methane (CH
4 ), and
ammonia (NH3).
Molecular Weight
The weight of a molecule, the molecular weight, is the total mass of the individual
atoms. Therefore, it is fairly simple to calculate the mass of any molecule if its formula
is known (that is, the elements and the number of each that make up the molecule). Note
that the terms mass and weight are used interchangeably in chemistry.
Rev. 0
Page 7
CH-01
DOE-HDBK-1015/1-93
Example 1:
The compound water has a formula of HO.
This means there is one atom of
2
oxygen and two atoms of hydrogen. Calculate the molecular weight.
Solution:
The molecular weight is calculated as follows:
1 atom
2 atoms
16.000 (the atomic weight of oxygen)

1.008 (the atomic weight of hydrogen)
molecular weight of water
16.000 amu
2.016 amu
18.016 amu
Example 2:
Calculate the molecular weight of HSO
2
4.
Solution:
hydrogen
sulfur
oxygen
2 atoms 1.008 amu

1 atom 32.064 amu
4 atoms 15.999 amu
molecular weight
2.016
32.064
63.996
98.076
amu
amu
amu
amu
Example 3:
Calculate the molecular weight of HCl.
Solution:
hydrogen
chlorine
1 atom 1.008 amu

1 atom 35.453 amu
molecular weight
1.008 amu
35.453 amu
36.461 amu
Avogadro's Number
Consider one atom of oxygen and one atom of sulfur, and compare their atomic weights.
Oxygen's atomic weight = 15.999 amu
Sulfur's atomic weight = 32.06 amu
The sulfur atom weighs approximately twice as much as the oxygen atom.
(32.06 15.99 2)
CH-01
Page 8
Rev. 0
DOE-HDBK-1015/1-93
Because the sulfur atom weighs twice as much as an oxygen atom, a one gram sample of oxygen
contains twice as many atoms as a one gram sample of sulfur. Thus, a two gram sample of sulfur
contains the same number of atoms as a one gram sample of oxygen.
From this previous example, one might suggest that a relationship exists between the weight of
a sample and the number of atoms in the sample. In fact, scientists have determined that there
is a definite relationship between the number of atoms in a sample and the sample's weight.
Experimentation has shown that, for any element, a sample containing the atomic weight in
grams contains 6.022 x 1023 atoms. Thus 15.999 grams of oxygen contains 6.022 x 1023 atoms,
and 32.06 grams of sulfur contains 6.022 x 1023 atoms. This number (6.022 x 1023) is known
as Avogadro's number. The importance of Avogadro's number to chemistry should be clear.
It represents the number of atoms in X grams of any element, where X is the atomic weight of
the element. It permits chemists to predict and use exact amounts of elements needed to cause
desired chemical reactions to occur.
The Mole
A single atom or a few atoms are rarely encountered. Instead, larger, macroscopic quantities
are used to quantify or measure collections of atoms or molecules, such as a glass of water, a
gallon of alcohol, or two aspirin. Chemists have introduced a large unit of matter, the mole, to
deal with macroscopic samples of matter.
One mole represents a definite number of objects, substances, or particles. (For example, a mole
of atoms, a mole of ions, a mole of molecules, and even, theoretically, a mole of elephants.) A
mole is defined as the quantity of a pure substance that contains 6.022 x 1023 units (atoms, ions,
molecules, or elephants) of that substance. In other words, a mole is Avogadro's number of
anything.
For any element, the mass of a mole of that element's
atoms is the atomic mass expressed in units of grams.
For example, to calculate the mass of a mole of
copper atoms, simply express the atomic mass of
copper in units of grams. Because the atomic mass of
copper is 63.546 amu, a mole of copper has a mass of
63.546 grams. The value for the atomic mass of gold
is 196.967 amu. Therefore, a mole of gold has a mass
of 196.967 grams. The mass of a mole of atoms is
called the gram atomic weight (GAW). The mole
concept allows the conversion of grams of a substance
to moles and vice versa.
Figure 2 contains a ball of gold and a ball of copper.
The two balls are of different masses and different
sizes, but each contains an identical number of atoms.
Rev. 0
Page 9
Figure 2 A Mole of Gold Compared to a

Mole of Copper
CH-01
DOE-HDBK-1015/1-93
Example 1:
A silver bar has a mass of 1870 grams. How many moles of silver are in the bar?
Solution:
Since the atomic mass of silver (Ag) is 107.87 amu, one mole of silver has a mass fo
107.87 grams. Therefore, there is one mole of Ag per 107.87 grams of Ag or
1 mole Ag
. There are 1870 grams of silver.
107.87 grams Ag
1870 grams Ag
1 mole Ag
1
107.87 grams Ag
17.3 mole Ag
Example 2:
Mercury (Hg) is the only metal that exists as a liquid at room temperature. It isused in
thermometers. A thermometer contains 0.004 moles of mercury. How many grams of
mercury are in the thermometer?
Solution:
Since the atomic mass of Hg is 201 amu, one mole of Hg has a mass of 201 grams of Hg
or
201 grams Hg
. There are 0.004 moles of Hg.
1 mole Hg
0.004 moles Hg
201 grams Hg
1
1 mole Hg
0.8 grams Hg
Mole of Molecules
The mass of a mole of molecules of a substance is the molecular mass expressed in grams. For
example, an oxygen molecule (O)
2 has a molecular mass equivalent to 32.0 grams because each
oxygen atom has a molecular mass of 16.0 grams. (Recall that to obtain the molecular mass, the
atomic masses of all atoms that appear in the formula are added.) If the atomic masses of th
e
carbon and four hydrogen atoms in methane, CH4, are added, the total is 16 amu. Therefore, one
mole of CH4 has a mass of 16 grams. The mass of a mole of molecules is called the molar mass
or gram molecular weight(GMW).
CH-01
Page 10
Rev. 0
DOE-HDBK-1015/1-93
Summary
The important information found in this chapter is summarized below.
Characteristics of Atoms Summary

&

States of matter is a term which refers to the physical forms in which
matter exists; solid, liquid and gas. Solids are characterized as having
both a definite shape and a definite volume. Liquids have definite
volumes but indefinite shapes and are slightly compressible. Gases
are readily compressible and capable of infinite expansion.
Atomic weight is defined as the weighted average of the masses of all
its natural occurring isotopes.
Molecular weight will be the total weight of the individual atoms of
a molecule.
A mole is Avogadro's number of any substance.
Gram atomic weight is the mass of a mole of atoms.
Gram molecular weight is the mass of a mole of molecules, (GMW).
&
The components of an atom are protons, neutrons, and electrons. A proton

has a mass of 1.0 amu and a positive charge (+1). The neutron also has a
mass of 1.0 amu but is neutral in charge. The electron has a mass of .00055
or 1/1835 amu and a negative charge (-1).
&
An atom is classified chemically by the number of protons in its nucleus.
Rev. 0
Page 11
CH-01
THE PERIODIC TABLE
DOE-HDBK-1015/1-93
THE PERIODIC TABLE

All known elements fall into a pattern when placed in a periodic table, and
the position in this pattern is decided by the element's atomic number. This
chapter will discuss the significance of this fact.
EO 1.4
DEFINE the following subdivisions of the periodic table:

a.
b.
c.
EO 1.5

Given a periodic table, IDENTIFY the

following subdivisions:
a.
b.
c.

EO 1.6
LIST the characteristics that elements in the

same group on the periodic table share.
EO 1.7
DEFINE the term valence.
Periodic Table
Over many years of chemical investigation, scientists have discovered a remarkable feature
of the elements. If the elements are arranged in the order of their atomic numbers, the
chemical properties of the elements are repeated somewhat regularly. To a lesser extent, the
physical properties are also repeated periodically. This periodic repetition can be seen in
Table 3. Compare the properties of lithium (Li), sodium (Na), and potassium (K), and also
those of beryllium (Be), magnesium (Mg), and calcium (Ca). In the list of elements shown
in Table 3 the properties are repeated every eighth element.
TABLE 3
Description of the Properties of the First Twenty Elements
Element
Symbol
Atomic Atomic
Number Weight
Description of Properties
Hydrogen
1.008
Colorless gas, reacts readily with oxygen to form H2O;

forms HCl with chlorine.
Helium
He
4.003
Colorless gas, very non-reactive chemically.
CH-01
Page 12
Rev. 0
DOE-HDBK-1015/1-93
THE PERIODIC TABLE
TABLE 3 (Cont.)
Description of the Properties of the First Twenty Elements
Lithium
Li
6.939
Silvery white, soft metal, very reactive chemically, forms Li2O and
LiCl readily.
Beryllium
Be
9.012
Grey metal, much harder than lithium, fairly reactive chemically,

forms BeO and BeCl2 easily.
Boron
10.811 Yellow or brown non-metal, very hard element, not very reactive, but
will form B2O3, and BCl3
Carbon
12.011 Black non-metal, brittle, non-reactive at room temperature. Forms

CO2 and CCl4.
Nitrogen
14.007 Colorless gas, not very reactive, will form N2O5 and NH3.
Oxygen
15.999 Colorless gas, moderately reactive,will combine with most elements,

forms CO2, MgO, etc.
Fluorine
18.998 Green-yellow gas, extremely reactive, irritating to smell,

forms NaF, MgF2.
Neon
Ne
10
20.183 Colorless gas, very non-reactive chemically.
Sodium
Na
11
22.990 Silvery soft metal, very reactive chemically, forms Na2O and NaCl.
Magnesium
Mg
12
24.312 Silvery white metal, much harder than sodium. Fairly reactive, forms
MgO and MgCl2.
Aluminum
Al
13
26.982 Silvery white metal, like magnesium but not as reactive. Forms
Al2O3 and AlCl3.
Silicon
Si
14
28.086 Gray, non-metallic, non-reactive at room temperature, forms SiO2

and SiCl4.
Phosphorus
15
30.974 Black, red, violet, or yellow solid, low melting point, quite reactive,
forms P2O5 and PCl3.
Sulfur
16
32.064 Yellow solid with low melting point. Moderately reactive, combines
with most elements, forms SO2, MgS, etc.
Chlorine
Cl
17
35.453 Greenish-yellow gas, extremely reactive, irritating to smell, forms

NaCl, MgCl2.
Argon
Ar
18
39.948 Colorless gas, very non-reactive chemically.
Potassium
19
39.102 Silver soft metal, very reactive chemically, forms K2O and KCl.
Calcium
Ca
20
40.080 Silver-white metal, much harder than potassium, fairly reactive,

forms CaO and CaCl2.
Rev. 0
Page 13
CH-01
THE PERIODIC TABLE
DOE-HDBK-1015/1-93
A table in which elements with similar chemical properties are grouped together is called a
periodic table. One of the most common versions is shown in Figure 3. In this table,
elements are arranged in order of increasing atomic number in succeeding rows. Each
horizontal row is called a period. Note that some periods are longer than others. Elements
with similar chemical properties appear in vertical columns called groups. Each group is
designated by a Roman numeral and a capital letter, except the one on the extreme right-hand
side, Group 0 (the inert gases). At the bottom of the periodic table are two long rows of
elements identified as the lanthanide series and the actinide series. They are separated from
the table primarily to keep it from becoming too wide. Also, the elements within each of
these two series show similar chemical properties.
The number directly below each element is its atomic number, and the number above each
element is its atomic weight. In several cases the atomic weights are in parentheses. This
indicates that these elements have no stable isotopes; that is, they are radioactive. The value
enclosed in parentheses and used for the atomic weight is the atomic mass number of the most
stable known isotope, as indicated by the longest half-life.
CH-01
Page 14
Rev. 0
DOE-HDBK-1015/1-93
THE PERIODIC TABLE
Figure 3 Periodic Table of the Elements
Rev. 0
Page 15
CH-01
THE PERIODIC TABLE
DOE-HDBK-1015/1-93
Classes of the Periodic Table

There are three broad classes of elements. These are the metals, the non-metals, and the
semi-metals. These three classes are grouped together on the periodic table as shown on
Figure 4.
Figure 4 Regional Schematic of Periodic Table
Metals
The metals constitute the largest class of elements and are located on the left and
toward the center of the periodic table as shown in Figure 4. In Figure 3, the heavy
line running step-wise from boron (B) to astatine (At) generally separates the metals
from the rest of the elements (elements in the actinide and lanthanide series are
metals). Metals tend to lose electrons to form positive ions rather than to gain
electrons and become negative ions.
CH-01
Page 16
Rev. 0
DOE-HDBK-1015/1-93
THE PERIODIC TABLE
Most people are familiar with metals' physical properties. They are usually hard and
strong, capable of being shaped mechanically (malleable and ductile), and good
conductors of heat and electricity, and they have lustrous surfaces when clean. More
important for chemical classification are the chemical properties of metals because the
physical properties are not common to all metals. For example, mercury (Hg) is a
metal, although it is a liquid at room temperature, and sodium is a metal although it
is not at all hard or strong. Metals can be involved in a wide range of chemical
reactions. Their reactions with water range from violent with sodium and potassium
to imperceptible with gold and platinum. Metals are divided into the following two
categories.
1.
The light metals, which are soft, have a low density, are very reactive
chemically, and are unsatisfactory as structural materials.
2.
The transition metals, which are hard, have a high density, do not react
readily, and are useful structural materials.
The metals in Category 1 are located at the far left of the table (Groups IA and IIA).
The metals in Category 2 are located in the middle of the table (the B groups).
Nonmetals
The nonmetals occupy the part of the periodic table to the right of the heavy, step-like
line. (refer to Figure 3 and Figure 4)
In general, the physical properties of the nonmetals are the opposite of those
attributed to metals. Nonmetals are often gases at room temperature. The nonmetals
that are solids are not lustrous, are not malleable or ductile, and are poor conductors
of heat and electricity. Some nonmetals are very reactive, but the nature of the
reactions is different from that of metals. Nonmetals tend to gain electrons to form
negative ions rather than to lose electrons to form positive ions.
The six elements in Group 0 represent a special subclass of nonmetals. They are all
very unreactive gases, so they are called the inert gases. For many years it was
believed that the inert gases would not and could not participate in chemical reactions.
In 1962, the first true compounds of an inert gas, XeF4 and XePtF6, were positively
identified.
Since that time, several other compounds have been prepared. The preparation of
these compounds requires special conditions; under ordinary conditions, the inert
gases may be considered nonreactive.
Semi-Metals
Rev. 0
Page 17
CH-01
THE PERIODIC TABLE
DOE-HDBK-1015/1-93
The obvious trend in the periodic table is that from left to right, across any period, the
elements change from distinctly metallic (Group IA) to distinctly nonmetallic
(Group VIIA). This change in character is not sharply defined, but is gradual.
Generally, elements well to the left of the heavy diagonal line are metals, and those well
to the right are nonmetals. Some of the elements near the line, however, exhibit
properties of metals under some conditions and properties of nonmetals under other
conditions. These elements are called the semi-metals and include boron (B),
silicon (Si), germanium (Ge), arsenic (As), and tellurium (Te). They are usually
classified as semi-conductors of electricity and are widely used in electrical components.
Group Characteristics
Each set of elements appearing in the vertical column of a periodic table is called a Group and
represents a family of elements that have similar physical and chemical properties. Group IA
is the Alkali Family; Group IIA is the Alkaline Earth Family; Group VIA is the Oxygen Family;
Group VIIA is the Halogen Family. On the left side of the table are Group IA elements (except
hydrogen), which are soft metals that undergo similar chemical reactions. The elements in
Group IIA form similar compounds and are much harder than their neighbors in Group IA.
As shown in the previous section, there are some exceptions to the generalizations concerning
chemical properties and the periodic table. The most accurate observation is that all elements
within a particular group have similar physical and chemical properties.
This observation is most accurate at the extreme sides of the table. All elements in Group 0 are
unreactive gases, and all elements in Group VIIA have similar chemical properties, although
there is a gradual change in physical properties. For example, fluorine (F) is a gas while
iodine (I) is a solid at room temperature.
Groups with a B designation (IB through VIIB) and Group VIII are called transition groups.
In this region of the table, exceptions begin to appear. Within any group in this region, all the
elements are metals, but their chemical properties may differ. In some cases, an element may
be more similar to neighbors within its period than it is to elements in its group. For example,
iron (Fe) is more similar to cobalt (Co) and nickel (Ni) than it is to ruthenium (Ru) and
osmium (Os). Most of these elements have several charges, and their ions in solution are
colored (ions of all other elements are colorless).
The line separating metals from nonmetals cuts across several groups. In this region of the
table, the rule of group similarities loses much of its usefulness. In Group IVA, for example,
carbon (C) is a nonmetal; silicon (Si) and germanium (Ge) are semi-metals; and tin (Sn) and
lead (Pb) are metals.
CH-01
Page 18
Rev. 0
DOE-HDBK-1015/1-93
THE PERIODIC TABLE
Chemical activity can also be determined from position in the periodic table. The most active
metals are the members of the Alkali Family, e.g., cesium (Cs) and francium (Fr). The most
active nonmetals are the members of the Halogen Family, e.g., fluorine (F) and chlorine (Cl).
The Noble Gases in Group 0 are inert. The activity of metals decreases when proceeding to the
right in the periodic table; the activity of nonmetals decreases when proceeding to the left.
Atomic Structure of Electrons

Based on experimental data, it is known that chemical reactions involve only the electrons in
atoms. In fact, only some of the electrons are involved. Because chemical properties are
periodic, there must also be a periodic characteristic about electrons. This characteristic is the
manner in which electrons are arranged in the atom. Electrons are in constant motion around
the nucleus. They have both kinetic and potential energy, and their total energy is the sum of
the two. The total energy is quantized; that is, there are definite, discrete values of total energy
that atomic electrons can possess. These energy states can be visualized as spherical shells
around the nucleus separated by forbidden areas where electrons cannot exist in a stable state.
This sort of arrangement is illustrated in Figure 5.
Figure 5 Electron Shells of Atoms
It is customary to speak of electron shells around the nucleus, and the shells are referred to by
number. The first, or No. 1, shell is the one nearest the nucleus; the second, or No. 2, shell is
next; then the third, or No. 3, shell; and so on in numerical order. In general, electrons closer
to the nucleus have a lower energy state. Atomic electrons always seek the lowest energy state
available.
Rev. 0
Page 19
CH-01
THE PERIODIC TABLE
DOE-HDBK-1015/1-93
The electron shells represent major energy states of electrons. Each shell contains one or more
subshells called orbitals, each with a slightly different energy. In order of increasing energy, the
orbitals are designated by the small letters s, p, d, f, g, h.
No two shells consist of the same number of orbitals. The first shell contains only one orbital,
an s orbital. The second shell contains s and p orbitals. In general, each higher shell contains
a new type of orbital:
the first shell contains an s orbital,
the second shell contains s and p orbitals,
the third shell contains s, p, and d orbitals,
the fourth shell contains s, p, d, and f orbitals,
and so on. Each orbital can hold a definite maximum number of electrons. There is also a limit
to the number of electrons in each shell and the limit increases as one goes to higher shells. The
numbers of electrons that can occupy the different orbitals and shells are shown in Table 4.
TABLE 4
Electrons, Orbital, and Shell Relationships in Atomic Structure
Shell Number
Type of Orbitals
Maximum Number of Electrons

in Each Orbital
Maximum Total
Electrons in shell
10
10
14
10
14
18
CH-01
18
32
Page 20
50
Rev. 0
DOE-HDBK-1015/1-93
THE PERIODIC TABLE
A more specific statement can now be made about which electrons are involved in chemical
reactions. Chemical reactions involve primarily the electrons in the outermost shell of an atom.
The term outermost shell refers to the shell farthest from the nucleus that has some or all of its
allotted number of electrons. Some atoms have more than one partially-filled shell. All of the
partially-filled shells have some effect on chemical behavior, but the outermost one has the
greatest effect. The outermost shell is called the valence shell, and the electrons in that shell
are called valence electrons. The term valence (of an atom) is defined as the number of
electrons an element gains or loses, or the number of pairs of electrons it shares when it
interacts with other elements.
The periodic chart is arranged so that the valence of an atom can be easily determined. For the
elements in the A groups of the periodic chart, the number of valence electrons is the same as
the group number; that is, carbon (C) is in Group IVA and has four valence electrons. The
noble gases (Group 0) have eight in their valence shell with the exception of helium, which has
two.
The arrangement in which the outermost shell is either completely filled (as with He and Ne)
or contains eight electrons (as with Ne, Ar, Kr, Xe, Rn) is called the inert gas configuration.
The inert gas configuration is exceptionally stable energetically because these inert gases are
the least reactive of all the elements.
The first element in the periodic table, hydrogen, does not have properties that satisfactorily
place it in any group. Hydrogen has two unique features: (a) the highest energy shell of a
hydrogen atom can hold only two electrons, in contrast to all others (except helium) that can
hold eight or more; and (b) when hydrogen loses its electron, the ion formed, H+, is a bare
nucleus. The hydrogen ion is very small in comparison with a positive ion of any other element,
which must still have some electrons surrounding the nucleus. Hydrogen can either gain or lose
an electron. It has some properties similar to Group IA elements, and some similar to
Group VIIA elements.
The number of electrons in the outer, or valence, shell determines the relative activity of the
element. The elements are arranged in the periodic table so that elements of the same group
have the same number of electrons in the outer shell (except for the Transition Groups). The
arrangement of electrons in the outer shell explains why some elements are chemically very
active, some are not very active, and others are inert. In general, the fewer electrons an element
must lose, gain, or share to reach a stable shell structure, the more chemically active the element
is. The likelihood of elements forming compounds is strongly influenced by this valence shell
and on the stability of the resulting molecule. The more stable the molecules are, the more
likely these molecules are to form.
Rev. 0
Page 21
CH-01
THE PERIODIC TABLE
DOE-HDBK-1015/1-93
Summary
Periodic Table Summary

&
The subdivisions of the periodic table are periods, groups, and classes. The
horizontal rows are called periods. The vertical columns are called groups.
The entire table consists of three classes: metals, non-metals, and semimetals.
&
The subdivisions of the periodic chart have been explained such that the
student should be able to identify them if given a periodic table.
&
Elements of the same group share certain physical and chemical

characteristics. Examples of the characteristics of several groups are listed
below.
Group 0 contains elements that are unreactive gases.
Group IA contains elements that are chemically active soft metals.
Group VIIA contains elements that are chemically active
nonmetals.
Groups IB through VIIB and VIII are called transition groups and
elements found in them display properties of metals.
&
CH-01
The valence of an atom is defined as the number of electrons an element

gains or loses, or the number of pairs of electrons it shares when it interacts
with other elements.
Page 22
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL BONDING
CHEMICAL BONDING
The development of matter, no matter what the form, is the result of the
practical application of the assumptions, hypotheses, theories, and laws that
chemists have formulated from their research into the nature of matter,
energy, and change. This chapter will address some of these theories and
laws. Chemical bonds and how atoms bond to form molecules will be
discussed. In addition, an introduction to organic chemistry is provided.
EO 2.1 DEFINE the following terms:
a.
b.
Ionic bonds
Van der Waals forces
c.
d.
Covalent bonds
Metallic bonds
EO 2.2 DESCRIBE the physical arrangement and bonding of a polar

molecule.
EO 2.3 DESCRIBE the three basic laws of chemical reactions.
EO 2.4 STATE how elements combine to form chemical compounds.
EO 2.5 EXPLAIN the probability of any two elements combining to
form a compound.
EO 2.6 DEFINE the following terms:
a.
b.
c.
Mixture
Solvent
Solubility
d.
e.
f.
Solute
Solution
Equilibrium
Chemical Bonding
As stated in the previous chapter, the number of electrons in the outer, or valence, shell
determines the relative activity of the element. The arrangement of electrons in the outer shell
explains why some elements are chemically very active, some are not very active, and others
are inert. In general, the fewer electrons an element must lose, gain, or share to reach a stable
shell structure, the more chemically active the element is. The likelihood of elements forming
compounds is strongly influenced by the completion of the valence shell and by the stability
of the resulting molecule. The more stable the resulting molecules are, the more likely these
molecules are to form. For example, an atom that "needs" two electrons to completely fill the
valence shell would rather react with another atom which must give up two electrons to
satisfy its valence.
Rev. 0
Page 23
CH-01
CHEMICAL BONDING
DOE-HDBK-1015/1-93
In the case of H+ + Br-, this is likely to take place because the exchange would satisfy the
needs of both atoms. Although there is far more to consider than just the number of valence
electrons, this is a good rule of thumb.
If the atom needed two electrons and only picked up one, it would still actively seek out an
additional electron. The reaction of H+ + Te-2 is far less likely to take place because the
resulting molecule would still have an incomplete valence shell. Of course, the combining of
two atoms, when both want to release or gain electrons, may take place (for example; H2 or
O2) but is less probable when other atoms are available.
Atoms are joined or bonded together through this interaction of their electrons. There are
several types of chemical bonds that hold atoms together; three will be discussed, ionic,
covalent, and metallic.
Ionic Bonds
An ionic bond is formed when one or more electrons is wholly transferred from one element
to another, and the elements are held together by the force of attraction due to the opposing
charges. An example of ionic bonding is shown in Figure 6(A) for sodium chloride (table salt).
Figure 6 Ionic Bond, Sodium Chloride
The sodium atom loses the one electron in its outer shell to the chlorine atom, which uses the
electron to fill its outer shell. When this occurs, the sodium atom is left with a +1 charge and
the chlorine atom a -1 charge. The ionic bond is formed as a result of the attraction of the two
oppositely-charged particles. No single negatively-charged ion has a greater tendency to bond
to a particular positively-charged ion than to any other ion.
CH-01
Page 24
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL BONDING
Because of this, the positive and negative ions arrange themselves in three dimensions, as
shown in Figure 6(B), to balance the charges among several ions. In sodium chloride, for
example, each chloride ion is surrounded by as many sodium ions as can easily crowd around
it, namely six. Similarly, each sodium ion is surrounded by six chloride ions. Therefore, each
chloride ion is bonded to the six nearest sodium ions and bonded to a lesser extent to the more
distant sodium ions. Accordingly, the ionic bond is a force holding many atoms or ions
together rather than a bond between two individual atoms or ions.
Covalent Bonds
A covalent bond is formed when one or more electrons from an atom pair off with one or more
electrons from another atom and form overlapping electron shells in which both atoms share the
paired electrons. Unlike an ionic bond, a covalent bond holds together specific atoms. Covalent
bonding can be single covalent, double covalent, or triple covalent depending on the number of
pairs of electrons shared. Figure 7 shows the bonding that occurs in the methane molecule,
which consists of four single covalent bonds between one carbon atom and four hydrogen atoms.
Figure 7 Covalent Bond, Methane CH4
Two double covalent bonds result when carbon dioxide, which consists of one carbon atom
and two oxygen atoms, is formed. Four pairs of electrons are shared by the carbon atom, two
from each of the two oxygen atoms as shown in Figure 8. A combination of two electrons
form a combination of lower energy than their energy when separated. This energy difference
represents the force that binds specific atoms together.
Rev. 0
Page 25
CH-01
CHEMICAL BONDING
DOE-HDBK-1015/1-93
Figure 8 Formation of the Carbon Dioxide Molecule
When both shared electrons in a covalent bond come from the same atom, the bond is called
a coordinate covalent bond. Although both shared electrons come from the same atom, a
coordinate covalent bond is a single bond similar in properties to a covalent bond. Figure 9
illustrates the bonds of the negatively-charged chlorate ion. The ion consists of one chlorine
atom and three oxygen atoms with a net charge of -1, and is formed with two coordinate
covalent bonds and one covalent bond. The chlorine atom has effectively gained an electron
through the covalent bond, which causes the overall negative charge.
Figure 9 Coordinate Covalent Bond, Chlorate Ion ClO3
Covalent bonds can be either polar or nonpolar. When the shared pair of electrons is not
shared equally, one end of the bond is positive, and the other end is negative. This produces
a bond with two poles called a polar covalent bond.
CH-01
Page 26
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL BONDING
Molecules having polar covalent bonds are called dipolar or polar molecules. Water is an
example of a polar molecule. When two atoms of the same element share one or more pairs
of electrons (such as H or N), each atom exerts the same attraction for the shared electron pair
or pairs. When the electron pairs are distributed or shared equally between the two like atoms,
the bond is called a nonpolar covalent bond. If all the bonds in a molecule are of this kind, the
molecule is called a nonpolar covalent molecule.
Metallic Bonds
Another chemical bonding mechanism is the metallic bond. In the metallic bond, an atom
achieves a more stable configuration by sharing the electrons in its outer shell with many other
atoms. Metallic bonds prevail in elements in which the valence electrons are not tightly bound
with the nucleus, namely metals, thus the name metallic bonding. In this type of bond, each
atom in a metal crystal contributes all the electrons in its valence shell to all other atoms in the
crystal.
Another way of looking at this mechanism is to imagine that the valence electrons are not
closely associated with individual atoms, but instead move around amongst the atoms within
the crystal. Therefore, the individual atoms can "slip" over one another yet remain firmly held
together by the electrostatic forces exerted by the electrons. This is why most metals can be
hammered into thin sheets (malleable) or drawn into thin wires (ductile). When an electrical
potential difference is applied, the electrons move freely between atoms, and a current flows.
Van der Waals Forces

In addition to chemical bonding between atoms, there is another type of attractive force that
exists between atoms, ions, or molecules known as van der Waals forces.
These forces occur between the molecules of nonpolar covalent substances such as H2, Cl2, and
He. These forces are generally believed to be caused by a temporary dipole, or unequal charge
distribution, as electrons constantly move about in an atom, ion, or molecule. At a given
instant, more electrons may be in one region than in another region, as illustrated in Figure 10.
The temporary dipole induces a similar temporary dipole on a nearby atom, ion, or molecule.
Every instant, billions of these temporary dipoles form, break apart, and reform to act as a weak
electrostatic force of attraction known as van der Waals forces.
It is important to note that van der Waals forces exist between all kinds of molecules. Some
molecules may have these forces, as well as dipole or other intermolecular forces. Van der
Waals forces, however, are the only intermolecular bonds between nonpolar covalent molecules
such as H2, Cl2, and CH4 . The number of electrons in a substance increases as the gram
molecular mass (mass in grams of one mole of compound) increases. Therefore, the strength
of the van der Waals forces between substances increases with increasing gram molecular mass.
Rev. 0
Page 27
CH-01
CHEMICAL BONDING
DOE-HDBK-1015/1-93
Figure 10 Van der Waals Forces
Van der Waals forces are small compared to the forces of chemical bonding and are significant
only when the molecules are very close together.
Organic Chemistry
Organic chemistry is defined as the chemistry of carbon compounds. The compounds of carbon
are in forms of living things and in synthetic fabrics and plastics. Organic chemistry is so broad
a topic that it is usually subdivided into smaller areas. How the carbon is combined and what
it is combined with determines the subdivision for a particular compound. These subdivisions
are referred to as families or classes.
The carbon atoms can combine to form straight chains, rings, or branched chains. The bonds
between carbon atoms can be single, double, triple or a combination of these. Other atoms (H,
O, N, S, P) and the halogens can be attached to the carbon atoms to yield derivatives.
The large family of organic compounds containing only carbon and hydrogen are called
hydrocarbons. These can be further divided into two broad classes, aliphatic (fatty) and
aromatic (fragrant).
Aliphatic hydrocarbons are divided into two categories, saturated and unsaturated and into
subdivisions alkanes, alkenes, and alkynes. These subdivisions reflect the type of bond between
the carbon atoms.
Alkanes
Alkanes are saturated compounds which have single bonds between carbon atoms and contain
the maximum number of hydrogen atoms possible. Each carbon is flanked by four covalent
bonds and each hydrogen atom shares one pair of electrons with a carbon atom, as illustrated
in Figure 11.
CH-01
Page 28
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL BONDING
The general formula for alkanes is CnH2n+2. The alkanes are

colorless, practically odorless, insoluble in water, and readily
soluble in nonpolar solvents such as benzene or ether.
Alkanes are low in reactivity. The reactions they do undergo
are called halogenation, thermal decomposition (cracking),
and combustion. These are summarized below.
Halogenation occurs when a hydrogen atom is replaced
with a halogen atom. This is referred to as a
substitution reaction. There is no limit to how many
hydrogen atoms can be replaced in one molecule.
Figure 11 Alkane
Thermal decomposition or cracking is the process of breaking large molecules into

smaller ones. Using heat as a catalyst, propane can be broken into methane and
ethylene:

Combustion occurs when an alkane is burned, the products being carbon dioxide gas,
water, and heat. These reactions are highly exothermic and as such the hydrocarbons
are frequently used for fuel.

Alkenes
Alkenes are hydrocarbons containing two fewer hydrogen
atoms than the corresponding alkane. The general formula for
alkenes is CnH2n. These molecules will have a double bond as
Because there are fewer hydrogen atoms than the maximum
possible, alkenes are unsaturated hydrocarbons. The chief
source for alkenes is the cracking of alkanes.

Rev. 0
Figure 12 Alkene
Page 29
CH-01
CHEMICAL BONDING
DOE-HDBK-1015/1-93
Alkynes
The third of the aliphatic hydrocarbons are the alkynes. These
compounds are unsaturated like the alkenes. They contain two
fewer hydrogens than the corresponding alkane, CnH2n-2. The
alkyne hydrocarbons contain a triple bond between at least one
set of carbon atoms as illustrated in Figure 13.
Aromatics
Figure 13 Alkyne
The other broad class of hydrocarbons is the aromatic

hydrocarbon. Rather than being arranged in straight chains, as
the aliphatics are, these are cyclic formations such as in
benzene. The derivatives of cyclic hydrocarbons have pleasant
(sometimes toxic) odors. The benzene in rubber cement is a
familiar odor. The cyclic compounds have alternating single double bonds as illustrated in Figure 14.
Aromatic hydrocarbons are very stable chemically, and act
very much like alkanes. They will undergo substitution
reactions rather than additions.
Figure 14 Aromatic
Alcohols
Alcohol is an aliphatic hydrocarbon with a hydroxyl (OH)
group substituting for one or more hydrogens as illustrated in
Figure 15.
The -OH functional group does not behave in an ionic manner
in the case of alcohols. The alcohols are molecular, not ionic,
in nature. Alcohols are versatile compounds which are often
used to make nearly every other kind of aliphatic compound.
Figure 15 Alcohol
CH-01
Page 30
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL BONDING
Aldehydes
Aldehydes are one of the oxidation products of the alcohols.
Each of these compounds contain a carbonyl group (a carbon
atom double bonded to an oxygen atom) as illustrated in
Figure 16.
The term "aldehyde" is a contraction of the term "alcohol
dehydrogenation" indicating that two hydrogen atoms are
removed from an end carbon when aldehydes are prepared
from primary alcohols. The functional group (-C=O) is always
at the end of the carbon chain.
Figure 16 Aldehyde
Basic Chemical Laws
As previously stated, all matter is composed of atoms that which are capable of uniting to
form chemical compounds. The various forms of matter can be summarized from a chemical
point of view as follows.
1.
Rev. 0
Molecules are groups or clusters of atoms held together firmly by means of

chemical bonding. There are two general types of molecules.
a.
Molecule of an element - Two single atoms of the same element, in

certain cases, can become fastened to one another by a chemical bond to
form a molecule. Examples of this are hydrogen (H2), oxygen (O2), and
bromine (Br2). Most gaseous elements exist as molecules of two atoms.
b.
Molecules of a compound - A compound contains at least two different

kinds of atoms. Molecules are the ultimate particles of chemical
compounds. Examples of compounds are hydrogen chloride (HCl),
water (H2O), methane (CH4), and ammonia (NH3).
2.
Elements are substances that cannot be decomposed by ordinary types of

chemical change nor made by chemical union.
3.
Compounds are substances containing more than one constituent element and
having properties different from those of the individual elements. The
composition of a specific compound is always definite.
4.
Mixtures consist of two or more substances intermingled with no constant

percentage composition. Each component retains its original properties.
Page 31
CH-01
CHEMICAL BONDING
DOE-HDBK-1015/1-93
Forming Chemical Compounds

Chemistry and all other sciences are based on facts established through experimentation. A
scientific law is a condensed statement of facts which has been discovered by experiment.
There are three basic laws that apply to chemical reactions. They are the Law of Conservation
of Mass, the Law of Definite Proportions, and the Law of Multiple Proportions. These laws
are described here to help the reader in understanding the reasons elements and compounds
behave as they do.
1.
The Law of Conservation of Mass

This law states that in a chemical reaction the total mass of the products equals
the total mass of the reactants. Antoine Lavoisier, a French chemist, discovered
that when tin reacts with air in a closed vessel, the weight of the vessel and its
contents is the same after the reaction as it was before. Scientists later
discovered that whenever energy (heat, light, radiation) is liberated during a
reaction, a very small change in mass does occur, but this change is insignificant
in ordinary chemical reactions.
2.
The Law of Definite Proportions

This law states that no matter how a given chemical compound is prepared, it
always contains the same elements in the same proportions by mass. John
Dalton, an English physicist, discovered that when various metals are burned or
oxidized in air, they always combine in definite proportions by weight.
For example, one part by weight of oxygen always combines with 1.52 parts by
weight of magnesium or 37.1 parts by weight of tin. This law results from the
fact that a compound is formed by the combination of a definite number of
atoms of one element with a definite number of atoms of another.
3.
The Law of Multiple Proportions

This law states that if two elements combine to form more than one compound,
the masses of one of the elements combining with a fixed mass of the other are
in a simple ratio to one another. For example, carbon forms two common
compounds with oxygen; carbon monoxide and carbon dioxide. With carbon
monoxide (CO), 1.33 grams of oxygen are combined with 1 gram of carbon.
With carbon dioxide (CO2), 2.67 grams of oxygen are combined with 1 gram of
carbon. Therefore, the masses of oxygen combining with a fixed mass of carbon
are in the ratio 2:1.
CH-01
Page 32
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL BONDING
Combining Elements
The Laws of Definite Proportions and Multiple Proportions and the related portions of atomic
theory form the bases for most quantitative calculations involving chemical reactions. Applying
the basic chemical laws to chemical bonding will help the reader to understand the probability
and proportions involved in chemical reactions. Regardless of the type of bond (ionic, covalent,
coordinate covalent, or metallic), specific amounts of one element will react with specific
amounts of the element(s) with which it is combined.
If two substances are placed together in a container, in any ratio, the result is a mixture. When
a teaspoon of sugar is added to a glass of water, it will slowly dissolve into the water and
disappear from view. As a result, the molecules of sugar are evenly distributed throughout the
water and become mixed with the water molecules. Because the sugar and water mixture is
uniform throughout, it is said to be homogeneous. A homogeneous mixture of two or more
substances is called a solution. The reason solutions are classified as mixtures rather than as
compounds is because the composition is not of fixed proportion.
All solutions consist of a solvent and one or more solutes. The solvent is the material that
dissolves the other substance(s). It is the dissolving medium. In the water-sugar solution, the
water is the solvent. The substances that dissolve in the solution are called solutes. In the
water-sugar solution, sugar is the solute. It is not always easy to identify which is the solvent
and which is the solute (for example, a solution of half water and half alcohol).
Solutions can exist in any of the three states of matter, solid, liquid, or gas. The earth's
atmosphere is a gaseous solution of nitrogen, oxygen, and lesser amounts of other gases. Wine
(water and alcohol) and beer (water, alcohol, and CO2) are examples of liquid solutions. Metal
alloys are solid solutions (14-karat gold is gold combined with silver or copper).
One factor that determines the degree and/or rate at which a reaction takes place is solubility.
Solubility is defined as the maximum amount of a substance that can dissolve in a given amount
of solvent at a specific temperature. At this point, the solution is said to be saturated. A
solution is saturated when equilibrium is established between the solute and the solvent at a
particular temperature. Equilibrium is the point at which the rates of the forward and reverse
reactions are exactly equal for a chemical reaction if the conditions of reaction are constant.
Kinetics is the study of the factors which affect the rates of chemical reactions. There are five
principle factors to consider: concentration, temperature, pressure, the nature of the reactants,
and the catalyst.
Rev. 0
Page 33
CH-01
CHEMICAL BONDING
DOE-HDBK-1015/1-93
Summary
Chemical Bonding Summary

& The following terms are defined in this chapter:
An ionic bond occurs where one or more electrons are wholly transferred
from one element to another, and the elements are held together by the force
of attraction due to the opposite polarity of the charge.
The van der Waals forces are attractions between the molecules of nonpolar
covalent substances. These forces are generally believed to be caused by a
temporary dipole, or unequal charge distribution, as electrons constantly
move about in an atom, ion, or molecule.
A covalent bond is a bond in which one or more electrons from an atom pair
off with one or more electrons from another atom and form overlapping
electron shells in which both atoms share the paired electrons.
Metallic bonds are bonds where the atoms achieve a more stable
configuration by sharing the electrons in their outer shell with many other
atoms.
A mixture is defined as two substances placed together in a container, in any
ratio and the composition is not of fixed proportion.
A solution is a homogeneous mixture of two or more substances.
A solute is defined as the substance that dissolves in a solution.
A solvent is defined as the material that dissolves the other substance(s) in
a solution. It is the dissolving medium.
Solubility is defined as the maximum amount of a substance which will
dissolve in a given amount of solvent at a specific temperature.
& When the shared pair of electrons which are forming the bond in a molecule are
not shared equally, the resulting molecule will have a positive end and a negative
end. This type of bond is a polar covalent bond. The molecules are called dipolar
or polar molecules.
CH-01
Page 34
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL BONDING
Chemical Bonding Summary (Cont.)

& In general, the fewer electrons an element must lose, gain, or share to reach a stable
shell structure, the more chemically active the element is. The likelihood of elements
forming compounds is strongly influenced by the valence shell and on the stability of
the resulting molecule. The more stable the molecules are, the more likely these
molecules are to form.
& Elements combine in specific ratios, regardless of the type of bond, to form molecules.
& The three basic laws of chemical reactions are discussed:
(1) The Law of Conservation of Mass - "In a chemical reaction the total mass of the
products equal the total mass of the reactants."
(2) The Law of Definite Proportions - "No matter how a given chemical compound
is prepared, it always contains the same elements in the same proportions by
mass."
(3) The Law of Multiple Proportions - "If two elements combine together to form
more than one compound, then the masses of one of these elements combining
with a fixed mass of the other are in a simple ratio to one another."
Rev. 0
Page 35
CH-01
CHEMICAL EQUATIONS
DOE-HDBK-1015/1-93
CHEMICAL EQUATIONS
This chapter will discuss the methods of qualifying solutions. The balancing
of the chemical equations will also be explained in this chapter.
EO 2.7
STATE Le Chatelier's principle.
EO 2.8

a.
b.
EO 2.9
ppm
Molarity
c.
d.
Density
Normality
BALANCE chemical equations that combine elements

and/or compounds.
Le Chatelier's Principle
The effect of temperature on solubility can be explained on the basis of Le Chatelier's Principle.
Le Chatelier's Principle states that if a stress (for example, heat, pressure, concentration of one
reactant) is applied to an equilibrium, the system will adjust, if possible, to minimize the effect
of the stress. This principle is of value in predicting how much a system will respond to a
change in external conditions. Consider the case where the solubility process is endothermic
(heat added).
solid
heat
solution
An increase in temperature puts a stress on the equilibrium condition and causes it to shift to
the right. The stress is relieved because the dissolving process consumes some of the heat.
Therefore, the solubility (concentration) increases with an increase in temperature. If the
process is exothermic (heat given off).
solid
solution
heat
A temperature rise will decrease the solubility by shifting the equilibrium to the left.
How much solute is dissolved in a solution is very important when the solution is being made
for a specific use. To say there is a little, a lot, or a bit would not be very accurate if a specific
concentration is required. There are a few common and accurate methods used to express
concentration. These are density, molarity, normality, and parts per million.
CH-01
Page 36
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL EQUATIONS
Density
Density is the measure of the mass per unit volume of a material (density = mass/volume).
Density is a characteristic of a substance; mass and volume are not. Mass and volume vary with
size but density will remain constant. Temperature will affect the density of a substance and
the temperature at which density for that substance was determined is usually reported along
with the density value.
Molarity
A useful way to express exact concentrations of solutions is molarity. Molarity is defined as
moles of solute per liter of solution. Molarity is symbolized by the capital letter M. It can be
expressed mathematically as follows.
moles of solute (n)
molarity (M)
liters of solution (V)
Notice that the moles of solute are divided by the liters of solution not solvent. One liter of one
molar solution will consist of one mole of solute plus enough solvent to make a final volume
of one liter.
Example 1:
Prepare one molar solution of NaCl.
Solution:
a)
Calculate the molecular weight of the salt

1 atom of Na
1 atom of Cl
1 molecule of NaCl
22.989 amu
35.453 amu
58.442 amu
One mole is equal to the gram molecular weight, so one mole = 58.442 grams.
b)
Rev. 0
58.442 grams of NaCl is weighed out and sufficient water is added to bring the
solution to one liter.
Page 37
CH-01
CHEMICAL EQUATIONS
DOE-HDBK-1015/1-93
Example 2:
Prepare 3 liters of a 2M NaOH solution.
Solution:
Calculate the amount of NaOH required to prepare the solution.
a)
b)
substituting:
Therefore, to prepare 3 liters of a 2M NaOH solution, 240 grams of NaOH must be

weighed out and dissolved in water to make a volume of exactly 3 liters.
Normality
The normal concentration is another method for expressing the concentration of solutions.
Normality (N) is defined as the number of equivalents of solute dissolved in one liter of
solution.
One equivalent of acid is the amount of acid necessary to give up one mole of hydrogen ions
in a chemical reaction. One equivalent of base is the amount of base that reacts with one mole
of hydrogen ions. When expressing the concentrations of bases, normality refers to the number
of available hydroxyl ions. Because hydrogen and hydroxyl ions combine on a one-to-one basis,
one OH- is equivalent to one H+ ion.
CH-01
a)
H+ClAcid
Na+OHBase
Na+ClSalt
H+OHWater
b)
H2SO4
Acid
2K+OH-
Base
K2SO4
Salt
2H+OHWater
Page 38
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL EQUATIONS
Notice that in reaction a), one mole of HCl yields one equivalent per mole or one mole of H+
ions. H2SO4 has two equivalents per mole or two H+ ions because each mole of the compound
can release two moles of hydrogen ions.
The number of equivalents of an acid or base can be determined from equivalent weight. The
equivalent weight is defined as the molecular weight of the acid or base divided by the number
of replaceable hydrogen or hydroxyl ions.
Example:
The equivalent weight of H2SO4 is:
This means 49 grams of H2SO4 is equal to one equivalent of H2SO4. If there is a one
liter solution that contains 78.32 grams H2SO4, the number of equivalents is:
Since normality is equal to the number of equivalents per liter, the normality of this
solution is 1.6 equivalents/liter, or 1.6 N.
Parts per Million

Another term used to describe the specific concentration of a solution is parts per million or
ppm. The term ppm is defined as the concentration of a solution in units of one part of solute
to one million parts solvent. One ppm equals one milligram of solute per liter of solution.
Another term, parts per billion (ppb), is defined as one part solute per one billion parts solvent.
One ppb is equal to one microgram solute per liter of solution. These two terms are usually
used for very dilute solutions.
Rev. 0
Page 39
CH-01
CHEMICAL EQUATIONS
DOE-HDBK-1015/1-93
Chemical Equations
The chemical equation is simply a representation of a chemical reaction in the chemist's
shorthand. In a chemical equation, the substances originally present are called the reactants and
the new substances being formed are called the products. In the chemical reaction, the reactants
are on the left of the arrow and the products are on the right of the arrow. For example, when
looking at the combination of hydrogen and oxygen into water, the water molecule would be
the product on the right.
2H2 + O2 2H2O
If looking at the decomposition of water, the hydrogen and oxygen would be the products and
the water is the reactant. The arrow means yields and is used to separate the reactants from the
products. It also indicates the direction of the reaction as illustrated below.
2H2O 2H2 + O2
The single arrow in the above equation implies that the reaction will proceed in only one
direction until it subsides or stops. If the reaction is reversible, that is, it can proceed left to
right and right to left until it reaches an equilibrium, then a double arrow is used.
2H2O ; 2H2 + O2
When writing an equation, always place the reactant on the left and the products on the right
even in the case of a reversible reaction.
A chemical equation represents not only the reaction, but also shows the number of atoms or
molecules entering into and produced by the reaction. The formulas must be balanced correctly
based on the valences of the constituent elements.
Balancing Chemical Equations

The number of atoms or molecules of each substance is shown by the coefficients in the
equation. Because atoms cannot be created or destroyed in a chemical reaction, a chemical
equation must be balanced so that there are exactly the same number of atoms of each element
on each side of the equation.
CH-01
Page 40
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL EQUATIONS
Example:
Explain the following chemical equation.

Solution:
This chemical equation shows that iron reacts with water to form ferric oxide and
hydrogen gas (the vertical arrow indicates a gas). This chemical equation also shows
that for every two atoms of iron that react, three molecules of water are used to form
one molecule of ferric oxide and three molecules of hydrogen gas. This is a balanced
chemical equation. There are two iron atoms on each side of the equation; there are six
hydrogen atoms on each side; and there are three oxygen atoms on each side.
There are no fixed rules for balancing chemical equations. Learning how is a matter of practice.
The balancing of most equations can be accomplished by following the guidelines explained
below.
Guidelines:
Rev. 0
a.
Once the correct chemical formula for a compound is written in an equation, do

not modify it.
b.
Select the compound with the greatest number of atoms. Then begin by balancing
the element in that compound with the most atoms. There must be the same
number of atoms of an element on each side of the equation. As a rule of thumb,
this first element should not be hydrogen, oxygen, or a polyatomic ion.
c.
Balance the atoms of each element in the compound by placing the appropriate
coefficient in front of the chemical symbol or formula.
d.
Next, balance the polyatomic ions. In some cases, the coefficient assigned in
guideline 2 may have to be changed to balance the polyatomic ion.
e.
Balance the hydrogen atoms next, then the oxygen atoms. If these elements
appear in the polyatomic ion it should not be necessary to balance them again.
f.
All coefficients will be whole numbers. The coefficients should be reduced to the
lowest possible ratios.
g.
As simple as it sounds, check off each element as it is accounted for since this
will prevent double inclusion or a missed atom.
Page 41
CH-01
CHEMICAL EQUATIONS
DOE-HDBK-1015/1-93
Example 1:
FeS2 + O2 Fe2O3 + SO2
Solution 1:
2Fe3O + 2SO , which
Starting with Fe2O3 (see guideline b), write 2FeS2 + O
2
balances the Fe on each side of the equation.
Now there are 4 S atoms on the left side so balance the S atoms by writing
2FeS2 + O2 Fe2O3 + 4SO2.
Everything is balanced except the O. There are now 2 O atoms on the left and 11 O
atoms on the right. To get 11 O atoms on the left write
2FeS2 + 5.5O2 Fe2O3 + 4SO2.
This makes both sides of the equation balanced except the coefficients must be whole
numbers (guideline f). To meet guideline f, multiply both sides by two which will bring
the left side to a whole number of O2 molecules.
Thus, the solution is 4FeS2 + 11O2 2Fe2O3 + 8SO2.
Example 2:
NH3 + CuO H2O + N2 + Cu
Solution 2:
Start with NH3 since there are two N atoms on the right of the equation. To balance the
N atoms write 2NH3 + CuO H2O + N2 + Cu (guideline b).
Since the H appears in only the NH3 and H2O and the NH3 has been balanced, the H2O
will be balanced. Write 2NH3 + CuO 3H2O + N2 + Cu (guideline e).
Oxygen appears only in CuO and in H2O, and since the H2 O has been already been
balanced write 2NH3 + 3CuO 3H2O + N2 + Cu (guideline e).
That leaves the Cu to be balanced. Thus, the solution is
2NH3 + 3CuO 3H2O + N2 + 3Cu.
CH-01
Page 42
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL EQUATIONS
Example 3:
Na2CO3 + Ca(OH)2 NaOH + CaCO3
Solution 3:
There are two Na atoms on the left so start with the Na by writing
Na2CO3 + Ca(OH)2 2NaOH + CaCO3 (guideline b).
By adding the 2, the equation is now completely balanced. This equation illustrates that
not all equations are that hard to balance.
Most chemical equations do not indicate a number of important facts about the chemical
reactions they represent. Chemical equations do not necessarily describe the path by which the
substances reacting are converted to products.
2H2 O2 2H2O
The equation would seem to imply that two molecules of hydrogen collide with one molecule
of oxygen, and two molecules of water are produced. The actual mechanism by which this
reaction takes place is much more complicated and involves a series of processes. Chemical
equations do not indicate the rate at which the reaction proceeds, or even whether the reaction
will occur in a finite time. In many cases, reactions will occur only under a particular set of
circumstances and then only at a definite rate. Chemical equations do not show whether the
reaction proceeds to completion or, if incomplete, the extent of reaction. In most cases, the
substances that react never completely disappear; however, their concentration may be
exceedingly small. Reactions that do not go to completion are usually represented in chemical
equations by using double horizontal arrows ; . In general, a reaction will go to completion only
if one or more of the products is removed from the field of the reaction. This is often
accomplished if one of the products is a gas or is insoluble in the reaction mixture.
In the discussion of chemical equations, emphasis is normally placed on the number of atoms or
molecules involved in the reaction. However, chemical equations are very effective in
representing chemical reactions on a macroscopic scale. Practical chemical calculations involve
very large numbers of atoms and molecules.
Rev. 0
Page 43
CH-01
CHEMICAL EQUATIONS
DOE-HDBK-1015/1-93
The equation weight in grams of a compound or element is defined as the gram molecular weight
times the number of molecules of the compound, as shown by the coefficients of the chemical
equation for the reaction. The sums of the equation weights on each side of a chemical equation
must be equal. Chemical calculations are based on the fact that every fraction or multiple of the
equation weights of substances that react gives a corresponding fraction or multiple of the
equation weights of the products of the reaction. In other words, if 30 grams of a substance that
has an equation weight of 15 grams reacts with some amount of another substance to form a
product with an equation weight of 20 grams, then 40 grams of that product will be formed.
Example:
How many grams of ferric oxide will be formed if 27.9 grams of iron reacts with water
according to the following equation.

Solution:
The equation weight of iron equals the gram atomic weight of iron times the number of
atoms shown reacting in the equation, which is two. Using Table 2:
Because 27.9 g of iron react, the fraction of the equation weight that reacts is:
Thus, 1/4 of the equation weight of ferric oxide will be formed.

The equation weight of ferric oxide equals the gram molecular weight of ferric oxide
times the number of molecules shown formed in the equation, which is one.
Using Table 2:

Thus, the amount of ferric oxide formed is:
CH-01
Page 44
Rev. 0
DOE-HDBK-1015/1-93
CHEMICAL EQUATIONS
Summary
Chemical Equations Summary

&
Le Chatelier's principle states that if a stress is applied to an equilibrium, the

system will adjust to minimize the effect of the stress.
&

Density is the measure of the mass per unit volume of a material
(density = mass/volume).
Molarity is moles of solute per liter of solution. Molar solutions are
symbolized by the capital letter M.
Normality, (N), is defined as the number of equivalents of solute
dissolved in one liter of solution.
ppm expresses the concentration of a solution in units of one part of
solute to one million parts solvent. One ppm equals one milligram of
solute per liter of solution.
&
Rev. 0
To balance chemical equations, the number of elemental constituents must be

the same on each side of the equation.
Page 45
CH-01
ACIDS, BASES, SALTS, AND pH
DOE-HDBK-1015/1-93

Different substances respond differently in solution. How substances behave
in water is of special interest to the power industry. The interactions of
water and acids, bases, or salts are of special interest because water is used
in many industries. This chapter will introduce the student to the general
behavior of these substances.
EO 3.1

a.
b.
c.
d.
Acid
Salt
pOH
Alkalies
e.
f.
g.
Base
pH
Dissociation constant of water
EO 3.2
STATE the formula for pH.
EO 3.3
STATE the formula for pOH.
EO 3.4
CALCULATE the pH of a specified solution.
Acids
Substances that form ions when they are dissolved in water are called electrolytes. The three
types of electrolytes are acids, bases, and salts.
Acids are substances that dissociate in water to produce hydrogen (H+). An example of a
common acid is sulfuric acid, H2SO4. In solution, H2 SO4 dissociates to form hydrogen and
sulfate ions according to the following equation. The designation in parenthesis in the
following formulas indicate the state of the reactants and the products, i.e., liquid (aq). solid (s),
or gas (g).

Additional examples of acids are vinegar, aspirin, and lemon juice. These substances share the
following common properties.
1.
Acid solutions taste sour (acid means "sour" in Latin).
2.
Acids react with many metals to form hydrogen gas.

CH-01
Page 46
Rev. 0
DOE-HDBK-1015/1-93
3.
Acids turn litmus paper red.
4.
Acid solutions conduct electricity.
5.
Acids react with bases to form a salt and water.
Example:

6.
Acids react with carbonates to form CO2 (carbon dioxide gas).

Example:

Bases
Bases are substances that produce hydroxide ions (OH-) in water solutions. An example of a
common base is sodium hydroxide, NaOH. In solution, it dissociates to form sodium ions and
hydroxide ions according to the following equation:

Common types of bases are lye, household ammonia, and most soaps. The following are four
characteristic properties of bases.
1.
Basic solutions taste bitter and feel slippery to the touch.
2.
Bases turn litmus paper blue.
3.
Basic solutions conduct electricity.
4.
Bases neutralize acids.

Example:

Rev. 0
Page 47
CH-01
DOE-HDBK-1015/1-93
Salts
When an acid reacts with a base, two products are formed; water and a salt. A salt is an ionic
compound composed of positive ions and negative ions. The ionic bond is what keeps salts in
their molecular form. Some compounds look like salts, but are actually covalent compounds
(have a covalent bond).
Example:

This type of acid-base reaction is called neutralization.

Certain soluble salts (principally sodium, potassium, magnesium, and calcium) that have the
property of combining with acids to form neutral salts are called alkalies. Two of the common
salts are sodium chloride (table salt) and calcium chloride (salt put on the road in winter).
Unlike acids and bases, salts vary greatly in all their properties except their ionic characteristics.
Salts may taste salty, sour, bitter, astringent, sweet, or tasteless. Solutions of salts may be
acidic, basic, or neutral to acid-base indicators. Fused salts and aqueous solutions of salts
conduct an electric current. The reactions of salts are numerous and varied.
pH
Many compounds dissolve in water and alter the hydrogen ion concentration. Compounds that
produce hydrogen ions directly when dissolved in water are called acids, and those that produce
hydroxyl ions directly when dissolved in water are called bases. To treat these aspects of
chemistry more precisely, a quantitative system of expressing acidity or basicity (alkalinity) is
needed. This need could be met by using the value of [H+], where [H+ ] is expressed in
moles/liter, as a measure of acidity. But, in most cases [H+] is in the range of -110 to
10-14 moles/liter. Because numbers of this magnitude are inconvenient to work with, an
alternate system for expressing the acidity of dilute solutions has been devised. This system is
based on a quantity called pH. ph is defined as the negative logarithm of the hydrogen
concentration, represented as [H+] in moles/liter.
pH
= -log [H+]
(1-1)
[H+] = 10-pH
(1-2)
The negative logarithm is specified because the logarithm of any number less than 1 is negative;
thus multiplication by -1 causes the values of pH to be positive over the range in which we are
interested. (The term pH was first defined by a Danish chemist and is derived from p for the
Danish word potenz (power) and H for hydrogen.)
CH-01
Page 48
Rev. 0
Example 1:
DOE-HDBK-1015/1-93
The hydrogen concentration, [H+], of a solution is 4.8 x 10-8 moles/liter. What

is the pH of the solution?
Solution 1:
Example 2:
Solution 2:
The pH of a solution is 3.83. What is the hydrogen concentration of the

solution?

pOH
It is also important to understand the relationship between the [H+] and the [OH
]
concentrations. The pOH of a solution is defined as the negative logarithm of the hydroxyl
concentration, represented as [OH-] in moles/liter.
pOH
= -log [OH-]
(1-3)
[OH-] = 10-pOH
(1-4)
For water solutions, the product of the hydrogen ion concentration and the hydroxyl
concentration is always 1 x 10-14 at 25(C. This means that the sum of pH and pOH is equal to
14 under these conditions.
[H+] x [OH-] = 1 x 10-14
pH + pOH
= 14
The following example illustrates this point.
Rev. 0
Page 49
CH-01
Example:
DOE-HDBK-1015/1-93
What is the hydrogen ion concentration [H+] and the hydroxyl concentration
[OH-] in a solution with a pH of 5.5?
Solution:
Dissociation Constant
The product of ionic concentrations, Kw = [H+] [OH-], is called the Ion Product Constant for
water, or more frequently, the Ionization Constant or Dissociation Constant. At 25(C, Kw
equals 1 x 10-14. Kw varies with temperature and, at 37(C (body temperature), the value is
about 3.4 x 10-14. Figure 17 illustrates the relationship of the Dissociation Constant with water
temperature. As indicated earlier, a change in temperature causes a change in equilibrium in
a chemical reaction. Because the ionization of water is an equilibrium process, it is also affected
by temperature. The Dissociation (or Ionization) Constant, Kw, for water increases with
increasing temperature up to about 500(F and then decreases. Experimental values of Kw at
various temperatures are listed in Table 5 and graphed in Figure 16. Notice in Table 5 that the
pH of pure water changes with temperature. For pure water at any temperature, however,
[H+] = [OH-]. It should be noted that the equation pH + pOH = 14 is true only at or near 25(C
(77(F).
CH-01
Page 50
Rev. 0
Example:
DOE-HDBK-1015/1-93
The hydroxyl concentration [OH-] of a water solution o at 25 C is

7.2 x 10-9 moles/liter. Calculate the pH of the solution.
Solution:

TABLE 5
Ion Product Constant and Neutral pH
for Water at Various Temperatures
Temperature
Ion Product Constant

for Water
pH of Pure
Water
64.4
18
0.64 x 10-14
7.10
77
25
1.0 x 10-14
7.00
140
60
8.9 x 10-14
6.54
212
100
6.1 x 10-13
6.10
302
150
2.2 x 10-12
5.83
392
200
5.0 x 10-12
5.65
482
250
6.6 x 10-12
5.59
572
300
6.4 x 10-12
5.60
662
350
4.7 x 10-12
5.66
At 25(C, an equilibrium exists between pure molecular water and its ions. The [H+] equals the
[OH-] and both have values of 1 x 10-7 moles/liter. Using the pH definition, it follows that the
pH of pure water at 25(C is 7. pH values less than 7 indicate an acidic solution and values
greater than 7 indicate a basic or alkaline solution.
Rev. 0
Page 51
CH-01
DOE-HDBK-1015/1-93
Figure 17 Ion Product Constant for Water
CH-01
Page 52
Rev. 0
DOE-HDBK-1015/1-93
Summary
Acids, Bases, Salts, and pH Summary

&
The following terms are defined in this chapter:

Acid - substances that produce hydrogen (H+) in water solutions
Base - substances that produce hydroxide ions (OH-) in water solutions
Salt - a compound composed of positive and negative ions held together
with an ionic bond
Alkalies - certain soluble salts, principally sodium, potassium, magnesium
and calcium, that have the property of combining with acids to form
neutral salts
pH - the negative logarithm of the hydrogen concentration [H+] in
moles/liter
pOH - the negative logarithm of the hydroxyl concentration [OH-] in
moles/liter
Dissociation constant of water (Kw) - the product of ionic
concentrations, ([H+] [OH-]); at 25(C Kw = 1 x 10-14
&
The formula for pH is: pH = -log [H+]

Therefore, [H+] = 10-pH
&
The formula for pOH is: pOH = -log [OH-]

Therefore, [OH] = 10 -pOH
Rev. 0
Page 53
CH-01
DOE-HDBK-1015/1-93
Intentionally Left Blank.
CH-01
Page 54
Rev. 0
PLANT CHEMISTRY
Appendix A
Basic Separation Theory
Appendix A
DOE-HDBK-1015/1-93
BASIC SEPARATION THEORY

Introduction
The fundamental principles upon which a gaseous diffusion plant is based are as follows.
1.
All the particles (atoms, molecules, or ions) which make up the gas are
continuously moving in straight lines in all directions. The particles collide
with anything in their path (e.g., other particles or the walls of the container),
thereby altering the course of moving particles but not their average velocities.
2.
All of the particles have the same average kinetic energy. Accordingly, if the
masses of the particles are different, so must their velocities be different with
the lighter particles having the greater average velocities.
On the basis of the two principles stated above, if a quantity of gas is confined by a porous
membrane or barrier, some of the gas will escape through the pores in the barrier. If the
confined gas is isotopic (a mixture of particles of different molecular weights), the lighter
particles of the gas will have a greater tendency to diffuse through the barrier because of their
greater average velocities. Consequently, the gas which has passed through the barrier will
be enriched in the light constituent while that gas which has not diffused through the barrier
will be depleted in the light constituent.
Isotopic Separation
The isotopes with which we are concerned are those of uranium; namely U235 and U238. In
order that the isotopes of uranium may be separated by the gaseous diffusion process, it is
necessary that the uranium be in a gaseous state. This is accomplished by combining the
uranium with fluorine to form uranium hexafluoride, which is a gas at workable temperatures
and pressures. Another advantageous quality of uranium hexafluoride is that fluorine has no
isotopes to further complicate the separation process. In general, the following discussion
is concerned with the separation of U235F6 and U238F6.
Rev. 0
Page A-1
CH-01
DOE-HDBK-1015/1-93
Appendix A
Separation Factor
The ability of a barrier to separate isotopes is expressed by a value called the separation
factor. It is denoted by the Greek letter , and is defined as the mole ratio of light
component to heavy component in the gas passing through the barrier at a given point
divided by a similar mole ratio on the high pressure surface of the barrier at the same
point. The separation factor can be expressed by the following equation.
In this equation, y and x are the mol fraction of light component on the low and high
pressure sides of the barrier respectively. It should be emphasized that , as shown in
Figure A-1, is a point value, and that x and y are concentrations at a given point on the
two surfaces of the barrier. In practice, point values are usually not determined. The
average 's of the surface of samples are calculated from experimental separation data.
As previously stated, the separation of isotopes is dependent upon the difference in the
mass of the particles. Under ideal conditions, the separation factor would be equal to
the ratio of the square roots of the molecular weights. For a mixture of U235F6 and
U238F6, this value is 1.0043 and is commonly referred to as the ideal separation factor.
In actual practice, however, these ideal conditions cannot be duplicated. For example,
to approach the ideal separation factor, only a small fraction of the total gas involved
could be diffused through the barrier. For such a process to be productive, the plant size
and its power consumption would be too large to be economically feasible. Limitations
of plant size and power consumption have, necessitated a reduction in the separation
factor to a lower value. This lower value is called the actual separation factor.
Stage Separation
The ratio of the total molar rate of flow through the barrier within a converter to the
total rate of flow into the same converter is called the cut and is designated by the Greek
letter .

In a production cascade, a cut of approximately 0.5 is the optimum value with respect
to operating efficiency and production.
CH-01
Page A-2
Rev. 0
Appendix A
DOE-HDBK-1015/1-93
Figure A-1 "R" Stage Separation
Rev. 0
Page A-3
CH-01
DOE-HDBK-1015/1-93
Appendix A
The actual separation achieved by a stage is expressed in terms of the mol fraction of the
light component and for the purpose of this discussion is designated by the capital letter
R. It can be defined as follows: if Y is the concentration of light component in the
enriched stream leaving a converter and X is its concentration in the depleted stream
leaving the same converter, then
Y
1 Y
.
X
1 X
This definition is similar to that of the separation factor, but, as shown in Figure A-1, the
value of R is based on the overall separation of a stage while that of the separation factor
is based on the performance of the barrier alone. The relation between the two is given
by the following equation.
R
E
1
1
ln

1
E is a correction factor called the mixing efficiency. It can be explained as follows:

since the light component passes through the barrier more rapidly than the heavy
component, the layer of gas at the surface on the high pressure side of the barrier
becomes more depleted in the light component than the bulk of the gas on the high
pressure side. Thus, there is a concentration gradient perpendicular to the surface of the
barrier which results in a decrease in separation. In the particular process of separation
of uranium isotopes, the value of R in the preceding equation differs very little from unity
(R = 1.003) and is somewhat inconvenient for use in calculations. By subtracting 1 from
each side of the equation, equating the symbol 5 (psi) to R - 1, and by making a slight
approximation, the equation becomes
5
Y X
.
X(1 X)
This equation is used frequently in the plant in making separation tests.
CH-01
Page A-4
Rev. 0
Appendix A
DOE-HDBK-1015/1-93
Barrier Measurements
The ability of a barrier to transmit gas is usually expressed as (gamma), the
permeability. This is a measure of the total flow through a barrier and may be defined
as the ratio of the number of molecules which pass through the barrier to the number
which would pass through the space if the barrier were not there. This total flow
through a barrier is known to be a combination of several different types; namely,
diffusive flow, film flow, and viscous flow. As was previously explained, the type of
flow that is of greatest importance for a gaseous diffusion plant is diffusive flow.
However, as film flow and viscous flow affect the separation through a barrier, they
cannot be ignored.
Film flow refers to the transport of molecules under the influence of the force field
between the molecules and the barrier surface. When such force fields are significant,
a large number of molecules will not have sufficient velocity normal to the surface to
escape from this field so that their motion will be confined to the barrier surface and
barrier pore surface. Such molecules would pass through the barrier as a film on the
surface of the pores.
Viscous flow occurs when molecules flow as a group in the manner of ordinary flow
through a tube. Referring back to permeability, it is known that the flow through a
barrier increases as the pressure increases. Also, as the pressure increases, so does the
viscous component of flow. The relation between permeability and viscous flow can best
be shown by the following equation.

o 1 S (Pf P b)
In this equation where Pf equals the fore or high side pressure and Pb equals the back or
low side pressure. o equals the permeability, , when
Pf + Pb = 0.
S is called the slope factor and is inversely proportional to the viscosity of the gas.
In the above equation, the term S(Pf + Pb ) is a measure of the viscous component of
flow. Figure A-2 illustrates the variation of permeability with the slope factor and
changes in pressure.
Rev. 0
Page A-5
CH-01
DOE-HDBK-1015/1-93
Appendix A
Figure A-2
Variation of Permeability with the Slope Factor and Change in Pressure
It should be noted that in practice, permeability is expressed in two different ways;

design and actual. Design permeability is expressed as a ratio as previously stated. It
is usually determined by testing the barrier with a non-toxic gas such as nitrogen. Actual
permeability is expressed as a percentage of the design permeability and is determined
from tests with the barrier in actual operation in the cascade. Its primary value is in
determining the performance of a barrier after being in use for a period of time.
Cascade Theory
In the operation of a diffusion cascade, it is often necessary to charge the plant with feed
material of different assays or concentrations of U235F6. This feed must be fed into the cascade
at a point where the assay of the gas already being processed is the same as that of the feed to
be charged.
CH-01
Page A-6
Rev. 0
Appendix A
DOE-HDBK-1015/1-93
To choose this feed point, therefore, it must be possible to calculate the concentration of
U235F6 in the process gas at any point in the cascade. These calculations can be made by
knowing two things: first, the concentration of U235F6 in the process gas at several points in
the cascade (determined by laboratory and instrument analysis); and second, the increase in the
concentration of U235F6 accomplished by each stage. This is called the stage enrichment and
should not be confused with the separation accomplished by a stage previously discussed.
Therefore, by knowing the stage enrichment and the U235F6 concentration at some point in the
cascade, it is possible to determine the concentration at other points.
The feed material ordinarily charged into a plant contains a very small percentage of U235F6
with the remainder being U238F6. Consequently, a far greater amount of the feed flows
downward in the cascade and is removed as tails than is removed at the top of the cascade as
U235F6 or product. For this reason, as we progress upward in the cascade from the feed point,
the total flow through the converters becomes progressively smaller. It follows, therefore, that
in the ideal design each stage would be different in size from the adjacent stages. However,
since the cost of construction of a production cascade is of great importance, a lower cost may
be achieved by the use of many identical units. For this reason, the cascade is composed of
a series of sections, each of which contains a large number of identical stages. The change in
equipment size is accomplished in a step-wise manner by varying the equipment size of each
so-called section.
Circuit Balances
Of major importance in a production cascade is the ability to calculate pressures, temperatures,
and flows of the process gas which cannot be practically or economically measured by
instrumentation. Since the cascade is made up of sections each of which contains a large
number of identical stages and since the stage is the smallest separating unit of a cascade, these
calculations are made on a stage basis. This system of calculating temperatures, pressures,
and flows is commonly referred to as a circuit balance and consists of a series of calculations
made from those pressures and temperatures ordinarily measured by instrumentation in the
cascade, and from experimental data obtained from test loop studies.
For illustration purposes, the pressures, temperatures, and flows in a typical X-31 stage which
are taken by instrumentation, plus those to be calculated, are shown in Figure A-3. It is
obvious that the cost to install instruments in every stage to measure all of the values indicated
would be prohibitive.
Rev. 0
Page A-7
CH-01
DOE-HDBK-1015/1-93
Appendix A
Figure A-3
Pressures, Temperatures, and Flows in a Typical V-31 Stage
CH-01
Page A-8
Rev. 0
Appendix A
DOE-HDBK-1015/1-93
Because of their number and complexity, the mathematical formulas used in calculating the
pressure points in Figure A-3 will not be presented. The operator will read and record only
those values which are measured by instruments and will not be required to perform any of the
mathematical calculations involved in completing a circuit balance. However, the following
discussion will give an indication as to the procedures involved in determining these values.
To calculate a circuit balance for Stage N in Figure A-3, pressures P1 and P2 and temperature
T1 are recorded. Then, knowing P 1 and T 1 and a constant previously determined in a test loop,
it is possible to calculate the flow WA (N - 1). Since the "A" barrel of the compressor has
essentially a constant suction volume in the normal operating range, the interstage flow is
proportional to the compressor "A" suction pressure and temperature. Next, it is known that
the flow in a cascade must operate at a steady state condition to prevent an accumulation of
deficiency of inventory in any one section. It may therefore be assumed that the flow
downward to a stage is equal to the flow upward from the same stage. (This assumption is
not valid for all stages in a cascade but for practical applications the error is negligible.) From
this assumption, WB is equal to WA (N - 1). With P2, WB, and pressure drop data obtained in
the test loop, P7 can be calculated.
In a test loop, data is taken on converters of different sizes and types to determine pressure
variations with different amounts of flow and cut. If WA is found in the same manner as WA
(N - 1), it is then possible with the test loop data to calculate Pb. Also, with the converter data,
and knowing WB, P7, and WT (WT = WA + WB), Po and subsequently, Pf are found.
Again using pressure drop data, P5 can be calculated from W T and P o. With P ,5 P 3is calculated
by knowing the "B" pressure ratio of the compressor.
From the calculated values obtained from a circuit balance, it is possible to make further
calculations which indicate the operational and productive characteristics of the cascade. For
example, Pf, Pb , and the flows through a converter must be known before the actual
permeability of the barrier can be calculated. Also, these values make it possible to accurately
predict horsepower requirements under varying conditions of flow and pressure. Another
important application of the circuit balance is in the determination of inventory in the cascade
where pressures and temperatures not otherwise measured are required.
Rev. 0
Page A-9
CH-01
DOE-HDBK-1015/1-93
Appendix A
CONVERTERS
Converters
The actual separation of U235F6 from U238F6 in a gaseous diffusion plant is accomplished in the
converter. The converter, sometimes referred to as a diffuser, contains the barrier tubing
through which diffusion takes place. In the previous section we studied the flow through the
converter as a part of a stage. In this section we will see what takes place inside the converter.
In all, the entire cascade contains over 4000 converters -- one in each stage. The stage size
varies with the location in the cascade as shown in the table below.
TABLE A-1
Converter Stage Size vs. Location
Equipment
Type
Converter
Type
Length
(inches)
Diameter
(inches)
Number
Used In
Cascade
33
000
291
155
640
31
00-2
221
105
500
29
185 or 215
90 or 105
600
27
129
47
720
25
129
38
1560
Converter Construction
Externally, the converter resembles a large cylindrical tank resting on its side (see Figure A-4).
There are openings at each end for the necessary piping connections. The outlet end of the
converter contains the "A" and "B" stream process gas outlets. The other end contains the
mixed process gas inlet and the stage coolant inlet and outlet. The cylindrical tank is called the
shell and is constructed of steel with welded joints. Its internal surface is nickel plated. There
are three external reinforcing flanges around the outside of the shell. The many hundreds of
barrier tubes, or tube bundles, contained in one converter are held in place by the spool, or
spool piece. The spool consists of struts and a central tube, or core, which is perforated and
allows part of the "A" stream leaving the barrier tubes to reach the converter outlet. On either
end of the core are tube sheets into the holes of which the barrier tubes are sealed by rolling or
swagging. Tube sheets are also mounted on the core between the end tube sheets to support
the barrier tubes.
CH-01
Page A-10
Rev. 0
Appendix A
DOE-HDBK-1015/1-93
Figure A-4 - Typical Converter
Rev. 0
Page A-11
CH-01
DOE-HDBK-1015/1-93
Appendix A
The remainder of the converter equipment, with the exception of the gas cooler, is designed to
direct the process gas flow inside the converter.
The Gas Cooler

The gas cooler's purpose is to remove the heat of compression from the process gas which has
just been discharged from a compressor. Certain type of stages use a gas cooler contained
within the converter as shown on Figure A-4. The gas coolers may be separate units placed
between the compressors and the converters.
Barrier Tubing
In the early stages of converter design, it was recognized that barriers made in the form of flat
sheets and stacked in a container would offer the most barrier area per unit volume. For
practical reasons, the barrier had to be made in the form of tubes. More engineering knowledge
was available for tubular construction and the urgency of the problem did not allow any
unnecessary development time. The use of tubes also allowed more satisfactory replacement
of damaged barrier material. As a result, the barrier is made in the form of thin-walled tubes.
Process Gas Flow

We can now trace the process gas flow within the converter. In the AB cooled converter of
Figure A-4, the process gas enters one end of the converter at the center and is directed to the
outside of the shell by a series of baffles. It flows through the gas cooler and is directed to the
outer section, or pass, of the barrier tubes. All of the flow enters the outer, or first pass, and
flows through the tubes. Part of the flow diffuses through the barrier tube walls and the
remainder of the flow passes through the tubes and is directed by a crossover to the second pass
of tubes. This crossover is sometimes called a doughnut because of its shape. The process gas
flow which does not diffuse through the barrier tube walls of the second pass is directed by a
second crossover to the third pass. The first crossover is sometimes refereed to as the 1-2
crossover because it directs gas flow from the first pass to the second pass. Similarly, the
second crossover is called the 2-3 crossover. The undiffused process gas which passes through
the third pass is directed to the "B" outlet of the converter and flows to the stage below. The
process gas which was diffused through the barrier tubes in all three passes is collected and
flows to the "A" outlet and on to the stage above.
Since some of the process gas flowing into the first pass will diffuse through the tube walls, a
reduced amount of process gas flow will enter the second pass. In order to maintain the same
flow velocity, the second pass contains fewer tubes than the first pass. Similarly, the third pass
will contain still fewer tubes. The velocity of process gas through the tubes affects the flow
through the tube walls and thus affects the separation efficiency. The efficiency is highest when
the flow velocity is the same in all of the tubes.
CH-01
Page A-12
Rev. 0
Appendix A
DOE-HDBK-1015/1-93
In the Badger stage, about 50% of the process gas entering a converter diffuses through the
tubing and flows to the stage above. This fraction is called the "cut." A cut of 50% has been
found to yield the best separation. As mentioned previously, the "cut" in a Badger Cluster stage
may be more or less than 50% depending upon its position in the cluster.
Diffusion
It is necessary to have a higher pressure inside the barrier tubes than outside in order to have
a flow through the walls of the tubes. This inside pressure is called the fore pressure or high
side pressure (H.S.P.), and is measured at an arbitrary point inside the tubes near the middle of
the second pass. The pressure outside the tubes is the back pressure or low side pressure
(L.S.P.), and is measured at an arbitrary point outside the tubes near the middle of the second
pass.
The fore pressure is regulated by a control valve in the "B" stream, or down flow, from the
converter. Actually, the control valve regulates the pressure immediately above it. This is
called the control pressure and is the pressure which is indicated at the cell panel. It is slightly
lower than the fore pressure due to the pressure drops in the converter and piping.
The rate of diffusion through the tubing walls for any given pressure drop across the barrier is
determined by the permeability of the barrier. Mathematically, this is a dimensionless quantity
which is the ratio of the rate of gas flow through the barrier to the rate of gas flow through the
same area which would take place if the barrier were not there. The term, usually called
permeability, is used to relate the actual permeability to the design permeability. For example,
if the flow through the barrier has decreased 10% due to plugging of the barrier holes, the
permeability would be 90%.
Rev. 0
Page A-13
CH-01
DOE-HDBK-1015/1-93
Appendix A
CH-01
Page A-14
Rev. 0
CHEMISTRY
Module 2
Corrosion
Corrosion
DOE-HDBK-1015/1-93
TABLE OF CONTENTS
TABLE OF CONTENTS
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
CORROSION THEORY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Electrochemical Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Oxidation-Reduction Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Passivity and Polarization of Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1
1
3
5
6
9
GENERAL CORROSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conditions Contributing to General Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corrosion of Iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Factors Affecting General Corrosion Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Prevention Chemistry Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corrosion of Aluminum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11
11
12
13
16
17
20
CRUD AND GALVANIC CORROSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Crud . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Galvanic Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Prevention of Galvanic Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
22
22
23
24
25
SPECIALIZED CORROSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pitting and Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Stress Corrosion Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
27
27
31
36
Rev. 0
Page i
CH-02
LIST OF FIGURES
DOE-HDBK-1015/1-93
Corrosion
LIST OF FIGURES
Figure 1 Formation of Ferrous (Fe++) Ions in the Corrosion of Iron . . . . . . . . . . . . . . . . . . 3
Figure 2 Metal Surface Showing Arrangement of Micro-cells . . . . . . . . . . . . . . . . . . . . . . 5
Figure 3 A Galvanic Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Figure 4 A Galvanic Cell Showing Absorbed Hydrogen Atoms on a Cathode . . . . . . . . . . 8
Figure 5 Simplified Schematic Diagram of Oxide Corrosion Film on the
Surface of a Metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Figure 6 Representation of Cathodic Depolarization by Oxygen . . . . . . . . . . . . . . . . . . . 14
Figure 7 Effect of pH on the Corrosion Rate of Iron in Water . . . . . . . . . . . . . . . . . . . . . 15
Figure 8 Effect of pH on the Relative Attack Rate of Iron in Water . . . . . . . . . . . . . . . . . 15
Figure 9 Effect of pH on Aluminum Corrosion and Oxide Solubility . . . . . . . . . . . . . . . . 19
Figure 10 Galvanic Corrosion at Iron-Copper Pipe Junction . . . . . . . . . . . . . . . . . . . . . . . 24
Figure 11 Differential Aeration Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Figure 12 Representation of Crevice Pitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Figure 13 Pit in Metal Surface Promoted by Depolarization . . . . . . . . . . . . . . . . . . . . . . . 30
Figure 14 Intergranular Corrosion Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Figure 15 Austenitic Stainless Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
CH-02
Page ii
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
LIST OF TABLES
LIST OF TABLES
Table 1 Electromotive - Force Series (77(F) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Rev. 0
Page iii
CH-02
REFERENCES
DOE-HDBK-1015/1-93
Corrosion
REFERENCES
&
Academic Program for Nuclear Plant Personnel, Volume II, Columbia, MD,
&
&
&
&
1974.
&
1967.
CH-02
Page iv
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
OBJECTIVES
TERMINAL OBJECTIVE
1.0
Without references, DESCRIBE the causes and effects of corrosion on metals and the
type of chemistry used in a plant to minimize corrosion.
ENABLING OBJECTIVES
1.1

a.
b.
c.
d.
e.
Ionization
Conductivity
Corrosion
Electrolysis
General corrosion
1.2
DESCRIBE an electrochemical cell with respect to the corrosion of metals.
1.3
STATE what happens to a metal during the oxidation step of the oxidation-reduction
process.
1.4
STATE what happens to a metal during the reduction step of the oxidation-reduction
process.
1.5

a.
b.
Passivity
Polarization
1.6
DESCRIBE the affects of passivity and polarization on the corrosion process.
1.7
LIST the two conditions that contribute to general corrosion.
1.8
DESCRIBE how the rate of corrosion occurring in the plant is affected by the following:
a.
b.
c.
d.
e.
Rev. 0
Temperature
Water velocity
Oxygen
pH
Condition and composition of the metal surface
Page v
CH-02
OBJECTIVES
DOR-HDBK-1015/1-93
Corrosion

1.9
LIST the three products that are formed from the general corrosion of iron.
1.10
IDENTIFY the action taken for initial fill of a reactor system to limit general corrosion.
1.11
STATE the four methods used to chemically control general plant corrosion.
1.12
LIST the six water chemistry conditions that limit corrosion of aluminum.
1.13

a.
b.
c.
Crud
Scale
Galvanic corrosion
1.14
IDENTIFY the five problems associated with the presence or release of crud into
reactor coolant.
1.15
STATE the four causes of crud bursts.
1.16
STATE the two conditions that can cause galvanic corrosion.
1.17
EXPLAIN the mechanism for galvanic corrosion.
1.18
IDENTIFY the two locations that are susceptible to galvanic corrosion.
1.19
STATE the five control measures used to minimize galvanic corrosion.
1.20

a.
b.
c.
Pitting corrosion
Crevice corrosion
Stress corrosion cracking
1.21
STATE the two conditions necessary for pitting corrosion to occur.
1.22
STATE the particular hazard associated with pitting corrosion.
1.23
STATE the four controls used to minimize pitting corrosion.
CH-02
Page vi
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
OBJECTIVES

1.24
IDENTIFY the three conditions necessary for stress corrosion cracking to occur.
1.25
DEFINE the term chemisorption.
1.26
STATE the hazard of stress corrosion cracking.
1.27
STATE the three controls used to prevent stress corrosion cracking.
1.28
DESCRIBE the two types of stress corrosion cracking that are of major concern to
nuclear facilities including:
a.
b.
Rev. 0
Conditions for occurrence

Method(s) used to minimize the probability of occurrence
Page vii
CH-02
DOE-HDBK-1015/1-93
Corrosion
CH-02
Page viii
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
CORROSION THEORY
CORROSION THEORY
Uncontrolled corrosion in DOE facilities can cause many serious problems.
Corrosion occurs continuously, and every metal in every facility is subject to
some type of corrosion. Even though corrosion cannot be eliminated, it can be
controlled.
EO 1.1

a.
b.
c.
d.
e.
Ionization
Conductivity
Corrosion
Electrolysis
General corrosion
EO 1.2
DESCRIBE an electrochemical cell with respect to the

corrosion of metals.
EO 1.3
STATE what happens to a metal during the oxidation step of

the oxidation-reduction process.
EO 1.4
STATE what happens to a metal during the reduction step of

the oxidation-reduction process.
EO 1.5

a.
b.
EO 1.6
Passivity
Polarization
DESCRIBE the affects of passivity and polarization on the

corrosion process.
Corrosion
In DOE facilities, especially reactor plants, many precautions are taken to control the corrosion
of metals used in the various primary and secondary systems. Uncontrolled corrosion of the
reactor systems is detrimental for the following reasons.
&
Rev. 0
Rapid localized corrosion may lead to penetration of the metal containing the coolant.
Radioactive coolant would then leak from the system and jeopardize safe operation.
Page 1
CH-02
CORROSION THEORY
DOE-HDBK-1015/1-93
Corrosion
&
Corrosion of the nuclear fuel cladding may cause the cladding to become brittle and less
ductile. The swelling from the generation of fission gases within the fuel may then cause
the cladding to crack or blister, and highly radioactive fission products may then be
released to the coolant.
&
Some of the metallic oxide corrosion products released to the coolant may be deposited
on surfaces in the reactor core. The neutron flux in the core produces nuclear reactions
in the corrosion products, and they become highly radioactive. Subsequently, these
activated corrosion products may be released from the core and redeposited on surfaces
outside the core region. The radiation fields resulting from this redeposited material may
then significantly increase radiation levels, thereby complicating maintenance and access
capabilities. The corrosion product oxides may also result in fouling of heat transfer
surfaces and in the accelerated wear of moving parts by corrosion products trapped in
or between them.
Current is the flow of electrons through a medium. An electric current can flow through a metal
conductor, and the metal will not show any obvious chemical changes. This type of conduction
of electricity is called metallic conduction.
Ionization is the process of adding electrons to or removing electrons from atoms or molecules,
creating ions. High temperatures, electrical discharges, and nuclear radiation can cause
ionization. Many metals have a tendency to lose electrons to atoms or ions that have a tendency
to gain electrons. Current can be conducted by the movement of these ions. The compounds
that conduct electric current by ion movement are called electrolytes, and this ionic motion is call
electrolytic conduction. Conductivity is a measure of the ability of a substance to allow electron
flow. In the context of corrosion, conductivity indicates the amount of ions in solution, which
relates directly to the potential of corrosion taking place.
Corrosion is the deterioration of a material due to interaction with its environment. Corrosion
can have many forms, both wet and dry. Electrolysis is the decomposition by electric current
(in the context of corrosion the use of electrical current to bring about chemical change). This
chapter will concentrate on the corrosion of metals in water-based environments (electrolytes).
An electrolyte is defined as an electricity-conducting fluid; that is, it has positive and negative
ions that can move and constitute an electrical current. Pure water has a limited number of
dissociated H+ and OH- ions and is a relatively poor conductor of electricity. Addition of acids,
bases, or salts that dissociate into ions increases the current-carrying capability of the water
(electrolyte).
CH-02
Page 2
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
CORROSION THEORY
Electrochemical Cells
Corrosion is electrochemical in nature because the corrosive chemical reactions involve transfer
of charge. Figure 1 shows the transfer of charge when iron is in contact with water or an acidic
water solution.
Iron goes into solution as Fe++ ions. As
these ions go into solution, the metal
becomes negatively charged (by the
electrons left behind) with respect to the
electrolyte. A potential difference (voltage)
is produced between the electrolyte and the
metal. The process in which electrons are
given up and positive metal ions are formed
is called oxidation. The sites at which the
oxidation takes place on the surface of the
metal become electrochemical cells made up
of micro-electrodes of the two different
substances; the metal and the electrolyte.
These micro-electrodes set up many
micro-cells connected through the bulk of
Figure 1 Formation of Ferrous (Fe++) Ions in
the Corrosion of Iron
the metal. If a different metal is used, it will
go into solution to a greater (or lesser)
extent producing a larger (or smaller) potential difference between the metal and electrolyte than
was the case for iron. For example, magnesium and zinc go into solution to a greater extent than
iron, and these metals will be more negative with respect to the electrolyte than iron. Nickel,
lead, and copper go into solution less readily and produce a smaller potential difference. Table 1
lists the potential differences for various metals in water. The order of the series can change for
different electrolytes (for example, different pH, ions in solution).
Electrochemical cells and oxidation potentials are very important in understanding most
corrosion processes. Examples of electrochemical cells include galvanic cells (cells made up of
electrodes of two different substances) and concentration cells (cells containing electrodes of the
same substance under different conditions of concentration).
Rev. 0
Page 3
CH-02
CORROSION THEORY
DOE-HDBK-1015/1-93
Corrosion
TABLE 1
Electromotive - Force Series (77((F)
Element
Electrode
Reaction
Standard Electrode
Potential, v
Sodium
Na Na+ + e
-2.712
Magnesium
Mg Mg++ + 2e
-2.34
Beryllium
Be Be++ + 2e
-1.70
Aluminum
Al Al+++ + 3e
-1.67
Manganese
Mn Mn++ + 2e
-1.05
Zinc
Zn Zn++ + 2e
-0.762
Chromium
Cr Cr+++ + 3e
-0.71
Iron
Fe Fe+++ + 3e
-0.44
Cadmium
Cd Cd++ + 2e
-0.402
Cobalt
Co Co++ + 2e
-0.277
Nickel
Ni Ni++ + 2e
-2.250
Tin
Sn Sn++ + 2e
-0.136
Lead
Pb Pb++ + 2e
-0.126
Hydrogen
H 2H+ + 2e
Copper
Cu Cu++ + 2e
+0.345
Copper
Cu Cu+ + e
+0.522
Silver
Ag Ag+ + e
+0.800
Platinum
Pt Pt++ + 2e
+1.2
Gold
Au Au+++ + 3e
+1.42
0.000 (reference)
The surface of any metal is a composite of a very large number of micro-electrodes, as illustrated
in Figure 2. In order for corrosion to occur, the micro-cells must also be connected through
some conducting path external to the metal. Usually the external connection is provided by
water or an aqueous solution and the cells produce a current, allowing the chemical reactions
responsible for corrosion to proceed.
CH-02
Page 4
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
CORROSION THEORY
Consider iron in water again. If the

surface of the iron and the water
solution were uniform, iron would go
into solution as Fe++ ions until the
difference in potential between the
positively-charged solution and the
negatively-charged metal stopped the
iron ions from leaving the surface. In
practice, though, impurities and
imperfections (for example, oxide
coatings) lead to preferential removal
Figure 2 Metal Surface Showing Arrangement of Micro-cells
of metal from certain parts of the
surface, and potential differences arise as in the two metal system. The corrosion cells, changing
as surface and solution differences change, cause general overall corrosion. If the cells do not
shift, pitting results.
Oxidation-Reduction Reactions
The corrosion of a metal (that is, the chemical transformation that is recognized as destructive
to the metal) is the oxidation step of the overall oxidation-reduction process. Oxidation is the
process of losing electrons; reduction is the process of gaining electrons. The metal atoms
release electrons (are oxidized) and become positive ions. The site at which this occurs is known
as the anode. Typical oxidation half-reactions include the following.

(2-1)
(2-2)
(2-3)
The cations (positive ions) may then go into solution, or they may combine with any available
anions (negative ions) or water to form ionic compounds. The exact fate of the cations is
important to subsequent processes, but the primary effect is that atoms leave the metallic state,
and the metal deteriorates.
An oxidation process cannot take place without a simultaneous reduction (gain of electrons)
process. The nature of the reduction step in corrosion sometimes varies with the metal and the
environment to which it is exposed. For most metals in an aqueous environment, the important
reduction half-reaction is the reduction of hydronium ions (a hydronium ion is simply a hydrogen
ion attached to a water molecule).

Rev. 0
Page 5
(2-4)
CH-02
CORROSION THEORY
DOE-HDBK-1015/1-93
Corrosion
Small concentration variations within a solution in contact with the metal may also affect the rate
and nature of corrosion reactions. Therefore, it is often impossible to predict the exact nature of
corrosion reactions. It is generally found, however, that for most metals exposed to an aqueous
environment the half-reactions involved in corrosion are the reduction reaction of Equation (2-4)
and an oxidation half-reaction of the type shown in Equations (2-1) through (2-3).
General corrosion is the process whereby the surface of a metal undergoes a slow, relatively
uniform; removal of material. This occurs on the surface of a single metal rather than dissimilar
metals. In general corrosion, a nearly infinite number of micro-cells are established on the metal
surface. Oxidation occurs at anodic areas and reduction at cathodic areas. The micro-cells are
uniformly distributed over the metallic surface, and as the reaction proceeds the cells may migrate,
or disappear and re-form. That is, any particular micro-region may be alternately anodic and
cathodic. The result is a uniform attack on the metal surface.
Under some conditions, relatively large regions become anodic or cathodic. Such regions have
less tendency to migrate and may remain operative for long periods of time. In this case, there
will be severe attack of the metal at the anodic (oxidation) region. The result may be a visible pit
in the metal surface.
Iron and steel are resistant to rapid corrosion in water despite the tendency of iron to oxidize as
indicated by its standard electrode potential listed in Table 1. The reasons for this resistance are
the passivating effect of the oxide film and cathodic polarization due to atomic hydrogen that
absorbs on the oxide surface, both of which are explained in the next section.
Passivity and Polarization of Metal

Metals that normally fall victim to corrosion will sometimes exhibit a passivity to corrosion.
Passivity is the characteristic of a metal exhibited when that metal does not become active in the
corrosion reaction. Passivity is caused by the buildup of a stable, tenacious layer of metal oxide
on the surface of the metal. This oxide layer is formed by corrosion on a clean metal surface,
where the corrosion products are insoluble in the particular environment to which the metal is
exposed. Once the layer, or film, is formed, it acts as a barrier separating the metal surface from
the environment. For further corrosion to occur, the reactants must diffuse through the oxide
film. Such diffusion is very slow or nonexistent, thus corrosion either decreases markedly or
stops.
Metals such as zirconium, chromium, aluminum, and the stainless steels form thin, tenacious oxide
films when exposed to the atmosphere or to pure water at room temperature. In some cases, the
film is extremely thin and may be invisible to the unaided eye, but it is still very effective in giving
these metals a marked passivity.
If there is a net conversion of reactants to products in a system, the system will be chemically
unstable, and the reaction will continue until a stable state is attained. This stable state is known
as equilibrium.
CH-02
Page 6
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
CORROSION THEORY
An active electrochemical cell (oxidation-reduction reaction) is an unstable chemical system.

The potential associated with a galvanic cell, for example, steadily decreases as current flows and
the oxidation-reduction reaction proceeds. Eventually, the potential falls to zero, the cell no
longer supplies electrical energy, and no further net reaction takes place. At this point the
system is at equilibrium. In electrochemical cells, the decrease in cell potential caused by the
operation of the cell (current flow) is called polarization.
This change in cell potential can be determined. Consider the zinc-copper galvanic cell shown
in Figure 3. As the reaction takes place, Zn+2 ions (produced by the oxidation of zinc metal) pass
into solution. The Cu+2 ions in solution are reduced as the copper metal plates out. Thus, the
concentration of Zn+2 in solution increases and the concentration of Cu+2 decreases according
to the following overall reaction.

(2-5)
Figure 3 A Galvanic Cell
As Zn+2 increases and Cu+2 decreases, the electrical potential decreases. This decrease in cell
potential, which results from changes in concentrations, is one form of polarization called
concentration polarization.
Rev. 0
Page 7
CH-02
CORROSION THEORY
DOE-HDBK-1015/1-93
Corrosion
Now consider a galvanic cell with zinc

and platinum electrodes, such as that
shown in Figure 4. The half-reactions
in the cell are as follows.
(2-4)
Again, as the cell operates, the cell

potential drops. The decrease is
partially due to the increase in Zn+2
concentration and the decrease in H3O+
concentration, but another type of
polarization also occurs in this cell.
This second type is associated with the
reduction half-reaction.
Figure 4 A Galvanic Cell Showing Absorbed Hydrogen
The hydrogen atoms formed by the
Atoms on a Cathode
reaction of Equation (2-4) absorb on
the surface of the metal and remain
there until removed by one of two processes: combination of two hydrogen atoms to form
molecular hydrogen, which is then released as a gas or reaction with dissolved oxygen to form
water. In the absence of oxygen (deaerated solutions), the first process applies.
(2-6)
Combining Equation (2-6) with Equation (2-4), the net reduction half-reaction is obtained.

(2-6)
(2-7)
Until the absorbed hydrogen atoms are removed from the metal surface, they effectively block
the sites at which the reaction of Equation (2-4) can occur. At low temperatures the reaction
of Equation (2-6) is slow relative to the reaction of Equation (2-4) because, although the
reaction is energetically favored, the combination of two hydrogen atoms requires a large
activation energy. Equation (2-6) shows the rate-controlling step of the net reduction
half-reaction. Because the oxidation half-reaction can occur no faster than the reduction
half-reaction, the rate of the overall oxidation-reduction reaction is controlled by the reaction
of Equation (2-6).
CH-02
Page 8
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
CORROSION THEORY
The layer of absorbed atomic hydrogen is said to polarize the cell. This type of polarization is
called activation polarization and is sometimes referred to as hydrogen polarization, or cathodic
polarization, because the polarizing reaction occurs at the cathode.
Both concentration and activation polarization decrease the net oxidation-reduction reaction
rate. In corrosion processes, activation polarization usually has the greater effect.
Summary
Corrosion Theory Summary

&
Ionization is the process of adding electrons to or removing electrons from atoms

or molecules which creates ions.
&
Conductivity is a measure of the ability of a substance to allow electron flow.
&
Corrosion is the deterioration of a material due to interaction with its

environment.
&
Electrolysis is the decomposition by electric current.
&
General corrosion is the process whereby the surface of a metal undergoes a slow,
relatively uniform, removal of material.
&
Corrosion is electrochemical in nature because the corrosive chemical reactions

involve a transfer of charge. The metal ions go into solution causing the metal to
become negatively charged with respect to the electrolyte. The difference in the
charge causes a potential to develop and produces a voltage between the
electrolyte and the metal.
&
The oxidation step of the oxidation-reduction process is where an atom (in this
case a metal atom) releases electron(s) and becomes a positively-charged ion.
The areas where oxidation takes place become electrochemical cells made up of
two different substances. The oxidation step results in a chemical transformation
that is destructive to the metal. The positive metal ions may go into solution, or
they may combine with any available negative ions or water to form ionic
compounds. An example of the oxidation step is:
Zn Zn+2 + 2e-
Rev. 0
Page 9
CH-02
CORROSION THEORY
DOE-HDBK-1015/1-93
Corrosion
Corrosion Theory Summary (Continued)

&
The reduction step of the oxidation-reduction process is where a

positively-charged ion gains electron(s). The reduction step for most metals,
in an aqueous environment, is the reduction of hydronium ions. An example of
the reduction step is:
H3O+ + e- H + H2O
&
Passivity is the buildup of a stable, tenacious layer of metal oxide on the surface
of the metal that acts as a barrier separating the metal surface from the
environment. Passivity decreases or stops the corrosion process because of the
formation of the layer.
&
Polarization is the decrease in cell potential caused by the operation of the

electrochemical cell. Polarization can be in two forms; concentration or
activation. Concentration polarization is associated with the concentration of
ions in solution which shields the metal, thereby causing a decrease in the
electrical potential of the cell. Activation polarization is the formation of a layer
containing absorbed hydrogen atoms that block the metal's surface from the
corrosion process.
CH-02
Page 10
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
GENERAL CORROSION
GENERAL CORROSION
This chapter describes the general corrosion processes of iron and carbon
steel (not stainless steels) in aqueous environments. Of particular interest
is the formation of the oxide film and the effects of system variables on the
corrosion process.
EO 1.7
LIST the two conditions that contribute to general

corrosion.
EO 1.8
DESCRIBE how the rate of corrosion occurring in the

plant is effected by the following:
a.
b.
c.
d.
e.
f.
Temperature
Water velocity
Oxygen
pH
Condition and composition of the metal surface
Dissolved solids
EO 1.9
LIST the three products that are formed from the

general corrosion of iron.
EO 1.10
IDENTIFY the action taken for initial fill of a reactor

system to limit general corrosion.
EO 1.11
STATE the four methods used to chemically control

general plant corrosion.
EO 1.12
LIST the six water chemistry conditions that limit

corrosion of aluminum.
Conditions Contributing to General Corrosion

General corrosion is the process whereby the surface of a metal undergoes a slow, relatively
uniform, removal of material. The two conditions typically required for a metal to undergo
general corrosion are: 1) metal and water in the same environment, and 2) a chemical reaction
between the metal and water that forms an oxide.
Rev. 0
Page 11
CH-02
GENERAL CORROSION
DOE-HDBK-1015/1-93
Corrosion
Corrosion of Iron
Unless noted otherwise, the following discussion applies to deaerated water at room temperature
and approximately neutral pH. The affects of temperature, oxygen, and pH are discussed later
in this chapter.
The oxidation and reduction half-reactions in the corrosion of iron are as follows.

(2-3)
(2-4)
The overall reaction is the sum of these half-reactions.

(2-8)
The Fe+2 ions readily combine with OH- ions at the metal surface, first forming Fe(OH)2, which
decomposes to FeO.

(2-9)
Ferrous oxide (FeO) then forms a layer on the surface of the metal. Below about 1000(F,
however, FeO is unstable and undergoes further oxidation.

(2-10)
Atomic hydrogen then reacts to form molecular hydrogen, as described previously, and a layer
of ferric oxide (Fe2O3) builds up on the FeO layer. Between these two layers is another layer
that has the apparent composition Fe3O4. It is believed that Fe3O4 is a distinct crystalline state
composed of O-2, Fe+2, and Fe+3 in proportions so that the apparent composition is Fe3O4. These
three layers are illustrated in Figure 5.
Once the oxide film begins to form, the metal surface is no longer in direct contact with the
aqueous environment. For further corrosion to occur, the reactants must diffuse through the
oxide barrier. It is believed that the oxidation step, Equation (2-3), occurs at the metal-oxide
interface. The Fe+2 ions and electrons then diffuse through the oxide layer toward the
oxide-water interface. Eventually, Fe+2 ions encounter OH- ions and form FeO. The electrons
participate in the reduction reaction with hydronium ions. These latter reactions are believed to
take place predominately at the oxide-water interface, but some reaction may occur within the
oxide layer by the diffusion of H+, OH-, and H2O into the layer.
CH-02
Page 12
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
GENERAL CORROSION
Figure 5 Simplified Schematic Diagram of Oxide Corrosion Film on the Surface of a Metal
Regardless of the exact diffusion mechanism, the oxide layer represents a barrier to continued
corrosion and tends to slow the corrosion rate. The exact effect of this layer on the corrosion
rate depends on the uniformity and tenacity of the film. If the film is loosely attached, develops
defects, or is removed, the metal surface is again exposed to the environment and corrosion
occurs more readily.
Factors Affecting General Corrosion Rate

Like most other chemical reactions, corrosion rates increase as temperature increases.
Temperature and pressure of the medium govern the solubilities of the corrosive species in the
fluid, such as oxygen (O2), carbon dioxide (CO2), chlorides, and hydroxides. A rule of thumb
is that the reaction rate doubles with a 20(F to 50(F temperature rise. This linear increase with
temperature does not continue indefinitely due, in part, to a change in the oxide film.
When water velocity is extremely high, the impact of the water tends to remove the protective
oxide layer and some of the metal under it (erosion), thus, exposing more metal to corrosion.
Water velocities of 30 to 40 ft per second are usually considered to cause erosion.
The presence of oxygen in water to which iron is exposed increases the corrosion rate. The
reason for this increase is the rapid reaction between oxygen and the polarizing layer of atomic
hydrogen absorbed on the oxide layer. The following reaction rapidly removes the polarizing
layer.
O2 + 4H 2H2O
(2-11)
Rev. 0
Page 13
CH-02
GENERAL CORROSION
DOE-HDBK-1015/1-93
Corrosion
The overall reaction can be obtained by combining Equations (2-4) and (2-11).

The controlling step is believed to be

diffusion of O2 to the metal surface
where it can react directly with iron or
with FeO.

(2-12)
(2-13)
Oxygen, therefore, has two effects: it

removes the polarizing layer of atomic
hydrogen, and it can react directly with
the metal or metal oxide; thus, the
corrosion rate increases. Substances,
such as O2 in this case, that remove the
absorbed atomic hydrogen are called
depolarizers. The depolarizing effect of
O2 is illustrated in Figure 6.
The effect of the pH of water to which
iron or steel is exposed is influenced by
temperature in the following manner.
The potential of hydrogen or symbol
(pH) is defined as the negative logarithm
of the hydrogen concentration,
represented as [H+] in moles/liter.
pH = -log [H+]
The pH value is used to represent the
acidity of a solution.
Figure 6 Representation of Cathodic Depolarization

by Oxygen
CH-02
Page 14
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
GENERAL CORROSION
First, consider the exposure of iron to aerated

water at room temperature (aerated water will
contain dissolved oxygen). The corrosion
rate for iron as a function of pH is illustrated
in Figure 7. In the range of pH 4 to pH 10,
the corrosion rate of iron is relatively
independent of the pH of the solution. In this
pH range, the corrosion rate is governed
largely by the rate at which oxygen reacts
with absorbed atomic hydrogen, thereby
depolarizing the surface and allowing the
reduction reaction to continue. For pH values
below 4.0, ferrous oxide (FeO) is soluble.
Figure 7 Effect of pH on the Corrosion Rate
Thus, the oxide dissolves as it is formed
of Iron in Water
rather than depositing on the metal surface to
form a film. In the absence of the protective
oxide film, the metal surface is in direct contact with the acid solution, and the corrosion reaction
proceeds at a greater rate than it does at higher pH values. It is also observed that hydrogen is
produced in acid solutions below a pH of 4, indicating that the corrosion rate no longer depends
entirely on depolarization by oxygen, but on a combination of the two factors (hydrogen
evolution and depolarization). For pH values above about pH 10, the corrosion rate is observed
to fall as pH is increased. This is believed to be due to an increase in the rate of the reaction of
oxygen with Fe(OH)2 (hydrated FeO) in the oxide layer to form the more protective Fe 2O 3 (note
that this effect is not observed in deaerated water at high temperatures).
A plot of the relative corrosion
rate for iron at various pH
values in 590(F, oxygen-free
water is presented as Figure 8.
The curve illustrates that the
corrosion rate of iron in high
temperature water is lower in
the pH range of 7 to 12 than it is
at either lower or higher pH
values (at very high pH values,
greater than pH 13.0, the oxide
film becomes increasingly more
soluble because of increased
formation of soluble FeO2 at
high
temperatures,
and
Figure 8 Effect of pH on the Relative Attack Rate of Iron in Water
corrosion rates increase). As a
result of the data plotted in
Figure 8 and other similar measurements, it is general practice to maintain high temperature
water in the alkaline condition (but below very high pH values) to minimize the corrosion of iron
and the steels exposed to the high temperature water.
Rev. 0
Page 15
CH-02
GENERAL CORROSION
DOE-HDBK-1015/1-93
Corrosion
The hydrogen normally dissolved in reactor coolant does not have any detectable direct effect
upon the corrosion rate of the iron and steels exposed to reactor coolant. It does, however, have
an important indirect effect by preventing the accumulation of dissolved oxygen in reactor
coolant, which would accelerate corrosion. Dissolved oxygen reacts with the protective
hydrogen gas layer at the cathode to form water.
The condition and composition of the metal surfaces affects the corrosion rate. Deposits, scale,
or irregular surfaces create areas on the metal where local corrosion can initiate and proceed at
a faster rate than normal. Certain alloys of metals have higher corrosion resistance than others,
as discussed in the Material Science Handbook.
When iron or steel is exposed to high temperature water, the rate of corrosion of the metal is
observed to decrease with exposure time during the early period of exposure. After a few
thousand hours, the corrosion rate becomes relatively constant at a low value. During the early
period of exposure, while the corrosion rate is decreasing, the oxide film on the surface of the
metal grows in thickness. However, the rate at which the film grows decreases with time. The
thickness of the oxide film soon reaches a relatively constant value, and thereafter film thickness
does not change appreciably with further exposure. As might be expected, a relatively constant
corrosion rate and oxide film thickness are attained at about the same time. Because a tightly
adhering corrosion film inhibits further corrosion, great care is taken during the initial fill of
reactor plants to promote formation of the best possible corrosion film. This process, referred
to as pretreatment, or pickling, involves careful control of reactor coolant water chemistry and
temperature during the pretreatment period.
Prevention Chemistry Control

Plant chemistry is used to control corrosion. The type of corrosion determines the method used
for preventing or minimizing the corrosion rate.
Passivators and Inhibitors

Passivation is the condition where a naturally active metal corrodes at a very low rate,
probably due to an oxide coating or an absorbed layer of oxygen. Some chemical
substances, called passivators or inhibitors, if added to water, can provide this type of
passivation by undergoing reduction at the metal surface. A common inhibitor is
potassium chromate.
Cathodic Protection
The use of cathodic protection, supplying an external electric current to the iron so that
it acts as a cathode and has no anodic areas, is another method of preventative chemical
control. This can be accomplished by the use of an external voltage source or by the use
of a sacrificial anode (e.g., zinc) which will corrode and provide the current.
CH-02
Page 16
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
GENERAL CORROSION
Removing Corrosive Agents

Chemistry control in the form of removal of corrosive agents from a system is a widely
used method. One method is using deaerators to remove dissolved oxygen and to a
lesser extent carbon dioxide. Treating the water by softening and demineralization
removes the dissolved solids and reduces the conductivity.
Chemical Addition
Chemical additions to a system that alter the chemical reaction or tie up a particular
corrodant is a common method of control. Filming amines (organic compounds that are
derivatives of ammonia) accomplish protection by forming adhering organic films on
metal surfaces to prevent contact between corrosive species in the condensate and the
metal surface. Phosphates and sodium hydroxide are used to adjust the system pH and
remove hardness.
Corrosion of Aluminum
The corrosion of aluminum is dependent upon a vast number of variables. These variables
include environment, temperature, alloy in question, flow velocities, impurities present in the
environment, and chemistry conditions to which it is exposed. An additional factor that affects
corrosion is pretreatment.
Many of the factors are controlled by design and construction, such as alloy type, temperature,
and flow velocities. Pretreatment, soluble and solid impurities, and chemistry are within the
control of the operator and will be discussed in this text.
Experiments have shown that prefilming limits corrosion on aluminum-clad fuel assemblies. In
the tests conducted, the ratios of oxide film thickness for nonprefilmed and prefilmed elements
were on the order of 2 to 3 and in some cases even greater.
Impurities are major contributors to the corrosion of aluminum. In most cases studied, the major
source of contaminants has been makeup water systems. Corrosion products from other plant
materials also contribute to the overall inventory of ionic and solid impurities. Finally, organic
impurities from the resin used in ion exchangers have been detected. These occur in some
installations because of the type of resin used and the particle filters normally installed on the ion
exchanger effluents. This problem has been reduced by improved resins and installing filters
capable of removing smaller particles.
Chemistry controls, including pH, dissolved oxygen, and conductivity, greatly influence the
formation and propagation of the oxide film on aluminum surfaces. Dissolved oxygen is
controlled for essentially the same reasons as for the corrosion of iron. Conductivity is a
quantitative indication of the impurities present in the system, and pH theoretically dictates the
value of conductivity.
Rev. 0
Page 17
CH-02
GENERAL CORROSION
DOE-HDBK-1015/1-93
Corrosion
For those reactor plants in which aluminum is used for cladding and other structural
components, pH is controlled in an acidic condition because of the corrosion properties of
aluminum. Plant pH has a marked effect on the rate of chemical reaction between the coolant
water and aluminum. In the area of the cladding, the corrosion reduces the thickness and forms
an oxide film that is a thermal barrier. Extensive tests carried out in support of DOE test
reactors have revealed that minimum aluminum corrosion results with a pH of 5.0 at normal
operating temperatures. Additionally, studies have shown that the aluminum corrosion
products also exhibit a minimum solubility at a pH near 5.5 at 25(C. The aluminum corrosion
products tend to reduce the substrate (base) aluminum metal corrosion rates. Because it is
desirable to maintain dissolved aluminum in the reactor coolant at the lowest practicable level,
it is desirable to maintain the system pH level in the range of minimum oxide solubility. Figure
9 shows the effect of pH on aluminum oxide solubilities for various forms of oxide, and the
effect of pH on corrosion rates. It should be noted that the values at which minimum corrosion
and solubility are found shift to a lower pH as the temperature is increased. For example, at
300(C, the value for minimum aluminum corrosion is near pH 3.0. Therefore, the optimum pH
for operation is determined by the operating temperature.
The conditions that have proven to be most effective in limiting corrosion of aluminum are as
follows.
CH-02
&
Maintaining pH slightly acidic with the value of the pH depending largely upon
operating temperature
&
Elimination of dissolved oxygen
&
Elimination of soluble and solid impurities
&
Prevention of the introduction of organic impurities
&
Pretreatment (or pickling)
&
Maintaining water purity
Page 18
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
GENERAL CORROSION
Figure 9 Effect of pH on Aluminum Corrosion and Oxide Solubility
Rev. 0
Page 19
CH-02
GENERAL CORROSION
DOE-HDBK-1015/1-93
Corrosion
Summary
The major points of this chapter are summarized below.
General Corrosion Summary

&
The two conditions that contribute to general corrosion are:

Metal and water in the same environment
Chemical reaction between the metal and water to form an oxide
&
The corrosion rate is affected by the following:

A temperature rise in the range of 20(F to 50(F doubles the corrosion rate
until the formation of the protective oxide film is complete.
An extremely high water velocity, 30 to 40 ft per second, tends to remove
the oxide film allowing the corrosion rate to increase.
The presence of oxygen in water to which iron is exposed increases the
corrosion rate. The reason for the corrosion rate increase is due to the
rapid reaction between the oxygen and the polarizing layer of hydrogen
absorbed on the oxide layer.
A pH between 4 and 10 results in minimal corrosion rate. If the pH falls
below or above this range, the corrosion will normally increase.
The condition and composition of the metal surfaces affects the corrosion
rate. Deposits, scale, or irregular surfaces create areas on the metal where
local corrosion can initiate and proceed at a faster rate than normal.
Dissolved solids tend to make it easier for current to flow, which results
in a higher corrosion rate.
&
CH-02
The three products formed from general corrosion of iron are FeO, Fe2O3, and
Fe3O4.
Page 20
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
GENERAL CORROSION
General Corrosion Summary (Cont.)

&
During the initial fill of a reactor system, great care is taken to promote the
formation of the best possible protective corrosion film. The protective film acts
as a barrier and stops further uncontrolled corrosion from taking place. This
process, called pretreatment or pickling, involves careful control of reactor
coolant water chemistry and temperature during the pretreatment period.
&
Four methods used to chemically control general plant corrosion are:

Passivators (inhibitors) consist of a naturally active metal that corrodes
at a very low rate. A common passivator is potassium chromate.
Cathodic protection is the external application of an external electric
current to the iron so that it acts as a cathode and has no anodic areas.
This is accomplished by using either an external electrical source or the
use of a sacrificial anode to provide the electrical current.
Removing corrodants to reduce the dissolved oxygen and lesser extent
carbon dioxide. Treating the water in this manner reduces the dissolved
solids and reduces the conductivity.
Chemical addition to alter the chemical reaction or tie up a particular
corrodant. Filming amines, phosphates, and sodium hydroxide are used
to provide organic films and adjust the system pH.
&
The six water chemistry conditions that limit corrosion of aluminum are:
Maintaining pH slightly acidic with the value of the pH depending largely
on operating temperature.
Elimination of dissolved oxygen
Elimination of soluble and solid impurities
Prevention of the introduction of organic impurities
Pretreatment (or pickling)
Maintaining water purity
Rev. 0
Page 21
CH-02
CRUD AND GALVANIC CORROSION
DOE-HDBK-1015/1-93
Corrosion

A major potential problem is crud. Crud can cause an increase in
background radiation levels. When two dissimilar metals are in close
vicinity, the opportunity for ion transfer is high. The result is a perfect
environment for galvanic corrosion. Because of the numerous types of
materials used in nuclear facilities, galvanic corrosion is a major concern.
EO 1.13

a.
b.
c.
Crud
Scale
Galvanic corrosion
EO 1.14
IDENTIFY the five problems associated with the presence or

release of crud into reactor coolant.
EO 1.15
STATE the four causes of crud bursts.
EO 1.16
STATE the two conditions that can cause galvanic corrosion.
EO 1.17
EXPLAIN the mechanism for galvanic corrosion.
EO 1.18
IDENTIFY the two locations that are susceptible to galvanic

corrosion.
EO 1.19
STATE the five control measures used to minimize galvanic

corrosion.
Crud
In addition to the corrosion film, corrosion products in the form of finely divided, insoluble oxide
particles called crud become suspended in the reactor coolant or loosely adhere to metal
surfaces. Crud has several undesirable characteristics. It can be transported throughout the
reactor coolant system. As a result, it can accumulate and foul heat-transfer surfaces or clog
flow passages. The most undesirable characteristic of crud, however, is that it becomes
activated when exposed to radiation. Because crud can be transported throughout the reactor
coolant system, it can collect outside the reactor core, causing radiation hot spots that increase
ambient radiation levels. Hot spots caused by collections of crud may occur at the entrance to
the purification heat exchanger and other areas of low flow velocity. Crud that is loosely
adhered to metal surfaces can suddenly become suspended in the reactor coolant.
CH-02
Page 22
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
The crud release can result from an increased oxygen concentration, a reduced (or significantly
changed) pH, a large temperature change (heatup or cooldown), or a physical shock to the
system. Physical shocks include starting, stopping, or changing pump speeds, or other
evolutions like a reactor scram or a relief valve lift. The result is a sudden increase in reactor
coolant activity. The release of crud in this fashion is termed a crud burst. Crud bursts often
lead to the removal of protective corrosion films and make the freshly exposed metal more
susceptible to additional corrosion. In addition to the corrosion film and crud, some of the
corrosion products are soluble and are easily transported throughout the system.
High crud concentrations in the system can also complicate disposal of primary coolant. Many
of the corrosion products have relatively long half-lives and represent significant biological
hazards. If, therefore, primary coolant is drained or leaks from the plant shortly after a crud
burst, additional procedures may need to be utilized to minimize the effects of this condition.
Therefore, if the conditions mentioned previously (O2, pH) are changed, the solubility of these
corrosion products will change, and they can then be transported to and deposited anywhere in
the reactor coolant system.
Another corrosion byproduct is scale, which is made up of deposits on surfaces from the
formation of insoluble compounds from normally soluble salts. Most common are calcium or
magnesium carbonates (CaCO3 or MgCO3).
Galvanic Corrosion
Galvanic corrosion is the corrosion that results when two dissimilar metals with different
potentials are placed in electrical contact in an electrolyte.
Of all the different types of corrosion, galvanic corrosion corresponds most closely to the
electrochemical cells described previously in this module because galvanic corrosion occurs when
two electrochemically dissimilar metals are joined together (in electrical contact) in a conducting
medium (electrolyte). It may also take place with one metal with heterogeneities (dissimilarities)
(for example, impurity inclusions, grains of different sizes, difference in composition of grains,
differences in mechanical stress); abnormal levels of pH; and high temperatures. A difference in
electrical potential exists between the different metals and serves as the driving force for electrical
current flow through the corrodant or electrolyte. This current results in corrosion of one of the
metals. The larger the potential difference, the greater the probability of galvanic corrosion.
Galvanic corrosion only causes deterioration of one of the metals. The less resistant, active metal
becomes the anodic corrosion site. The stronger, more noble metal is cathodic and protected.
If there were no electrical contact, the two metals would be uniformly attacked by the corrosive
medium as if the other metal were absent. Two locations susceptible to galvanic corrosion is a
piping transition from one metal to another and a sacrificial anode (such as zinc).
Rev. 0
Page 23
CH-02
DOE-HDBK-1015/1-93
Corrosion
Figure 10 illustrates that galvanic corrosion occurs when two different metals are in contact and
exposed to an electrolyte.
Figure 10 Galvanic Corrosion at Iron-Copper Pipe Junction
Figure 10 shows the junction of iron and copper pipes containing a solution of a copper salt. The
oxidation potential of iron is sufficiently greater than that of copper so that iron is capable of
reducing Cu+2 ions to copper metal. In this case, iron corrodes near the junction, and additional
copper builds up on the copper pipe near the junction.
The solution to which the metal junction is exposed need not contain a salt of one of the metals
for galvanic corrosion to occur. If the iron-copper junction were exposed to water without Cu+2
ions, the reduction reaction would be as shown in Equation (2-4).
H3O + e H + H2O
(2-4)
Again, iron would corrode near the junction, but in this case hydrogen would be formed on the
surface of the copper.
Prevention of Galvanic Corrosion

A method called cathodic protection, discussed previously in this module, is often used to retard
or eliminate galvanic corrosion. One of several ways of accomplishing this is to attach a third
metal to the metals to be protected. This metal must have an oxidation potential even greater
than that of the metal to be protected. The most active metal then tends to corrode in place of
the protected metal. The metal that corrodes to protect another metal is called a sacrificial anode.
This method is applied in the original design of structural materials. Zinc is a common sacrificial
anode and is often used in cooling water systems that contain seawater.
CH-02
Page 24
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
Galvanic corrosion can also be limited by: 1) using only metals that are close on the activity
series (discussed in the chapter on Corrosion Theory), 2) electrical insulation of dissimilar metals,
and 3) using poorly-conducting electrolytes (very pure water).
The relative surface areas of the two metals are also important. A much larger surface area of
the non-active metal, compared to the active metal, will accelerate the attack. It has been
determined that the relative surface area is the determining factor in the corrosion rates.
The required electrical current for galvanic corrosion will be stopped if the dissimilar metals are:
&
&
&
separated by a non-conducting junction,

separated from a conductive environment, and
located in a poorly conducting electrolyte (pure water).
Summary
The important information of this chapter is summarized below.
Crud and Galvanic Corrosion Summary

&
Crud is corrosion products in the form of finely divided, insoluble oxide particles
suspended in the reactor coolant or loosely adhered to metal surfaces or activated
corrosion and wear products.
&
Scale is the deposition on the surfaces of the piping from the formation of insoluble
compounds from normally soluble salts. Most common are calcium or magnesium
carbonates.
&
Galvanic corrosion is the corrosion that results when two dissimilar metals with
different potentials are placed in electrical contact in an electrolyte.
&
The problems of crud in reactor plants are:

Fouling of coolant flow paths
Fouling of heat transfer surfaces
High general background (ambient) radiation levels
Radiation hot spots
Radioactive waste disposal
Rev. 0
Page 25
CH-02
DOE-HDBK-1015/1-93
Corrosion
Crud and Galvanic Corrosion Summary (Cont.)

&
The causes of a crud burst in the reactor coolant are:

Increased oxygen concentration
Reduced (or significantly changed) pH
Large temperature change
Physical shock (for example, starting and stopping pumps,
changing speeds of pumps, reactor scram, or relief valve lift)
&
Galvanic corrosion functions on the principle of the electrochemical cell, and

occurs when two electrochemically dissimilar metals are joined together in a
conducting medium. The two dissimilar metals generate an electrical potential,
and this electrical potential serves as the driving force for the electrical current
flow through the corrodant or electrolyte. The less resistant metal, called the
active metal, becomes anodic. The other metal, called the noble metal, becomes
cathodic.
&
The two locations susceptible to galvanic corrosion are piping transitions between
two dissimilar metals and at sacrificial anodes.
&
Measures used to control galvanic corrosion include:

Cathodic protection by introducing a third metal (sacrificial anode,
normally zinc) to the metals being protected or using only metals that are
close on the activity series.
Choosing relative surface areas such that the material to be protected has
a larger surface area than the active metal.
Separating dissimilar metals with a non-conducting material
Separating the metals from a conductive environment
Use of poorly conducting electrolytes (pure water)
CH-02
Page 26
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
SPECIALIZED CORROSION
The environment in which a metal exists has direct bearing on the corrosion
rate of that metal. Because of the unique environment possible in the nuclear
industry, there are a few specialized types of corrosion that must be considered.
EO 1.20

a.
b.
c.
Pitting corrosion
Crevice corrosion
Stress corrosion cracking
EO 1.21
STATE the two conditions necessary for pitting corrosion to

occur.
EO 1.22
STATE the particular hazard associated with pitting

corrosion.
EO 1.23
STATE the four controls used to minimize pitting corrosion.
EO 1.24
IDENTIFY the three conditions necessary for stress corrosion

cracking to occur.
EO 1.25
DEFINE the term chemisorption.
EO 1.26
STATE the hazard of stress corrosion cracking.
EO 1.27
STATE the three controls used to prevent stress corrosion

cracking.
EO 1.28
DESCRIBE the two types of stress corrosion cracking that

are of major concern to nuclear facilities including:
a.
b.
Conditions for occurrence

Method(s) used to minimize the probability of occurrence
Pitting and Crevice Corrosion

Another possible effect of dissolved oxygen is accelerated localized attack. This is especially
likely in areas of limited circulation. The resulting corrosion is called pitting corrosion.
Rev. 0
Page 27
CH-02
DOE-HDBK-1015/1-93
Corrosion
Pitting corrosion occurs where the anodic site becomes fixed in a small area and the formation
of holes (deep attack) in an otherwise unaffected area takes place. Crevice corrosion is a type
of pitting corrosion that occurs specifically within the low flow region of a crevice.
Figure 11 Differential Aeration Cell
To illustrate pitting attack, consider a special type of galvanic cell called a differential aeration
cell such as the one illustrated in Figure 11. This particular differential aeration cell is showing
current flow as a result of depolarization of one electrode (cathode) by oxygen. In this type of
cell, two iron electrodes are exposed to a dilute solution of an electrolyte (NaCl, for example).
Air (or oxygen) is bubbled around one electrode, and nitrogen is bubbled around the other. A
current flows through the wire connecting the two electrodes. The difference in potential is a
result of the difference in oxygen concentration at the two electrode surfaces. At the electrode
exposed to nitrogen, electrons are given up by the iron as it is oxidized. These electrons readily
flow through the external circuit to the electrode exposed to oxygen. At this depolarized
electrode they can participate in a reduction reaction. As a result, oxidation occurs at the
electrode exposed to nitrogen and reduction occurs at the aerated electrode. Oxidation at one
electrode and reduction at the other creates a potential and a flow of current through the
connecting wire. Note that loss of metal occurs at the electrode that is deficient in oxygen.
CH-02
Page 28
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
In iron that is exposed to water, a similar action can occur if adjacent areas of the metal surface
become exposed to solutions with different oxygen concentrations. For example, the solution
in a crevice exchanges slowly with the bulk of the solution outside the crevice. Oxygen in the
solution inside the crevice will be depleted initially by the corrosion reaction.

(2-12)
This reaction alone does not produce a protective film on the metal. Because of restricted flow
into the crevice, replenishment of oxygen will be very slow; therefore, the solution inside the
crevice will have a low oxygen concentration relative to that outside the crevice as shown in
Figure 12. The two adjacent areas then establish a concentration cell with electrons flowing
from the region of low oxygen concentration to the region of high concentration. Thus, metal
goes into solution (oxidation) inside the crevice, and reduction occurs outside the crevice.
Metal ions diffuse out of the crevice, more metal dissolves, and the process continues. This
results in the formation of a pit inside the crevice.
Figure 12 Representation of Crevice Pitting
Rev. 0
Page 29
CH-02
DOE-HDBK-1015/1-93
Corrosion
The presence of oxygen can also promote pitting at areas on the metal surface that are initially
anodic with respect to an adjacent area. For example, suppose that adjacent areas on a metal
surface exhibit slightly different oxidation potentials. Oxidation, or loss of metal, proceeds at
the region of higher potential. Corrosion in the region of higher potential leads to formation
(at least initially) of a porous oxide film. The thickness of the film formed on the adjacent
cathodic region will be much less. Oxygen in the bulk of solution can reach the cathodic surface
(with the thin film) more readily than it can the nearby anodic surface region (with the thicker
oxide film). Depolarization of the cathodic region (thin film) by oxygen tends to maintain this
region cathodic, while a deficiency of oxygen under the thicker porous corrosion film assists
in maintaining an anodic condition in this region. The overall result is corrosion, or wasting
away, of the metal in the anodic region under the thicker film. Thus, a pit in the metal surface
is formed under the mound of surface oxide, as illustrated in Figure 13. Pitting of this type is
common in both low temperature and high temperature iron-water systems if precautions are
not taken to remove the oxygen from the water within the system.
Figure 13 Pit in Metal Surface Promoted by Depolarization
It is also found that certain ions, notably chloride ions, cause pitting of iron and steel. The exact
mechanism by which this occurs is not clear, but in some way chloride ions cause defects in the
passivating oxide layer on the metal surface. The defects are highly localized and are
surrounded by large passive areas that tend to be cathodic. Thus, a small anodic (oxidation)
site is surrounded by a large cathodic (reduction) area. The current density will then be very
large at the anodic site, and attack on the metal will be rapid. In some test cases, deep pits have
been observed within a few hours.
CH-02
Page 30
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
Pitting and crevice corrosion are a major hazard to a nuclear facility because of the rapid
penetration of the metal with little overall loss of mass. A nuclear facility minimizes pitting and
crevice corrosion by the following actions.
&
Avoiding stagnant or low flow conditions.
&
Using metals and alloys that are less susceptible to the corrosion.
&
Avoiding agents in the medium that cause pitting (for example, chlorides and
oxygen).
&
Designing the system and components such that no crevices are present.
Stress Corrosion Cracking

Stress corrosion cracking (SCC) is a type of intergranular attack corrosion that occurs at the
grain boundaries under tensile stress. Grain boundaries are discussed in detail in the Material
Science Handbook. SCC occurs in susceptible alloys when the alloy is exposed to a particular,
specific environment if the alloy is in a stressed condition. Stress corrosion cracking appears
to be relatively independent of general uniform corrosion processes. Thus, the extent of general
corrosion can be essentially nil, and stress cracking can still occur. Most pure metals are
immune to this type of attack.
According to the most widely accepted theory, stress corrosion cracking is caused by a process
called chemisorption. Unlike relatively weak physical absorption, such as hydrogen gas on
platinum metal, chemisorption may be thought of as the formation of a compound between the
metal atoms on the surface as a monomolecular layer of the chemisorbed substance, such as Cl-,
OH-, Br-, and some other ions. The formation of this chemisorbed layer greatly reduces the
attraction between neighboring metal atoms. A defect initially present then grows as the metal
atoms separate under stress, more chemisorption occurs, and the process continues. In very
severe cases, the time required for this cracking to occur is only a matter of minutes.
Many stainless steels are susceptible to stress corrosion cracking. Stainless steels containing
18 percent chromium and 8 percent nickel are susceptible to cracking in environments
containing chloride ions and in concentrated caustic environments (that is, in environments
where the hydroxyl ion concentration is high). On the other hand, these types of stainless steels
do not exhibit any tendency to crack when they are exposed to water environments containing
nitrate (NO3-), sulfite (SO3--), and ammonium (NH3+) ions.
SCC is of great concern because it can readily crack metal of appreciable thickness. If the
environment is severe enough, cracking can occur in a very short period of time. The crack can
then lead to a serious failure of the component, or the system, and all the attendant results (for
example, contamination, loss of coolant, and loss of pressure).
Rev. 0
Page 31
CH-02
DOE-HDBK-1015/1-93
Corrosion
The most effective means for preventing SCC are proper design, reducing stress, removing
critical environmental contributors (for example, hydroxides, chlorides, and oxygen), and
avoiding stagnant areas and crevices in heat exchangers where chlorides and hydroxides might
become concentrated. Low alloy steels are less susceptible than high alloy steels, but they are
subject to SCC in water containing chloride ions. Nickel based alloys are not affected by
chloride or hydroxide ions.
Two types of SCC are of major concern to a nuclear facility.
Chloride Stress Corrosion Cracking (Stainless Steels)

The three conditions that must be present for chloride stress corrosion to occur are as
follows.
&
Chloride ions are present in the environment
&
Dissolved oxygen is present in the environment
&
Metal is under tensile stress
Austenitic stainless steel is a non-magnetic alloy consisting of iron, chromium, and

nickel, with a low carbon content. This alloy is highly corrosion resistant and has
desirable mechanical properties. One type of corrosion which can attack austenitic
stainless steel is chloride stress corrosion. Chloride stress corrosion is a type of
intergranular corrosion.
Chloride stress corrosion involves selective attack of the metal along grain boundaries.
In the formation of the steel, a chromium-rich carbide precipitates at the grain boundaries
leaving these areas low in protective chromium, and thereby, susceptible to attack. It has
been found that this is closely associated with certain heat treatments resulting from
welding. This can be minimized considerably by proper annealing processes.
This form of corrosion is controlled by maintaining low chloride ion and oxygen content
in the environment and the use of low carbon steels. Environments containing dissolved
oxygen and chloride ions can readily be created in auxiliary water systems. Chloride ions
can enter these systems via leaks in condensers or at other locations where auxiliary
systems associated with the nuclear facility are cooled by unpurified cooling water.
Dissolved oxygen can readily enter these systems with feed and makeup water. Thus,
chloride stress corrosion cracking is of concern, and controls must be used to prevent
its occurrence.
CH-02
Page 32
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
Figure 14 illustrates intergranular stress corrosion cracking. The pressure of a tensile

stress opens up intergranular cracks and accelerates further corrosion. Chloride stress
corrosion is a particularly significant problem in the operation of nuclear facilities
because of the wide use of austenitic stainless steel, and the inherent presence of high
tensile stresses associated with pressurization. Chloride stress corrosion cracks have
been known to propagate in austenitic stainless steel at stresses of about one-fifth yield
strength with chloride concentrations of less than 50 ppm. Yield strength is discussed
in detail in the Material Science Handbook.
Figure 14 Intergranular Corrosion Cracking
Tests show that the 18-8 stainless steels are susceptible to chloride stress attack when
both the chloride ion concentration and dissolved oxygen concentration are above certain
values. The region of susceptibility for austenitic stainless steel is illustrated in Figure
15. Note that when dissolved oxygen is present at about 1 ppm, chloride stress
corrosion cracking can be initiated at chloride ion concentrations near 1 ppm. However,
when the concentration of dissolved oxygen is very low, susceptibility to chloride stress
corrosion cracking is reduced.
High temperature tends to decrease the time required for chloride-induced cracking to
occur, but there appears to be no practical temperature limit below which cracking will
not occur, given sufficient time and severe conditions. The curve in Figure 15 is valid for
temperatures in the range 470(F to 500(F.
Rev. 0
Page 33
CH-02
DOE-HDBK-1015/1-93
Corrosion
Figure 15 Austenitic Stainless Steel
Caustic Stress Corrosion Cracking

Caustic stress corrosion, or caustic embrittlement, is another form of intergranular
corrosion cracking. The mechanism is similar to that of chloride stress corrosion. Mild
steels (steels with low carbon and low alloy content) and stainless steels will crack if they
are exposed to concentrated caustic (high pH) environments with the metal under a
tensile stress. In stress cracking that is induced by a caustic environment, the presence
of dissolved oxygen is not necessary for the cracking to occur.
Caustic stress corrosion cracking was first encountered in the operation of riveted steam
boilers. These boilers were found to fail on occasion along riveted seams. Failure was
attributed to caustic-induced cracking at the highly stressed regions near and under the
rivets. Boiler water could easily flow into the crevices which existed under the rivets.
Radiative heating would cause the water in the crevices to boil. As steam was formed,
it would escape from the crevice. More boiler water would then flow into the crevice,
boil, and pass from the crevice as steam. The net result of this continuing process was
concentration of caustic under the rivet. The combination of high stress and high caustic
concentrations eventually led to destructive cracking of the boiler vessel.
CH-02
Page 34
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
Where the rate of steam generation (boiling) is high, it is more difficult to eliminate the
problem of solute concentration in regions of the boiler. Caustic stress corrosion may
concentrate in such regions as the water evaporates rapidly, but sufficient concentration
of caustic by such a mechanism to induce stress cracking is considered unlikely.
Available data indicates that caustic concentrations greater than 10,000 ppm, and
probably up to 50,000 ppm, are required to induce caustic stress cracking (40,000 ppm
NaOH is equivalent to 40 grams per liter or 1 mole per liter). The pH of such a solution
is on the order of 14. An alkaline environment is produced and controlled by use of a
solution having some properties of a buffer, that is, one that tends to retard or slow a
reaction or tends to force it in one direction or the other.
Rev. 0
Page 35
CH-02
DOE-HDBK-1015/1-93
Corrosion
Summary
The important information of this chapter is summarized below.
Specialized Corrosion Summary

&
Pitting corrosion occurs where the anodic site becomes fixed in a small area and
the formation of holes in an otherwise unaffected area takes place.
&
Crevice corrosion is a type of pitting corrosion that occurs specifically within

the low flow region of a crevice.
&
Stress corrosion cracking (SCC) is a type of intergranular attack corrosion that

occurs at the grain boundaries under tensile stress.
&
Pitting corrosion requires two conditions to occur, low flow and areas of both
high and low oxygen concentration. When these conditions are met a
differential aeration cell is established which produces an electron flow from the
point of low oxygen concentration to the area of high oxygen concentration.
The difference in oxygen concentration is usually due to a low flow condition.
&
Pitting corrosion is a hazard due to the possible rapid penetration of the metal
with little overall loss of mass. Pitting corrosion is minimized by:
Avoiding stagnant conditions
Using the correct metals and alloys that are less susceptible to the
corrosion
Avoiding agents in the medium that cause pitting
Designing the system and components such that no crevices are present
&
Stress corrosion cracking occurs when three conditions are met; the alloy is
susceptible to stress corrosion cracking, the alloy is exposed to specific
environment, and the alloy is in a stressed condition.
&
Chemisorption is the formation of a monomolecular layer of a compound

between the metal's surface atoms. This layer separates the metal's atoms
thereby weakening the metal and allowing any existing defects to propagate
when a stress is applied.
CH-02
Page 36
Rev. 0
Corrosion
DOE-HDBK-1015/1-93
Specialized Corrosion Summary (Cont.)

&
Stress corrosion cracking (SCC) is a great concern due to the hazard that it can
readily crack metal of appreciable thickness. The crack can lead to a serious
failure of the component, or system, and all the attendant results such as:
Contamination
Loss of coolant
Loss of pressure
&
SCC is prevented in reactor system by:

Proper design
Reducing stress levels
Avoiding stagnant areas and crevices in heat exchangers, where chlorides
and hydroxides might become concentrated.
&
Chloride stress corrosion

The three conditions that must be present for chloride stress corrosion to occur
are:
Chloride ions present
Dissolved oxygen present
Metal under tensile stress
Chloride stress corrosion is controlled by maintaining low chloride ion and
oxygen content in the environment and the use of low carbon steels.
&
Caustic stress corrosion

Caustic stress corrosion is similar to chloride stress corrosion. The metals
involved are mild steels (steel with low carbon and low alloy content). The
metals are exposed to concentrated caustic environments and under tensile stress.
The presence of oxygen is not required for cracking to initiate. Concentration of
greater than 10,000 ppm is required for cracking to initiate. The level may be
higher for different caustic environments.
Rev. 0
Page 37
CH-02
DOE-HDBK-1015/1-93
Corrosion
CH-02
Page 38
Rev. 0
DOE-HDBK-1019/1-93
JANUARY 1993

NUCLEAR PHYSICS
AND REACTOR THEORY
Volume 1 of 2

FSC-6910
Technical Information. P.O. Box 62, Oak Ridge, TN 37831.
DOE-HDBK-1019/1-93
NUCLEAR PHYSICS AND REACTOR THEORY
ABSTRACT
The Nuclear Physics and Reactor Theory Handbook was developed to assist nuclear
facility operating contractors in providing operators, maintenance personnel, and the technical
staff with the necessary fundamentals training to ensure a basic understanding of nuclear physics
and reactor theory. The handbook includes information on atomic and nuclear physics; neutron
characteristics; reactor theory and nuclear parameters; and the theory of reactor operation. This
information will provide personnel with a foundation for understanding the scientific principles
that are associated with various DOE nuclear facility operations and maintenance.
Training Material, Atomic Physics, The Chart of the Nuclides, Radioactivity,

Radioactive Decay, Neutron Interaction, Fission, Reactor Theory, Neutron Characteristics,
Neutron Life Cycle, Reactor Kinetics
Key Words:
Rev. 0
NP
DOE-HDBK-1019/1-93
F OREWOR D
The Departm ent of Energy (DOE) Fundam entals Handbooks consist of ten academic
The DOE Fundam entals Handbooks represent the needs of various DOE nuclear facilities'
The DOE Fundam entals Handbooks have been prepared for the Assistant Secretary for
Rev. 0
NP
DOE-HDBK-1019/1-93
OVERVIEW
The Departm ent of Energy Fundam entals Handbook entitled Nuclear Physics and Reactor
Theory was prepared as an information resource for personnel who are responsible for the
operation of the Department's nuclear facilities. Almost all processes that take place in a nuclear
facility involves the transfer of some type of energy. A basic understanding of nuclear physics
and reactor theory is necessary for DOE nuclear facility operators, maintenance personnel, and
the technical staff to safely operate and maintain the facility and facility support systems. The
information in this handbook is presented to provide a foundation for applying engineering
concepts to the job. This knowledge will help personnel understand the impact that their actions
may have on the safe and reliable operation of facility components and systems.
The Nuclear Physics and Reactor Theory handbook consists of four modules that are
contained in two volumes. The following is a brief description of the information presented in
each module of the handbook.
Volume 1 of 2
Module 1 - Atomic and Nuclear Physics
Introduces concepts of atomic physics including the atomic nature of matter, the
chart of the nuclides, radioactivity and radioactive decay, neutron interactions and
fission, and the interaction of radiation with matter.
Module 2 - Reactor Theory (Nuclear Parameters)
Provides information on reactor theory and neutron characteristics. Includes topics
such as neutron sources, neutron flux, neutron cross sections, reaction rates,
neutron moderation, and prompt and delayed neutrons.
Rev. 0
NP
DOE-HDBK-1019/1-93
OVERVIEW (Cont.)
Volume 2 of 2
Explains the nuclear parameters associated with reactor theory. Topics include the
neutron life cycle, reactivity and reactivity coefficients, neutron poisons, and
control rods.
Module 4 - Reactor Theory (Reactor Operations)
Introduces the reactor operations aspect of reactor theory. Topics include
subcritical multiplication, reactor kinetics, and reactor operation.
The information contained in this handbook is not all-encompassing. An attempt to
present the entire subject of nuclear physics and reactor theory would be impractical. However,
the Nuclear Physics and Reactor Theory handbook presents enough information to provide the
reader with the fundamental knowledge necessary to understand the advanced theoretical concepts
presented in other subject areas, and to understand basic system and equipment operation.
Rev. 0
NP
NUCLEAR PHYSICS
AND REACTOR THEORY
Module 1
Atomic and Nuclear Physics
DOE-HDBK-1019/1-93
TABLE OF CONTENTS
TABLE OF CONTENTS
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vi
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
ATOMIC NATURE OF MATTER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Structure of Matter . . . . . . . . . . . . .
Subatomic Particles . . . . . . . . . . . . .
Bohr Model of the Atom . . . . . . . . .
Measuring Units on the Atomic Scale
Nuclides . . . . . . . . . . . . . . . . . . . . .
Isotopes . . . . . . . . . . . . . . . . . . . . .
Atomic and Nuclear Radii . . . . . . . .
Nuclear Forces . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
CHART OF THE NUCLIDES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Chart of the Nuclides . . . . . . . . .
Information for Stable Nuclides .
Information for Unstable Nuclides
Neutron - Proton Ratios . . . . . . .
Natural Abundance of Isotopes . .
Enriched and Depleted Uranium .
Summary . . . . . . . . . . . . . . . . .
MASS DEFECT AND BINDING ENERGY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
17
Rev. 0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Page i
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
11
11
13
13
14
15
15
16
.
.
.
.
.
.
.
.
.
.
.
.
1
2
3
4
4
6
6
7
9
.
.
.
.
.
.
.
Mass Defect . . . . . . . . . . . .
Binding Energy . . . . . . . . . .
Energy Levels of Atoms . . .
Energy Levels of the Nucleus
Summary . . . . . . . . . . . . . .
...
...
..
...
...
...
...
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
17
18
19
20
21
NP-01
TABLE OF CONTENTS
DOE-HDBK-1019/1-93

MODES OF RADIOACTIVE DECAY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Stability of Nuclei . . . . . . . . . . .
Natural Radioactivity . . . . . . . . .
Nuclear Decay . . . . . . . . . . . . .
Alpha Decay () . . . . . . . . . . . .
Beta Decay () . . . . . . . . . . . . .
Electron Capture (EC, K-capture)
Gamma Emission () . . . . . . . . .
Internal Conversion . . . . . . . . . .
Isomers and Isomeric Transition .
Decay Chains . . . . . . . . . . . . . .
Predicting Type of Decay . . . . . .
Summary . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
22
22
23
24
24
25
26
26
26
27
27
29
RADIOACTIVITY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
30
Radioactive Decay Rates . . . . . . . . . .

Units of Measurement for Radioactivity
Variation of Radioactivity Over Time .
Radioactive Half-Life . . . . . . . . . . . .
Plotting Radioactive Decay . . . . . . . . .
Radioactive Equilibrium . . . . . . . . . . .
Transient Radioactive Equilibrium . . . .
Summary . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
NP-01
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Page ii
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
43
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
NEUTRON INTERACTIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
30
31
31
32
35
38
40
41
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Scattering . . . . . . . .
Elastic Scattering . . .
Inelastic Scattering .
Absorption Reactions
Radiative Capture . .
Particle Ejection . . .
Fission . . . . . . . . . .
Summary . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
22
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
43
43
45
46
46
46
46
47
Rev. 0
DOE-HDBK-1019/1-93
TABLE OF CONTENTS

NUCLEAR FISSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fission . . . . . . . . . . . . . . . . . . . . .
Liquid Drop Model of a Nucleus . .
Critical Energy . . . . . . . . . . . . . . .
Fissile Material . . . . . . . . . . . . . . .
Fissionable Material . . . . . . . . . . . .
Fertile Material . . . . . . . . . . . . . . .
Binding Energy Per Nucleon (BE/A)
Summary . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
48
49
50
50
51
52
53
54
ENERGY RELEASE FROM FISSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
56
Calculation of Fission Energy .

Estimation of Decay Energy . .
Distribution of Fission Energy
Summary . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Rev. 0
.
.
.
.
.
.
.
Page iii
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
63
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
INTERACTION OF RADIATION WITH MATTER . . . . . . . . . . . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
56
60
61
62
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Interaction of Radiation With Matter

Alpha Radiation . . . . . . . . . . . . . .
Beta Minus Radiation . . . . . . . . . .
Positron Radiation . . . . . . . . . . . . .
Neutron Radiation . . . . . . . . . . . . .
Gamma Radiation . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
48
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
63
64
64
65
65
66
67
NP-01
LIST OF FIGURES
DOE-HDBK-1019/1-93
LIST OF FIGURES
Figure 1 Bohr's Model of the Hydrogen Atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Figure 2 Nomenclature for Identifying Nuclides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Figure 3 Nuclide Chart for Atomic Numbers 1 to 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Figure 4 Stable Nuclides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Figure 5 Unstable Nuclides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Figure 6 Neutron - Proton Plot of the Stable Nuclides . . . . . . . . . . . . . . . . . . . . . . . . . 14
Figure 7 Energy Level Diagram - Nickel-60 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Figure 8 Orbital Electron Capture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Figure 9 Types of Radioactive Decay Relative to the Line of Stability . . . . . . . . . . . . . . 28
Figure 10 Radioactive Decay as a Function of Time in Units of Half-Life . . . . . . . . . . . 33
Figure 11 Linear and Semi-Log Plots of Nitrogen-16 Decay . . . . . . . . . . . . . . . . . . . . . 37
Figure 12 Combined Decay of Iron-56, Manganese-54, and Cobalt-60 . . . . . . . . . . . . . . 38
Figure 13 Cumulative Production of Sodium-24 Over Time . . . . . . . . . . . . . . . . . . . . . 39
Figure 14 Approach of Sodium-24 to Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Figure 15 Transient Equilibrium in the Decay of Barium-140 . . . . . . . . . . . . . . . . . . . . 41
Figure 16 Elastic Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Figure 17 Inelastic Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Figure 18 Liquid Drop Model of Fission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Figure 19 Conversion of Fertile Nuclides to Fissile Nuclides . . . . . . . . . . . . . . . . . . . . 52
Figure 20 Binding Energy per Nucleon vs. Mass Number . . . . . . . . . . . . . . . . . . . . . . . 53
Figure 21 Uranium-235 Fission Yield vs. Mass Number . . . . . . . . . . . . . . . . . . . . . . . . 57
Figure 22 Change in Binding Energy for Typical Fission . . . . . . . . . . . . . . . . . . . . . . . 58
NP-01
Page iv
Rev. 0
DOE-HDBK-1019/1-93
LIST OF TABLES
LIST OF TABLES
Table 1 Properties of Subatomic Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Table 2 Calculated Values for Nuclear Radii . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Table 3 Forces Acting in the Nucleus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Table 4 Critical Energies Compared to Binding Energy of Last Neutron . . . . . . . . . . .
51
Table 5 Binding Energies Calculated from Binding Energy per Nucleon Curve . . . . . . .
58
Table 6 Instantaneous Energy from Fission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
61
Table 7 Delayed Energy from Fission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
61
Rev. 0
Page v
NP-01
REFERENCES
DOE-HDBK-1019/1-93
REFERENCES
Foster, Arthur R. and Wright, Robert L. Jr., Basic Nuclear Engineering, 3rd Edition, Allyn
and Bacon, Inc., 1977.
Jacobs, A.M., Kline, D.E., and Remick, F.J., Basic Principles of Nuclear Science and
Reactors, Van Nostrand Company, Inc., 1960.
Kaplan, Irving, Nuclear Physics, 2nd Edition, Addison-Wesley Company, 1962.
Knief, Ronald Allen, Nuclear Energy Technology: Theory and Practice of Commercial
Nuclear Power, McGraw-Hill, 1981.
Lamarsh, John R., Introduction to Nuclear Engineering, Addison-Wesley Company, 1977.
Lamarsh, John R., Introduction to Nuclear Reactor Theory, Addison-Wesley Company,
1972.
General Electric Company, Nuclides and Isotopes: Chart of the Nuclides, 14th Edition,
General Electric Company, 1989.
Academic Program for Nuclear Power Plant Personnel, Volume III, Columbia, MD,
Glasstone, Samuel, Sourcebook on Atomic Energy, Robert F. Krieger Publishing
Company, Inc., 1979.
Glasstone, Samuel and Sesonske, Alexander, Nuclear Reactor Engineering, 3rd Edition,
Van Nostrand Reinhold Company, 1981.
NP-01
Page vi
Rev. 0
DOE-HDBK-1019/1-93
OBJECTIVES
TERMINAL OBJECTIVE
1.0
Given sufficient information, DESCRIB E atoms, including components, structure, and

nomenclature.
ENABLING OBJECTIVES
1.1
STATE the characteristics of the following atomic particles, including mass, charge, and
location within the atom:
a.
b.
c.
Proton
Neutron
Electron
1.2
DESCRIB E the Bohr model of an atom.
1.3
a.
b.
1.4
c.
d.
Atomic number
Mass number
Given the standard AZX notation for a particular nuclide, DETERMINE the following:
a.
b.
c.
1.5
Nuclide
Isotope
Number of protons
Number of neutrons
Number of electrons
DESCRIB E the three forces that act on particles within the nucleus and affect the stability
of the nucleus.
1.6
a.
b.
1.7
a.
b.
1.8
Rev. 0
Enriched uranium
Depleted uranium
Mass defect
Binding energy
Given the atomic mass for a nuclide and the atomic masses of a neutron, proton, and
electron, CALCULATE the mass defect and binding energy of the nuclide.
Page vii
NP-01
OBJECTIVES
DOE-HDBK-1019/1-93
TERMINAL OBJECTIVE
2.0
Given necessary references, DESCRIB E the various modes of radioactive decay.
ENABLING OBJECTIVES
2.1
DESCRIB E the following processes:
a.
b.
c.
Alpha decay
Beta-minus decay
Beta-plus decay
d.
e.
f.
Electron capture
Internal conversions
Isomeric transitions
2.2
Given a Chart of the Nuclides, WRITE the radioactive decay chain for a nuclide.
2.3
EXPLAIN why one or more gamma rays typically accompany particle emission.
2.4
Given the stability curve on the Chart of the Nuclides, DETERMINE the type of
radioactive decay that the nuclides in each region of the chart will typically undergo.
2.5
a.
b.
c.
Radioactivity
Curie
Becquerel
d.
e.
Radioactive decay constant

Radioactive half-life
2.6
Given the number of atoms and either the half-life or decay constant of a nuclide,
CALCULATE the activity.
2.7
Given the initial activity and the decay constant of a nuclide, CALCULATE the activity
at any later time.
2.8
CONVERT between the half-life and decay constant for a nuclide.
2.9
Given the Chart of the Nuclides and the original activity, PLOT the radioactive decay
curve for a nuclide on either linear or semi-log coordinates.
2.10
a.
b.
NP-01
Radioactive equilibrium
Transient radioactive equilibrium
Page viii
Rev. 0
DOE-HDBK-1019/1-93
OBJECTIVES
TERMINAL OBJECTIVE
3.0
Without references, DESCRIB E the different nuclear interactions initiated by neutrons.
ENABLING OBJECTIVES
3.1
DESCRIB E the following scattering interactions between a neutron and a nucleus:
a.
b.
3.2
Elastic scattering
Inelastic scattering
STATE the conservation laws that apply to an elastic collision between a neutron and a
nucleus.
3.3
DESCRIB E the following reactions where a neutron is absorbed in a nucleus:
a.
b.
Rev. 0
Radiative capture
Particle ejection
Page ix
NP-01
OBJECTIVES
DOE-HDBK-1019/1-93
TERMINAL OBJECTIVE
4.0
Without references, DESCRIB E the fission process.
ENABLING OBJECTIVES
4.1
EXPLAIN the fission process using the liquid drop model of a nucleus.
4.2
a.
b.
4.3
Excitation energy
Critical energy
a.
b.
c.
Fissile material
Fissionable material
Fertile material
4.4
DESCRIB E the processes of transmutation, conversion, and breeding.
4.5
DESCRIB E the curve of Binding Energy per Nucleon versus mass number and give a
qualitative description of the reasons for its shape.

4.6
EXPLAIN why only the heaviest nuclei are easily fissioned.
4.7
EXPLAIN why uranium-235 fissions with thermal neutrons and uranium-238 fissions only
with fast neutrons.

4.8
CHARACTERIZE the fission products in terms of mass groupings and radioactivity.
4.9
Given the nuclides involved and their masses, CALCULATE the energy released from
fission.
4.10
Given the curve of Binding Energy per Nucleon versus mass number, CALCULATE the
energy released from fission.
NP-01
Page x
Rev. 0
DOE-HDBK-1019/1-93
OBJECTIVES
TERMINAL OBJECTIVE
5.0
Without references, DESCRIB E how the various types of radiation interact with matter.
ENABLING OBJECTIVES
5.1
DESCRIB E interactions of the following with matter:
a.
b.
5.2
c.
d.
Positron
Neutron
DESCRIB E the following ways that gamma radiation interacts with matter:
a.
b.
c.
Rev. 0
Alpha particle
Beta particle
Compton scattering
Photoelectric effect
Pair production
Page xi
NP-01
OBJECTIVES
DOE-HDBK-1019/1-93
NP-01
Page xii
Rev. 0
DOE-HDBK-1019/1-93
ATOMIC NATURE OF MATTER

All matter is composed of atoms. The atom is the smallest amount of
matter that retains the properties of an element. Atoms themselves are
composed of smaller particles, but these smaller particles no longer have
the same properties as the overall element.
EO 1.1
STATE the characteristics of the following atomic particles,

including mass, charge, and location within the atom:
a.
b.
c.
Proton
Neutron
Electron
EO 1.2
DESCRIBE the Bohr model of an atom.
EO 1.3

a.
b.
EO 1.4
c.
d.
Atomic number
M ass num ber
Given the standard AZ X notation for a particular nuclide,

DETERMINE the following:
a.
b.
c.
EO 1.5
Nuclide
Isotope
Number of protons
Number of neutrons
Number of electrons
DESCRIB E the three forces that act on particles within the nucleus
and affect the stability of the nucleus.
Structure of Matter
Early Greek philosophers speculated that the earth was made up of different combinations of
basic substances, or elements. They considered these basic elements to be earth, air, water, and
fire. Modern science shows that the early Greeks held the correct concept that matter consists
of a combination of basic elements, but they incorrectly identified the elements.
Rev. 0
Page 1
NP-01
DOE-HDBK-1019/1-93
In 1661 the English chemist Robert Boyle published the modern criterion for an element. He
defined an element to be a basic substance that cannot be broken down into any simpler
substance after it is isolated from a compound, but can be combined with other elements to form
compounds. To date, 105 different elements have been confirmed to exist, and researchers claim
to have discovered three additional elements. Of the 105 confirmed elements, 90 exist in nature
and 15 are man-made.
Another basic concept of matter that the Greeks debated was whether matter was continuous or
discrete. That is, whether matter could be continuously divided and subdivided into ever smaller
particles or whether eventually an indivisible particle would be encountered. Democritus in about
450 B.C. argued that substances were ultimately composed of small, indivisible particles that he
labeled atoms. He further suggested that different substances were composed of different atoms
or combinations of atoms, and that one substance could be converted into another by rearranging
the atoms. It was impossible to conclusively prove or disprove this proposal for more than 2000
years.
The modern proof for the atomic nature of matter was first proposed by the English chemist John
Dalton in 1803. Dalton stated that each chemical element possesses a particular kind of atom,
and any quantity of the element is made up of identical atoms of this kind. What distinguishes
one element from another element is the kind of atom of which it consists, and the basic physical
difference between kinds of atoms is their weight.
Subatomic Particles
For almost 100 years after Dalton established the atomic nature of atoms, it was considered
impossible to divide the atom into even smaller parts. All of the results of chemical experiments
during this time indicated that the atom was indivisible. Eventually, experimentation into
electricity and radioactivity indicated that particles of matter smaller than the atom did indeed
exist. In 1906, J. J. Thompson won the Nobel Prize in physics for establishing the existence of
electrons. Electrons are negatively-charged particles that have 1/1835 the mass of the hydrogen
atom. Soon after the discovery of electrons, protons were discovered. Protons are relatively
large particles that have almost the same mass as a hydrogen atom and a positive charge equal
in magnitude (but opposite in sign) to that of the electron. The third subatomic particle to be
discovered, the neutron, was not found until 1932. The neutron has almost the same mass as the
proton, but it is electrically neutral.
NP-01
Page 2
Rev. 0
DOE-HDBK-1019/1-93
Bohr Model of the Atom

The British physicist Ernest Rutherford postulated that the positive charge in an atom is
concentrated in a small region called a nucleus at the center of the atom with electrons existing
in orbits around it. Niels Bohr, coupling Rutherford's postulation with the quantum theory
introduced by Max Planck, proposed that the atom consists of a dense nucleus of protons
surrounded by electrons traveling in discrete orbits at fixed distances from the nucleus. An
electron in one of these orbits or shells has a specific or discrete quantity of energy (quantum).
When an electron moves from one allowed orbit to another allowed orbit, the energy difference
between the two states is emitted or absorbed in the form of a single quantum of radiant energy
called a photon. Figure 1 is Bohr's model of the hydrogen atom showing an electron as having
just dropped from the third shell to the first shell with the emission of a photon that has an
energy = hv . (h = Planck's constant = 6.63 x 10-34 J-s and v = frequency of the photon.) Bohr's
theory was the first to successfully account for the discrete energy levels of this radiation as
measured in the laboratory. Although Bohr's atomic model is designed specifically to explain
the hydrogen atom, his theories apply generally to the structure of all atoms. Additional
information on electron shell theory can be found in the Chemistry Fundamentals Handbook.
Figure 1 Bohr's Model of the Hydrogen Atom
Rev. 0
Page 3
NP-01
DOE-HDBK-1019/1-93
Properties of the three subatomic particles are listed in Table 1.
TABLE 1
Properties of Subatomic Particles
Particle
Location
Charge
Mass
Neutron
Nucleus
none
1.008665 amu
Proton
Nucleus
+1
1.007277 amu
Electron
Shells around nucleus
-1
0.0005486 amu
Measuring Units on the Atomic Scale

The size and mass of atoms are so small that the use of normal measuring units, while possible,
is often inconvenient. Units of measure have been defined for mass and energy on the atomic
scale to make measurements more convenient to express. The unit of measure for mass is the
atomic mass unit (amu). One atomic mass unit is equal to 1.66 x 10-24 grams. The reason for
this particular value for the atomic mass unit will be discussed in a later chapter. Note from
Table 1 that the mass of a neutron and a proton are both about 1 amu. The unit for energy is
the electron volt (eV). The electron volt is the amount of energy acquired by a single electron
when it falls through a potential difference of one volt. One electron volt is equivalent to
1.602 x 10-19 joules or 1.18 x 10-19 foot-pounds.
Nuclides
The total number of protons in the nucleus of an atom is called the atom ic num ber of the atom
and is given the symbol Z. The number of electrons in an electrically-neutral atom is the same
as the number of protons in the nucleus. The number of neutrons in a nucleus is known as the
neutron number and is given the symbol N. The m ass num ber of the nucleus is the total number
of nucleons, that is, protons and neutrons in the nucleus. The mass number is given the symbol
A and can be found by the equation Z + N = A.
Each of the chemical elements has a unique atomic number because the atoms of different
elements contain a different number of protons. The atomic number of an atom identifies the
particular element.
NP-01
Page 4
Rev. 0
DOE-HDBK-1019/1-93
Each type of atom that contains a unique combination of

protons and neutrons is called a nuclide. Not all
combinations of numbers of protons and neutrons are
possible, but about 2500 specific nuclides with unique
combinations of neutrons and protons have been
identified. Each nuclide is denoted by the chemical
symbol of the element with the atomic number written as
a subscript and the mass number written as a superscript,
as shown in Figure 2. Because each element has a
unique name, chemical symbol, and atomic number, only
one of the three is necessary to identify the element. For
this reason nuclides can also be identified by either the
Figure 2 Nomenclature for
chemical name or the chemical symbol followed by the
Identifying Nuclides
mass number (for example, U-235 or uranium-235).
Another common format is to use the abbreviation of the
chemical element with the mass number superscripted (for example, 235U). In this handbook the
format used in the text will usually be the element's name followed by the mass number. In
equations and tables, the format in Figure 2 will usually be used.
Example:
State the name of the element and the number of protons, electrons, and neutrons in the
nuclides listed below.
1
1
Rev. 0
10
5
14
7
114
48
Cd
239
94
Pu
Page 5
NP-01
DOE-HDBK-1019/1-93
Solution:
The name of the element can be found from the Periodic Table (refer to Chemistry
Fundamentals Handbook) or the Chart of the Nuclides (to be discussed later). The
number of protons and electrons are equal to Z. The number of neutrons is equal
to Z - A.
Nuclide
1
1
Element
Protons
Electrons
Neutrons
hydrogen
boron
nitrogen
Cd
cadmium
48
48
66
plutonium
94
94
145
10
5
14
7
114
48
239
94
Pu
Isotopes
Isotopes are nuclides that have the same atomic number and are therefore the same element, but
differ in the number of neutrons. Most elements have a few stable isotopes and several unstable,
radioactive isotopes. For example, oxygen has three stable isotopes that can be found in nature
(oxygen-16, oxygen-17, and oxygen-18) and eight radioactive isotopes. Another example is
hydrogen, which has two stable isotopes (hydrogen-1 and hydrogen-2) and a single radioactive
isotope (hydrogen-3).
The isotopes of hydrogen are unique in that they are each commonly referred to by a unique
name instead of the common chemical element name. Hydrogen-1 is almost always referred to
as hydrogen, but the term protium is infrequently used also. Hydrogen-2 is commonly called
deuterium and symbolized 21D. Hydrogen-3 is commonly called tritium and symbolized 31T. This
text will normally use the symbology 21H and 31H for deuterium and tritium, respectively.
Atomic and Nuclear Radii

The size of an atom is difficult to define exactly due to the fact that the electron cloud, formed
by the electrons moving in their various orbitals, does not have a distinct outer edge. A
reasonable measure of atomic size is given by the average distance of the outermost electron
from the nucleus. Except for a few of the lightest atoms, the average atomic radii are
approximately the same for all atoms, about 2 x 10 -8 cm.
Like the atom the nucleus does not have a sharp outer boundary. Experiments have shown that
the nucleus is shaped like a sphere with a radius that depends on the atomic mass number of the
atom. The relationship between the atomic mass number and the radius of the nucleus is shown
in the following equation.
NP-01
Page 6
Rev. 0
DOE-HDBK-1019/1-93
r = (1.25 x 10 -13 cm) A1/3

where:
r = radius of the nucleus (cm)
A = atomic mass number (dimensionless)
The values of the nuclear radii for some light, intermediate, and heavy nuclides are shown in
Table 2.
TABLE 2
Calculated Values for Nuclear
Radii
Nuclide
1
1
10
5
56
26
Radius of Nucleus
1.25 x 10 -13 cm
2.69 x 10 -13 cm
Fe
4.78 x 10 -13 cm
178
72
Hf
238
92
252
98
7.01 x 10 -13 cm
7.74 x 10 -13 cm
Cf
7.89 x 10 -13 cm
From the table, it is clear that the radius of a typical atom (e.g. 2 x 10 -8 cm) is more than 25,000
times larger than the radius of the largest nucleus.
Nuclear Forces
In the Bohr model of the atom, the nucleus consists of positively-charged protons and electricallyneutral neutrons. Since both protons and neutrons exist in the nucleus, they are both referred to
as nucleons. One problem that the Bohr model of the atom presented was accounting for an
attractive force to overcome the repulsive force between protons.
Two forces present in the nucleus are (1) electrostatic forces between charged particles and (2)
gravitational forces between any two objects that have mass. It is possible to calculate the
magnitude of the gravitational force and electrostatic force based upon principles from classical
physics.
Rev. 0
Page 7
NP-01
DOE-HDBK-1019/1-93
Newton stated that the gravitational force between two bodies is directly proportional to the
masses of the two bodies and inversely proportional to the square of the distance between the
bodies. This relationship is shown in the equation below.
G m1 m2
Fg
r2
where:
Fg
m1
m2
G
r
=
=
=
=
=
gravitational force (newtons)

mass of first body (kilograms)
mass of second body (kilograms)
gravitational constant (6.67 x 10 -11 N-m2/kg2)
distance between particles (meters)
The equation illustrates that the larger the masses of the objects or the smaller the distance
between the objects, the greater the gravitational force. So even though the masses of nucleons
are very small, the fact that the distance between nucleons is extremely short may make the
gravitational force significant. It is necessary to calculate the value for the gravitational force and
compare it to the value for other forces to determine the significance of the gravitational force
in the nucleus. The gravitational force between two protons that are separated by a distance of
10 -20 meters is about 10 -24 newtons.
Coulomb's Law can be used to calculate the force between two protons. The electrostatic force
is directly proportional to the electrical charges of the two particles and inversely proportional
to the square of the distance between the particles. Coulomb's Law is stated as the following
equation.
K Q1 Q2
Fe
r2
where:
Fe
K
Q1
Q2
r
=
=
=
=
=
electrostatic force (newtons)

electrostatic constant (9.0 x 109 N-m2/C2)
charge of first particle (coulombs)
charge of second particle (coulombs)
distance between particles (meters)
Using this equation, the electrostatic force between two protons that are separated by a distance
of 10 -20 meters is about 1012 newtons. Comparing this result with the calculation of the
gravitational force (10-24 newtons) shows that the gravitational force is so small that it can be
neglected.
NP-01
Page 8
Rev. 0
DOE-HDBK-1019/1-93
If only the electrostatic and gravitational forces existed in the nucleus, then it would be
impossible to have stable nuclei composed of protons and neutrons. The gravitational forces are
much too small to hold the nucleons together compared to the electrostatic forces repelling the
protons. Since stable atoms of neutrons and protons do exist, there must be another attractive
force acting within the nucleus. This force is called the nuclear force.
The nuclear force is a strong attractive force that is independent of charge. It acts equally only
between pairs of neutrons, pairs of protons, or a neutron and a proton. The nuclear force has a
very short range; it acts only over distances approximately equal to the diameter of the nucleus
(10 -13 cm). The attractive nuclear force between all nucleons drops off with distance much faster
than the repulsive electrostatic force between protons.
TABLE 3
Forces Acting in the Nucleus
Force
Interaction
Range
Gravitational
Very weak attractive force

between all nucleons
Relatively long
Electrostatic
Strong repulsive force between

like charged particles (protons)
Relatively long
Nuclear Force
Strong attractive force between

all nucleons
Extremely short
In stable atoms, the attractive and repulsive forces in the nucleus balance. If the forces do not
balance, the atom cannot be stable, and the nucleus will emit radiation in an attempt to achieve
a more stable configuration.
Summary
The important information in this chapter is summarized on the following page.
Rev. 0
Page 9
NP-01
DOE-HDBK-1019/1-93
Atomic Nature of Matter Summary

Atoms consist of three basic subatomic particles. These particles are the proton, the
neutron, and the electron.
Protons are particles that have a positive charge, have about the same mass as a
hydrogen atom, and exist in the nucleus of an atom.
Neutrons are particles that have no electrical charge, have about the same mass as a
hydrogen atom, and exist in the nucleus of an atom.
Electrons are particles that have a negative charge, have a mass about eighteen
hundred times smaller than the mass of a hydrogen atom, and exist in orbital shells
around the nucleus of an atom.
The Bohr model of the atom consists of a dense nucleus of protons and neutrons
(nucleons) surrounded by electrons traveling in discrete orbits at fixed distances
from the nucleus.
Nuclides are atoms that contain a particular number of protons and neutrons.
Isotopes are nuclides that have the same atomic number and are therefore the same
element, but differ in the number of neutrons.
The atomic number of an atom is the number of protons in the nucleus.
The mass number of an atom is the total number of nucleons (protons and neutrons) in
the nucleus.
The notation AZX is used to identify a specific nuclide. "Z" represents the atomic
number, which is equal to the number of protons. "A" represents the mass
number, which is equal to the number of nucleons. "X" represents the chemical
symbol of the element.
Number of protons = Z
Number of electrons = Z
Number of neutrons = A - Z
The stability of a nucleus is determined by the different forces interacting within
it. The electrostatic force is a relatively long-range, strong, repulsive force that
acts between the positively charged protons. The nuclear force is a relatively
short-range attractive force between all nucleons. The gravitational force the
long range, relatively weak attraction between masses, is negligible compared to
the other forces.
NP-01
Page 10
Rev. 0
DOE-HDBK-1019/1-93
CHART OF THE NUCLIDES

The Chart of the Nuclides, like the Periodic Table, is a convenient format
for presenting a large amount of scientific information in an organized
manner.
EO 1.6

a.
b.
Enriched uranium
Depleted uranium
Chart of the Nuclides

A tabulated chart called the Chart of the Nuclides lists the stable and unstable nuclides in addition
to pertinent information about each one. Figure 3 shows a small portion of a typical chart. This
chart plots a box for each individual nuclide, with the number of protons (Z) on the vertical axis
and the number of neutrons (N = A - Z) on the horizontal axis.
The completely gray squares indicate stable isotopes. Those in white squares are artificially
radioactive, meaning that they are produced by artificial techniques and do not occur naturally.
By consulting a complete chart, other types of isotopes can be found, such as naturally occurring
radioactive types (but none are found in the region of the chart that is illustrated in Figure 3).
Located in the box on the far left of each horizontal row is general information about the
element. The box contains the chemical symbol of the element in addition to the average atomic
weight of the naturally occurring substance and the average thermal neutron absorption cross
section, which will be discussed in a later module. The known isotopes (elements with the same
atomic number Z but different mass number A) of each element are listed to the right.
Rev. 0
Page 11
NP-01
DOE-HDBK-1019/1-93
Page 12
Rev. 0
Figure 3 Nuclide Chart for Atomic Numbers 1 to 6
NP-01
DOE-HDBK-1019/1-93
Information for Stable Nuclides

For the stable isotopes, in addition to the symbol and the atomic mass number, the number
percentage of each isotope in the naturally occurring element is listed, as well as the thermal
neutron activation cross section and the mass in atomic mass units (amu). A typical block for
a stable nuclide from the Chart of the Nuclides is shown in Figure 4.
Figure 4 Stable Nuclides
Information for Unstable Nuclides

For unstable isotopes the additional information includes the half life, the mode of decay (for
example, -, ), the total disintegration energy in MeV (million electron volts), and the mass in
amu when available. A typical block for an unstable nuclide from the Chart of the Nuclides is
shown in Figure 5.
Figure 5 Unstable Nuclides
Rev. 0
Page 13
NP-01
DOE-HDBK-1019/1-93
Neutron - Proton Ratios

Figure 6 shows the distribution of the stable nuclides plotted on the same axes as the Chart of
the Nuclides. As the mass numbers become higher, the ratio of neutrons to protons in the
nucleus becomes larger. For helium-4 (2 protons and 2 neutrons) and oxygen-16 (8 protons and
8 neutrons) this ratio is unity. For indium-115 (49 protons and 66 neutrons) the ratio of neutrons
to protons has increased to 1.35, and for uranium-238 (92 protons and 146 neutrons) the neutronto-proton ratio is 1.59.
Figure 6 Neutron - Proton Plot of the Stable Nuclides
If a heavy nucleus were to split into two fragments, each fragment would form a nucleus that
would have approximately the same neutron-to-proton ratio as the heavy nucleus. This high
neutron-to-proton ratio places the fragments below and to the right of the stability curve
displayed by Figure 6. The instability caused by this excess of neutrons is generally rectified
by successive beta emissions, each of which converts a neutron to a proton and moves the
nucleus toward a more stable neutron-to-proton ratio.
NP-01
Page 14
Rev. 0
DOE-HDBK-1019/1-93
Natural Abundance of Isotopes

The relative abundance of an isotope in nature compared to other isotopes of the same element
is relatively constant. The Chart of the Nuclides presents the relative abundance of the naturally
occurring isotopes of an element in units of atom percent. Atom percent is the percentage of
the atoms of an element that are of a particular isotope. Atom percent is abbreviated as a/o.
For example, if a cup of water contains 8.23 x 1024 atoms of oxygen, and the isotopic abundance
of oxygen-18 is 0.20%, then there are 1.65 x 1022 atoms of oxygen-18 in the cup.
The atomic weight for an element is defined as the average atomic weight of the isotopes of the
element. The atomic weight for an element can be calculated by summing the products of the
isotopic abundance of the isotope with the atomic mass of the isotope.
Example:
Calculate the atomic weight for the element lithium. Lithium-6 has an atom percent
abundance of 7.5% and an atomic mass of 6.015122 amu. Lithium-7 has an atomic
abundance of 92.5% and an atomic mass of 7.016003 amu.
Solution:
The other common measurement of isotopic abundance is weight percent (w/o). Weight percent
is the percent weight of an element that is a particular isotope. For example, if a sample of
material contained 100 kg of uranium that was 28 w/o uranium-235, then 28 kg of uranium-235
was present in the sample.
Enriched and Depleted Uranium

Natural uranium mined from the earth contains the isotopes uranium-238, uranium-235 and
uranium-234. The majority (99.2745%) of all the atoms in natural uranium are uranium-238.
Most of the remaining atoms (0.72%) are uranium-235, and a slight trace (0.0055%) are
uranium-234. Although all isotopes of uranium have similar chemical properties, each of the
isotopes has significantly different nuclear properties. For reasons that will be discussed in later
modules, the isotope uranium-235 is usually the desired material for use in reactors.
A vast amount of equipment and energy are expended in processes that separate the isotopes of
uranium (and other elements). The details of these processes are beyond the scope of this
module. These processes are called enrichment processes because they selectively increase the
proportion of a particular isotope. The enrichment process typically starts with feed material
that has the proportion of isotopes that occur naturally. The process results in two types of
Rev. 0
Page 15
NP-01
DOE-HDBK-1019/1-93
In the case of uranium, the natural uranium ore is 0.72 a/o uranium-235. The desired outcome
of the enrichment process is to produce enriched uranium. Enriched uranium is defined as
uranium in which the isotope uranium-235 has a concentration greater than its natural value. The
enrichment process will also result in the byproduct of depleted uranium. Depleted uranium is
defined as uranium in which the isotope uranium-235 has a concentration less than its natural
value. Although depleted uranium is referred to as a by-product of the enrichment process, it
does have uses in the nuclear field and in commercial and defense industries.
Summary
Chart of the Nuclides Summary

Enriched uranium is uranium in which the isotope uranium-235 has a
concentration greater than its natural value of 0.7%.
Depleted uranium is uranium in which the isotope uranium-235 has a
concentration less than its natural value of 0.7%.
NP-01
Page 16
Rev. 0
DOE-HDBK-1019/1-93
MASS DEFECT AND BINDING ENERGY

The separate laws of Conservation of Mass and Conservation of Energy are not
applied strictly on the nuclear level. It is possible to convert between mass and
energy. Instead of two separate conservation laws, a single conservation law
states that the sum of mass and energy is conserved. Mass does not magically
appear and disappear at random. A decrease in mass will be accompanied by a
corresponding increase in energy and vice versa.
EO 1.7

a.
b.
EO 1.8
M ass defect
Binding energy
Given the atomic mass for a nuclide and the atomic masses of
a neutron, proton, and electron, CALCULATE the mass defect
and binding energy of the nuclide.
Mass Defect
Careful measurements have shown that the mass of a particular atom is always slightly less than
the sum of the masses of the individual neutrons, protons, and electrons of which the atom
consists. The difference between the mass of the atom and the sum of the masses of its parts is
called the mass defect (m). The mass defect can be calculated using Equation (1-1). In
calculating the mass defect it is important to use the full accuracy of mass measurements because
the difference in mass is small compared to the mass of the atom. Rounding off the masses of
atoms and particles to three or four significant digits prior to the calculation will result in a
calculated mass defect of zero.
m = [ Z(mp + me) + (A-Z)mn ] - matom
(1-1)
where:
m
mp
mn
me
matom
Z
A
Rev. 0
=
=
=
=
=
=
=
mass defect (amu)

mass of a proton (1.007277 amu)
mass of a neutron (1.008665 amu)
mass of an electron (0.000548597 amu)
mass of nuclide AZX (amu)
atomic number (number of protons)
mass number (number of nucleons)
Page 17
NP-01
DOE-HDBK-1019/1-93
Example:
Calculate the mass defect for lithium-7. The mass of lithium-7 is 7.016003 amu.
Solution:
m
Z mp
3 1.007826 amu
0.0421335 amu
me
Z mn
7
matom
3 1.008665 amu
7.016003 amu
Binding Energy
The loss in mass, or mass defect, is due to the conversion of mass to binding energy when the
nucleus is formed. Binding energy is defined as the amount of energy that must be supplied to
a nucleus to completely separate its nuclear particles (nucleons). It can also be understood as
the amount of energy that would be released if the nucleus was formed from the separate
particles. Binding energy is the energy equivalent of the mass defect. Since the mass defect
was converted to binding energy (BE) when the nucleus was formed, it is possible to calculate
the binding energy using a conversion factor derived by the mass-energy relationship from
Einstein's Theory of Relativity.
Einstein's famous equation relating mass and energy is E = mc2 where c is the velocity of light
(c = 2.998 x 108 m/sec). The energy equivalent of 1 amu can be determined by inserting this
quantity of mass into Einstein's equation and applying conversion factors.
m c2
1 amu
1.6606 x 10 27 kg
1 amu
1.4924 x 10 10 J
2.998 x 108
m
sec
1 N
kg m
1
sec2
1 J
1 N m
1 MeV
1.6022 x 10 13 J
931.5 MeV
Conversion Factors:
1
1
1
1
NP-01
amu
newton
joule
MeV
=
=
=
=
1.6606 x 10 -27 kg
1 kg-m/sec2
1 newton-meter
1.6022 x 10-13 joules
Page 18
Rev. 0
DOE-HDBK-1019/1-93
Since 1 amu is equivalent to 931.5 MeV of energy, the binding energy can be calculated using
Equation (1-2).
B.E.
m 931.5 MeV
1 amu
(1-2)
Example:
Calculate the mass defect and binding energy for uranium-235. One uranium-235 atom
has a mass of 235.043924 amu.
Solution:
Step 1: Calculate the mass defect using Equation (1-1).
m
Z mp
Z mn
92 1.007826 amu
235
1.91517 amu
me
matom
92 1.008665 amu
235.043924 amu
Step 2: Use the mass defect and Equation (1-2) to calculate the binding energy.
B.E.
931.5 MeV
1 amu
1.91517 amu 931.5 MeV

1 amu
1784 MeV
Energy Levels of Atoms

The electrons that circle the nucleus move in fairly well-defined orbits. Some of these electrons
are more tightly bound in the atom than others. For example, only 7.38 eV is required to
remove the outermost electron from a lead atom, while 88,000 eV is required to remove the
innermost electron. The process of removing an electron from an atom is called ionization, and
the energy required to remove the electron is called the ionization energy.
In a neutral atom (number of electrons = Z) it is possible for the electrons to be in a variety of
different orbits, each with a different energy level. The state of lowest energy is the one in which
the atom is normally found and is called the ground state. When the atom possesses more energy
than its ground state energy, it is said to be in an excited state.
Rev. 0
Page 19
NP-01
DOE-HDBK-1019/1-93
An atom cannot stay in the excited state for an indefinite period of time. An excited atom will
eventually transition to either a lower-energy excited state, or directly to its ground state, by
emitting a discrete bundle of electromagnetic energy called an x-ray. The energy of the x-ray
will be equal to the difference between the energy levels of the atom and will typically range
from several eV to 100,000 eV in magnitude.
Energy Levels of the Nucleus

The nucleons in the nucleus of an atom, like the electrons that circle the nucleus, exist in shells
that correspond to energy states. The energy shells of the nucleus are less defined and less
understood than those of the electrons. There is a state of lowest energy (the ground state) and
discrete possible excited states for a nucleus. Where the discrete energy states for the electrons
of an atom are measured in eV or keV, the energy levels of the nucleus are considerably greater
and typically measured in MeV.
A nucleus that is in the excited state will not remain at that energy level for an indefinite period.
Like the electrons in an excited atom, the nucleons in an excited nucleus will transition towards
their lowest energy configuration and in doing so emit a discrete bundle of electromagnetic
radiation called a gamma ray (-ray). The only differences between x-rays and -rays are their
energy levels and whether they are emitted from the electron shell or from the nucleus.
The ground state and the excited states of
a nucleus can be depicted in a nuclear
energy-level diagram.
The nuclear
energy-level diagram consists of a stack of
horizontal bars, one bar for each of the
excited states of the nucleus. The vertical
distance between the bar representing an
excited state and the bar representing the
ground state is proportional to the energy
level of the excited state with respect to
the ground state. This difference in
energy between the ground state and the
excited state is called the excitation energy
of the excited state. The ground state of
a nuclide has zero excitation energy. The
bars for the excited states are labeled with
their respective energy levels. Figure 7 is
the energy level diagram for nickel-60.
Figure 7
NP-01
Page 20
Energy Level Diagram - Nickel-60
Rev. 0
DOE-HDBK-1019/1-93
Summary
Mass Defect and Binding Energy Summary

Mass defect is the difference between the mass of the atom and the sum of the
masses of its constituent parts.
Binding energy is the amount of energy that must be supplied to a nucleus to
completely separate its nuclear particles. Binding energy is the energy equivalent
of the mass defect.
Mass defect can be calculated by using the equation below.

m = [ Z(mp + me) + (A-Z)mn ] - matom
Binding energy can be calculated by multiplying the mass defect by the factor
of 931.5 MeV per amu.
Rev. 0
Page 21
NP-01
MODES OF RADIOACTIVE DECAY
DOE-HDBK-1019/1-93

Most atoms found in nature are stable and do not emit particles or energy that
change form over time. Some atoms, however, do not have stable nuclei. These
atoms emit radiation in order to achieve a more stable configuration.
EO 2.1
DESCRIBE the following processes:

a.
b.
c.
Alpha decay
Beta-m inus decay
Beta-plus decay
d.
e.
f.
Electron capture
Internal conversions
Isomeric transitions
EO 2.2
Given a Chart of the Nuclides, W RITE the radioactive decay

chain for a nuclide.
EO 2.3
EXPLAIN why one or more gamma rays typically accompany

particle em ission.
EO 2.4
Given the stability curve on the Chart of the Nuclides,

DETERM INE the type of radioactive decay that the nuclides in
each region of the chart will typically undergo.
Stability of Nuclei
As mass numbers become larger, the ratio of neutrons to protons in the nucleus becomes larger
for the stable nuclei. Non-stable nuclei may have an excess or deficiency of neutrons and
undergo a transformation process known as beta () decay. Non-stable nuclei can also undergo
a variety of other processes such as alpha () or neutron (n) decay. As a result of these decay
processes, the final nucleus is in a more stable or more tightly bound configuration.
Natural Radioactivity
In 1896, the French physicist Becquerel discovered that crystals of a uranium salt emitted rays
that were similar to x-rays in that they were highly penetrating, could affect a photographic
plate, and induced electrical conductivity in gases. Becquerel's discovery was followed in 1898
by the identification of two other radioactive elements, polonium and radium, by Pierre and
Marie Curie.
NP-01
Page 22
Rev. 0
DOE-HDBK-1019/1-93
Heavy elements, such as uranium or thorium, and their unstable decay chain elements emit
radiation in their naturally occurring state. Uranium and thorium, present since their creation
at the beginning of geological time, have an extremely slow rate of decay. All naturally
occurring nuclides with atomic numbers greater than 82 are radioactive.
Nuclear Decay
Whenever a nucleus can attain a more stable (i.e., more tightly bound) configuration by emitting
radiation, a spontaneous disintegration process known as radioactive decay or nuclear decay may
occur. In practice, this "radiation" may be electromagnetic radiation, particles, or both.
Detailed studies of radioactive decay and nuclear reaction processes have led to the formulation
of useful conservation principles. The four principles of most interest in this module are
discussed below.
Conservation of electric charge implies that charges are neither created nor destroyed. Single
positive and negative charges may, however, neutralize each other. It is also possible for a
neutral particle to produce one charge of each sign.
Conservation of mass number does not allow a net change in the number of nucleons. However,
the conversion of a proton to a neutron and vice versa is allowed.

Conservation of mass and energy implies that the total of the kinetic energy and the energy
equivalent of the mass in a system must be conserved in all decays and reactions. Mass can be
converted to energy and energy can be converted to mass, but the sum of mass and energy must
be constant.
Conservation of momentum is responsible for the distribution of the available kinetic energy
among product nuclei, particles, and/or radiation. The total amount is the same before and after
the reaction even though it may be distributed differently among entirely different nuclides
and/or particles.
Rev. 0
Page 23
NP-01
DOE-HDBK-1019/1-93
Alpha Decay ()

Alpha decay is the emission of alpha particles (helium nuclei) which may be represented as either
4
4
2He or 2 . When an unstable nucleus ejects an alpha particle, the atomic number is reduced by 2
and the mass number decreased by 4. An example is uranium-234 which decays by the ejection
of an alpha particle accompanied by the emission of a 0.068 MeV gamma.

The combined kinetic energy of the daughter nucleus (Thorium-230) and the particle is designated
as KE. The sum of the KE and the gamma energy is equal to the difference in mass between the
original nucleus (Uranium-234) and the final particles (equivalent to the binding energy released,
since m = BE). The alpha particle will carry off as much as 98% of the kinetic energy and, in most
cases, can be considered to carry off all the kinetic energy.
Beta Decay ()

Beta decay is the emission of electrons of nuclear rather than orbital origin. These particles are
electrons that have been expelled by excited nuclei and may have a charge of either sign.
If both energy and momentum are to be conserved, a third type of particle, the neutrino, , must be
involved. The neutrino is associated with positive electron emission, and its antiparticle, the
antineutrino, , is emitted with a negative electron. These uncharged particles have only the
weakest interaction with matter, no mass, and travel at the speed of light. For all practical purposes,
they pass through all materials with so few interactions that the energy they possess cannot be
recovered. The neutrinos and antineutrinos are included here only because they carry a portion of
the kinetic energy that would otherwise belong to the beta particle, and therefore, must be considered
for energy and momentum to be conserved. They are normally ignored since they are not significant
in the context of nuclear reactor applications.
Negative electron emission, represented as -10e, -10, or simply as e- or -, effectively converts a neutron
to a proton, thus increasing the atomic number by one and leaving the mass number unchanged.
This is a common mode of decay for nuclei with an excess of neutrons, such as fission fragments
below and to the right of the neutron-proton stability curve (refer to Figure 6). An example of a
typical beta minus-decay reaction is shown below.
NP-01

Page 24
Rev. 0
DOE-HDBK-1019/1-93
Positively charged electrons (beta-plus) are known as positrons. Except for sign, they are nearly
identical to their negatively charged cousins. When a positron, represented as +10e, +10, or simply as
e+ or +, is ejected from the nucleus, the atomic number is decreased by one and the mass number
remains unchanged. A proton has been converted to a neutron. An example of a typical positron
(beta-plus) decay is shown below.

Electron Capture (EC, K-capture)

Nuclei having an excess of protons may capture an electron from one of the inner orbits which
immediately combines with a proton in the nucleus to form a neutron. This process is called electron
capture (EC). The electron is normally captured from the innermost orbit (the K-shell), and,
consequently, this process is sometimes called K-capture. The following example depicts electron
capture.
A neutrino is formed at the same

time that the neutron is formed, and
energy carried off by it serves to
conserve momentum. Any energy
that is available due to the atomic
mass of the product being
appreciably less than that of the
parent will appear as gamma
radiation. Also, there will always
be characteristic x-rays given off
when an electron from one of the
higher energy shells moves in to fill
the vacancy in the K-shell.
Electron capture is shown
graphically in Figure 8.
Electron capture and positron
emission result in the production of
Figure 9 Orbital Electron Capture
the same daughter product, and
they exist as competing processes.
For positron emission to occur, however, the mass of the daughter product must be less than the
mass of the parent by an amount equal to at least twice the mass of an electron. This mass difference
between the parent and daughter is necessary to account for two items present in the parent but not
in the daughter. One item is the positron ejected from the nucleus of the parent. The other item is
that the daughter product has one less orbital electron than the parent. If this requirement is not met,
then orbital electron capture takes place exclusively.
Rev. 0
Page 25
NP-01
DOE-HDBK-1019/1-93
Gamma Emission ()
Gamma radiation is a high-energy electromagnetic radiation that originates in the nucleus. It is
emitted in the form of photons, discrete bundles of energy that have both wave and particle
properties. Often a daughter nuclide is left in an excited state after a radioactive parent nucleus
undergoes a transformation by alpha decay, beta decay, or electron capture. The nucleus will drop
to the ground state by the emission of gamma radiation.
Internal Conversion
The usual method for an excited nucleus to go from the excited state to the ground state is by
emission of gamma radiation. However, in some cases the gamma ray (photon) emerges from the
nucleus only to interact with one of the innermost orbital electrons and, as a result, the energy of the
photon is transferred to the electron. The gamma ray is then said to have undergone internal
conversion. The conversion electron is ejected from the atom with kinetic energy equal to the
gamma energy minus the binding energy of the orbital electron. An orbital electron then drops to
a lower energy state to fill the vacancy, and this is accompanied by the emission of characteristic
x-rays.
Isomers and Isomeric Transition

Isomeric transition commonly occurs immediately after particle emission; however, the nucleus may
remain in an excited state for a measurable period of time before dropping to the ground state at its
own characteristic rate. A nucleus that remains in such an excited state is known as a nuclear isomer
because it differs in energy and behavior from other nuclei with the same atomic number and mass
number. The decay of an excited nuclear isomer to a lower energy level is called an isomeric
transition. It is also possible for the excited isomer to decay by some alternate means, for example,
by beta emission.
An example of gamma emission accompanying particle emission is illustrated by the decay of
nitrogen-16 below.

NP-01

Page 26
Rev. 0
DOE-HDBK-1019/1-93
Decay Chains
When an unstable nucleus decays, the resulting daughter nucleus is not necessarily stable. The
nucleus resulting from the decay of a parent is often itself unstable, and will undergo an additional
decay. This is especially common among the larger nuclides.
It is possible to trace the steps of an unstable atom as it goes through multiple decays trying to
achieve stability. The list of the original unstable nuclide, the nuclides that are involved as
intermediate steps in the decay, and the final stable nuclide is known as the decay chain. One
common method for stating the decay chain is to state each of the nuclides involved in the standard
A
ZX format. Arrows are used between nuclides to indicate where decays occur, with the type of decay
indicated above the arrow and the half-life below the arrow. The half-life for decay will be
discussed in the next chapter.
Example:
Write the decay chains for rubidium-91 and actinium-215. Continue the chains until a stable
nuclide or a nuclide with a half-life greater than 1 x 106 years is reached.
Solution:

Predicting Type of Decay

Radioactive nuclides tend to decay in a way that results in a daughter nuclide that lies closer to the
line of stability. Due to this, it is possible to predict the type of decay that a nuclide will undergo
based on its location relative to the line of stability on the Chart of the Nuclides.
Figure 9 illustrates the type of decay nuclides in different regions of the chart will typically undergo.
Nuclides that are below and to the right of the line of stability will usually undergo - decay.
Nuclides that are above and to the left of the line of stability will usually undergo either + decay or
electron capture. Most nuclides that will undergo decay are found in the upper right hand region
of the chart. These are general rules that have many exceptions, especially in the region of the heavy
nuclides.
Rev. 0
Page 27
NP-01
Figure 9
NP-01
DOE-HDBK-1019/1-93
Types of Radioactive Decay Relative to the Line of Stability
Page 28
Rev. 0
DOE-HDBK-1019/1-93
Summary
M odes of Radioactive Decay Summary

Alpha decay is the emission of an alpha particle (2 protons and 2 neutrons) from
an unstable nucleus. The daughter nuclide has an atomic number 2 less than the
parent nuclide and a mass number 4 less than the parent nuclide. The daughter
nucleus commonly releases its excitation energy by gamma emission.
Beta-minus decay effectively converts a neutron to a proton and an electron,
which is immediately ejected from the nucleus. The daughter nuclide has its
atomic number increased by 1 and the same mass number compared to the
parent.
Beta-plus decay effectively converts a proton to a neutron and a positron, which
is immediately ejected from the nucleus. The daughter nuclide has its atomic
number decreased by 1 and the same mass number compared to the parent.
In electron capture, the nucleus absorbs an electron from the innermost orbit.
This electron combines with a proton to form a neutron.
Internal conversion occurs when a gamma ray, emitted by the nucleus as it goes
from the excited state to the ground state, interacts with one of the innermost
electrons of the same atom. The electron is ejected from the atom.
An isomeric transition is the decay of an excited nucleus to a lower-energy level
by the emission of a gamma ray.
Decay chains can be found by tracing the steps an unstable atom goes through
as it tries to achieve stability.
Many modes of radioactive decay result in a daughter nuclide that has an energy
level above the ground state. This excitation energy is usually released
immediately in the form of a gamma ray.
The type of decay that a nuclide will typically undergo can be determined by its
relationship to the line of stability on the Chart of the Nuclides. Nuclides that
lie below and to the right of the line of stability will typically beta minus decay.
Nuclides above and to the left of the line will typically either beta plus decay or
electron capture. Most alpha emitters are found in the upper, right-hand corner
of the chart.
Rev. 0
Page 29
NP-01
RADIOACTIVITY
DOE-HDBK-1019/1-93
RADIOACTIVITY
The rate at which a sample of radioactive material decays is not constant. As
individual atoms of the material decay, there are fewer of those types of atoms
remaining. Since the rate of decay is directly proportional to the number of
atoms, the rate of decay will decrease as the number of atoms decreases.
EO 2.5

a.
b.
c.
Radioactivity
Curie
Becquerel
d.
e.
Radioactive decay constant

Radioactive half-life
EO 2.6
Given the num ber of atoms and either the half-life or decay
constant of a nuclide, CALCULATE the activity.
EO 2.7
Given the initial activity and the decay constant of a nuclide,

CALCULATE the activity at any later time.
EO 2.8
CONVERT between the half-life and decay constant for a

nuclide.
EO 2.9
Given the Chart of the Nuclides and the original activity, PLOT
the radioactive decay curve for a nuclide on either linear or
sem i-log coordinates.
EO 2.10

a.
b.
Radioactive equilibrium
Transient radioactive equilibrium
Radioactive Decay Rates

Radioactivity is the property of certain nuclides of spontaneously emitting particles or gamma
radiation. The decay of radioactive nuclides occurs in a random manner, and the precise time
at which a single nucleus will decay cannot be determined. However, the average behavior of
a very large sample can be predicted accurately by using statistical methods. These studies have
revealed that there is a certain probability that in a given time interval a certain fraction of the
nuclei within a sample of a particular nuclide will decay. This probability per unit time that an
atom of a nuclide will decay is known as the radioactive decay constant, . The units for the
decay constant are inverse time such as 1/second, 1/minute, 1/hour, or 1/year. These decay
constant units can also be expressed as second-1, minute-1, hour-1, and year-1.
NP-01
Page 30
Rev. 0
DOE-HDBK-1019/1-93
RADIOACTIVITY
The activity (A) of a sample is the rate of decay of that sample. This rate of decay is usually
measured in the number of disintegrations that occur per second. For a sample containing
millions of atoms, the activity is the product of the decay constant and the number of atoms
present in the sample.
The relationship between the activity, number of atoms, and decay constant is shown in
Equation (1-3).
A = N
(1-3)
where:
A = Activity of the nuclide (disintegrations/second)
= decay constant of the nuclide (second-1)
N = Number of atoms of the nuclide in the sample
Since is a constant, the activity and the number of atoms are always proportional.
Units of Measurement for Radioactivity

Two common units to measure the activity of a substance are the curie (Ci) and becquerel (Bq).
A curie is a unit of measure of the rate of radioactive decay equal to 3.7 x 1010 disintegrations
per second. This is approximately equivalent to the number of disintegrations that one gram of
radium-226 will undergo in one second. A becquerel is a more fundamental unit of measure of
radioactive decay that is equal to 1 disintegration per second. Currently, the curie is more
widely used in the United States, but usage of the becquerel can be expected to broaden as the
metric system slowly comes into wider use. The conversion between curies and becquerels is
shown below.
1 curie = 3.7 x 10 10 becquerels
Variation of Radioactivity Over Time

The rate at which a given radionuclide sample decays is stated in Equation (1-3) as being equal
to the product of the number of atoms and the decay constant. From this basic relationship it
is possible to use calculus to derive an expression which can be used to calculate how the
number of atoms present will change over time. The derivation is beyond the scope of this text,
but Equation (1-4) is the useful result.

(1-4)
where:
N
No

t
Rev. 0
=
=
=
=
number of atoms present at time t

number of atoms initially present
decay constant (time-1)
time
Page 31
NP-01
RADIOACTIVITY
DOE-HDBK-1019/1-93
Since the activity and the number of atoms are always proportional, they may be used
interchangeably to describe any given radionuclide population. Therefore, the following is true.
A
Ao e
A
Ao
=
=
=
=
(1-5)
where:
activity present at time t

activity initially present
decay constant (time-1)
time
Radioactive Half-Life
One of the most useful terms for estimating how quickly a nuclide will decay is the radioactive
half-life. The radioactive half-life is defined as the amount of time required for the activity to
decrease to one-half of its original value. A relationship between the half-life and decay constant
can be developed from Equation (1-5). The half-life can be calculated by solving Equation (1-5)
for the time, t, when the current activity, A, equals one-half the initial activity Ao.
First, solve Equation (1-5) for t.
A
A
Ao
ln
A
Ao
Ao e
e
ln
t
A
Ao
If A is equal to one-half of Ao, then A/Ao is equal to one-half. Substituting this in the equation
above yields an expression for t1/2.
1
ln
2
t 1/2
(1-6)
t 1/2
NP-01
ln 2
0.693
Page 32
Rev. 0
DOE-HDBK-1019/1-93
RADIOACTIVITY
The basic features of decay of a radionuclide sample are shown by the graph in Figure 10.
Figure 10 Radioactive Decay as a Function of Time in Units of Half-Life
Assuming an initial number of atoms No, the population, and consequently, the activity may be
noted to decrease by one-half of this value in a time of one half-life. Additional decreases occur
so that whenever one half-life elapses, the number of atoms drops to one-half of what its value
was at the beginning of that time interval. After five half-lives have elapsed, only 1/32, or
3.1%, of the original number of atoms remains. After seven half-lives, only 1/128, or 0.78%,
of the atoms remains. The number of atoms existing after 5 to 7 half-lives can usually be
assumed to be negligible. The Chemistry Fundamentals Handbook contains additional
information on calculating the number of atoms contained within a sample.
Rev. 0
Page 33
NP-01
RADIOACTIVITY
DOE-HDBK-1019/1-93
Example:
A sample of material contains 20 micrograms of californium-252.
Californium-252 has a half-life of 2.638 years.
Calculate:
(a)
(b)
(c)
(d)
The number of californium-252 atoms initially present

The activity of the californium-252 in curies
The number of californium-252 atoms that will remain in 12 years
The time it will take for the activity to reach 0.001 curies
Solution:
(a)
The number of atoms of californium-252 can be determined as below.

(b)
First, use Equation (1-6) to calculate the decay constant.
Use this value for the decay constant in Equation (1-3) to determine the activity.
NP-01
Page 34
Rev. 0
(c)
DOE-HDBK-1019/1-93
RADIOACTIVITY
The number of californium atoms that will remain in 12 years can be calculated
from Equation (1-4).
N
No e
4.78 x 1016 e
(0.263/yr) (12 yr)
2.04 x 1015
(d)
The time that it will take for the activity to reach 0.001 Ci can be determined
from Equation (1-5). First, solve Equation (1-5) for time.
A
A
Ao
ln
Ao e
e
A
Ao
ln
t
A
Ao
Inserting the appropriate values in the right side of this equation will result in the
required time.
ln
t
0.001 Ci
0.0108 Ci
0.263 year
t
9.05 years
Plotting Radioactive Decay

It is useful to plot the activity of a nuclide as it changes over time. Plots of this type can be
used to determine when the activity will fall below a certain level. This plot is usually done
showing activity on either a linear or a logarithmic scale. The decay of the activity of a single
nuclide on a logarithmic scale will plot as a straight line because the decay is exponential.
Rev. 0
Page 35
NP-01
RADIOACTIVITY
DOE-HDBK-1019/1-93
Example:
Plot the radioactive decay curve for nitrogen-16 over a period of 100 seconds. The
initial activity is 142 curies and the half-life of nitrogen-16 is 7.13 seconds. Plot the
curve on both linear rectangular coordinates and on a semi-log scale.
Solution:
First, use Equation (1-6) to calculate the decay constant corresponding to a half-life of
7.13 seconds.
t1/2
0.693
0.693
t1/2
0.693
7.13 seconds
0.0972 second
Use the decay constant determined above to calculate the activity at various times using
Equation (1-5).
A
Ao e
Activity
Time
NP-01
0 seconds
142 Ci
20 seconds
20.3 Ci
40 seconds
2.91 Ci
60 seconds
0.416 Ci
80 seconds
0.0596 Ci
100 seconds
0.00853 Ci
Page 36
Rev. 0
DOE-HDBK-1019/1-93
RADIOACTIVITY
Plotting the data points calculated above on both linear and semilog scales results in the graphs
shown in Figure 11.
Figure 11 Linear and Semi-log Plots of Nitrogen-16 Decay
If a substance contains more than one radioactive nuclide, the total activity is the sum of the
individual activities of each nuclide. As an example, consider a sample of material that
contained 1 x 106 atoms of iron-59 that has a half-life of 44.51 days ( = 1.80 x 10-7 sec-1 ),
1 x 106 atoms of manganese-54 that has a half-life of 312.2 days ( = 2.57 x 10-8 sec-1), and 1
x 106 atoms of cobalt-60 that has a half-life of 1925 days ( = 4.17 x 10-9 sec-1).
The initial activity of each of the nuclides would be the product of the number of atoms and the
decay constant.

Rev. 0
Page 37
NP-01
RADIOACTIVITY
DOE-HDBK-1019/1-93
Plotting the manner in which the activities of each of the three nuclides decay over time
demonstrates that initially the activity of the shortest-lived nuclide (iron-59) dominates the total
activity, then manganese-54 dominates. After almost all of the iron and manganese have
decayed away, the only contributor to activity will be the cobalt-60. A plot of this combined
decay is shown in Figure 12.
Figure 12 Combined Decay of Iron-56, Manganese-54, and Cobalt-60
Radioactive Equilibrium
Radioactive equilibrium exists when a radioactive nuclide is decaying at the same rate at which
it is being produced. Since the production rate and decay rate are equal, the number of atoms
present remains constant over time.
An example of radioactive equilibrium is the concentration of sodium-24 in the coolant
circulating through a sodium-cooled nuclear reactor. Assume that the sodium-24 is being
produced at a rate of 1 x 106 atoms per second. If the sodium-24 were stable and did not decay,
the amount of sodium-24 present after some period of time could be calculated by multiplying
the production rate by the amount of time. Plotting the amount of material present would result
in the graph in Figure 13.
However, sodium-24 is not stable, and it decays with a half-life of 14.96 hours. If no
sodium-24 is present initially and production starts at a rate of 1 x 106 atoms per second, the rate
of decay will initially be zero because there is no sodium-24 present to decay. The rate of decay
of sodium-24 will increase as the amount of sodium-24 increases.
NP-01
Page 38
Rev. 0
DOE-HDBK-1019/1-93
RADIOACTIVITY
Figure 13 Cumulative Production of Sodium-24 Over Time
The amount of sodium-24 present will initially increase rapidly, then it will increase at a
continually decreasing rate until the rate of decay is equal to the rate of production. It is possible
to calculate how much sodium-24 will be present at equilibrium by setting the production rate
(R) equal to the decay rate ( N).
where:
R = production rate (atoms/second)
= decay constant (second-1)
N = number of atoms
It is possible to calculate the equilibrium value for sodium-24 being produced at a rate of
1 x 106 atoms/second.
Rev. 0
Page 39
NP-01
RADIOACTIVITY
DOE-HDBK-1019/1-93
The development of the equation to calculate how the amount of sodium-24 changes over time
as it approaches the equilibrium value is beyond the scope of this handbook. However, the
equation is presented below.
This equation can be used to calculate the values of the amount of sodium-24 present at different
times. As the time increases, the exponential term approaches zero, and the number of atoms
present will approach R/. A plot of the approach of sodium-24 to equilibrium is shown in
Figure 14.
Figure 14 Approach of Sodium-24 to Equilibrium
Transient Radioactive Equilibrium

Transient radioactive equilibrium occurs when the parent nuclide and the daughter nuclide
decay at essentially the same rate.
For transient equilibrium to occur, the parent must have a long half-life when compared to the
daughter. An example of this type of compound decay process is barium-140, which decays by
beta emission to lanthanum-140, which in turn decays by beta emission to stable cerium-140.
NP-01
Page 40
Rev. 0
DOE-HDBK-1019/1-93
RADIOACTIVITY
The decay constant for barium-140 is considerably smaller than the decay constant for
lanthanum-140. Remember that the rate of decay of both the parent and daughter can be
represented as N. Although the decay constant for barium-140 is smaller, the actual rate of
decay (N) is initially larger than that of lanthanum-140 because of the great difference in their
initial concentrations. As the concentration of the daughter increases, the rate of decay of the
daughter will approach and eventually match the decay rate of the parent. When this occurs,
they are said to be in transient equilibrium. A plot of the barium-lanthanum-cerium decay chain
reaching transient equilibrium is shown in Figure 15.
Figure 15 Transient Equilibrium in the Decay of Barium-140
Secular equilibrium occurs when the parent has an extremely long half-life. In the long decay
chain for a naturally radioactive element, such as thorium-232, where all of the elements in the
chain are in secular equilibrium, each of the descendants has built up to an equilibrium amount
and all decay at the rate set by the original parent. The only exception is the final stable element
on the end of the chain. Its number of atoms is constantly increasing.
Summary
Rev. 0
Page 41
NP-01
RADIOACTIVITY
DOE-HDBK-1019/1-93
Radioactivity Summary
&
Radioactivity is the decay of unstable atoms by the emission of particles and

electromagnetic radiation.
&
A curie (Ci) is a unit of radioactivity equal to 3.7 x 1010 disintegrations per

second.
&
A becquerel (Bq) is a unit of radioactivity equal to 1 disintegration per second.
&
The radioactive decay constant () is the probability per unit time that an atom
will decay.
&
The radioactive half-life is the amount of time required for the activity to
decrease to one-half its original value.
&
The activity of a substance can be calculated from the number of atoms and the
decay constant based on the equation below.

&
The amount of activity remaining after a particular time can be calculated from
the equation below.

&
The relationship between the decay constant and the half-life is shown below.
&
Plots of radioactive decay can be useful to describe the variation of activity over
time. If decay is plotted using semi-log scale the plot results in a straight line.
&
Radioactive equilibrium exists when the production rate of a material is equal to

the removal rate.
&
Transient radioactive equilibrium exists when the parent nuclide and the daughter
nuclide decay at essentially the same rate. This occurs only when the parent has a
long half-life compared to the daughter.
NP-01
Page 42
Rev. 0
DOE-HDBK-1019/1-93
NEUTRON INTERACTIONS
Neutrons can cause many different types of interactions. The neutron may simply
scatter off the nucleus in two different ways, or it may actually be absorbed into
the nucleus. If a neutron is absorbed into the nucleus, it may result in the
emission of a gamma ray or a subatomic particle, or it may cause the nucleus to
fission.
EO 3.1
DESCRIBE the following scattering interactions between a

neutron and a nucleus:
a.
b.
Elastic scattering
Inelastic scattering
EO 3.2
STATE the conservation laws that apply to an elastic collision

between a neutron and a nucleus.
EO 3.3
DESCRIBE the following reactions where a neutron is

absorbed in a nucleus:
a.
b.
Radiative capture
Particle ejection
Scattering
A neutron scattering reaction occurs when a nucleus, after having been struck by a neutron,
emits a single neutron. Despite the fact that the initial and final neutrons do not need to be (and
often are not) the same, the net effect of the reaction is as if the projectile neutron had merely
"bounced off," or scattered from, the nucleus. The two categories of scattering reactions, elastic
and inelastic scattering, are described in the following paragraphs.
Elastic Scattering
In an elastic scattering reaction between a neutron and a target nucleus, there is no energy
transferred into nuclear excitation. Momentum and kinetic energy of the "system" are conserved
although there is usually some transfer of kinetic energy from the neutron to the target nucleus.
The target nucleus gains the amount of kinetic energy that the neutron loses.
Rev. 0
Page 43
NP-01
DOE-HDBK-1019/1-93
Figure 16 Elastic Scattering
Figure 16 illustrates the process of elastic scattering of a neutron off a target nucleus. In the
elastic scattering reaction, the conservation of momentum and kinetic energy is represented by
the equations below.
Conservation of momentum (mv)
mn vn,i
mT vT,i
Conservation of kinetic energy
1
2
mn vn,i
2
mn vn,f
mT vT,f
1
m v2
2
1
2
mT vT,i
2
1
2
mn vn,f
2
1
2
mT vT,f
2
where:
mn
mT
vn,i
vn,f
vT,i
vT,f
NP-01
=
=
=
=
=
=
mass of the neutron

mass of the target nucleus
initial neutron velocity
final neutron velocity
initial target velocity
final target velocity
Page 44
Rev. 0
DOE-HDBK-1019/1-93
Elastic scattering of neutrons by nuclei can occur in two ways. The more unusual of the two
interactions is the absorption of the neutron, forming a compound nucleus, followed by the
re-emission of a neutron in such a way that the total kinetic energy is conserved and the nucleus
returns to its ground state. This is known as resonance elastic scattering and is very dependent
upon the initial kinetic energy possessed by the neutron. Due to formation of the compound
nucleus, it is also referred to as compound elastic scattering. The second, more usual method,
is termed potential elastic scattering and can be understood by visualizing the neutrons and
nuclei to be much like billiard balls with impenetrable surfaces. Potential scattering takes place
with incident neutrons that have an energy of up to about 1 MeV. In potential scattering, the
neutron does not actually touch the nucleus and a compound nucleus is not formed. Instead, the
neutron is acted on and scattered by the short range nuclear forces when it approaches close
enough to the nucleus.
Inelastic Scattering
In inelastic scattering , the incident neutron is absorbed by the target nucleus, forming a
compound nucleus. The compound nucleus will then emit a neutron of lower kinetic energy
which leaves the original nucleus in an excited state. The nucleus will usually, by one or more
gamma emissions, emit this excess energy to reach its ground state. Figure 17 shows the
process of inelastic scattering.
Figure 17 Inelastic Scattering
For the nucleus that has reached its ground state, the sum of the kinetic energy of the exit
neutron, the target nucleus, and the total gamma energy emitted is equal to the initial kinetic
energy of the incident neutron.
Rev. 0
Page 45
NP-01
DOE-HDBK-1019/1-93
Absorption Reactions
Most absorption reactions result in the loss of a neutron coupled with the production of a
charged particle or gamma ray. When the product nucleus is radioactive, additional radiation
is emitted at some later time. Radiative capture, particle ejection, and fission are all categorized
as absorption reactions and are briefly described below.
Radiative Capture
In radiative capture the incident neutron enters the target nucleus forming a compound nucleus.
The compound nucleus then decays to its ground state by gamma emission. An example of a
radiative capture reaction is shown below.
1
0
238
92
239
92
239
92
Particle Ejection
In a particle ejection reaction the incident particle enters the target nucleus forming a compound
nucleus. The newly formed compound nucleus has been excited to a high enough energy level
to cause it to eject a new particle while the incident neutron remains in the nucleus. After the
new particle is ejected, the remaining nucleus may or may not exist in an excited state depending
upon the mass-energy balance of the reaction. An example of a particle ejection reaction is
shown below.
1
0
10
5
11
5
7
3
Li
4
2
Fission
One of the most important interactions that neutrons can cause is fission, in which the nucleus
that absorbs the neutron actually splits into two similarly sized parts. Fission will be discussed
in detail in the next chapter.
NP-01
Page 46
Rev. 0
DOE-HDBK-1019/1-93
Summary
Neutron Interactions Summary

Interactions where a neutron scatters off a target nucleus are either elastic or
inelastic. In elastic scattering, kinetic energy and momentum are conserved and
no energy is transferred into excitation energy of the target nucleus. In inelastic
scattering, some amount of kinetic energy is transferred into excitation energy of
the target nucleus.
The conservation principles that apply to an elastic collision are conservation of
kinetic energy and conservation of momentum.
Radiative capture is the absorption of a neutron by the target nucleus, resulting
in an excited nucleus which subsequently (typically within a small fraction of a
second) releases its excitation energy in the form of a gamma ray.
Particle ejection occurs when a neutron is absorbed by a target nucleus, resulting
in the formation of a compound nucleus. The compound nucleus immediately
ejects a particle (for example, alpha or proton).
Rev. 0
Page 47
NP-01
NUCLEAR FISSION
DOE-HDBK-1019/1-93
NUCLEAR FISSION
Nuclear fission is a process in which an atom splits and releases energy, fission
products, and neutrons. The neutrons released by fission can, in turn, cause
the fission of other atoms.
EO 4.1
EXPLAIN the fission process using the liquid drop model

of a nucleus.
EO 4.2

a.
b.
EO 4.3
Excitation energy (Eexc)

Critical energy (Ecrit)

a.
b.
c.
Fissile material
Fissionable material
Fertile material
EO 4.4
DESCRIBE the processes of transmutation, conversion,

and breeding.
EO 4.5
DESCRIBE the curve of Binding Energy per Nucleon

versus mass number and give a qualitative description of
the reasons for its shape.
EO 4.6
EXPLAIN why only the heaviest nuclei are easily fissioned.
EO 4.7
EXPLAIN why uranium-235 fissions with thermal

neutrons and uranium-238 fissions only with fast neutrons.
Fission
In the fission reaction the incident neutron enters the heavy target nucleus, forming a compound
nucleus that is excited to such a high energy level (Eexc > Ecrit ) that the nucleus "splits"
(fissions) into two large fragments plus some neutrons. An example of a typical fission
reaction is shown below.
1
0
235
92
236
92
140
55
Cs
93
37
Rb
1
0
A large amount of energy is released in the form of radiation and fragment kinetic energy.
NP-01
Page 48
Rev. 0
DOE-HDBK-1019/1-93
NUCLEAR FISSION
Liquid Drop M odel of a Nucleus

The nucleus is held together by the attractive nuclear force between nucleons, which was
discussed in a previous chapter. The characteristics of the nuclear force are listed below.
(a)
very short
( 10-13 cm)
range, with essentially no effect beyond nuclear dimensions
(b)
stronger than the repulsive electrostatic forces within the nucleus
(c)
independent of nucleon pairing, in that the attractive forces between pairs of

neutrons are no different than those between pairs of protons or a neutron and a
proton
(d)
saturable, that is, a nucleon can attract only a few of its nearest neighbors
One theory of fission considers the fissioning of a nucleus similar in some respects to the splitting
of a liquid drop. This analogy is justifiable to some extent by the fact that a liquid drop is held
together by molecular forces that tend to make the drop spherical in shape and that try to resist
any deformation in the same manner as nuclear forces are assumed to hold the nucleus together.
By considering the nucleus as a liquid drop, the fission process can be described.
Referring to Figure 18(A), the nucleus in the ground state is undistorted, and its attractive nuclear
forces are greater than the repulsive electrostatic forces between the protons within the nucleus.
When an incident particle (in this instance a neutron) is absorbed by the target nucleus, a
compound nucleus is formed. The compound nucleus temporarily contains all the charge and
mass involved in the reaction and exists in an excited state. The excitation energy added to the
compound nucleus is equal to the binding energy contributed by the incident particle plus the
kinetic energy possessed by that particle. Figure 18(B) illustrates the excitation energy thus
imparted to the compound nucleus, which may cause it to oscillate and become distorted. If the
excitation energy is greater than a certain critical energy, the oscillations may cause the
compound nucleus to become dumbbell-shaped. When this happens, the attractive nuclear forces
(short-range) in the neck area are small due to saturation, while the repulsive electrostatic forces
(long-range) are only slightly less than before. When the repulsive electrostatic forces exceed
the attractive nuclear forces, nuclear fission occurs, as illustrated in Figure 18(C).
Rev. 0
Page 49
NP-01
NUCLEAR FISSION
DOE-HDBK-1019/1-93
Figure 18 Liquid Drop Model of Fission
Critical Energy
The measure of how far the energy level of a nucleus is above its ground state is called the
excitation energy (Eexc). For fission to occur, the excitation energy must be above a particular
value for that nuclide. The critical energy (Ecrit) is the minimum excitation energy required for
fission to occur.
Fissile Material
A fissile material is composed of nuclides for which fission is possible with neutrons of any
energy level. What is especially significant about these nuclides is their ability to be fissioned
with zero kinetic energy neutrons (thermal neutrons). Thermal neutrons have very low kinetic
energy levels (essentially zero) because they are roughly in equilibrium with the thermal motion
of surrounding materials. Therefore, in order to be classified as fissile, a material must be
capable of fissioning after absorbing a thermal neutron. Consequently, they impart essentially
no kinetic energy to the reaction. Fission is possible in these materials with thermal neutrons,
since the change in binding energy supplied by the neutron addition alone is high enough to
exceed the critical energy. Some examples of fissile nuclides are uranium-235, uranium-233, and
plutonium-239.
NP-01
Page 50
Rev. 0
DOE-HDBK-1019/1-93
NUCLEAR FISSION
Fissionable Material
A fissionable material is composed of nuclides for which fission with neutrons is possible. All
fissile nuclides fall into this category. However, also included are those nuclides that can be
fissioned only with high energy neutrons. The change in binding energy that occurs as the result
of neutron absorption results in a nuclear excitation energy level that is less than the required
critical energy. Therefore, the additional excitation energy must be supplied by the kinetic energy
of the incident neutron. The reason for this difference between fissile and fissionable materials
is the so-called odd-even effect for nuclei. It has been observed that nuclei with even numbers
of neutrons and/or protons are more stable than those with odd numbers. Therefore, adding a
neutron to change a nucleus with an odd number of neutrons to a nucleus with an even number
of neutrons produces an appreciably higher binding energy than adding a neutron to a nucleus
already possessing an even number of neutrons. Some examples of nuclides requiring high
energy neutrons to cause fission are thorium-232, uranium-238, and plutonium-240. Table 4
indicates the critical energy (Ecrit) and the binding energy change for an added neutron (BEn) to
target nuclei of interest. For fission to be possible, the change in binding energy plus the kinetic
energy must equal or exceed the critical energy (BE + KE > Ecrit).
TAB LE 4
Critical Energies Compared to Binding Energy of Last Neutron
Target
Nucleus
Critical Energy
Ecrit
Binding Energy of
Last Neutron BEn
BEn - Ecrit
7.5 MeV
5.4 MeV
-2.1 MeV
238
92
7.0 MeV
5.5 MeV
-1.5 MeV
235
92
6.5 MeV
6.8 MeV
+0.3 MeV
233
92
6.0 MeV
7.0 MeV
+1.0 MeV
239
94
Pu
5.0 MeV
6.6 MeV
+1.6 MeV
232
90
Th
U
U
Uranium-235 fissions with thermal neutrons because the binding energy released by the
absorption of a neutron is greater than the critical energy for fission; therefore uranium-235 is
a fissile material. The binding energy released by uranium-238 absorbing a thermal neutron is
less than the critical energy, so additional energy must be possessed by the neutron for fission
to be possible. Consequently, uranium-238 is a fissionable material.
Rev. 0
Page 51
NP-01
NUCLEAR FISSION
DOE-HDBK-1019/1-93
Fertile Material
All of the neutron absorption reactions that do not result in fission lead to the production of new
nuclides through the process known as transmutation . These nuclides can, in turn, be transmuted
again or may undergo radioactive decay to produce still different nuclides. The nuclides that are
produced by this process are referred to as transmutation products. Because several of the fissile
nuclides do not exist in nature, they can only be produced by nuclear reactions (transmutation).
The target nuclei for such reactions are said to be fertile. Fertile materials are materials that can
undergo transmutation to become fissile materials. Figure 19 traces the transmutation mechanism
by which two fertile nuclides, thorium-232 and uranium-238, produce uranium-233 and
plutonium-239, respectively.
Figure 19 Conversion of Fertile Nuclides to Fissile Nuclides
If a reactor contains fertile material in addition to its fissile fuel, some new fuel will be produced
as the original fuel is burned up. This is called conversion. Reactors that are specifically
designed to produce fissionable fuel are called "breeder" reactors. In such reactors, the amount
of fissionable fuel produced is greater than the amount of fuel burnup. If less fuel is produced
than used, the process is called conversion, and the reactor is termed a "converter."
NP-01
Page 52
Rev. 0
DOE-HDBK-1019/1-93
NUCLEAR FISSION
Binding Energy Per Nucleon (BE/A)

As the number of particles in a nucleus increases, the total binding energy also increases. The
rate of increase, however, is not uniform. This lack of uniformity results in a variation in the
amount of binding energy associated with each nucleon within the nucleus. This variation in the
binding energy per nucleon (BE/A) is easily seen when the average BE/A is plotted versus atomic
mass number (A), as shown in Figure 20.
Figure 20 Binding Energy per Nucleon vs. Mass Number
Figure 20 illustrates that as the atomic mass number increases, the binding energy per nucleon
decreases for A > 60. The BE/A curve reaches a maximum value of 8.79 MeV at A = 56 and
decreases to about 7.6 MeV for A = 238. The general shape of the BE/A curve can be explained
using the general properties of nuclear forces. The nucleus is held together by very short-range
attractive forces that exist between nucleons. On the other hand, the nucleus is being forced apart
by long range repulsive electrostatic (coulomb) forces that exist between all the protons in the
nucleus.
Rev. 0
Page 53
NP-01
NUCLEAR FISSION
DOE-HDBK-1019/1-93
As the atomic number and the atomic mass number increase, the repulsive electrostatic forces
within the nucleus increase due to the greater number of protons in the heavy elements. To
overcome this increased repulsion, the proportion of neutrons in the nucleus must increase to
maintain stability. This increase in the neutron-to-proton ratio only partially compensates for the
growing proton-proton repulsive force in the heavier, naturally occurring elements. Because the
repulsive forces are increasing, less energy must be supplied, on the average, to remove a nucleon
from the nucleus. The BE/A has decreased. The BE/A of a nucleus is an indication of its degree
of stability. Generally, the more stable nuclides have higher BE/A than the less stable ones. The
increase in the BE/A as the atomic mass number decreases from 260 to 60 is the primary reason
for the energy liberation in the fission process. In addition, the increase in the BE/A as the atomic
mass number increases from 1 to 60 is the reason for the energy liberation in the fusion process,
which is the opposite reaction of fission.
The heaviest nuclei require only a small distortion from a spherical shape (small energy addition)
for the relatively large coulomb forces forcing the two halves of the nucleus apart to overcome
the attractive nuclear forces holding the two halves together. Consequently, the heaviest nuclei
are easily fissionable compared to lighter nuclei.
Summary
NP-01
Page 54
Rev. 0
DOE-HDBK-1019/1-93
NUCLEAR FISSION
Nuclear Fission Summary

The fission process can be explained using the liquid drop model of a nucleus.
In the ground state the nucleus is nearly spherical in shape. After the absorption
of a neutron, the nucleus will be in an excited state and start to oscillate and
become distorted. If the oscillations cause the nucleus to become shaped like a
dumbbell, the repulsive electrostatic forces will overcome the short-range
attractive nuclear forces, and the nucleus will split in two.
Excitation energy is the amount of energy a nucleus has above its ground state.
Critical energy is the minimum excitation energy that a nucleus must have before
it can fission.
Fissile material is material for which fission is possible with neutrons that have
zero kinetic energy. Fissionable material is material for which fission caused by
neutron absorption is possible provided the kinetic energy added with the binding
energy is greater than the critical energy. Fertile material is material that can
undergo transmutation to become fissile material.
Transmutation is the process of neutron absorption and subsequent decay, which
changes one nuclide to another nuclide. Conversion is the process of transmuting
fertile material into fissile material in a reactor, where the amount of fissile
material produced is less than the amount of fissile material consumed. Breeding
is the same as conversion, except the amount of fissile material produced is more
than the amount of fissile material consumed.
The curve of binding energy per nucleon increases quickly through the light
nuclides and reaches a maximum at a mass number of about 56. The curve
decreases slowly for mass numbers greater than 60.
The heaviest nuclei are easily fissionable because they require only a small
distortion from the spherical shape to allow the coulomb forces to overcoming
the attractive nuclear force, forcing the two halves of the nucleus apart.
Uranium-235 fissions with thermal neutrons because the binding energy released
by the absorption of a neutron is greater than the critical energy for fission. The
binding energy released by uranium-238 absorbing a neutron is less than the
critical energy, so additional kinetic energy must be possessed by the neutron for
fission to be possible.
Rev. 0
Page 55
NP-01
ENERGY RELEASE FROM FISSION
DOE-HDBK-1019/1-93
Fission of heavy nuclides converts a small amount of mass into an enormous

amount of energy. The amount of energy released by fission can be
determined based on either the change in mass that occurs during the reaction
or by the difference in binding energy per nucleon between the fissile nuclide
and the fission products.
EO 4.8
CHARACTERIZE the fission products in terms of mass

groupings and radioactivity.
EO 4.9
Given the nuclides involved and their masses, CALCULATE

the energy released from fission.
EO 4.10
Given the curve of Binding Energy per nucleon versus mass

number, CALCULATE the energy released from fission.
Calculation of Fission Energy

Nuclear fission results in the release of enormous quantities of energy. It is necessary to be able
to calculate the amount of energy that will be produced. The logical manner in which to pursue
this is to first investigate a typical fission reaction such as the one listed below.
1
0
235
92
236
92
140
55
Cs
93
37
Rb
1
0
It can be seen that when the compound nucleus splits, it breaks into two fission fragments,
rubidium-93, cesium-140, and some neutrons. Both fission products then decay by multiple emissions as a result of the high neutron-to-proton ratio possessed by these nuclides.
In most cases, the resultant fission fragments have masses that vary widely. Figure 21 gives the
percent yield for atomic mass numbers. The most probable pair of fission fragments for the
thermal fission of the fuel uranium-235 have masses of about 95 and 140. Note that the vertical
axis of the fission yield curve is on a logarithmic scale. Therefore, the formation of fission
fragments of mass numbers of about 95 and 140 is highly likely.
NP-01
Page 56
Rev. 0
DOE-HDBK-1019/1-93
Figure 21 Uranium-235 Fission Yield vs.

Mass Number
Referring now to the binding energy per nucleon curve (Figure 20), we can estimate the amount
of energy released by our "typical" fission by plotting this reaction on the curve and calculating
the change in binding energy (BE) between the reactants on the left-hand side of the fission
equation and the products on the right-hand side. Plotting the reactant and product nuclides on
the curve shows that the total binding energy of the system after fission is greater than the total
binding energy of the system before fission. When there is an increase in the total binding
energy of a system, the system has become more stable by releasing an amount of energy equal
to the increase in total binding energy of the system. Therefore, in the fission process, the energy
liberated is equal to the increase in the total binding energy of the system.
Rev. 0
Page 57
NP-01
DOE-HDBK-1019/1-93
Figure 22 Change in Binding Energy for Typical Fission
Figure 22 graphically depicts that the binding energy per nucleon for the products (C,
rubidium-93 and B, cesium-140) is greater than that for the reactant (A, uranium-235). The total
binding energy for a nucleus can be found by multiplying the binding energy per nucleon by the
number of nucleons.
TAB LE 5
Binding Energies Calculated from
Binding Energy per Nucleon Curve
Nuclide
93
37
Rb
140
55
Cs
235
92
NP-01
B.E. per Nucleon

(BE/A)
Mass Number
(A)
Binding Energy
(BE/A) x (A)
8.7 MeV
93
809 MeV
8.4 MeV
140
1176 MeV
7.6 MeV
235
1786 MeV
Page 58
Rev. 0
DOE-HDBK-1019/1-93
The energy released will be equivalent to the difference in binding energy ( BE) between the
reactants and the products.
BE
BEproducts
BERb
BEreactants
BECs
93
809 MeV
BEU
140
1176 MeV
235
1786 MeV
199 MeV
The energy liberation during the fission process can also be explained from the standpoint of the
conservation of mass-energy. During the fission process, there is a decrease in the mass of the
system. There must, therefore, be energy liberated equal to the energy equivalent of the mass
lost in the process. This method is more accurate than the previously illustrated method and is
used when actually calculating the energy liberated during the fission process.
Again, referring to the "typical" fission reaction.
1
0
235
92
236
92
140
55
93
Cs
37
Rb
1
0
EInst, the instantaneous energy, is the energy released immediately after the fission process. It
is equal to the energy equivalent of the mass lost in the fission process. It can be calculated as
shown below.
Mass of the Reactants
Mass of the Products
235
92
93
37
1
0
235.043924 amu
140
55
1.008665 amu
236.052589 amu
Mass difference
Rb
92.91699 amu
Cs
139.90910 amu
3 (10n)
3.02599 amu
235.85208 amu
Mass of Reactants
236.052589 amu
Mass of Products
235.85208 amu
0.200509 amu
This mass difference can be converted to an energy equivalent.
EInst
0.020059 amu
931.5 MeV
amu
186.8 MeV
Rev. 0
Page 59
NP-01
DOE-HDBK-1019/1-93
The total energy released per fission will vary from the fission to the next depending on what
fission products are formed, but the average total energy released per fission of uranium-235
with a thermal neutron is 200 MeV.
As illustrated in the preceding example, the majority of the energy liberated in the fission
process is released immediately after the fission occurs and appears as the kinetic energy of the
fission fragments, kinetic energy of the fission neutrons, and instantaneous gamma rays. The
remaining energy is released over a period of time after the fission occurs and appears as kinetic
energy of the beta, neutrino, and decay gamma rays.
Estimation of Decay Energy

In addition to this instantaneous energy release during the actual fission reaction, there is
additional energy released when the fission fragments decay by - emission. This additional
energy is called decay energy, EDecay. The decay chains for rubidium-93 and cesium-140 are
shown below.
93
37
93
Rb
140
55
38
140
Cs
93
Sr
56
39
140
Ba
93
57
40
93
Zr
La
41
140
58
Nb
Ce
The energy released during the decay for each chain will be equivalent to the mass difference
between the original fission product and the sum of the final stable nuclide and the beta particles
emitted.
The energy released in the decay chain of rubidium-93 is calculated below.
E Decay
mRb
93
mNb
92.91699 amu
0.008416 amu
93
4 melectron
92.90638 amu
931.5MeV
amu
4 0.0005486 amu
931.5 MeV
amu
931.5 MeV
amu
7.84 MeV
NP-01
Page 60
Rev. 0
DOE-HDBK-1019/1-93
The energy released in the decay chain of cesium-140 is calculated below.

E Decay
mRb
mNb
93
93
139.90910 amu
0.000202 amu
3 melectron
931.5MeV
amu
139.90543 amu
3 0.0005486 amu
931.5 MeV
amu
931.5 MeV
amu
1.89 MeV
The total decay energy is the sum of the energies of the two chains, or 9.73 MeV.
Distribution of Fission Energy

The average energy distribution for the energy released per fission with a thermal neutron in
uranium-235 is shown in Tables 6 and 7.
TABLE 6
Instantaneous Energy from Fission
Kinetic Energy of Fission Products
167 Mev
Energy of Fission Neutrons
5 MeV
Instantaneous Gamma-ray Energy
5 MeV
Capture Gamma-ray Energy
10 MeV
Total Instantaneous Energy
187 MeV
TABLE 7
Delayed Energy from Fission
Rev. 0
Beta Particles From Fission Products
7 Mev
Gamma-rays from Fission Products
6 MeV
Neutrinos
10 MeV
Total Delayed Energy
23 MeV
Page 61
NP-01
DOE-HDBK-1019/1-93
Because the 10 MeV of neutrino energy shown in Table 7 is not absorbed in the reactor, the
average value of 200 MeV per fission is still accurate. Note in Table 6 that some fission
neutrons undergo radiative capture and the resultant gamma ray emission provides an additional
10 MeV of instantaneous energy, which contributes to the total of 187 MeV instantaneous
energy.
All of the energy released, with the exception of the neutrino energy, is ultimately transformed
into heat through a number of processes. The fission fragments, with their high positive charge
and kinetic energy, cause ionization directly as they rip orbital electrons from the surrounding
atoms. In this ionization process, kinetic energy is transferred to the surrounding atoms of the
fuel material, resulting in an increase in temperature. The beta particles and gamma rays also
give up their energy through ionization, and the fission neutrons interact and lose their energy
through elastic scattering. Of the 200 MeV released per fission, about seven percent (13 MeV)
is released at some time after the instant of fission. When a reactor is shut down, fissions
essentially cease, but energy is still being released from the decay of fission products. The heat
produced by this decay energy is referred to as "decay heat." Although decay energy represents
about seven percent of reactor heat production during reactor operation, once the reactor is shut
down the decay heat production drops off quickly to a small fraction of its value while operating.
The decay heat produced is significant, however, and systems must be provided to keep the
reactor cool even after shutdown.
Summary
Energy Release From Fission Summary

Fission products have some general characteristics in common.
They generally decay by - emission.
The most common mass numbers are grouped near 95 and 140.
The energy released by fission can be calculated based on the difference in mass
between the masses of the reactants before fission and the fission fragments and
fission neutrons after fission.
Another method to determine the energy released by fission is based on the
change in binding energy per nucleon between the fissile nuclide and the fission
products.
NP-01
Page 62
Rev. 0
DOE-HDBK-1019/1-93
INTERACTION OF RADIATION WITH MATTER

Different types of radiation interact with matter in widely different ways. A large,
massive, charged alpha particle cannot penetrate a piece of paper and even has
a limited range in dry air.
A neutrino, at the other extreme, has a low
probability of interacting with any matter, even if it passed through the diameter
of the earth.
EO 5.1
DESCRIBE interactions of the following with matter:

a.
b.
EO 5.2
Alpha particle
Beta particle
c.
d.
Positron
Neutron
DESCRIBE the following ways that gamma radiation interacts

with m atter:
a.
b.
c.
Photoelectric effect
Compton scattering
Pair production
Interaction of Radiation With Matter

Radiation can be classified into two general groups, charged and uncharged; therefore, it may be
expected that interactions with matter fall into two general types. Charged particles directly
ionize the media through which they pass, while uncharged particles and photons can cause
ionization only indirectly or by secondary radiation.
A moving charged particle has an electrical field surrounding it, which interacts with the atomic
structure of the medium through which it is passing. This interaction decelerates the particle and
accelerates electrons in the atoms of the medium. The accelerated electrons may acquire enough
energy to escape from the parent atom. This process, whereby radiation "strips" off orbital
electrons, is called ionization. Uncharged moving particles have no electrical field, so they can
only lose energy and cause ionization by such means as collisions or scattering. A photon can
lose energy by the photoelectric effect, Compton effect, or pair production.
Rev. 0
Page 63
NP-01
DOE-HDBK-1019/1-93
Because ionizing radiation creates ions in pairs, the intensity of ionization or the specific
ionization is defined as the number of ion-pairs formed per centimeter of travel in a given
material. The amount of ionization produced by a charged particle per unit path length, which
is a measure of its ionizing power, is roughly proportional to the particle's mass and the square
of its charge as illustrated in the equation below.
I
m z2
K.E.
where:
I is the ionizing power
m is the mass of the particle
z is the number of unit charges it carries
K.E. is its kinetic energy
Since m for an alpha particle is about 7300 times as large as m for a beta particle, and z is twice
as great, an alpha will produce much more ionization per unit path length than a beta particle
of the same energy. This phenomenon occurs because the larger alpha particle moves slower
for a given energy and thus acts on a given electron for a longer time.
Alpha Radiation
Alpha radiation is normally produced from the radioactive decay of heavy nuclides and from
certain nuclear reactions. The alpha particle consists of 2 neutrons and 2 protons, so it is
essentially the same as the nucleus of a helium atom. Because it has no electrons, the alpha
particle has a charge of +2. This positive charge causes the alpha particle to strip electrons
from the orbits of atoms in its vicinity. As the alpha particle passes through material, it removes
electrons from the orbits of atoms it passes near. Energy is required to remove electrons and
the energy of the alpha particle is reduced by each reaction. Eventually the particle will expend
its kinetic energy, gain 2 electrons in orbit, and become a helium atom. Because of its strong
positive charge and large mass, the alpha particle deposits a large amount of energy in a short
distance of travel. This rapid, large deposition of energy limits the penetration of alpha
particles. The most energetic alpha particles are stopped by a few centimeters of air or a sheet
of paper.
Beta-Minus Radiation
A beta-minus particle is an electron that has been ejected at a high velocity from an unstable
nucleus. An electron has a small mass and an electrical charge of -1. Beta particles cause
ionization by displacing electrons from atom orbits. The ionization occurs from collisions with
orbiting electrons. Each collision removes kinetic energy from the beta particle, causing it to
slow down. Eventually the beta particle will be slowed enough to allow it to be captured as an
NP-01
Page 64
Rev. 0
DOE-HDBK-1019/1-93
orbiting electron in an atom. Although more penetrating than the alpha, the beta is relatively
easy to stop and has a low power of penetration. Even the most energetic beta radiation can be
stopped by a few millimeters of metal.
Positron Radiation
Positively charged electrons are called positrons. Except for the positive charge, they are
identical to beta-minus particles and interact with matter in a similar manner. Positrons are very
short-lived, however, and quickly are annihilated by interaction with a negatively charged
electron, producing two gammas with a combined energy (calculated below) equal to the rest
mass of the positive and negative electrons.
2 electrons
0.000549 amu
electron
931.5 MeV
amu
1.02 MeV
Neutron Radiation
Neutrons have no electrical charge. They have nearly the same mass as a proton (a hydrogen
atom nucleus). A neutron has hundreds of times more mass than an electron, but 1/4 the mass
of an alpha particle. The source of neutrons is primarily nuclear reactions, such as fission, but
they may also be produced from the decay of radioactive nuclides. Because of its lack of
charge, the neutron is difficult to stop and has a high penetrating power.
Neutrons are attenuated (reduced in energy and numbers) by three major interactions, elastic
scatter, inelastic scatter, and absorption. In elastic scatter, a neutron collides with a nucleus and
bounces off. This reaction transmits some of the kinetic energy of the neutron to the nucleus
of the atom, resulting in the neutron being slowed, and the atom receives some kinetic energy
(motion). This process is sometimes referred to as "the billiard ball effect."
As the mass of the nucleus approaches the mass of the neutron, this reaction becomes more
effective in slowing the neutron. Hydrogenous material attenuates neutrons most effectively.
In the inelastic scatter reaction, the same neutron/nucleus collision occurs as in elastic scatter.
However, in this reaction, the nucleus receives some internal energy as well as kinetic energy.
This slows the neutron, but leaves the nucleus in an excited state. When the nucleus decays to
its original energy level, it normally emits a gamma ray.
In the absorption reaction, the neutron is actually absorbed into the nucleus of an atom. The
neutron is captured, but the atom is left in an excited state. If the nucleus emits one or more
gamma rays to reach a stable level, the process is called radiative capture. This reaction occurs
at most neutron energy levels, but is more probable at lower energy levels.
Rev. 0
Page 65
NP-01
DOE-HDBK-1019/1-93
Ga mma Radiation
Gamma radiation is electromagnetic radiation. It is commonly referred to as a gamma ray and
is very similar to an x-ray. The difference is that gamma rays are emitted from the nucleus of
an atom, and x-rays are produced by orbiting electrons. The x-ray is produced when orbiting
electrons move to a lower energy orbit or when fast-moving electrons approaching an atom are
deflected and decelerated as they react with the atom's electrical field (called Bremsstrahlung).
The gamma ray is produced by the decay of excited nuclei and by nuclear reactions. Because
the gamma ray has no mass and no charge, it is difficult to stop and has a very high penetrating
power. A small fraction of the original gamma stream will pass through several feet of concrete
or several meters of water.
There are three methods of attenuating gamma rays. The first method is referred to as the
photo-electric effect. When a low energy gamma strikes an atom, the total energy of the gamma
is expended in ejecting an electron from orbit. The result is ionization of the atom and expulsion
of a high energy electron. This reaction is most predominant with low energy gammas
interacting in materials with high atomic weight and rarely occurs with gammas having an energy
above 1 MeV. Annihilation of the gamma results. Any gamma energy in excess of the binding
energy of the electron is carried off by the electron in the form of kinetic energy.
The second method of attenuation of gammas is called Compton scattering. The gamma interacts
with an orbital or free electron; however, in this case, the photon loses only a fraction of its
energy. The actual energy loss depending on the scattering angle of the gamma. The gamma
continues on at lower energy, and the energy difference is absorbed by the electron. This
reaction becomes important for gamma energies of about 0.1 MeV and higher.
At higher energy levels, a third method of attenuation is predominant. This method is
pair-production. When a high energy gamma passes close enough to a heavy nucleus, the gamma
completely disappears, and an electron and a positron are formed. For this reaction to take place,
the original gamma must have at least 1.02 MeV energy. Any energy greater than 1.02 MeV
becomes kinetic energy shared between the electron and positron. The probability of pairproduction increases significantly for higher energy gammas.
NP-01
Page 66
Rev. 0
DOE-HDBK-1019/1-93
Summary
Interaction of Radiation with Matter Summary

An alpha particle deposits a large amount of energy in a short distance of travel
due to its large mass and charge.
Beta-minus particles interact with the electrons orbiting the nucleus of atoms,
causing ionization by displacing the electrons. The beta particle loses energy with
each interaction. After the beta particle loses enough energy, it is captured in the
orbital shells of an atom.
Positrons interact with matter much the same way as beta minus particles. After
the positron has lost most of its energy by ionizing atoms, it is annihilated by
interaction with an electron. The electron-positron pair disappear and are replaced
by two gammas, each with the energy equivalent of the mass of an electron (0.51
MeV).
Neutrons interact with matter by elastic scattering, inelastic scattering, or
absorption.
Photoelectric effect is where a gamma interacts with an electron orbiting an atom.
The entire energy of the gamma is transferred to the electron, and the electron is
ejected from its orbit.
In Compton scattering a gamma interacts with an orbital electron, but only part of
the gamma energy is transferred to the electron. The electron is ejected from its
orbit, and the gamma is scattered off at a lower energy.
In pair-production, a gamma interacts with the electric field of a nucleus and is
converted into an electron-positron pair. The gamma must have an energy greater
than 1.02 MeV for this to occur.
Rev. 0
Page 67
NP-01
DOE-HDBK-1019/1-93
NP-01
Page 68
Rev. 0
NUCLEAR PHYSICS
AND REACTOR THEORY
Module 2
Reactor Theory (Neutron Characteristics)
Reactor Theory (Neutron Characteristics) DOE-HDBK-1019/1-93
TABLE OF CONTENTS
TABLE OF CONTENTS
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vi
NEUTRON SOURCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Neutron Sources . . . . . . .
Intrinsic Neutron Sources
Installed Neutron Sources
Summary . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
1
3
4
NUCLEAR CROSS SECTIONS AND NEUTRON FLUX . . . . . . . . . . . . . . . . . . . . . .
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Atom Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cross Sections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mean Free Path . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Calculation of Macroscopic Cross Section and Mean Free Path
Effects of Temperature on Cross Section . . . . . . . . . . . . . . .
Neutron Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Self-Shielding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.. 6
.. 6
.. 7
. 10
. 11
. 14
. 15
. 16
. 16
REACTION RATES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reaction Rates . . . . . . . . . . . . . . . . .
Reactor Power Calculation . . . . . . . . .
Relationship Between Neutron Flux and
Summary . . . . . . . . . . . . . . . . . . . .
...........
...........
Reactor Power
...........
.
.
.
.
18
20
21
22
NEUTRON MODERATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
23
Neutron Slowing Down and Thermalization

Macroscopic Slowing Down Power . . . . . .
Moderating Ratio . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . .
Rev. 0
Page i
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
18
.
.
.
.
.
.
.
.
23
26
27
28
NP-02
TABLE OF CONTENTS
DOE-HDBK-1019/1-93 Reactor Theory (Neutron Characteristics)

PROMPT AND DELAYED NEUTRONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
29
Neutron Classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Neutron Generation Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
29
30
31
NEUTRON FLUX SPECTRUM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
33
Prompt Neutron Energies . . . . . . . . . . . . . . . . . .

Thermal and Fast Breeder Reactor Neutron Spectra
Most Probable Neutron Velocities . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . .
NP-02
Page ii
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
33
34
35
37
Rev. 0
Reactor Theory (Neutron Characteristics) DOE-HDBK-1019/1-93
LIST OF FIGURES
LIST OF FIGURES
Figure 1 Typical Neutron Absorption Cross Section vs. Neutron Energy . . . . . . . . . . . . . 9
Figure 2 Prompt Fission Neutron Energy Spectrum for Thermal Fission
of Uranium-235 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Figure 3 Comparison of Neutron Flux Spectra for Thermal and Fast Breeder Reactor . . . 34
Rev. 0
Page iii
NP-02
LIST OF TABLES
DOE-HDBK-1019/1-93
LIST OF TABLES
Table 1 Neutron Production by Spontaneous Fission . . . . . . . . . . . . . . . . . . . . . . . . .
Table 2 Moderating Properties of Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
27
Table 3 Delayed Neutron Precursor Groups for Thermal Fission in Uranium-235 . . . . .
30
NP-02
Page iv
Rev. 0
DOE-HDBK-1019/1-93
REFERENCES
REFERENCES
Jacobs, A.M., Kline, D.E., and Remick, F. J., Basic Principles of Nuclear Science and
1972.
Rev. 0
Page v
NP-02
OBJECTIVES
DOE-HDBK-1019/1-93
TERMINAL OBJECTIVE
1.0
Without references, EXPLAIN how neutron sources produce neutrons.
ENABLING OBJECTIVES
1.1
a.
b.
Intrinsic neutron source

Installed neutron source
1.2
LIST three examples of reactions that produce neutrons in intrinsic neutron sources.
1.3
LIST three examples of reactions that produce neutrons in installed neutron sources.
NP-02
Page vi
Rev. 0
DOE-HDBK-1019/1-93
OBJECTIVES
TERMINAL OBJECTIVE
2.0
Given the necessary information for calculations, EXPLAIN basic concepts in reactor
physics and perform calculations.
ENABLING OBJECTIVES
2.1
a.
b.
c.
Atom density
Neutron flux
Microscopic cross section
d.
e.
f.
Barn
Macroscopic cross section
Mean free path
2.2
EXPRESS macroscopic cross section in terms of microscopic cross section.
2.3
DESCRIBE how the absorption cross section of typical nuclides varies with neutron
energy at energies below the resonance absorption region.

2.4
DESCRIBE the cause of resonance absorption in terms of nuclear energy levels.
2.5
DESCRIBE the energy dependence of resonance absorption peaks for typical light and
heavy nuclei.
2.6
EXPRESS mean free path in terms of macroscopic cross section.
2.7
Given the number densities (or total density and component fractions) and microscopic
cross sections of components, CALCULATE the macroscopic cross section for a mixture.
2.8
CALCULATE a macroscopic cross section given a material density, atomic mass, and
microscopic cross section.

2.9
EXPLAIN neutron shadowing or self-shielding.
2.10
Given the neutron flux and macroscopic cross section, CALCULATE the reaction rate.
2.11
DESCRIBE the relationship between neutron flux and reactor power.
Rev. 0
Page vii
NP-02
OBJECTIVES
DOE-HDBK-1019/1-93

2.12
DEFINE the following concepts:
a.
b.
c.
Thermalization
Moderator
Moderating ratio
d.
e.
Average logarithmic energy decrement

Macroscopic slowing down power
2.13
LIST three desirable characteristics of a moderator.
2.14
Given an average fractional energy loss per collision, CALCULATE the energy loss after
a specified number of collisions.
NP-02
Page viii
Rev. 0
DOE-HDBK-1019/1-93
OBJECTIVES
TERMINAL OBJECTIVE
3.0
Without references, EXPLAIN the production process and effects on fission of prompt
and delayed neutrons.
ENABLING OBJECTIVES
3.1
STATE the origin of prompt neutrons and delayed neutrons.
3.2
STATE the approximate fraction of neutrons that are born as delayed neutrons from the
fission of the following nuclear fuels:

a.
b.
Uranium-235
Plutonium-239
3.3
EXPLAIN the mechanism for production of delayed neutrons.
3.4
EXPLAIN prompt and delayed neutron generation times.
3.5
Given prompt and delayed neutron generation times and delayed neutron fraction,
CALCULATE the average generation time.
3.6
EXPLAIN the effect of delayed neutrons on reactor control.
Rev. 0
Page ix
NP-02
OBJECTIVES
DOE-HDBK-1019/1-93
TERMINAL OBJECTIVE
4.0
Without references, DESCRIBE the neutron energy spectrum for the type of reactor
presented in this module.
ENABLING OBJECTIVES
4.1
STATE the average energy at which prompt neutrons are produced.
4.2
DESCRIBE the neutron energy spectrum in the following reactors:
a.
b.
4.3
Fast reactor
Thermal reactor
EXPLAIN the reason for the particular shape of the fast, intermediate, and slow energy
regions of the neutron flux spectrum for a thermal reactor.
NP-02
Page x
Rev. 0
DOE-HDBK-1019/1-93
NEUTRON SOURCES
NEUTRON SOURCES
Neutrons from a variety of sources are always present in a reactor core. This is
true even when the reactor is shut down. Some of these neutrons are produced by
naturally occurring (intrinsic) neutron sources, while others may be the result of
fabricated (installed) neutron sources that are incorporated into the design of the
reactor. The neutrons produced by sources other than neutron-induced fission
are often grouped together and classified as source neutrons.
EO 1.1

a.
b.
Intrinsic neutron source

Installed neutron source
EO 1.2
LIST three examples of reactions that produce neutrons in

intrinsic neutron sources.
EO 1.3
LIST three examples of reactions that produce neutrons in

installed neutron sources.
Neutron Sources
In addition to neutron-induced fission, neutrons are produced by other reactions. The neutrons
produced by reactions other than neutron-induced fission are called source neutrons. Source
neutrons are important because they ensure that the neutron population remains high enough to
allow a visible indication of neutron level on the most sensitive monitoring instruments while the
reactor is shutdown and during the startup sequence. This verifies instrument operability and
allows monitoring of neutron population changes. Source neutrons can be classified as either
intrinsic or installed neutron sources.
Intrinsic Neutron Sources

Some neutrons will be produced in the materials present in the reactor due to a variety of
unavoidable reactions that occur because of the nature of these materials. Intrinsic neutron
sources are those neutron-producing reactions that always occur in reactor materials.
Rev. 0
Page 1
NP-02
NEUTRON SOURCES
DOE-HDBK-1019/1-93
A limited number of neutrons will always be present, even in a reactor core that has never been
operated, due to spontaneous fission of some heavy nuclides that are present in the fuel. Uranium238, uranium-235, and plutonium-239 undergo spontaneous fission to a limited extent. Uranium238, for example, yields almost 60 neutrons per hour per gram. Table 1 illustrates a comparison
of the rate at which different heavy nuclides produce neutrons by spontaneous fission.
Californium-252 is not an intrinsic neutron source, but will be discussed in the section on installed
neutron sources.
TABLE 1
Neutron Production by Spontaneous Fission
Nuclide
T1/2 (Fission)
T1/2 (-decay)
neutrons/sec/gram
235
92
1.8 x 1017 years
6.8 x 108 years
8.0 x 10-4
238
92
8.0 x 1015 years
4.5 x 109 years
1.6 x 10-2
239
94
Pu
5.5 x 105 years
2.4 x 104 years
3.0 x 10-2
240
94
Pu
1.2 x 1011 years
6.6 x 103 years
1.0 x 103
2.65 years
2.3 x 1012
252
98
Cf
66.0 years
Another intrinsic neutron source is a reaction involving natural boron and fuel. In some reactors,
natural boron is loaded into the reactor core as a neutron absorber to improve reactor control or
increase core life-time. Boron-11 (80.1% of natural boron) undergoes a reaction with the alpha
particle emitted by the radioactive decay of heavy nuclides in the fuel to yield a neutron as shown
below.

The boron-11 must be mixed with, or in very close proximity to, the fuel for this reaction because
of the short path length of the alpha particle. For a reactor core with this configuration, this (,n)
reaction is an important source of neutrons for reactor startup.
In a reactor that has been operated, another source of neutrons becomes significant. Neutrons may
be produced by the interaction of a gamma ray and a deuterium nucleus. This reaction is commonly
referred to as a photoneutron reaction because it is initiated by electromagnetic radiation and results
in the production of a neutron. The photoneutron reaction is shown below.
NP-02
Page 2
Rev. 0
DOE-HDBK-1019/1-93
NEUTRON SOURCES
There is an abundant supply of high energy gammas in a reactor that has been operated because
many of the fission products are gamma emitters.
All water-cooled reactors have some
deuterium present in the coolant in the reactor core because a small fraction of natural hydrogen
is the isotope deuterium. The atom percentage of deuterium in the water ranges from close to
the naturally occurring value (0.015%) for light water reactors to above 90% deuterium for heavy
water reactors. Therefore, the required conditions for production of photoneutrons exist.
The supply of gamma rays decreases with time after shutdown as the gamma emitters decay;
therefore, the photoneutron production rate also decreases. In a few particular reactors,
additional D2O (heavy water) may be added to the reactor to increase the production of
photoneutrons following a long shutdown period.
Installed Neutron Sources

Because intrinsic neutron sources can be relatively weak or dependent upon the recent power
history of the reactor, many reactors have artificial sources of neutrons installed. These neutron
sources ensure that shutdown neutron levels are high enough to be detected by the nuclear
instruments at all times. This provides a true picture of reactor conditions and any change in
these conditions. An installed neutron source is an assembly placed in or near the reactor for
the sole purpose of producing source neutrons.
One strong source of neutrons is the artificial nuclide californium-252, which emits neutrons at
the rate of about 2 x 1012 neutrons per second per gram as the result of spontaneous fission.
Important drawbacks for some applications may be its high cost and its short half-life (2.65
years).
Many installed neutron sources use the (,n) reaction with beryllium. These sources are
composed of a mixture of metallic beryllium (100% beryllium-9) with a small quantity of an
alpha particle emitter, such as a compound of radium, polonium, or plutonium. The reaction
that occurs is shown below.

The beryllium is intimately (homogeneously) mixed with the alpha emitter and is usually
enclosed in a stainless steel capsule.
Another type of installed neutron source that is widely used is a photoneutron source that
employs the (,n) reaction with beryllium. Beryllium is used for photoneutron sources because
its stable isotope beryllium-9 has a weakly attached last neutron with a binding energy of only
1.66 MeV. Thus, a gamma ray with greater energy than 1.66 MeV can cause neutrons to be
ejected by the (,n) reaction as shown below.
Rev. 0
Page 3
NP-02
NEUTRON SOURCES
DOE-HDBK-1019/1-93
Many startup sources of this type use antimony and beryllium because after activation with
neutrons the radioactive antimony becomes an emitter of high energy gammas. The photoneutron
sources of this type are constructed somewhat differently from the (,n) types. One design
incorporates a capsule of irradiated antimony enclosed in a beryllium sleeve. The entire assembly
is then encased in a stainless steel cladding. A large reactor may have several neutron sources of
this type installed within the core.
Summary
Neutron Sources Summary
&
Intrinsic neutron sources are sources of neutrons from materials that are in
the reactor for other purposes such as fuel, burnable poison, or moderator.
&
Installed neutron sources are materials or components placed in the reactor

specifically for the purpose of producing source neutrons.
&
Examples of intrinsic neutron sources are listed below.

Spontaneous fission of heavy nuclides in fuel, such as uranium-238,
uranium-235, and plutonium-239, results in fission fragments and
free neutrons.
Boron-11 mixed with the fuel undergoes an alpha-neutron reaction
and becomes nitrogen-14.
Deuterium present in the reactor coolant undergoes a gammaneutron reaction and becomes hydrogen-1.
&
Examples of installed neutron sources are listed below.

Spontaneous fission of californium-252 results in fission fragments
and free neutrons.
Beryllium-9 undergoes an alpha-neutron reaction (alpha from the
decay of plutonium, polonium, or radium) and becomes carbon-12.
Beryllium-9 undergoes a gamma-neutron reaction (high energy
gamma from decay of antimony-124) and becomes beryllium-8.
NP-02
Page 4
Rev. 0
DOE-HDBK-1019/1-93
NUCLEAR CROSS SECTIONS AND NEUTRON FLUX

To determine the frequency of neutron interactions, it is necessary to describe the
availability of neutrons to cause interaction and the probability of a neutron
interacting with material. The availability of neutrons and the probability of
interaction are quantified by the neutron flux and nuclear cross section.
EO 2.1

a.
b.
c.
Atom density
Neutron flux
Microscopic cross section
d.
e.
f.
Barn
Macroscopic cross section
Mean free path
EO 2.2
EXPRESS macroscopic cross section in terms of microscopic cross

section.
EO 2.3
DESCRIBE how the absorption cross section of typical nuclides

varies with neutron energy at energies below the resonance
absorption region.
EO 2.4
DESCRIBE the cause of resonance absorption in terms of nuclear

energy levels.
EO 2.5
DESCRIBE the energy dependence of resonance absorption peaks

for typical light and heavy nuclei.
EO 2.6
EXPRESS mean free path in terms of macroscopic cross section.
EO 2.7
Given the number densities (or total density and component

fractions) and microscopic cross sections of components,
CALCULATE the macroscopic cross section for a mixture.
EO 2.8
CALCULATE a macroscopic cross section given a material density,

atomic mass, and microscopic cross section.
EO 2.9
EXPLAIN neutron shadowing or self-shielding.
Rev. 0
Page 5
NP-02
DOE-HDBK-1019/1-93
Introduction
Fission neutrons are born with an average energy of about 2 MeV. These fast neutrons interact
with the reactor core materials in various absorption and scattering reactions. Collisions that
result in scattering are useful in slowing neutrons to thermal energies. Thermal neutrons may
be absorbed by fissile nuclei to produce more fissions or be absorbed in fertile material for
conversion to fissionable fuel. Absorption of neutrons in structural components, coolant, and
other non-fuel material results in the removal of neutrons without fulfilling any useful purpose.
To safely and efficiently operate a nuclear reactor it is necessary to predict the probability that
a particular absorption or scattering reaction will occur. Once these probabilities are known, if
the availability of neutrons can be determined, then the rate at which these nuclear reactions take
place can be predicted.
Atom Density
One important property of a material is the atom density. The atom density is the number of
atoms of a given type per unit volume of the material. To calculate the atom density of a
substance use Equation (2-1).
'
(2-1)
where:
N
=
' =
NA =
M =
NP-02
atom density (atoms/cm3)

density (g/cm3)
Avogadro's number (6.022 x 1023 atoms/mole)
gram atomic weight
Page 6
Rev. 0
DOE-HDBK-1019/1-93
Example:
A block of aluminum has a density of 2.699 g/cm3. If the gram atomic weight of
aluminum is 26.9815 g, calculate the atom density of the aluminum.
Solution:
NA
M
2.699
g
cm
6.022 x 1023
26.9815
6.024 x 1022
atoms
mole
g
mole
atoms
cm 3
Cross Sections
The probability of a neutron interacting with a nucleus for a particular reaction is dependent
upon not only the kind of nucleus involved, but also the energy of the neutron. Accordingly,
the absorption of a thermal neutron in most materials is much more probable than the absorption
of a fast neutron. Also, the probability of interaction will vary depending upon the type of
reaction involved.
The probability of a particular reaction occurring between a neutron and a nucleus is called the
microscopic cross section ( ) of the nucleus for the particular reaction. This cross section will
vary with the energy of the neutron. The microscopic cross section may also be regarded as the
effective area the nucleus presents to the neutron for the particular reaction. The larger the
effective area, the greater the probability for reaction.
Because the microscopic cross section is an area, it is expressed in units of area, or square
centimeters. A square centimeter is tremendously large in comparison to the effective area of
a nucleus, and it has been suggested that a physicist once referred to the measure of a square
centimeter as being "as big as a barn" when applied to nuclear processes. The name has
persisted and microscopic cross sections are expressed in terms of barns. The relationship
between barns and cm2 is shown below.
1 barn = 10-24 cm2
Rev. 0
Page 7
NP-02
DOE-HDBK-1019/1-93
Whether a neutron will interact with a certain volume of material depends not only on the
microscopic cross section of the individual nuclei but also on the number of nuclei within that
volume. Therefore, it is necessary to define another kind of cross section known as the
macroscopic cross section ( ). The macroscopic cross section is the probability of a given
reaction occurring per unit travel of the neutron. is related to the microscopic cross section
( ) by the relationship shown below.
(2-2)
where:
= macroscopic cross section (cm-1)
N = atom density of material (atoms/cm3)
= microscopic cross-section (cm2)
The difference between the microscopic and macroscopic cross sections is extremely important
and is restated for clarity. The microscopic cross section ( ) represents the effective target area
that a single nucleus presents to a bombarding particle. The units are given in barns or cm2.
The macroscopic cross section ( ) represents the effective target area that is presented by all of
the nuclei contained in 1 cm3 of the material. The units are given as 1/cm or cm-1.
A neutron interacts with an atom of the material it enters in two basic ways. It will either
interact through a scattering interaction or through an absorption reaction. The probability of
a neutron being absorbed by a particular atom is the microscopic cross section for absorption,
a. The probability of a neutron scattering off of a particular nucleus is the microscopic cross
section for scattering, s. The sum of the microscopic cross section for absorption and the
microscopic cross section for scattering is the total microscopic cross section, T.
T
Both the absorption and the scattering microscopic cross sections can be further divided. For
instance, the scattering cross section is the sum of the elastic scattering cross section ( se) and
the inelastic scattering cross section ( si).
s
se
si
The microscopic absorption cross section ( a) includes all reactions except scattering. However,
for most purposes it is sufficient to merely separate it into two categories, fission ( f) and
capture ( c). Radiative capture of neutrons was described in the Neutron Interactions chapter
of Module 1.
a
NP-02
Page 8
Rev. 0
DOE-HDBK-1019/1-93
The variation of absorption cross sections with neutron energy is often complicated. For many
elements the absorption cross sections are small, ranging from a fraction of a barn to a few
barns for slow (or thermal) neutrons.
For a considerable number of nuclides of moderately high (or high) mass numbers, an
examination of the variation of the absorption cross section with the energy of the incident
neutron reveals the existence of three regions on a curve of absorption cross section versus
neutron energy. This cross section is illustrated in Figure 1. First, the cross section decreases
steadily with increasing neutron energy in a low energy region, which includes the thermal range
(E < 1 eV). In this region the absorption cross section, which is often high, is inversely
proportional to the velocity (v). This region is frequently referred to as the "1/v region,"
because the absorption cross section is proportional to 1/v, which is the reciprocal of neutron
velocity. Following the 1/v region, there occurs the "resonance region" in which the cross
sections rise sharply to high values called "resonance peaks" for neutrons of certain energies,
and then fall again. These energies are called resonance energies and are a result of the affinity
of the nucleus for neutrons whose energies closely match its discrete, quantum energy levels.
That is, when the binding energy of a neutron plus the kinetic energy of the neutron are exactly
equal to the amount required to raise a compound nucleus from its ground state to a quantum
level, resonance absorption occurs. The following example problem further illustrates this point.
Figure 1 Typical Neutron Absorption Cross Section vs. Neutron Energy
Rev. 0
Page 9
NP-02
DOE-HDBK-1019/1-93
Assuming that uranium-236 has a nuclear quantum energy level at 6.8 MeV above its ground
state, calculate the kinetic energy a neutron must possess to undergo resonant absorption in
uranium-235 at this resonance energy level.
BE = [Mass( 235U) + Mass(neutron) - Mass(236U)] x 931 MeV/amu
BE = (235.043925 + 1.008665 - 236.045563) x 931 MeV/amu
BE = (0.007025 amu) x 931 MeV/amu = 6.54 MeV
6.8 MeV - 6.54 MeV = 0.26 MeV
The difference between the binding energy and the quantum energy level equals the amount of
kinetic energy the neutron must possess. The typical heavy nucleus will have many closelyspaced resonances starting in the low energy (eV) range. This is because heavy nuclei are
complex and have more possible configurations and corresponding energy states. Light nuclei,
being less complex, have fewer possible energy states and fewer resonances that are sparsely
distributed at higher energy levels.
For higher neutron energies, the absorption cross section steadily decreases as the energy of the
neutron increases. This is called the "fast neutron region." In this region the absorption cross
sections are usually less than 10 barns.
With the exception of hydrogen, for which the value is fairly large, the elastic scattering cross
sections are generally small, for example, 5 barns to 10 barns. This is close to the magnitude
of the actual geometric cross sectional area expected for atomic nuclei. In potential scattering,
the cross section is essentially constant and independent of neutron energy. Resonance elastic
scattering and inelastic scattering exhibit resonance peaks similar to those associated with
absorption cross sections. The resonances occur at lower energies for heavy nuclei than for light
nuclei. In general, the variations in scattering cross sections are very small when compared to
the variations that occur in absorption cross sections.
Mean Free Path

If a neutron has a certain probability of undergoing a particular interaction in one centimeter of
travel, then the inverse of this value describes how far the neutron will travel (in the average
case) before undergoing an interaction. This average distance traveled by a neutron before
interaction is known as the mean free path for that interaction and is represented by the symbol
. The relationship between the mean free path () and the macroscopic cross section (*) is
shown below.
NP-02
(2-3)
Page 10
Rev. 0
DOE-HDBK-1019/1-93
Calculation of Macroscopic Cross Section and Mean Free Path

Most materials are composed of several elements, and because most elements are composed of
several isotopes, most materials involve many cross sections, one for each isotope involved.
Therefore, to include all the isotopes within a given material, it is necessary to determine the
macroscopic cross section for each isotope and then sum all the individual macroscopic cross
sections. Equation (2-4) can be used to determine the macroscopic cross section for a composite
material.
= N1 )1 + N2 )2 + N3 )3 + ....... Nn)n
(2-4)
where:
Nn = the number of nuclei per cm3 of the nth element
)n = the microscopic cross section of the nth element
The following example problems illustrate the calculation of the macroscopic cross section for
a single element and for combinations of materials.
Example 1:
Find the macroscopic thermal neutron absorption cross section for iron, which has a
density of 7.86 g/cm3. The microscopic cross section for absorption of iron is 2.56 barns
and the gram atomic weight is 55.847 g.
Solution:
Step 1:
Using Equation (2-1), calculate the atom density of iron.
'
Step 2:
Use this atom density in Equation (2-2) to calculate the macroscopic

cross section.
Rev. 0
Page 11
NP-02
DOE-HDBK-1019/1-93
Example 2:
An alloy is composed of 95% aluminum and 5% silicon (by weight). The density of the
alloy is 2.66 g/cm3. Properties of aluminum and silicon are shown below.
Element
Gram Atomic Weight
)a (barns)
)s (barns)
Aluminum
26.9815
0.23
1.49
Silicon
28.0855
0.16
2.20
1.
Calculate the atom densities for the aluminum and silicon.
2.
Determine the absorption and scattering macroscopic cross sections for thermal
neutrons.
3.
Calculate the mean free paths for absorption and scattering.
Solution:
Step 1:
The density of the aluminum will be 95% of the total density. Using
Equation (2-1) yields the atom densities.
'
'
NP-02
Page 12
Rev. 0
Step 2:
NAl
a,Al
The macroscopic cross sections for absorption and scattering are

calculated using Equation (2-4).
NSi
5.64 x 1022
a,Si
atoms
cm
0.0134 cm
NAl
NSi
s,Al
5.64 x 1022
Step 3:
0.23 x 10
24
cm 2
2.85 x 1021
atoms
cm
0.16 x 10
24
cm 2
2.20 x 10
24
cm 2
s,Si
atoms
cm
0.0903 cm
DOE-HDBK-1019/1-93
1.49 x 10
24
cm 2
2.85 x 1021
atoms
cm
The mean free paths are calculated by inserting the macroscopic cross
sections calculated above into Equation (2-3).
1
a
a
1
1
0.01345 cm
74.3 cm
1
s
s
1
0.0903 cm
11.1 cm
Thus, a neutron must travel an average of 74.3 cm to interact by absorption in this alloy, but it
must travel only 11.1 cm to interact by scattering.
Rev. 0
Page 13
NP-02
DOE-HDBK-1019/1-93
Effects of Temperature on Cross Section

As discussed, the microscopic absorption cross section varies significantly as neutron energy
varies. The microscopic cross sections provided on most charts and tables are measured for a
standard neutron velocity of 2200 meters/second, which corresponds to an ambient temperature
of 68(F. Therefore, if our material is at a higher temperature, the absorption cross section will
be lower than the value for 68(F, and any cross sections which involve absorption (for example,
)a, )c, )f ) must be corrected for the existing temperature.
The following formula is used to correct microscopic cross sections for temperature. Although
the example illustrates absorption cross section, the same formula may be used to correct capture
and fission cross sections.
)
)
where:
) = microscopic cross section corrected for temperature

)o = microscopic cross section at reference temperature (68(F or 20(C)
To = reference temperature (68(F) in degrees Rankine ((R) or Kelvin ((K)
T = temperature for which corrected value is being calculated
NOTE: When using this formula, all temperatures must be converted to (R or (K.
(R
(K
= (F + 460
= (C + 273
Example:
What is the value of )f for uranium-235 for thermal neutrons at 500(F? Uranium-235
has a )f of 583 barns at 68(F.
Solution:
)
)
(
(

NP-02
Page 14
Rev. 0
DOE-HDBK-1019/1-93
Neutron Flux
Macroscopic cross sections for neutron reactions with materials determine the probability of one
neutron undergoing a specific reaction per centimeter of travel through that material. If one
wants to determine how many reactions will actually occur, it is necessary to know how many
neutrons are traveling through the material and how many centimeters they travel each second.
It is convenient to consider the number of neutrons existing in one cubic centimeter at any one
instant and the total distance they travel each second while in that cubic centimeter. The number
of neutrons existing in a cm3 of material at any instant is called neutron density and is
represented by the symbol n with units of neutrons/cm3. The total distance these neutrons can
travel each second will be determined by their velocity.
A good way of defining neutron flux (1) is to consider it to be the total path length covered by
all neutrons in one cubic centimeter during one second. Mathematically, this is the equation
below.
1 = nv
(2-5)
where:
1 = neutron flux (neutrons/cm2-sec)

n = neutron density (neutrons/cm3)
v = neutron velocity (cm/sec)
The term neutron flux in some applications (for example, cross section measurement) is used
as parallel beams of neutrons traveling in a single direction. The intensity (I) of a neutron beam
is the product of the neutron density times the average neutron velocity. The directional beam
intensity is equal to the number of neutrons per unit area and time (neutrons/cm2-sec) falling on
a surface perpendicular to the direction of the beam.
One can think of the neutron flux in a reactor as being comprised of many neutron beams
traveling in various directions. Then, the neutron flux becomes the scalar sum of these
directional flux intensities (added as numbers and not vectors), that is, 1 = I1 + I2 + I3 +...In .
Since the atoms in a reactor do not interact preferentially with neutrons from any particular
direction, all of these directional beams contribute to the total rate of reaction. In reality, at a
given point within a reactor, neutrons will be traveling in all directions.
Rev. 0
Page 15
NP-02
DOE-HDBK-1019/1-93
Self-Shielding
In some locations within the reactor, the flux level may be significantly lower than in other areas
due to a phenomenon referred to as neutron shadowing or self-shielding. For example, the
interior of a fuel pin or pellet will "see" a lower average flux level than the outer surfaces since
an appreciable fraction of the neutrons will have been absorbed and therefore cannot reach the
interior of the fuel pin. This is especially important at resonance energies, where the absorption
cross sections are large.
Summary
NP-02
Page 16
Rev. 0
DOE-HDBK-1019/1-93
Nuclear Cross Section and Neutron Flux Summary

&
Atom density (N) is the number of atoms of a given type per unit volume of
material.
&
Microscopic cross section ()) is the probability of a given reaction occurring

between a neutron and a nucleus.
&
Microscopic cross sections are measured in units of barns, where 1 barn = 10-24
cm2.
&
Macroscopic cross section (*) is the probability of a given reaction occurring per
unit length of travel of the neutron. The units for macroscopic cross section are
cm-1.
&
The mean free path () is the average distance that a neutron travels in a material
between interactions.
&
Neutron flux (1) is the total path length traveled by all neutrons in one cubic
centimeter of material during one second.
&
The macroscopic cross section for a material can be calculated using the equation
below.
* = N)
&
The absorption cross section for a material usually has three distinct regions. At
low neutron energies (<1 eV) the cross section is inversely proportional to the
neutron velocity.
&
Resonance absorption occurs when the sum of the kinetic energy of the neutron
and its binding energy is equal to an allowed nuclear energy level of the nucleus.
&
Resonance peaks exist at intermediate energy levels. For higher neutron energies,
the absorption cross section steadily decreases as the neutron energy increases.
&
The mean free path equals 1/*.
&
The macroscopic cross section for a mixture of materials can be calculated using
the equation below.
* = N1 )1 + N2 )2 + N3 )3 + ....... Nn)n
&
Rev. 0
Self-shielding is where the local neutron flux is depressed within a material due to
neutron absorption near the surface of the material.
Page 17
NP-02
REACTION RATES
DOE-HDBK-1019/1-93
REACTION RATES
It is possible to determine the rate at which a nuclear reaction will take place
based on the neutron flux, cross section for the interaction, and atom density of the
target. This relationship illustrates how a change in one of these items affects the
reaction rate.
EO 2.10
Given the neutron flux and macroscopic cross section,

CALCULATE the reaction rate.
EO 2.11
DESCRIBE the relationship between neutron flux and reactor

power.
Reaction Rates
If the total path length of all the neutrons in a cubic centimeter in a second is known, (neutron
flux (1)), and if the probability of having an interaction per centimeter path length is also known
(macroscopic cross section (*)), multiply them together to get the number of interactions taking
place in that cubic centimeter in one second. This value is known as the reaction rate and is
denoted by the symbol R. The reaction rate can be calculated by the equation shown below.
R =
1*
(2-6)
where:
R = reaction rate (reactions/sec)
1 = neutron flux (neutrons/cm2-sec)
* = macroscopic cross section (cm-1)
Substituting the fact that * = N ) into Equation (2-6) yields the equation below.
where:
= microscopic cross section (cm2)

N = atom density (atoms/cm3)
NP-02
Page 18
Rev. 0
DOE-HDBK-1019/1-93
REACTION RATES
The reaction rate calculated will depend on which macroscopic cross section is used in the
calculation. Normally, the reaction rate of greatest interest is the fission reaction rate.
Example:
If a one cubic centimeter section of a reactor has a macroscopic fission cross section of
0.1 cm-1, and if the thermal neutron flux is 1013 neutrons/cm2-sec, what is the fission rate
in that cubic centimeter?
Solution:
Rf
neutrons
1 x 1013
cm
1 x 1012
0.1 cm
sec
fissions
cm 3 sec
In addition to using Equation (2-6) to determine the reaction rate based on the physical properties
of material, it is also possible to algebraically manipulate the equation to determine physical
properties if the reaction rate is known.
Example:
A reactor operating at a flux level of 3 x 1013 neutrons/cm2-sec contains 1020 atoms of
uranium-235 per cm3. The reaction rate is 1.29 x 1012 fission/cm3. Calculate f and f.
Solution:
Step 1:
The macroscopic cross section can be determined by solving

Equation (2-6) for f and substituting the appropriate values.
Rf
Rf
f
1.29 x 1012
3 x 1013
0.043 cm
Rev. 0
fissions
cm 3 sec
neutrons
cm 2 sec
1
Page 19
NP-02
REACTION RATES
DOE-HDBK-1019/1-93
Step 2:
To find the microscopic cross section, replace

for f.
Rf
with (N x f) and solve
Rf
f
N
1.29 x 1012
1 x 1020
4.3 x 10
22
atoms
cm 3
fissions
cm 3 sec
3 x 1013
neutrons
cm 2 sec
1 barn
cm 2
1 x 10
24
cm 2
430 barns
Reactor Power Calculation

Multiplying the reaction rate per unit volume by the total volume of the core results in the total
number of reactions occurring in the core per unit time. If the amount of energy involved in each
reaction were known, it would be possible to determine the rate of energy release (power) due
to a certain reaction.
In a reactor where the average energy per fission is 200 MeV, it is possible to determine the
number of fissions per second that are necessary to produce one watt of power using the
following conversion factors.
1 fission
1 MeV
1 erg
1 watt
=
=
=
200 MeV
1.602 x 10-6 ergs
1 x 10-7 watt-sec
1 erg
1 x 10
watt sec
1 MeV
1.602 x 10 6erg
1 fission
200 MeV
3.12 x 1010
fissions
second
This is equivalent to stating that 3.12 x 1010 fissions release 1 watt-second of energy.
NP-02
Page 20
Rev. 0
DOE-HDBK-1019/1-93
REACTION RATES
The power released in a reactor can be calculated based on Equation (2-6). Multiplying the
reaction rate by the volume of the reactor results in the total fission rate for the entire reactor.
Dividing by the number of fissions per watt-sec results in the power released by fission in the
reactor in units of watts. This relationship is shown mathematically in Equation (2-7) below.
th
f
10
3.12 x 10
(2-7)
fissions
watt sec
where:
P
th
f
=
=
=
=
power (watts)
thermal neutron flux (neutrons/cm2-sec)
macroscopic cross section for fission (cm-1)
volume of core (cm3)
Relationship Between Neutron Flux and Reactor Power

In an operating reactor the volume of the reactor is constant. Over a relatively short period of
time (days or weeks), the number density of the fuel atoms is also relatively constant. Since the
atom density and microscopic cross section are constant, the macroscopic cross section must also
be constant. Examining Equation (2-7), it is apparent that if the reactor volume and macroscopic
cross section are constant, then the reactor power and the neutron flux are directly proportional.
This is true for day-to-day operation. The neutron flux for a given power level will increase very
slowly over a period of months due to the burnup of the fuel and resulting decrease in atom
density and macroscopic cross section.
Rev. 0
Page 21
NP-02
REACTION RATES
DOE-HDBK-1019/1-93
Summary
Reaction Rates Summary

&
The reaction rate is the number of interactions of a particular type occurring in a

cubic centimeter of material in a second.
&
The reaction rate can be calculated by the equation below.

R=1*
&
NP-02
Over a period of several days, while the atom density of the fuel can be considered
constant, the neutron flux is directly proportional to reactor power.
Page 22
Rev. 0
DOE-HDBK-1019/1-93
NEUTRON MODERATION
NEUTRON MODERATION
In thermal reactors, the neutrons that cause fission are at a much lower energy
than the energy level at which they were born from fission. In this type of
reactor, specific materials must be included in the reactor design to reduce the
energy level of the neutrons in an efficient manner.
EO 2.12 DEFINE the following concepts:
a. Thermalization
b. Moderator
c. Moderating ratio
d. Average logarithmic energy decrement

e. Macroscopic slowing down power
EO 2.13 LIST three desirable characteristics of a moderator.

EO 2.14 Given an average fractional energy loss per collision,
CALCULATE the energy loss after a specified number of
collisions.
Neutron Slowing Down and Thermalization

Fission neutrons are produced at an average energy level of 2 MeV and immediately begin to
slow down as the result of numerous scattering reactions with a variety of target nuclei. After
a number of collisions with nuclei, the speed of a neutron is reduced to such an extent that it has
approximately the same average kinetic energy as the atoms (or molecules) of the medium in
which the neutron is undergoing elastic scattering. This energy, which is only a small fraction
of an electron volt at ordinary temperatures (0.025 eV at 20(C), is frequently referred to as the
thermal energy, since it depends upon the temperature. Neutrons whose energies have been
reduced to values in this region (< 1 eV) are designated thermal neutrons. The process of
reducing the energy of a neutron to the thermal region by elastic scattering is referred to as
thermalization, slowing down, or moderation. The material used for the purpose of thermalizing
neutrons is called a moderator. A good moderator reduces the speed of neutrons in a small
number of collisions, but does not absorb them to any great extent. Slowing the neutrons in as
few collisions as possible is desirable in order to reduce the amount of neutron leakage from the
core and also to reduce the number of resonance absorptions in non-fuel materials. Neutron
leakage and resonance absorption will be discussed in the next module.
Rev. 0
Page 23
NP-02
NEUTRON MODERATION
DOE-HDBK-1019/1-93
The ideal moderating material (moderator) should have the following nuclear properties.
large scattering cross section
small absorption cross section
large energy loss per collision
A convenient measure of energy loss per collision is the logarithmic energy decrement. The
average logarithmic energy decrement is the average decrease per collision in the logarithm of
the neutron energy. This quantity is represented by the symbol (Greek letter xi).
ln Ei
ln Ef
(2-8)
Ei
ln
Ef
where:
Ei
Ef
= average logarithmic energy decrement

= average initial neutron energy
= average final neutron energy
The symbol is commonly called the average logarithmic energy decrement because of the fact
that a neutron loses, on the average, a fixed fraction of its energy per scattering collision. Since
the fraction of energy retained by a neutron in a single elastic collision is a constant for a given
material, is also a constant. Because it is a constant for each type of material and does not
depend upon the initial neutron energy, is a convenient quantity for assessing the moderating
ability of a material.
The values for the lighter nuclei are tabulated in a variety of sources. The following commonly
used approximation may be used when a tabulated value is not available.
2
A
2
3
This approximation is relatively accurate for mass numbers (A) greater than 10, but for some low
values of A it may be in error by over three percent.
NP-02
Page 24
Rev. 0
DOE-HDBK-1019/1-93
NEUTRON MODERATION
Since represents the average logarithmic energy loss per collision, the total number of collisions
necessary for a neutron to lose a given amount of energy may be determined by dividing into
the difference of the natural logarithms of the energy range in question. The number of collisions
(N) to travel from any energy, Ehigh, to any lower energy, Elow, can be calculated as shown below.
ln Ehigh
ln
ln Elow
Ehigh
Elow
Example:
How many collisions are required to slow a neutron from an energy of 2 MeV to a
thermal energy of 0.025 eV, using water as the moderator? Water has a value of 0.948
for .
Solution:
ln
N
ln
Ehigh
Elow
2 x 106 eV
0.025 eV
0.948
19.2 collisions
Sometimes it is convenient, based upon information known, to work with an average fractional
energy loss per collision as opposed to an average logarithmic fraction. If the initial neutron
energy level and the average fractional energy loss per collision are known, the final energy level
for a given number of collisions may be computed using the following formula.
Rev. 0
Page 25
NP-02
NEUTRON MODERATION
DOE-HDBK-1019/1-93
(2-9)
where:
Eo
EN
x
N
=
=
=
=
initial neutron energy

neutron energy after N collisions
average fractional energy loss per collision
number of collisions
Example:
If the average fractional energy loss per collision in hydrogen is 0.63, what will be the
energy of a 2 MeV neutron after (a) 5 collisions? (b) 10 collisions?
Solution:
a)
b)
Macroscopic Slowing Down Power

Although the logarithmic energy decrement is a convenient measure of the ability of a material
to slow neutrons, it does not measure all necessary properties of a moderator. A better measure
of the capabilities of a material is the macroscopic slowing down power. The macroscopic
slowing down power (MSDP) is the product of the logarithmic energy decrement and the
macroscopic cross section for scattering in the material. Equation (2-10) illustrates how to
calculate the macroscopic slowing down power.
NP-02
! (
(2-10)
Page 26
Rev. 0
DOE-HDBK-1019/1-93
NEUTRON MODERATION
Moderating Ratio
Macroscopic slowing down power indicates how rapidly a neutron will slow down in the material
in question, but it still does not fully explain the effectiveness of the material as a moderator. An
element such as boron has a high logarithmic energy decrement and a good slowing down power,
but it is a poor moderator because of its high probability of absorbing neutrons.
The most complete measure of the effectiveness of a moderator is the moderating ratio. The
moderating ratio is the ratio of the macroscopic slowing down power to the macroscopic cross
section for absorption. The higher the moderating ratio, the more effectively the material
performs as a moderator. Equation (2-11) shows how to calculate the moderating ratio of a
material.
MR
(2-11)
Moderating properties of different materials are compared in Table 2.
TABLE 2
Moderating Properties of Materials
Material
Rev. 0
Number of
Collisions to
Thermalize
Macroscopic
Slowing Down
Power
Moderating
Ratio
H2O
0.927
19
1.425
62
D2O
0.510
35
0.177
4830
Helium
0.427
42
9 x 10-6
51
Beryllium
0.207
86
0.154
126
Boron
0.171
105
0.092
0.00086
Carbon
0.158
114
0.083
216
Page 27
NP-02
NEUTRON MODERATION
DOE-HDBK-1019/1-93
Summary
Neutron Moderation Summary

&
Thermalization is the process of reducing the energy level of a neutron from the
energy level at which it is produced to an energy level in the thermal range.
&
The moderator is the reactor material that is present for the purpose of
thermalizing neutrons.
&
Moderating ratio is the ratio of the macroscopic slowing down power to the
macroscopic cross section for absorption.
&
The average logarithmic energy decrement (!) is the average change in the
logarithm of neutron energy per collision.
&
Macroscopic slowing down power is the product of the average logarithmic energy
decrement and the macroscopic cross section for scattering.
&
There are three desirable characteristics of a moderator.

1.
2.
3.
&
large scattering cross section

small absorption cross section
large energy loss per collision
The energy loss after a specified number of collisions can be calculated using the
equation below.
EN = Eo (1 - x)N
NP-02
Page 28
Rev. 0
DOE-HDBK-1019/1-93
PROMPT AND DELAYED NEUTRONS

Not all neutrons are released at the same time following fission. Most neutrons
are released virtually instantaneously and are called prompt neutrons. A very
small fraction of neutrons are released after the decay of fission products and are
called delayed neutrons. Although delayed neutrons are a very small fraction of
the total number of neutrons, they play an extremely important role in the control
of the reactor.
EO 3.1
STATE the origin of prompt neutrons and delayed neutrons.
EO 3.2
STATE the approximate fraction of neutrons that are born as

delayed neutrons from the fission of the following nuclear fuels:
a.
b.
Uranium-235
Plutonium-239
EO 3.3
EXPLAIN the mechanism for production of delayed neutrons.
EO 3.4
EXPLAIN prompt and delayed neutron generation times.
EO 3.5
Given prompt and delayed neutron generation times and

delayed neutron fraction, CALCULATE the average generation
time.
EO 3.6
EXPLAIN the effect of delayed neutrons on reactor control.
Neutron Classification
The great majority (over 99%) of the neutrons produced in fission are released within about 10-13
seconds of the actual fission event. These are called prompt neutrons. A small portion of fission
neutrons are delayed neutrons, which are produced for some time after the fission process has
taken place. The delayed neutrons are emitted immediately following the first beta decay of a
fission fragment known as a delayed neutron precursor. An example of a delayed neutron
precursor is bromine-87, shown below.
Rev. 0
Page 29
NP-02
DOE-HDBK-1019/1-93
For most applications, it is convenient to combine the known precursors into groups with
appropriately averaged properties. These groups vary somewhat depending on the fissile
material in use. Table 3 lists the characteristics for the six precursor groups resulting from
thermal fission of uranium-235. The fraction of all neutrons that are produced by each of these
precursors is called the delayed neutron fraction for that precursor. The total fraction of all
neutrons born as delayed neutrons is called the delayed neutron fraction (). The fraction of
delayed neutrons produced varies depending on the predominant fissile nuclide in use. The
delayed neutron fractions () for the fissile nuclides of most interest are as follows: uranium-233
(0.0026), uranium-235 (0.0065), uranium-238 (0.0148), and plutonium-239 (0.0021).
TABLE 3
Delayed Neutron Precursor Groups
for Thermal Fission in Uranium-235
Group
Half-Life
(sec)
55.7
0.00021
0.25
22.7
0.00142
0.46
6.2
0.00127
0.41
2.3
0.00257
0.45
0.61
0.00075
0.41
0.23
0.00027
0.0065
Total
Delayed Neutron
Fraction
Average Energy
(MeV)
Neutron Generation Time

The neutron generation time is the time required for neutrons from one generation to cause the
fissions that produce the next generation of neutrons. The generation time for prompt neutrons
(5* - pronounced "ell-star") is the total time from birth to rebirth. Three time intervals are
involved: (a) the time it takes a fast neutron to slow down to thermal energy, (b) the time the
now thermal neutron exists prior to absorption in fuel, and (c) the time required for a fissionable
nucleus to emit a fast neutron after neutron absorption.
Fast neutrons slow to thermal energies or leak out of the reactor in 10-4 seconds to 10-6 seconds,
depending on the moderator. In water moderated reactors, thermal neutrons tend to exist for
about 10-4 seconds before they are absorbed. Fission and fast neutron production following
neutron absorption in a fissionable nucleus occurs in about 10-13 seconds. Thus, fast reactors
have an 5* of about 10-6 seconds, while thermal reactors have an 5* of about 10-6 seconds + 10-4
seconds, which is about 10-4 seconds to 10-5 seconds.
NP-02
Page 30
Rev. 0
DOE-HDBK-1019/1-93
On the other hand, the average generation time for the six delayed neutron groups is the total
time from the birth of the fast neutron to the emission of the delayed neutron. Again, three time
intervals are involved: (a) the time it takes a fast neutron to slow down to thermal energy,
(b) the time the thermal neutron exists prior to absorption, and (c) the average time from neutron
absorption to neutron emission by the six precursor groups. The average time for decay of
precursors from uranium-235 is 12.5 seconds. The other terms in the delayed neutron
generation time are insignificant when compared to this value, and the average delayed neutron
generation time becomes 12.5 seconds.
A neutron generation time in the range of 10-4 seconds to 10-5 seconds or faster could result in
very rapid power excursions, and control would not be possible without the dependence upon
delayed neutrons to slow down the rate of the reaction. The average generation time, and hence
the rate that power can rise, is determined largely by the delayed neutron generation time. The
following equation shows this mathematically.

(2-12)
Example:
Assume a prompt neutron generation time for a particular reactor of 5 x 10-5 seconds and
a delayed neutron generation time of 12.5 seconds. If is 0.0065, calculate the average
generation time.
Solution:

This example demonstrates the effect delayed neutrons have on the neutron generation time and
thus reactor control. If a reactor were to be operated in a sustained chain reaction using only
prompt neutrons ( = 0), the generation time from the previous example would be about
5 x 10-5 seconds. However, by operating the reactor such that a 0.0065 fraction of neutrons are
delayed, the generation life time is extended to 0.0813 seconds, providing time for adequate
operator control. Therefore, although only a small fraction of the total neutron population,
delayed neutrons are extremely important to the control and maintenance of a sustained fission
chain reaction.
Summary
Rev. 0
Page 31
NP-02
DOE-HDBK-1019/1-93
Prompt and Delayed Neutrons Summary
&
Prompt neutrons are released directly from fission within 10-13 seconds of the
fission event.
&
Delayed neutrons are released from the decay of fission products that are called
delayed neutron precursors. Delayed neutron precursors are grouped according to
half-life. Half-lives vary from fractions of a second to almost a minute.
&
The fraction of neutrons born as delayed neutrons is different for different fuel
materials. Following are values for some common fuel materials.
Uranium-235
Plutonium-239
0.0065
0.0021
&
Delayed neutrons are produced by a classification of fission products known as

delayed neutron precursors. When a delayed neutron precursor undergoes a
- decay, it results in an excited daughter nucleus which immediately ejects a
neutron. Therefore, these delayed neutrons appear with a half-life of the delayed
neutron precursor.
&
The delayed neutron generation time is the total time from the birth of the fast
neutron to the emission of the delayed neutron in the next generation. Delayed
neutron generation times are dominated by the half-life of the delayed neutron
precursor. The average delayed neutron generation time is about 12.5 seconds.
&
A prompt neutron generation time is the sum of the amount of time it takes a fast
neutron to thermalize, the amount of time the neutron exists as a thermal neutron
before it is absorbed, and the amount of time between a fissionable nuclide
absorbing a neutron and fission neutrons being released. Prompt neutron
generation time is about 5 x 10-5 seconds.
&
The average neutron generation time can be calculated from the prompt and
delayed neutron generation times and the delayed neutron fraction using
Equation (2-12).
&
NP-02

Delayed neutrons are responsible for the ability to control the rate at which power
can rise in a reactor. If only prompt neutrons existed, reactor control would not be
possible due to the rapid power changes.
Page 32
Rev. 0
DOE-HDBK-1019/1-93
NEUTRON FLUX SPECTRUM

The number of neutrons that exist at a given energy level varies. A plot of either
the fraction of neutrons or the neutron flux at a given energy versus the energy
level is called a neutron energy spectrum. The neutron energy spectrum varies
widely for different types of reactors.
EO 4.1
STATE the average energy at which prompt neutrons are

produced.
EO 4.2
DESCRIBE the neutron energy spectrum in the following

reactors:
a.
b.
EO 4.3
Fast reactor
Thermal reactor
EXPLAIN the reason for the particular shape of the fast,

intermediate, and slow energy regions of the neutron flux
spectrum for a thermal reactor.
Prompt Neutron Energies

The neutrons produced by fission
are high energy neutrons, and
almost all fission neutrons have
energies between 0.1 MeV and
10 MeV. The neutron energy
distribution, or spectrum, may best
be described by plotting the
fraction of neutrons per MeV as a
function of neutron energy, as
shown in Figure 2. From this
figure it can be seen that the most
probable neutron energy is about
0.7 MeV. Also, from this data it
can be shown that the average
energy of fission neutrons is about
2 MeV. Figure 2 is the neutron
energy spectrum for thermal
fission in uranium-235. The values
will vary slightly for other
nuclides.
Rev. 0
Figure 2 Prompt Fission Neutron Energy Spectrum for

Thermal Fission of Uranium-235
Page 33
NP-02
DOE-HDBK-1019/1-93
Thermal and Fast Breeder Reactor Neutron Spectra

The spectrum of neutron energies produced by fission varies significantly from the energy
spectrum, or flux, existing in a reactor at a given time. Figure 3 illustrates the difference in
neutron flux spectra between a thermal reactor and a fast breeder reactor. The energy
distribution of neutrons from fission is essentially the same for both reactors, so the differences
in the curve shapes may be attributed to the neutron moderation or slowing down effects.
Figure 3 Comparison of Neutron Flux Spectra for

Thermal and Fast Breeder Reactor
No attempt is made to thermalize or slow down neutrons in the fast breeder reactor (liquid metal
cooled); therefore, an insignificant number of neutrons exist in the thermal range. For the
thermal reactor (water moderated), the spectrum of neutrons in the fast region (> 0.1 MeV) has
a shape similar to that for the spectrum of neutrons emitted by the fission process.
In the thermal reactor, the flux in the intermediate energy region (1 eV to 0.1 MeV) has
approximately a 1/E dependence. That is, if the energy (E) is halved, the flux doubles. This
1/E dependence is caused by the slowing down process, where elastic collisions remove a
constant fraction of the neutron energy per collision (on the average), independent of energy;
thus, the neutron loses larger amounts of energy per collision at higher energies than at lower
energies. The fact that the neutrons lose a constant fraction of energy per collision causes the
neutrons to tend to "pile up" at lower energies, that is, a greater number of neutrons exist at the
lower energies as a result of this behavior.
NP-02
Page 34
Rev. 0
DOE-HDBK-1019/1-93
In the thermal region the neutrons achieve a thermal equilibrium with the atoms of the moderator
material. In any given collision they may gain or lose energy, and over successive collisions
will gain as much energy as they lose. These thermal neutrons, even at a specific temperature,
do not all have the same energy or velocity; there is a distribution of energies, usually referred
to as the Maxwell distribution (e.g., Figure 2). The energies of most thermal neutrons lie close
to the most probable energy, but there is a spread of neutrons above and below this value.
Most Probable Neutron Velocities

The most probable velocity (vp) of a thermal neutron is determined by the temperature of the
medium and can be determined by Equation (2-13) .
vp
2 k T
m
(2-13)
where:
vp
k
T
m
=
=
=
=
most probable velocity of neutron (cm/sec)

Boltzman's constant (1.38 x 10-16 erg/ K)
absolute temperature in degrees Kelvin ( K)
mass of neutron (1.66 x 10-24 grams)
Example:
Calculate the most probable velocities for neutrons in thermal equilibrium with their
surroundings at the following temperatures. a) 20 C, b) 260 C.
Solution:
a)
Calculate the most probable velocity for 20 C using Equation (2-13).
vp
2 k T
m
2 1.38 x 10
16
erg
K
1.66 x 10
2.2 x 105
2200
Rev. 0
cm
sec
24
293 K
g
1 m
100 cm
m
sec
Page 35
NP-02
b)
DOE-HDBK-1019/1-93
Calculate the most probable velocity for 260 C using Equation (2-13).
vp
2 k T
m
2 1.38 x 10
16
erg
K
1.66 x 10
2.977 x 105
2977
cm
sec
24
533 K
g
1 m
100 cm
m
sec
From these calculations it is evident that the most probable velocity of a thermal neutron
increases as temperature increases. The most probable velocity at 20 C is of particular
importance since reference data, such as nuclear cross sections, are tabulated for a neutron
velocity of 2200 meters per second.
NP-02
Page 36
Rev. 0
DOE-HDBK-1019/1-93
Summary
Neutron Flux Spectrum Summary

&
Prompt neutrons are born at energies between 0.1 MeV and 10 MeV. The
average prompt neutron energy is about 2 MeV.
&
Fast reactors have a neutron energy spectrum that has the same shape as the
prompt neutron energy spectrum.
&
Thermal reactors have a neutron energy spectrum that has two pronounced
peaks, one in the thermal energy region where the neutrons are in thermal
equilibrium with the core materials and another in the fast region at energies
where neutrons are produced. The flux in the intermediate region (1 eV to
0.1 MeV) has a roughly 1/E dependence.
&
The neutron flux spectrum for the fast energy region of a thermal reactor has a
shape similar to that of the spectrum of neutrons emitted by the fission process.
&
The reason for the 1/E flux dependence at intermediate energy levels in a
thermal reactor is due to the neutrons' tendency to lose a constant fraction of
energy per collision. Since the neutrons lose a greater amount at the higher
energies, the neutrons tend to "pile up" at lower energies where they lose less
energy per collision.
&
The neutron flux spectrum for the slow region of a thermal reactor contains a
peak at the energy where the neutrons are in thermal equilibrium with the atoms
of the surrounding material.
Rev. 0
Page 37
NP-02
DOE-HDBK-1019/1-93
NP-02
Page 38
Rev. 0
DOE-HDBK-1019/2-93
JANUARY 1993

NUCLEAR PHYSICS
AND REACTOR THEORY
Volume 2 of 2

FSC-6910
Technical Information, P.O. Box 62, Oak Ridge, TN 37831.
Available to the public from the National Technical Information Service, U.S.
DOE-HDBK-1019/1-93
ABSTRACT
The Nuclear Physics and Reactor Theory Handbook was developed to assist nuclear
facility operating contractors in providing operators, maintenance personnel, and the technical
staff with the necessary fundamentals training to ensure a basic understanding of nuclear physics
and reactor theory. The handbook includes information on atomic and nuclear physics; neutron
characteristics; reactor theory and nuclear parameters; and the theory of reactor operation. This
information will provide personnel with a foundation for understanding the scientific principles
that are associated with various DOE nuclear facility operations and maintenance.
Key Words: Training Material, Atomic Physics, The Chart of the Nuclides, Radioactivity,
Radioactive Decay, Neutron Interaction, Fission, Reactor Theory, Neutron Characteristics,
Neutron Life Cycle, Reactor Kinetics
Rev. 0
NP
DOE-HDBK-1019/1-93
F OREWOR D
The DOE Fundamentals Handbooks represent the needs of various DOE nuclear facilities'
Each handbook contains an abstract, a foreword, an overview, learning objectives, and
text material, and is divided into modules so that content and order may be modified by
individual DOE contractors to suit their specific training needs. Each handbook is supported by
a separate examination bank with an answer key.
Rev. 0
NP
DOE-HDBK-1019/1-93
OVERVIEW
The Department of Energy Fundamentals Handbook entitled Nuclear Physics and Reactor
Theory was prepared as an information resource for personnel who are responsible for the
operation of the Department's nuclear facilities. Almost all processes that take place in a nuclear
facility involves the transfer of some type of energy. A basic understanding of nuclear physics
and reactor theory is necessary for DOE nuclear facility operators, maintenance personnel, and
the technical staff to safely operate and maintain the facility and facility support systems. The
information in this handbook is presented to provide a foundation for applying engineering
concepts to the job. This knowledge will help personnel understand the impact that their actions
may have on the safe and reliable operation of facility components and systems.
The Nuclear Physics and Reactor Theory handbook consists of four modules that are
contained in two volumes. The following is a brief description of the information presented in
each module of the handbook.
Volume 1 of 2
Module 1 - Atomic and Nuclear Physics
Introduces concepts of atomic physics including the atomic nature of matter, the
chart of the nuclides, radioactivity and radioactive decay, neutron interactions and
fission, and the interaction of radiation with matter.
Provides information on reactor theory and neutron characteristics. Includes
topics such as neutron sources, neutron flux, neutron cross sections, reaction rates,
neutron moderation, and prompt and delayed neutrons.
Rev. 0
NP
DOE-HDBK-1019/1-93
OVERVIEW (Cont.)
Volume 2 of 2
Explains the nuclear parameters associated with reactor theory. Topics include
the neutron life cycle, reactivity and reactivity coefficients, neutron poisons, and
control rods.
Module 4 - Reactor Theory (Reactor Operations)
Introduces the reactor operations aspect of reactor theory. Topics include
subcritical multiplication, reactor kinetics, and reactor operation.
The information contained in this handbook is not all-encompassing. An attempt to
present the entire subject of nuclear physics and reactor theory would be impractical. However,
the Nuclear Physics and Reactor Theory handbook presents enough information to provide the
reader with the fundamental knowledge necessary to understand the advanced theoretical
concepts presented in other subject areas, and to understand basic system and equipment
operation.
Rev. 0
NP
NUCLEAR PHYSICS
AND REACTOR THEORY
M odule 3
Reactor Theory (Nuclear Parameters)
DOE-HDBK-1019/2-93
TABLE OF CONTENTS
TABLE OF C ONTENTS
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii

LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vi
NEUTRON LIFE CYCLE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Infinite Multiplication Factor, k . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Four Factor Formula . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fast Fission Factor, ( ) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Resonance Escape Probability, (p) . . . . . . . . . . . . . . . . . . . . . . . . . . .
Thermal Utilization Factor, (f) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reproduction Factor, () . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Effective Multiplication Factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fast Non-Leakage Probability ( f) . . . . . . . . . . . . . . . . . . . . . . . . . . .
Thermal Non-Leakage Probability ( t) . . . . . . . . . . . . . . . . . . . . . . . . .
Six Factor Formula . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Neutron Life Cycle of a Fast Reactor . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
... 2
... 2
... 3
... 3
... 4
... 6
... 8
... 9
... 9
. . 10
. . 14
. . 14
REACTIVITY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Application of the Effective Multiplication Factor
Reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . .
Units of Reactivity . . . . . . . . . . . . . . . . . . . . .
Reactivity Coefficients and Reactivity Defects . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . .
17
18
19
21
22
REACTIVITY COEFFICIENTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
23
Rev. 0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Page i
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
17
.
.
.
.
.
Moderator Effects . . . . . . . . . . . .
Moderator Temperature Coefficient
Fuel Temperature Coefficient . . . .
Pressure Coefficient . . . . . . . . . .
Void Coefficient . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
24
26
26
27
27
28
NP-03
TABLE OF CONTENTS
DOE-HDBK-1019/2-93
TABLE OF C ONTENTS (Cont.)

NEUTRON POISONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fixed Burnable Poisons
Soluble Poisons . . . . .
Non-Burnable Poisons .
Summary . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
30
31
32
33
XENON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
34
Fission Product Poisons . . . . . . . . . . . . . . . . .

Production and Removal of Xenon-135 . . . . . .
Xenon-135 Response to Reactor Shutdown . . . .
Xenon-135 Oscillations . . . . . . . . . . . . . . . . .
Xenon-135 Response to Reactor Power Changes
Summary . . . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
NP-03
Page ii
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
48
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
CONTROL RODS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
43
45
46
47
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Selection of Control Rod Materials . . . . . .

Types of Control Rods . . . . . . . . . . . . . .
Control Rod Effectiveness . . . . . . . . . . . .
Integral and Differential Control Rod Worth
Rod Control Mechanisms . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
43
.
.
.
.
.
.
.
.
.
.
.
.
.
.
SAMARIUM AND OTHER FISSION PRODUCT POISONS . . . . . . . . . . . . . . . . . . .

.
.
.
.
.
.
.
.
.
.
.
.
.
.
34
35
38
39
40
41
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Production and Removal of Samarium-149 . . .

Samarium-149 Response to Reactor Shutdown
Other Neutron Poisons . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
30
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
48
49
50
51
57
57
Rev. 0
DOE-HDBK-1019/2-93
LIST OF FIGURES
LIST OF FIGURES
Figure 1
Neutron Life Cycle with keff = 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Figure 2
Effects of Over and Under Moderation on keff . . . . . . . . . . . . . . . . . . . . . . . 25
Figure 3
Effect of Fuel Temperature on Resonance Absorption Peaks . . . . . . . . . . . . . 27
Figure 4
Equilibrium Iodine-135 and Xenon-135 Concentrations Versus Neutron Flux . . 37
Figure 5
Xenon-135 Reactivity After Reactor Shutdown . . . . . . . . . . . . . . . . . . . . . . 38
Figure 6
Xenon-135 Variations During Power Changes . . . . . . . . . . . . . . . . . . . . . . . 40
Figure 7
Behavior of Samarium-149 in a Typical Light Water Reactor . . . . . . . . . . . . . 46
Figure 8
Effect of Control Rod on Radial Flux Distribution . . . . . . . . . . . . . . . . . . . . 50
Figure 9
Integral Control Rod Worth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
Figure 10 Differential Control Rod Worth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

Figure 11 Rod Worth Curves for Example Problems . . . . . . . . . . . . . . . . . . . . . . . . . 53
Figure 12 Rod Worth Curves From Example 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Rev. 0
Page iii
NP-03
LIST OF TABLES
DOE-HDBK-1019/2-93
LIST OF TABLES
Table 1 Average Number of Neutrons Liberated in Fission . . . . . . . . . . . . . . . . . . . . . . 7
NP-03
Page iv
Rev. 0
DOE-HDBK-1019/2-93
REFERENCES
REFERENCES
1972.
Rev. 0
Page v
NP-03
OBJECTIVES
DOE-HDBK-1019/2-93
TERMINAL OBJECTIVE
1.0
Using appropriate references, DESCRIBE the neutron life cycle discussed in this
module.
ENABLING OBJECTIVE S
1.1
a.
b.
c.
d.
e.
1.2
Infinite multiplication factor, k

Effective multiplication factor, keff
Subcritical
Critical
Supercritical
DEFINE each term in the six factor formula using the ratio of the number of neutrons
present at different points in the neutron life cycle.

1.3
Given the macroscopic cross sections for various materials, CALCULATE the thermal
utilization factor.
1.4
Given microscopic cross sections for absorption and fission, atom density, and ,
CALCULATE the reproduction factor.
1.5
Given the numbers of neutrons present at the start of a generation and values for each
factor in the six factor formula, CALCULATE the number of neutrons that will be
present at any point in the life cycle.
1.6
LIST physical changes in the reactor core that will have an effect on the thermal
utilization factor, reproduction factor, or resonance escape probability.
1.7
EXPLAIN the effect that temperature changes will have on the following factors:
a.
b.
c.
d.
1.8
NP-03
Thermal utilization factor

Resonance escape probability
Fast non-leakage probability
Thermal non-leakage probability
Given the number of neutrons in a reactor core and the effective multiplication factor,
CALCULATE the number of neutrons present after any number of generations.
Page vi
Rev. 0
DOE-HDBK-1019/2-93
OBJECTIVES

1.9
DEFINE the term reactivity.
1.10
CONVERT between reactivity and the associated value of keff.
1.11
CONVERT measures of reactivity between the following units:
a.
b.
k/k
%k/k
c.
d.
10-4 k/k
Percent millirho (pcm)
1.12
EXPLAIN the relationship between reactivity coefficients and reactivity defects.
Rev. 0
Page vii
NP-03
OBJECTIVES
DOE-HDBK-1019/2-93
TERMINAL OBJECTIVE
2.0
From memory, EXPLAIN how reactivity varies with the thermodynamic properties of
the moderator and the fuel.
2.1
EXPLAIN the conditions of over moderation and under moderation.
2.2
EXPLAIN why many reactors are designed to be operated in an under moderated
condition.
2.3
STATE the effect that a change in moderator temperature will have on the moderator to
fuel ratio.
2.4
DEFINE the temperature coefficient of reactivity.
2.5
EXPLAIN why a negative temperature coefficient of reactivity is desirable.
2.6
EXPLAIN why the fuel temperature coefficient is more effective than the moderator
temperature coefficient in terminating a rapid power rise.

2.7
EXPLAIN the concept of Doppler broadening of resonance absorption peaks.
2.8
LIST two nuclides that are present in some types of reactor fuel assemblies that have
significant resonance absorption peaks.
2.9
DEFINE the pressure coefficient of reactivity.
2.10
EXPLAIN why the pressure coefficient of reactivity is usually negligible in a reactor
cooled and moderated by a subcooled liquid.

2.11
DEFINE the void coefficient of reactivity.
2.12
IDENTIFY the moderator conditions under which the void coefficient of reactivity
becomes significant.
NP-03
Page viii
Rev. 0
DOE-HDBK-1019/2-93
OBJECTIVES
TERMINAL OBJECTIVE
3.0
Without references, DESCRIBE the use of neutron poisons.
3.1
a.
b.
c.
Burnable poison
Non-burnable poison
Chemical shim
3.2
EXPLAIN the use of burnable neutron poisons in a reactor core.
3.3
LIST the advantages and disadvantages of chemical shim over fixed burnable poisons.
3.4
STATE two reasons why fixed non-burnable neutron poisons are used in reactor cores.
3.5
STATE an example of a material used as a fixed non-burnable neutron poison.
Rev. 0
Page ix
NP-03
OBJECTIVES
DOE-HDBK-1019/2-93
TERMINAL OBJECTIVE
4.0
Without references, DESCRIBE the effects of fission product poisons on a reactor.
4.1
LIST two methods of production and two methods of removal for xenon-135 during
reactor operation.
4.2
STATE the equation for equilibrium xenon-135 concentration.
4.3
DESCRIBE how equilibrium xenon-135 concentration varies with reactor power level.
4.4
DESCRIBE the causes and effects of a xenon oscillation.
4.5
DESCRIBE how xenon-135 concentration changes following a reactor shutdown from
steady-state conditions.
4.6
EXPLAIN the effect that pre-shutdown power levels have on the xenon-135
concentration after shutdown.
4.7
STATE the approximate time following a reactor shutdown at which the reactor can be
considered "xenon free."

4.8
EXPLAIN what is meant by the following terms:
a.
b.
4.9
Xenon precluded startup

Xenon dead time
DESCRIBE how xenon-135 concentration changes following an increase or a decrease
in the power level of a reactor.

4.10
DESCRIBE how samarium-149 is produced and removed from the reactor core during
reactor operation.
4.11
STATE the equation for equilibrium samarium-149 concentration.
4.12
DESCRIBE how equilibrium samarium-149 concentration varies with reactor power
level.
NP-03
Page x
Rev. 0
DOE-HDBK-1019/2-93
OBJECTIVES

4.13
DESCRIBE
how samarium-149 concentration

shutdown from steady-state conditions.
changes
following
reactor
4.14
DESCRIBE how samarium-149 concentration changes following a reactor startup.
4.15
STATE the conditions under which helium-3 will have a significant effect on the
reactivity of a reactor.
Rev. 0
Page xi
NP-03
OBJECTIVES
DOE-HDBK-1019/2-93
TERMINAL OBJECTIVE
5.0
Without references, DESCRIBE how control rods affect the reactor core.
5.1
DESCRIBE the difference between a "grey" neutron absorbing material and a "black"
neutron absorbing material.

5.2
EXPLAIN why a "grey" neutron absorbing material may be preferable to a "black"
neutron absorbing material for use in control rods.

5.3
EXPLAIN why resonance absorbers are sometimes preferred over thermal absorbers as
a control rod material.
5.4
a.
b.
5.5
Integral control rod worth

Differential control rod worth
DESCRIBE the shape of a typical differential control rod worth curve and explain the
reason for the shape.

5.6
DESCRIBE the shape of a typical integral control rod worth curve and explain the reason
for the shape.

5.7
Given an integral or differential control rod worth curve, CALCULATE the reactivity
change due to a control rod movement between two positions.
5.8
Given differential control rod worth data, PLOT differential and integral control rod
worth curves.
NP-03
Page xii
Rev. 0
DOE-HDBK-1019/2-93
NEUTRON LIFE CYCLE
NEUTRON LIFE C YCLE

Some number of the fast neutrons produced by fission in one generation will
eventually cause fission in the next generation. The series of steps that fission
neutrons go through as they slow to thermal energies and are absorbed in the
reactor is referred to as the neutron life cycle. The neutron life cycle is markedly
different between fast reactors and thermal reactors. This chapter presents the
neutron life cycle for thermal reactors.
EO 1.1

a.
b.
c.
d.
e.
Critical
Supercritical
EO 1.2
DEFINE each term in the six factor formula using the ratio of
the num ber of neutrons present at different points in the
neutron life cycle.
EO 1.3
Given the macroscopic cross sections for various materials,

CALCULATE the thermal utilization factor.
EO 1.4
Given m icroscopic cross sections for absorption and fission,

atom density, and , CALCULATE the reproduction factor.
EO 1.5
Given the numbers of neutrons present at the start of a generation

and values for each factor in the six factor formula, CALCULATE the
num ber of neutrons that will be present at any point in the life
cycle.
EO 1.6
LIST physical changes in the reactor core that will have an effect
on the thermal utilization factor, reproduction factor, or
resonance escape probability.
EO 1.7
EXPLAIN the effect that temperature changes will have on the

following factors:
a.
b.
c.
d.
Rev. 0
Infinite multiplication factor, k

Effective multiplication factor, k eff
Subcritical
Thermal utilization factor

Resonance escape probability
Fast non-leakage probability
Thermal non-leakage probability
Page 1
NP-03
NEUTRON LIFE CYCLE
DOE-HDBK-1019/2-93
Infinite M ultiplication Factor, k

Not all of the neutrons produced by fission will have the opportunity to cause new fissions
because some neutrons will be absorbed by non-fissionable material. Some will be absorbed
parasitically in fissionable material and will not cause fission, and others will leak out of the
reactor. For the maintenance of a self-sustaining chain reaction, however, it is not necessary
that every neutron produced in fission initiate another fission. The minimum condition is for
each nucleus undergoing fission to produce, on the average, at least one neutron that causes
fission of another nucleus. This condition is conveniently expressed in terms of a multiplication
factor.
The number of neutrons absorbed or leaking out of the reactor will determine the value of this
multiplication factor, and will also determine whether a new generation of neutrons is larger,
smaller, or the same size as the preceding generation. Any reactor of a finite size will have
neutrons leak out of it. Generally, the larger the reactor, the lower the fraction of neutron
leakage. For simplicity, we will first consider a reactor that is infinitely large, and therefore
has no neutron leakage. A measure of the increase or decrease in neutron flux in an infinite
reactor is the infinite multiplication factor, k. The infinite multiplication factor is the ratio of
the neutrons produced by fission in one generation to the number of neutrons lost through
absorption in the preceding generation. This can be expressed mathematically as shown below.
k
neutron production from fission in one generation

neutron absorption in the preceding generation
Four Factor Formula

A group of fast neutrons produced by fission can enter into several reactions. Some of these
reactions reduce the size of the neutron group while other reactions allow the group to increase
in size or produce a second generation. There are four factors that are completely independent
of the size and shape of the reactor that give the inherent multiplication ability of the fuel and
moderator materials without regard to leakage. This four factor formula accurately represents the
infinite multiplication factor as shown in the equation below.
k =
pf
where:
=
p =
f =
=
fast fission factor

resonance escape probability
thermal utilization factor
reproduction factor
Each of these four factors, which are explained in the following subsections, represents a process that
adds to or subtracts from the initial neutron group produced in a generation by fission.
NP-03
Page 2
Rev. 0
DOE-HDBK-1019/2-93
NEUTRON LIFE CYCLE
Fast Fission Factor, ( )

The first process that the neutrons of one generation may undergo is fast fission. Fast fission
is fission caused by neutrons that are in the fast energy range. Fast fission results in the net
increase in the fast neutron population of the reactor core. The cross section for fast fission in
uranium-235 or uranium-238 is small; therefore, only a small number of fast neutrons cause
fission. The fast neutron population in one generation is therefore increased by a factor called
the fast fission factor. The fast fission factor ( ) is defined as the ratio of the net number of fast
neutrons produced by all fissions to the number of fast neutrons produced by thermal fissions.
The mathematical expression of this ratio is shown below.
number of fast neutrons produced by all fissions
number of fast neutrons produced by thermal fissions
In order for a neutron to be absorbed by a fuel nucleus as a fast neutron, it must pass close
enough to a fuel nucleus while it is a fast neutron. The value of will be affected by the
arrangement and concentrations of the fuel and the moderator. The value of is essentially 1.00
for a homogenous reactor where the fuel atoms are surrounded by moderator atoms. However,
in a heterogeneous reactor, all the fuel atoms are packed closely together in elements such as
pins, rods, or pellets. Neutrons emitted from the fission of one fuel atom have a very good
chance of passing near another fuel atom before slowing down significantly. The arrangement
of the core elements results in a value of about 1.03 for in most heterogeneous reactors. The
value of is not significantly affected by variables such as temperature, pressure, enrichment,
or neutron poison concentrations. Poisons are non-fuel materials that easily absorb neutrons and
will be discussed in more detail later.
Resonance Escape Probability, (p)

After increasing in number as a result of some fast fissions, the neutrons continue to diffuse
through the reactor. As the neutrons move they collide with nuclei of fuel and non-fuel material
and moderator in the reactor losing part of their energy in each collision and slowing down.
While they are slowing down through the resonance region of uranium-238, which extends from
about 6 eV to 200 eV, there is a chance that some neutrons will be captured. The probability
that a neutron will not be absorbed by a resonance peak is called the resonance escape
probability. The resonance escape probability (p) is defined as the ratio of the number of
neutrons that reach thermal energies to the number of fast neutrons that start to slow down. This
ratio is shown below.
p
Rev. 0
number of neutrons that reach thermal energy

number of fast neutrons that start to slow down
Page 3
NP-03
NEUTRON LIFE CYCLE
DOE-HDBK-1019/2-93
The value of the resonance escape probability is determined largely by the fuel-moderator
arrangement and the amount of enrichment of uranium-235 (if any is used). To undergo
resonance absorption, a neutron must pass close enough to a uranium-238 nucleus to be absorbed
while slowing down. In a homogeneous reactor the neutron does its slowing down in the region
of the fuel nuclei, and this condition is easily met. This means that a neutron has a high
probability of being absorbed by uranium-238 while slowing down; therefore, its escape
probability is lower. In a heterogeneous reactor, however, the neutron slows down in the
moderator where there are no atoms of uranium-238 present. Therefore, it has a low probability
of undergoing resonance absorption, and its escape probability is higher.
The value of the resonance escape probability is not significantly affected by pressure or poison
concentration. In water moderated, low uranium-235 enrichment reactors, raising the
temperature of the fuel will raise the resonance absorption in uranium-238 due to the doppler
effect (an apparent broadening of the normally narrow resonance peaks due to thermal motion
of nuclei). The increase in resonance absorption lowers the resonance escape probability, and
the fuel temperature coefficient for resonance escape is negative (explained in detail later). The
temperature coefficient of resonance escape probability for the moderator temperature is also
negative. As water temperature increases, water density decreases. The decrease in water density
allows more resonance energy neutrons to enter the fuel and be absorbed. The value of the
resonance escape probability is always slightly less than one (normally 0.95 to 0.99).
The product of the fast fission factor and the resonance escape probability ( p) is the ratio of
the number of fast neutrons that survive slowing down (thermalization) compared to the number
of fast neutrons originally starting the generation.
Thermal Utilization Factor, (f)

Once thermalized, the neutrons continue to diffuse throughout the reactor and are subject to
absorption by other materials in the reactor as well as the fuel. The thermal utilization factor
describes how effectively thermal neutrons are absorbed by the fuel, or how well they are
utilized within the reactor. The thermal utilization factor (f) is defined as the ratio of the
number of thermal neutrons absorbed in the fuel to the number of thermal neutrons absorbed in
any reactor material. This ratio is shown below.
f
number of thermal neutrons absorbed in the fuel

number of thermal neutrons absorbed in all reactor materials
The thermal utilization factor will always be less than one because some of the thermal neutrons
absorbed within the reactor will be absorbed by atoms of non-fuel materials.
NP-03
Page 4
Rev. 0
DOE-HDBK-1019/2-93
NEUTRON LIFE CYCLE
An equation can be developed for the thermal utilization factor in terms of reaction rates as
follows.
f
rate of absorption of thermal neutrons by the fuel

rate of absorption of thermal neutrons by all reactor materials
Ua U V U
Ua U V U
ma m V m
pa p V p
The superscripts U, m, and p refer to uranium, moderator, and poison, respectively. In a

heterogeneous reactor, the flux will be different in the fuel region than in the moderator region
due to the high absorption rate by the fuel. Also, the volumes of fuel, moderator, and poisons
will be different. Although not shown in the above equation, other non-fuel materials, such as
core construction materials, may absorb neutrons in a heterogeneous reactor. These other
materials are often lumped together with the superscript designation OS, for "other stuff." To
be completely accurate, the above equation for the thermal utilization factor should include all
neutron-absorbing reactor materials when dealing with heterogeneous reactors. However, for the
purposes of this text, the above equation is satisfactory.
In a homogeneous reactor the neutron flux seen by the fuel, moderator, and poisons will be the
same. Also, since they are spread throughout the reactor, they all occupy the same volume. This
allows the previous equation to be rewritten as shown below.
Ua
Ua
ma
(3-1)
pa
Equation (3-1) gives an approximation for a heterogeneous reactor if the fuel and moderator are
composed of small elements distributed uniformly throughout the reactor.
Since absorption cross sections vary with temperature, it would appear that the thermal
utilization factor would vary with a temperature change. But, substitution of the temperature
correction formulas (see Module 2) in the above equation will reveal that all terms change by
the same amount, and the ratio remains the same. In heterogeneous water-moderated reactors,
there is another important factor. When the temperature rises, the water moderator expands, and
a significant amount of it will be forced out of the reactor core. This means that Nm, the number
of moderator atoms per cm3, will be reduced, making it less likely for a neutron to be absorbed
by a moderator atom. This reduction in Nm results in an increase in thermal utilization as
moderator temperature increases because a neutron now has a better chance of hitting a fuel atom.
Because of this effect, the temperature coefficient for the thermal utilization factor is positive.
The amount of enrichment of uranium-235 and the poison concentration will affect the thermal
utilization factor in a similar manner as can be seen from the equation above.
Rev. 0
Page 5
NP-03
NEUTRON LIFE CYCLE
DOE-HDBK-1019/2-93
Example:
Calculate the thermal utilization factor for a homogeneous reactor. The macroscopic
absorption cross section of the fuel is 0.3020 cm-1, the macroscopic absorption cross
section of the moderator is 0.0104 cm-1, and the macroscopic absorption cross section of
the poison is 0.0118 cm-1.
Solution:
f
Ua
Ua
ma
0.3020 cm
pa
1
0.3020 cm 1
0. 0104cm 1
0. 0118cm 1
0. 932
Reproduction Factor, ()
Most of the neutrons absorbed in the fuel cause fission, but some do not. The reproduction factor
() is defined as the ratio of the number of fast neurtons produces by thermal fission to the number
of themal neutrons absorbed in the fuel. The reproduction factor is shown below.
number of fast neutrons produced by thermal fission

The reproduction factor can also be stated as a ratio of rates as shown below.
rate of production of fast neutrons by thermal fission

rate of absorption of thermal neutrons by the fuel
The rate of production of fast neutrons by thermal fission can be determined by the product of the
fission reaction rate (fuu) and the average number of neutrons produced per fission (). The
average number of neutrons released in thermal fission of uranium-235 is 2.42. The rate of
absorption of thermal neutrons by the fuel is auu. Substituting these terms into the equation
above results in the following equation.
Uf U
Ua U
Table 1 lists values of and for fission of several different materials by thermal neutrons and
fast neutrons.
NP-03
Page 6
Rev. 0
DOE-HDBK-1019/2-93
NEUTRON LIFE CYCLE
TAB LE 1
Average Number of Neutrons Liberated in Fission
Fissile Nucleus
Thermal Neutrons
Fast Neutrons
Uranium-233
2.49
2.29
2.58
2.40
Uranium-235
2.42
2.07
2.51
2.35
Plutonium-239
2.93
2.15
3.04
2.90
In the case where the fuel contains several fissionable materials, it is necessary to account for
each material. In the case of a reactor core containing both uranium-235 and uranium-238, the
reproduction factor would be calculated as shown below.
N U 235 Uf 235 U 235

N U 235 Ua 235
(3-2)
NU 238 aU 238
Example:
Calculate the reproduction factor for a reactor that uses 10% enriched uranium fuel. The
microscopic absorption cross section for uranium-235 is 694 barns. The cross section
for uranium-238 is 2.71 barns. The microscopic fission cross section for uranium-235 is
582 barns. The atom density of uranium-235 is 4.83 x 1021 atoms/cm3. The atom density
of uranium-238 is 4.35 x 1022 atoms/cm3. is 2.42.
Solution:
Use Equation (3-2) to calculate the reproduction factor.
N U 235 Uf 235 U 235
N U 235 Ua 235
N U 238 Ua 238
4.83 x 1021
4.83 x 1021
atoms
cm 3
atoms
cm 3
582 x 10 24 cm 2 2.42
694 x 10 24 cm 2
4.35 x 1022
atoms
cm 3
2.71 x 10 24 cm 2
1.96
Rev. 0
Page 7
NP-03
NEUTRON LIFE CYCLE
DOE-HDBK-1019/2-93
As temperature varies, each absorption and fission microscopic cross section varies according to
the 1/v relationship (see Module 2). Since both the numerator and the denominator change
equally, the net change in is zero. Therefore, changes only as uranium-235 enrichment
changes. increases with enrichment because there is less uranium-238 in the reactor making
it more likely that a neutron absorbed in the fuel will be absorbed by uranium-235 and cause
fission.
To determine the reproduction factor for a single nuclide rather than for a mixture, the
calculation may be further simplified to the one shown below.
f
a
Effective M ultiplication Factor

The infinite multiplication factor can fully represent only a reactor that is infinitely large,
because it assumes that no neutrons leak out of the reactor. To completely describe the neutron
life cycle in a real, finite reactor, it is necessary to account for neutrons that leak out. The
multiplication factor that takes leakage into account is the effective multiplication factor (keff),
which is defined as the ratio of the neutrons produced by fission in one generation to the number
of neutrons lost through absorption and leakage in the preceding generation.
The effective multiplication factor may be expressed mathematically as shown below.
keff
neutron production from fission in one generation

neutron absorption in the
neutron leakage in the
preceding generation
preceding generation
So, the value of keff for a self-sustaining chain reaction of fissions, where the neutron population
is neither increasing nor decreasing, is one. The condition where the neutron chain reaction is
self-sustaining and the neutron population is neither increasing nor decreasing is referred to as
the critical condition and can be expressed by the simple equation keff = 1 .
If the neutron production is greater than the absorption and leakage, the reactor is called
supercritical. In a supercritical reactor, keff is greater than one, and the neutron flux increases
each generation. If, on the other hand, the neutron production is less than the absorption and
leakage, the reactor is called subcritical. In a subcritical reactor, keff is less than one, and the
flux decreases each generation.
NP-03
Page 8
Rev. 0
DOE-HDBK-1019/2-93
NEUTRON LIFE CYCLE
When the multiplication factor of a reactor is not equal to exactly one, the neutron flux will
change and cause a change in the power level. Therefore, it is essential to know more about
how this factor depends upon the contents and construction of the reactor. The balance between
production of neutrons and their absorption in the core and leakage out of the core determines
the value of the multiplication factor. If the leakage is small enough to be neglected, the
multiplication factor depends upon only the balance between production and absorption, and is
called the infinite multiplication factor (k) since an infinitely large core can have no leakage.
When the leakage is included, the factor is called the effective multiplication factor (k eff).
The effective multiplication factor (keff) for a finite reactor may be expressed mathematically in
terms of the infinite multiplication factor and two additional factors which account for neutron
leakage as shown below.
keff = k
Fast Non-Leakage Probability (
In a realistic reactor of finite size, some of the fast neutrons leak out of the boundaries of the
reactor core before they begin the slowing down process. The fast non-leakage probability ( f)
is defined as the ratio of the number of fast neutrons that do not leak from the reactor core to
the number of fast neutrons produced by all fissions. This ratio is stated as follows.
number of fast neutrons that do not leak from reactor

Thermal Non-Leakage Probability (
Neutrons can also leak out of a finite reactor core after they reach thermal energies. The
thermal non-leakage probability ( t) is defined as the ratio of the number of thermal neutrons
that do not leak from the reactor core to the number of neutrons that reach thermal energies. The
thermal non-leakage probability is represented by the following.
number of thermal neutrons that do not leak from reactor

number of neutrons that reach thermal energies
The fast non-leakage probability ( f) and the thermal non-leakage probability ( t) may be
combined into one term that gives the fraction of all neutrons that do not leak out of the reactor
core. This term is called the total non-leakage probability and is given the symbol T, where
T =
f t.
f and
t are both effected by a change in coolant temperature in a heterogeneous
water-cooled, water-moderated reactor. As coolant temperature rises, the coolant expands. The
density of the moderator is lower; therefore, neutrons must travel farther while slowing down.
This effect increases the probability of leakage and thus decreases the non-leakage probability.
Consequently, the temperature coefficient (defined later) for the non-leakage probabilities is
negative, because as temperature rises, f and t decrease.
Rev. 0
Page 9
NP-03
NEUTRON LIFE CYCLE
DOE-HDBK-1019/2-93
Six Factor Formula

With the inclusion of these last two factors it is possible to determine the fraction of neutrons that
remain after every possible process in a nuclear reactor. The effective multiplication factor (keff)
can then be determined by the product of six terms.
keff =
(3-3)
Equation (3-3) is called the six factor formula. Using this six factor formula, it is possible to
trace the entire neutron life cycle from production by fission to the initiation of subsequent
fissions. Figure 1 illustrates a neutron life cycle with nominal values provided for each of the
six factors. Refer to Figure 1 for the remainder of the discussion on the neutron life cycle and
sample calculations. The generation begins with 1000 neutrons. This initial number is
represented by No. The first process is fast fission and the population has been increased by the
neutrons from this fast fission process. From the definition of the fast fission factor it is
possible to calculate its value based on the number of neutrons before and after fast fission
occur.
1040
1000
1.04
The total number of fast neutrons produced by thermal and fast fission is represented by the
quantity No .
Next, it can be seen that 140 neutrons leak from the core before reaching the thermal energy
range. The fast non-leakage probability is calculated from its definition, as shown below.

1040 140
1040
0.865
The number of neutrons that remain in the core during the slowing down process is represented
by the quantity No
f.
NP-03
Page 10
Rev. 0
Figure 1
Rev. 0
DOE-HDBK-1019/2-93
NEUTRON LIFE CYCLE
Neutron Life Cycle with keff = 1
Page 11
NP-03
NEUTRON LIFE CYCLE
DOE-HDBK-1019/2-93
The next step in the analysis is to consider the number of neutrons that are absorbed in the
intermediate energy level. The probability of escaping this resonance absorption (p) is stated
as follows.
720
900
0.80
The number of neutrons entering the thermal energy range is now represented by the quantity
No
f p.
After reaching thermal energies, 100 neutrons leak from the core. The value for
calculated by substitution of the known values in the definition as shown below.
can be

620
720
0.861
The number of thermal neutrons available for absorption anywhere in the core is represented by
the quantity No
f p
t.
Figure 1 indicates that 125 neutrons were absorbed in non-fuel materials. Since a total of 620
thermal neutrons were absorbed, the number absorbed by the fuel equals 620 - 125 = 495.
Therefore, the thermal utilization factor can be calculated as follows.
f

number of thermal neutrons absorbed in any reactor material
495
620
0.799
NP-03
Page 12
Rev. 0
DOE-HDBK-1019/2-93
NEUTRON LIFE CYCLE
The final factor numerically describes the production of fission neutrons resulting from thermal
neutrons being absorbed in the fuel. This factor is called the reproduction factor (). The value
for the reproduction factor can be determined as shown below.

1000
495
2.02
The number of fission neutrons that exist at the end of the life cycle which are available to start
a new generation and cycle is represented by the quantity No
f p
t f .
In the example illustrated in Figure 1, keff is equal to one. Therefore, 1000 neutrons are
available to start the next generation.
Example:
10,000 neutrons exist at the beginning of a generation. The values for each factor of the
six factor formula are listed below. Calculate the number of neutrons that exist at the
points in the neutron life cycle listed below.
1)
2)
3)
4)
5)
6)
Number
Number
Number
Number
Number
Number
= 1.031
p = 0.803
of
of
of
of
of
of
f
t
neutrons that exist after fast fission.

neutrons that start to slow down in the reactor.
neutrons that reach thermal energies.
thermal neutrons that are absorbed in the reactor.
thermal neutrons absorbed in the fuel.
neutrons produced from thermal fission.
= 0.889
= 0.905
f = 0.751
= 2.012
Solution:
1)
2)
3)
4)
5)
6)
Rev. 0
N
N
N
N
N
N
=
=
=
=
=
=
No
No
No
No
No
No
= 10,310
f = 9,166
f p = 7,360
f p
t = 6,661
p
f
t f = 5,002
f p
t f = 10,065
Page 13
NP-03
NEUTRON LIFE CYCLE
DOE-HDBK-1019/2-93
Neutron Life Cycle of a Fast Reactor

The neutron life cycle in a fast reactor is markedly different than that for a thermal reactor. In
a fast reactor, care is taken during the reactor design to minimize thermalization of neutrons.
Virtually all fissions taking place in a fast reactor are caused by fast neutrons. Due to this, many
factors that are taken into account by the thermal reactor neutron life cycle are irrelevant to the
fast reactor neutron life cycle. The resonance escape probability is not significant because very
few neutrons exist at energies where resonance absorption is significant. The thermal
non-leakage probability does not exist because the reactor is designed to avoid the thermalization
of neutrons. A separate term to deal with fast fission is not necessary because all fission is fast
fission and is handled by the reproduction factor.
The thermal utilization factor is modified to describe the utilization of fast neutrons instead of
thermal neutrons. The reproduction factor is similarly modified to account for fast fission
instead of thermal fission.
Summary
The important information in this chapter is summarized on the following pages.
NP-03
Page 14
Rev. 0
DOE-HDBK-1019/2-93
NEUTRON LIFE CYCLE
Neutron Life Cycle Summary

The infinite multiplication factor, k, is the ratio of the neutrons produced by fission
in one generation to the number of neutrons lost through absorption in the preceding
generation.
The effective multiplication factor, keff, is the ratio of the number of neutrons
produced by fission in one generation to the number of neutrons lost through
absorption and leakage in the preceding generation.
Critical is the condition where the neutron chain reaction is self-sustaining and the
neutron population is neither increasing nor decreasing.
Subcritical is the condition in which the neutron population is decreasing each
generation.
Supercritical is the condition in which the neutron population is increasing each
generation.
The six factor formula is stated as keff =
f p
t f . Each of the six factors is
defined below.
f



number of thermal neutrons absorbed in all reactor materials
Rev. 0


Page 15
NP-03
NEUTRON LIFE CYCLE
DOE-HDBK-1019/2-93
Neutron Life Cycle Summary (Cont.)

The thermal utilization factor can be calculated from the macroscopic cross section
for absorption of reactor materials using Equation (3-1).
Ua
Ua
ma
pa
The reproduction factor can be calculated based on the characteristics of the reactor
fuel using Equation (3-2).
N U 235 Uf 235 U 235

N U 235 Ua 235
N U 238 Ua 238
The number of neutrons present at any point in the neutron life cycle can be
calculated as the product of the number of neutrons present at the start of the
generation and all the factors preceding that point in the life cycle.
The thermal utilization factor is effected by the enrichment of uranium-235, the
amount of neutron poisons, and the moderator-to-fuel ratio.
The reproduction factor is effected by the enrichment of uranium-235.
The resonance escape probability is effected by the enrichment of uranium-235, the
temperature of the fuel, and the temperature of the moderator.
An increase in moderator temperature will have the following effects.
Increase the thermal utilization factor
Decrease resonance escape probability
Decrease fast non-leakage probability
Decrease thermal non-leakage probability
NP-03
Page 16
Rev. 0
DOE-HDBK-1019/2-93
REACTIVITY
REACTIVITY
Reactivity is a measure of the departure of a reactor from criticality. The
reactivity is related to the value of keff . Reactivity is a useful concept to predict
how the neutron population of a reactor will change over time.
EO 1.8
Given the number of neutrons in a reactor core and the

effective m ultiplication factor, CALCULATE the number of
neutrons present after any number of generations.
EO 1.9
DEFINE the term reactivity.
EO 1.10
CONVERT between reactivity and the associated value of k eff.
EO 1.11
CONVERT measures of reactivity between the following units:

a.
b.
EO 1.12
k/k
% k/k
c.
d.
10 -4 k/k
Percent millirho (pcm)
EXPLAIN the relationship between reactivity coefficients and

reactivity defects.
Application of the Effective M ultiplication Factor

When keff remains constant from generation to generation, it is possible to determine the number
of neutrons beginning any particular generation by knowing only the value of keff and the number
of neutrons starting the first generation. If No neutrons start the first generation, then No(keff)
neutrons start the second generation. Equation (3-4) can be used to calculate the number of
neutrons after the completion of "n" generations.
Nn
Rev. 0
N o keff
(3-4)
Page 17
NP-03
REACTIVITY
DOE-HDBK-1019/2-93 Reactor Theory (Nuclear Parameters)
Example:
The number of neutrons in the core at time zero is 1000 and keff = 1.002. Calculate the
number of neutrons after 50 generations.
Solution:
Use Equation (3-4) to calculate the number of neutrons.
n
Nn
N o keff
N50
1000 neutrons 1.002
50
1105 neutrons
Reactivity
If there are No neutrons in the preceding generation, then there are No(keff) neutrons in the
present generation. The numerical change in neutron population is (Nokeff - No). The gain or
loss in neutron population (Nokeff - No), expressed as a fraction of the present generation (Nokeff),
is shown below.
No keff
No
No keff
This relationship represents the fractional change in neutron population per generation and is
referred to as reactivity (). Cancelling out the term No from the numerator and denominator,
the reactivity is determined as shown in the equation below.
keff
(3-5)
keff
From Equation (3-5) it may be seen that may be positive, zero, or negative, depending upon
the value of keff. The larger the absolute value of reactivity in the reactor core, the further the
reactor is from criticality. It may be convenient to think of reactivity as a measure of a reactor's
departure from criticality.
NP-03
Page 18
Rev. 0
Reactor Theory (Nuclear Parameters) DOE-HDBK-1019/2-93
REACTIVITY
Example:
Calculate the reactivity in the reactor core when keff is equal to 1.002 and 0.998.
Solution:
The reactivity for each case is determined by substituting the value of keff into
Equation (3-5).
keff
keff
keff
keff
1.002 1
1.002
0.998 1
0.998
0.001996
0.0020
Units of Reactivity
Reactivity is a dimensionless number. It does not have dimensions of time, length, mass, or any
combination of these dimensions. It is simply a ratio of two quantities that are dimensionless.
As shown in the calculation in the previous example, the value of reactivity is often a small
decimal value. In order to make this value easier to express, artificial units are defined.
By definition, the value for reactivity that results directly from the calculation of Equation (3-5)
is in units of k/k. Alternative units for reactivity are %k/k and pcm (percent millirho). The
conversions between these units of reactivity are shown below.
1% k
k
1 pcm
0.01 k
k
0.00001
k
k
Another unit of reactivity that is used at some reactors is equivalent to 10-4 k/k. This unit of
reactivity does not have a unique name. Special units for reactivity that do have unique names
are dollars and cents. These units and their applications will be described in a later chapter.
Rev. 0
Page 19
NP-03
REACTIVITY
Example:
Convert the values of reactivity listed below to the indicated units.
a.
b.
c.
0.000421 k/k =
0.0085 k/k =
16 x 10-4 k/k =
pcm
% k/k
k/k
Solution:
a.
b.
c.
42.1 pcm
0.85% k/k
0.0016 k/k
If the reactivity is known, the effective multiplication factor can be determined by solving
Equation (3-5) for keff in terms of the reactivity. This results in the following relationship.
keff
(3-6)
Reactivity must be in units of k/k for use in Equation (3-6).
Example:
Given a reactivity of -20.0 x 10-4 k/k, calculate keff.
Solution:
keff
1
1
1
( 20.0 x 10 4)
0. 998
NP-03
Page 20
Rev. 0
Reactor Theory (Nuclear Parameters) DOE-HDBK-1019/2-93
REACTIVITY
Reactivity Coefficients and Reactivity Defects

The amount of reactivity () in a reactor core determines what the neutron population, and
consequently the reactor power, are doing at any given time. The reactivity can be effected by
many factors (for example, fuel depletion, temperature, pressure, or poisons). The next several
chapters discuss the factors affecting reactivity and how they are used to control or predict
reactor behavior.
To quantify the effect that a variation in parameter (that is, increase in temperature, control rod
insertion, increase in neutron poison) will have on the reactivity of the core, reactivity
coefficients are used. Reactivity coefficients are the amount that the reactivity will change for
a given change in the parameter. For instance, an increase in moderator temperature will cause
a decrease in the reactivity of the core. The amount of reactivity change per degree change in
the moderator temperature is the moderator temperature coefficient. Typical units for the
moderator temperature coefficient are pcm/oF. Reactivity coefficients are generally symbolized
by x, where x represents some variable reactor parameter that affects reactivity. The definition
of a reactivity coefficient in equation format is shown below.
x
If the parameter x increases and positive reactivity is added, then x is positive. If the parameter
x increases and negative reactivity is added, then x is negative.
Reactivity defects () are the total reactivity change caused by a variation in a parameter.
Reactivity defects can be determined by multiplying the change in the parameter by the average
value of the reactivity coefficient for that parameter. The equation below shows the general
method for relating reactivity coefficients to reactivity defects.
= x x
Example:
The moderator temperature coefficient for a reactor is -8.2 pcm/oF.
reactivity defect that results from a temperature decrease of 5oF.
Solution:
Calculate the
T T
8.2
pcm
F
5 F
41 pcm
The reactivity addition due to the temperature decrease was positive because of the
negative temperature coefficient.
Rev. 0
Page 21
NP-03
REACTIVITY
Summary
Reactivity Summary
The number of neutrons present in the core after a given number of generations is
calculated using Equation (3-4).
Nn
N o keff
Reactivity is the fractional change in neutron population per generation.

Reactivity and keff are represented in Equation (3-5) and Equation (3-6),
respectively.
keff
keff
keff
1
1
The relationship between units of reactivity are listed below.

1%
k
k
1 pcm
0.01
k
k
0.00001 k
k
A reactivity coefficient is the amount of change in reactivity per unit change in the
parameter. A reactivity defect is the total reactivity change caused by a change in
the parameter. The reactivity defect is the product of the reactivity coefficient and
the magnitude of the parameter change.
NP-03
Page 22
Rev. 0
DOE-HDBK-1019/2-93
REACTIVITY COEFFICIENTS
REACTIVITY C OEFFICIENTS
Changes in the physical properties of the materials in the reactor will result in
changes in the reactivity. Reactivity coefficients are useful in quantifying the
reactivity change that will occur due to the change in a physical property such as
the temperature of the moderator or fuel.
Rev. 0
EO 2.1
EXPLAIN the conditions of over m oderation and under

m oderation.
EO 2.2
EXPLAIN why many reactors are designed to be operated in

an under moderated condition.
EO 2.3
STATE the effect that a change in moderator temperature will

have on the moderator to fuel ratio.
EO 2.4
DEFINE the temperature coefficient of reactivity.
EO 2.5
EXPLAIN why a negative temperature coefficient of reactivity

is desirable.
EO 2.6
EXPLAIN why the fuel temperature coefficient is more

effective than the moderator temperature coefficient in
term inating a rapid power rise.
EO 2.7
EXPLAIN the concept of Doppler broadening of resonance

absorption peaks.
EO 2.8
LIST two nuclides that are present in some types of reactor

fuel assem blies that have significant resonance absorption
peaks.
EO 2.9
DEFINE the pressure coefficient of reactivity.
EO 2.10
EXPLAIN why the pressure coefficient of reactivity is usually

negligible in a reactor cooled and moderated by a subcooled
liquid.
EO 2.11
DEFINE the void coefficient of reactivity.
EO 2.12
IDENTIFY the moderator conditions under which the void

coefficient of reactivity becomes significant.
Page 23
NP-03
M oderator Effects
As discussed in the previous module, a moderator possesses specific desirable characteristics.
(a) large neutron scattering cross section
(b) low neutron absorption cross section
(c) large neutron energy loss per collision
With the exception of the Liquid Metal Fast Breeder Reactor (LMFBR), the remaining major
reactor types that are currently employed use moderating materials to reduce fission neutron
energies to the thermal range. Light moderators (composed of light nuclei) are found to be more
effective than heavy moderators because the light moderator removes more energy per collision
than a heavy moderator. Therefore, the neutrons reach thermal energy more rapidly and they are
less likely to be lost through resonance absorption.
As discussed in a previous module, the ability of a given material to slow down neutrons is
referred to as the macroscopic slowing down power (MSDP) and is defined as the product of
the logarithmic energy decrement per collision () times the macroscopic scattering cross section
for neutrons as follows.
M S DP
Macroscopic slowing down power indicates how rapidly slowing down occurs in the material
in question, but it does not completely define the effectiveness of the material as a moderator.
An element such as boron has a high logarithmic energy decrement and a good slowing down
power, but is a poor moderator. It is a poor moderator because of its high probability of
absorbing neutrons, and may be accounted for by dividing the macroscopic slowing down power
by the macroscopic absorption cross section. This relationship is called the moderating ratio
(MR).
MR
s
a
The moderating ratio is merely the ratio of slowing down power to the macroscopic absorption
cross section. The higher the moderating ratio, the more effectively the material performs as a
moderator.
Another ratio, the moderator-to-fuel ratio (Nm/Nu), is very important in the discussion of
moderators. As the reactor designer increases the amount of moderator in the core (that is,
Nm/Nu increases), neutron leakage decreases. Neutron absorption in the moderator (ma) increases
and causes a decrease in the thermal utilization factor. Having insufficient moderator in the core
(that is, Nm/Nu decreases) causes an increase in slowing down time and results in a greater loss
of neutrons by resonance absorption. This also causes an increase in neutron leakage. The
effects of varying the moderator-to-fuel ratio on the thermal utilization factor and the resonance
probability are shown in Figure 2.
NP-03
Page 24
Rev. 0
Figure 2
DOE-HDBK-1019/2-93
Effects of Over and Under Moderation on keff
Because the moderator-to-fuel ratio affects the thermal utilization factor and the resonance escape
probability, it also affects keff. The remaining factors in the six factor formula are also affected
by the moderator-to-fuel ratio, but to a lesser extent than f and p. As illustrated in Figure 2,
which is applicable to a large core fueled with low-enriched fuel, there is an optimum point
above which increasing the moderator-to-fuel ratio decreases keff due to the dominance of the
decreasing thermal utilization factor. Below this point, a decrease in the moderator-to-fuel ratio
decreases keff due to the dominance of the increased resonance absorption in the fuel. If the ratio
is above this point, the core is said to be over moderated, and if the ratio is below this point, the
core is said to be under moderated.
In practice, water-moderated reactors are designed with a moderator-to-fuel ratio so that the
reactor is operated in an under moderated condition. The reason that some reactors are designed
to be under moderated is if the reactor were over moderated, an increase in temperature would
decrease the Nm/Nu due to the expansion of the water as its density became lower. This decrease
in Nm/Nu would be a positive reactivity addition, increasing keff and further raising power and
temperature in a dangerous cycle. If the reactor is under moderated, the same increase in
temperature results in the addition of negative reactivity, and the reactor becomes more
self-regulating.
Rev. 0
Page 25
NP-03
M oderator Temperature Coefficient

The change in reactivity per degree change in temperature is called the temperature coefficient
of reactivity. Because different materials in the reactor have different reactivity changes with
temperature and the various materials are at different temperatures during reactor operation,
several different temperature coefficients are used. Usually, the two dominant temperature
coefficients are the moderator temperature coefficient and the fuel temperature coefficient.
The change in reactivity per degree change in moderator temperature is called the moderator
temperature coefficient of reactivity. The magnitude and sign (+ or -) of the moderator
temperature coefficient is primarily a function of the moderator-to-fuel ratio. If a reactor is
under moderated, it will have a negative moderator temperature coefficient. If a reactor is over
moderated, it will have a positive moderator temperature coefficient. A negative moderator
temperature coefficient is desirable because of its self-regulating effect. For example, an
increase in reactivity causes the reactor to produce more power. This raises the temperature of
the core and adds negative reactivity, which slows down, or turns, the power rise.
Fuel Temperature Coefficient

Another temperature coefficient of reactivity, the fuel temperature coefficient, has a greater effect
than the moderator temperature coefficient for some reactors. The fuel temperature coefficient
is the change in reactivity per degree change in fuel temperature. This coefficient is also called
the "prompt" temperature coefficient because an increase in reactor power causes an immediate
change in fuel temperature. A negative fuel temperature coefficient is generally considered to
be even more important than a negative moderator temperature coefficient because fuel
temperature immediately increases following an increase in reactor power. The time for heat to
be transferred to the moderator is measured in seconds. In the event of a large positive reactivity
insertion, the moderator temperature cannot turn the power rise for several seconds, whereas the
fuel temperature coefficient starts adding negative reactivity immediately.
Another name applied to the fuel temperature coefficient of reactivity is the fuel doppler
reactivity coefficient. This name is applied because in typical low enrichment, light watermoderated, thermal reactors the fuel temperature coefficient of reactivity is negative and is the
result of the doppler effect, also called doppler broadening. The phenomenon of the doppler
effect is caused by an apparent broadening of the resonances due to thermal motion of nuclei as
illustrated in Figure 3. Stationary nuclei absorb only neutrons of energy Eo. If the nucleus is
moving away from the neutron, the velocity (and energy) of the neutron must be greater than Eo
to undergo resonance absorption. Likewise, if the nucleus is moving toward the neutron, the
neutron needs less energy than Eo to be absorbed. Raising the temperature causes the nuclei to
vibrate more rapidly within their lattice structures, effectively broadening the energy range of
neutrons that may be resonantly absorbed in the fuel. Two nuclides present in large amounts in
the fuel of some reactors with large resonant peaks that dominate the doppler effect are
uranium-238 and plutonium-240.
NP-03
Page 26
Rev. 0
Figure 3
DOE-HDBK-1019/2-93
Effect of Fuel Temperature on Resonance Absorption Peaks
Pressure Coefficient
The reactivity in a reactor core can be affected by the system pressure. The pressure coefficient
of reactivity is defined as the change in reactivity per unit change in pressure. The pressure
coefficient of reactivity for the reactor is the result of the effect of pressure on the density of the
moderator. For this reason, it is sometimes referred to as the moderator density reactivity
coefficient. As pressure increases, density correspondingly increases, which increases the
moderator-to-fuel ratio in the core. In the typical under moderated core the increase in the
moderator-to-fuel ratio will result in a positive reactivity addition. In reactors that use water as
a moderator, the absolute value of the pressure reactivity coefficient is seldom a major factor
because it is very small compared to the moderator temperature coefficient of reactivity.
Void Coefficient
In systems with boiling conditions, such as boiling water reactors (BWR), the pressure
coefficient becomes an important factor due to the larger density changes that occur when the
vapor phase of water undergoes a pressure change. Of prime importance during operation of
a BWR, and a factor in some other water-moderated reactors, is the void coefficient. The void
coefficient is caused by the formation of steam voids in the moderator. The void coefficient of
reactivity is defined as the change in reactivity per percent change in void volume. As the
reactor power is raised to the point where the steam voids start to form, voids displace moderator
from the coolant channels within the core. This displacement reduces the moderator-to-fuel
ratio, and in an under moderated core, results in a negative reactivity addition, thereby limiting
reactor power rise. The void coefficient is significant in water-moderated reactors that operate
at or near saturated conditions.
Rev. 0
Page 27
NP-03
Summary
Reactivity Coefficients Summary

The temperature coefficient of reactivity is the change in reactivity per degree
change in temperature.
A reactor is under moderated when a decrease in the moderator-to-fuel ratio
decreases keff due to the increased resonance absorption. A reactor is over
moderated when an increase in the moderator-to-fuel ratio decreases keff due to
the decrease in the thermal utilization factor.
Reactors are usually designed to operate in an under moderated condition so that
the moderator temperature coefficient of reactivity is negative.
Increasing the moderator temperature will decrease the moderator-to-fuel ratio.
Decreasing the moderator temperature will increase the moderator-to-fuel ratio.
A negative temperature coefficient of reactivity is desirable because it makes the
reactor more self-regulating. An increase in power, resulting in an increase in
temperature, results in negative reactivity addition due to the temperature
coefficient. The negative reactivity addition due to the temperature increase will
slow or stop the power increase.
The fuel temperature coefficient is more effective than the moderator temperature
coefficient in terminating a rapid power rise because the fuel temperature
immediately increases following a power increase, while the moderator
temperature does not increase for several seconds.
The Doppler broadening of resonance peaks occurs because the nuclei may be
moving either toward or away from the neutron at the time of interaction.
Therefore, the neutron may actually have either slightly more or slightly less than
the resonant energy, but still appear to be at resonant energy relative to the
nucleus.
Uranium-238 and plutonium-240 are two nuclides present in some reactor fuels
that have large resonance absorption peaks.
NP-03
Page 28
Rev. 0
DOE-HDBK-1019/2-93
Reactivity Coefficients Summary (Cont.)

The pressure coefficient of reactivity is the change in reactivity per unit change
in pressure.
The pressure coefficient of reactivity is usually negligible in reactors moderated
by subcooled liquids because the density of the liquid does not change
significantly within the operating pressure range.
The void coefficient of reactivity is the change in reactivity per unit change in
void volume.
The void coefficient of reactivity becomes significant in a reactor in which the
moderator is at or near saturated conditions.
Rev. 0
Page 29
NP-03
NEUTRON POISONS
DOE-HDBK-1019/2-93
NEUTRON P OISON S
In some reactors, neutron-absorbing materials called poisons are intentionally
designed into the reactor for specific purposes. Some of these poisons deplete as
they absorb neutrons during reactor operation, and others remain relatively
constant.
EO 3.1

a.
b.
c.
Burnable poison
Non-burnable poison
Chem ical shim
EO 3.2
EXPLAIN the use of burnable neutron poisons in a reactor

core.
EO 3.3
LIST the advantages and disadvantages of chemical shim over

fixed burnable poisons.
EO 3.4
STATE two reasons why fixed non-burnable neutron poisons

are used in reactor cores.
EO 3.5
STATE an exam ple of a material used as a fixed non-burnable

neutron poison.
Fixed Burnable Poisons

During operation of a reactor the amount of fuel contained in the core constantly decreases. If
the reactor is to operate for a long period of time, fuel in excess of that needed for exact
criticality must be added when the reactor is built. The positive reactivity due to the excess fuel
must be balanced with negative reactivity from neutron-absorbing material. Moveable control
rods containing neutron-absorbing material are one method used to offset the excess fuel. Control
rods will be discussed in detail in a later chapter. Using control rods alone to balance the excess
reactivity may be undesirable or impractical for several reasons. One reason for a particular core
design may be that there is physically insufficient room for the control rods and their large
mechanisms.
NP-03
Page 30
Rev. 0
DOE-HDBK-1019/2-93
NEUTRON POISONS
To control large amounts of excess fuel without adding additional control rods, burnable poisons
are loaded into the core. Burnable poisons are materials that have a high neutron absorption
cross section that are converted into materials of relatively low absorption cross section as the
result of neutron absorption. Due to the burnup of the poison material, the negative reactivity
of the burnable poison decreases over core life. Ideally, these poisons should decrease their
negative reactivity at the same rate the fuel's excess positive reactivity is depleted. Fixed
burnable poisons are generally used in the form of compounds of boron or gadolinium that are
shaped into separate lattice pins or plates, or introduced as additives to the fuel. Since they can
usually be distributed more uniformly than control rods, these poisons are less disruptive to the
core power distribution.
Soluble Poisons
Soluble poisons, also called chemical shim , produce a spatially uniform neutron absorption when
dissolved in the water coolant. The most common soluble poison in commercial pressurized
water reactors (PWR) is boric acid, which is often referred to as "soluble boron," or simply
"solbor." The boric acid in the coolant decreases the thermal utilization factor, causing a
decrease in reactivity. By varying the concentration of boric acid in the coolant (a process
referred to as boration and dilution), the reactivity of the core can be easily varied. If the boron
concentration is increased, the coolant/moderator absorbs more neutrons, adding negative
reactivity. If the boron concentration is reduced (dilution), positive reactivity is added. The
changing of boron concentration in a PWR is a slow process and is used primarily to compensate
for fuel burnout or poison buildup. The variation in boron concentration allows control rod use
to be minimized, which results in a flatter flux profile over the core than can be produced by
rod insertion. The flatter flux profile is due to the fact that there are no regions of depressed
flux like those that would be produced in the vicinity of inserted control rods.
DOE reactors typically do not use soluble neutron poisons during normal operation. Some DOE
reactors do, however, include emergency shutdown systems that inject solutions containing
neutron poisons into the system that circulates reactor coolant. Various solutions, including
sodium polyborate and gadolinium nitrate, are used.
Fixed burnable poisons possess some advantages over chemical shim. Fixed burnable poisons
may be discretely loaded in specific locations in order to shape or control flux profiles in the
core. Also, fixed burnable poisons do not make the moderator temperature reactivity coefficient
less negative as chemical shim does. With chemical shim, as temperature rises and the
moderator expands, some moderator is pushed out of the active core area. Boron is also moved
out, and this has a positive effect on reactivity. This property of chemical shim limits the
allowable boron concentration because any greater concentration makes the moderator
temperature coefficient of reactivity positive.
Rev. 0
Page 31
NP-03
NEUTRON POISONS
DOE-HDBK-1019/2-93
Non-Burnable Poisons
A non-burnable poison is one that maintains a constant negative reactivity worth over the life
of the core. While no neutron poison is strictly non-burnable, certain materials can be treated
as non-burnable poisons under certain conditions. One example is hafnium. The removal (by
absorption of neutrons) of one isotope of hafnium leads to the production of another neutron
absorber, and continues through a chain of five absorbers. This absorption chain results in a
long-lived burnable poison which approximates non-burnable characteristics. Absorbers with low
neutron absorption cross sections can also be treated as non-burnable under most conditions.
It is possible to make the reactivity of a poison material that is usually a burnable poison more
uniform over core life through the use of self-shielding. In self-shielding, the poison material
is thick enough that only the outer layer of the poison is exposed to the neutron flux. The
absorptions that take place in the outer layers reduce the number of neutrons that penetrate to the
inner material. As the outer layers of poison absorb neutrons and are converted to non-poison
materials, the inner layers begin absorbing more neutrons, and the negative reactivity of the
poison is fairly uniform.
The normal use of fixed non-burnable poisons is in power shaping, or to prevent excessive flux
and power peaking near moderator regions of the reactor.
NP-03
Page 32
Rev. 0
DOE-HDBK-1019/2-93
NEUTRON POISONS
Summary
Neutron Poisons Summary

A burnable neutron poison is a material that has a high neutron absorption cross
section that is converted into a material of relatively low absorption cross section
as the result of neutron absorption.
A non-burnable neutron poison is a material that has relatively constant neutron
absorption characteristics over core life. The absorption of a neutron by one isotope
in the material produces another isotope that also has a high absorption cross
section.
Chemical shim is a soluble neutron poison that is circulated in the coolant during
normal operation.
Burnable neutron poisons are used in reactor cores to compensate for the excess
positive reactivity of the fuel when the reactor is initially started up.
Chemical shim has several advantages over fixed burnable poisons.
Has a spatially uniform effect
Possible to increase or decrease amount of poison in the core during
reactor operation
Fixed burnable poisons have several advantages over chemical shim.
Can be used to shape flux profiles
Do not have an adverse effect on moderator temperature coefficient
Two reasons for using non-burnable neutron poisons in reactor cores are to shape power
and to prevent excessive flux and power peaking near moderator regions.
An example of a material that is used as a fixed non-burnable neutron poison is
hafnium.
Rev. 0
Page 33
NP-03
XENON
DOE-HDBK-1019/2-93
XENON
Xenon-135 has a tremendous impact on the operation of a nuclear reactor. It is
important to understand the mechanisms that produce and remove xenon from the
reactor to predict how the reactor will respond following changes in power level.
EO 4.1
LIST two m ethods of production and two methods of removal

for xenon-135 during reactor operation.
EO 4.2
STATE the equation for equilibrium xenon-135 concentration.
EO 4.3
DESCRIBE how equilibrium xenon-135 concentration varies

with reactor power level.
EO 4.4
DESCRIBE the causes and effects of a xenon oscillation.
EO 4.5
DESCRIBE how xenon-135 concentration changes following a

reactor shutdown from steady-state conditions.
EO 4.6
EXPLAIN the effect that pre-shutdown power levels have on

the xenon-135 concentration after shutdown.
EO 4.7
STATE the approximate time following a reactor shutdown at

which the reactor can be considered "xenon free."
EO 4.8
EXPLAIN what is meant by the following terms:

a.
b.
EO 4.9
Xenon precluded startup

Xenon dead tim e
DESCRIBE how xenon-135 concentration changes following an

increase or a decrease in the power level of a reactor.
Fission Product Poisons

Fission fragments generated at the time of fission decay to produce a variety of fission products.
Fission products are of concern in reactors primarily because they become parasitic absorbers of
neutrons and result in long term sources of heat. Although several fission products have
significant neutron absorption cross sections, xenon-135 and samarium-149 have the most
substantial impact on reactor design and operation. Because these two fission product poisons
remove neutrons from the reactor, they will have an impact on the thermal utilization factor and
thus keff and reactivity.
NP-03
Page 34
Rev. 0
DOE-HDBK-1019/2-93
XENON
Production and Removal of Xenon-135

Xenon-135 has a 2.6 x 106 barns neutron absorption cross section. It is produced directly by
some fissions, but is more commonly a product of the tellurium-135 decay chain shown below.
The fission yield () for xenon-135 is about 0.3%, while for tellurium-135 is about 6%.
135
135
135
135
Ba (stable)
I
Xe
Cs
56
53
54
55
19.0 sec
6.57 hr
9.10 hr
2.3x106 yr
135
Te
52
The half-life for tellurium-135 is so short compared to the other half-lives that it can be assumed
that iodine-135 is produced directly from fission. Iodine-135 is not a strong neutron absorber,
but decays to form the neutron poison xenon-135. Ninety-five percent of all the xenon-135
produced comes from the decay of iodine-135. Therefore, the half-life of iodine-135 plays an
important role in the amount of xenon-135 present.
The rate of change of iodine concentration is equal to the rate of production minus the rate of
removal. This can be expressed in the equation below.
rate of change of iodine concentration = yield from fission - decay rate - burnup rate
or
dNI
dt
I fuel
I NI
Ia NI
where:
NI
135
fission yield of
ffuel
macroscopic fission cross section fuel
thermal neutron flux
decay constant for
Ia
microscopic absorption cross section
I concentration
135
135
I
135
Since the Ia is very small, the burn up rate term may be ignored, and the expression for the rate
of change of iodine concentration is modified as shown below.
dNI
dt
I fuel
I NI
When the rate of production of iodine equals the rate of removal of iodine, equilibrium exists.
The iodine concentration remains constant and is designated NI(eq). The following equation for
the equilibrium concentration of iodine can be determined from the preceding equation by setting
the two terms equal to each other and solving for NI(eq).
NP-03
Page 35
Rev. 0
XENON
DOE-HDBK-1019/2-93
N I(eq)
I fuel
f
I
Since the equilibrium iodine concentration is proportional to the fission reaction rate, it is also
proportional to reactor power level.
The rate of change of the xenon concentration is equal to the rate of production minus the rate
of removal. Recall that 5% of xenon comes directly from fission and 95% comes from the decay
of iodine. The rate of change of xenon concentration is expressed by the following equations.
rate of change of
xenon 135 concentration
dNXe
dt
Xe fuel
where:
xenon 135 yield

from fission
I NI
Xe NXe
iodine 135
decay
xenon 135
decay
xenon 135
burnup
Xe
a N Xe
NXe
135
Xe
fission yield of
ffuel
macroscopic fission cross section of the fuel
thermal neutron flux
decay constant for
NI
135
Xe
decay constant for
Xe
a
microscopic absorption cross section135Xe
Xe concentration
135
Xe
135
I concentration
135
Xe
The xenon burnup term above refers to neutron absorption by xenon-135 by the following
reaction.
135
1
136
n
Xe
Xe
54
0
54
Xenon-136 is not a significant neutron absorber; therefore, the neutron absorption by xenon-135
constitutes removal of poison from the reactor. The burnup rate of xenon-135 is dependent upon
the neutron flux and the xenon-135 concentration.
The equilibrium concentration of xenon-135 is designated NXe(eq), and is represented as shown
below.
Xe fuel
I NI
f
N Xe (eq)
Xe Xe
a
NP-03
Page 36
Rev. 0
DOE-HDBK-1019/2-93
XENON
For xenon-135 to be in equilibrium, iodine-135 must also be in equilibrium. Substituting the

expression for equilibrium iodine-135 concentration into the equation for equilibrium xenon
results in the following.
NXe (eq)
Xe
fuel
f
I
Xe
Xe
a
From this equation it can be seen that the equilibrium value for xenon-135 increases as power
increases, because the numerator is proportional to the fission reaction rate. Thermal flux is also
Xe
term
in the denominator; therefore, as the thermal flux exceeds 1012 neutrons/cm 2-sec, the a
begins to dominate, and at approximately 1015 neutrons/cm 2-sec, the xenon-135 concentration
approaches a limiting value. The equilibrium iodine-135 and xenon-135 concentrations as a
function of neutron flux are illustrated in Figure 4.
Figure 4 Equilibrium Iodine-135 and Xenon-135 Concentrations Versus Neutron Flux
The higher the power level, or flux, the higher the equilibrium xenon-135 concentration, but
equilibrium xenon-135 is not directly proportional to power level. For example, equilibrium
xenon-135 at 25% power is more than half the value for equilibrium xenon-135 at 100% power
for many reactors. Because the xenon-135 concentration directly affects the reactivity level in
the reactor core, the negative reactivity due to the xenon concentrations for different power
levels or conditions are frequently plotted instead of the xenon concentration.
NP-03
Page 37
Rev. 0
XENON
DOE-HDBK-1019/2-93
Xenon-135 Response to Reactor Shutdown

When a reactor is shutdown, the neutron flux is reduced essentially to zero. Therefore, after
shutdown, xenon-135 is no longer produced by fission and is no longer removed by burnup. The
only remaining production mechanism is the decay of the iodine-135 which was in the core at
the time of shutdown. The only removal mechanism for xenon-135 is decay.
dNXe
dt
I NI
Xe NXe
Because the decay rate of iodine-135 is faster than the decay rate of xenon-135, the xenon
concentration builds to a peak. The peak is reached when the product of the terms INI is equal
to XeNXe (in about 10 to 11 hours). Subsequently, the production from iodine decay is less than
the removal of xenon by decay, and the concentration of xenon-135 decreases. The greater the
flux level prior to shutdown, the greater the concentration of iodine-135 at shutdown; therefore,
the greater the peak in xenon-135 concentration after shutdown. This phenomenon can be seen
in Figure 5, which illustrates the negative reactivity value of xenon-135 following shutdown from
various neutron flux levels.
Figure 5
NP-03
Xenon-135 Reactivity After Reactor Shutdown
Page 38
Rev. 0
DOE-HDBK-1019/2-93
XENON
Negative xenon reactivity, also called xenon poisoning, may provide sufficient negative reactivity
to make the reactor inoperable because there is insufficient positive reactivity available from
control rod removal or chemical shim dilution (if used) to counteract it. The inability of the
reactor to be started due to the effects of xenon is sometimes referred to as a xenon precluded
startup . The period of time where the reactor is unable to "override" the effects of xenon is
called xenon dead time. Because the amount of excess core reactivity available to override the
negative reactivity of the xenon is usually less than 10% k/k, thermal power reactors are
normally limited to flux levels of about 5 x 1013 neutrons/cm2-sec so that timely restart can be
ensured after shutdown. For reactors with very low thermal flux levels (~5 x 1012 neutrons/cm2-sec
or less), most xenon is removed by decay as opposed to neutron absorption. For these cases,
reactor shutdown does not cause any xenon-135 peaking effect.
Following the peak in xenon-135 concentration about 10 hours after shutdown, the xenon-135
concentration will decrease at a rate controlled by the decay of iodine-135 into xenon-135 and
the decay rate of xenon-135. For some reactors, the xenon-135 concentration about 20 hours
after shutdown from full power will be the same as the equilibrium xenon-135 concentration at
full power. About 3 days after shutdown, the xenon-135 concentration will have decreased to
a small percentage of its pre-shutdown level, and the reactor can be assumed to be xenon free
without a significant error introduced into reactivity calculations.
Xenon-135 Oscillations
Large thermal reactors with little flux coupling between regions may experience spatial power
oscillations because of the non-uniform presence of xenon-135. The mechanism is described in
the following four steps.
(1)
An initial lack of symmetry in the core power distribution (for example, individual control
rod movement or misalignment) causes an imbalance in fission rates within the reactor
core, and therefore, in the iodine-135 buildup and the xenon-135 absorption.
(2)
In the high-flux region, xenon-135 burnout allows the flux to increase further, while in
the low-flux region, the increase in xenon-135 causes a further reduction in flux. The
iodine concentration increases where the flux is high and decreases where the flux is low.
(3)
As soon as the iodine-135 levels build up sufficiently, decay to xenon reverses the initial
situation. Flux decreases in this area, and the former low-flux region increases in power.
(4)
Repetition of these patterns can lead to xenon oscillations moving about the core with
periods on the order of about 15 hours.
With little change in overall power level, these oscillations can change the local power levels by
a factor of three or more. In a reactor system with strongly negative temperature coefficients,
the xenon-135 oscillations are damped quite readily. This is one reason for designing reactors
to have negative moderator-temperature coefficients.
NP-03
Page 39
Rev. 0
XENON
DOE-HDBK-1019/2-93
Xenon-135 Response to Reactor Power Changes

During periods of steady state operation, at a constant neutron flux level, the xenon-135
concentration builds up to its equilibrium value for that reactor power in about 40 to 50 hours.
Figure 6 illustrates a typical xenon transient that occurs as a result of a change in reactor power
level. At time zero, reactor power is raised from 50% power to 100% power. When the
reactor power is increased, xenon concentration initially decreases because the burnup is
increased at the new higher power level. Because 95% of the xenon production is from
iodine-135 decay, which has a 6 to 7 hour half-life, the production of xenon remains constant
for several hours. After a few hours (roughly 4 to 6 hours depending on power levels) the rate
of production of xenon from iodine and fission equals the rate of removal of xenon by burnup
and decay. At this point, the xenon concentration reaches a minimum. The xenon concentration
then increases to the new equilibrium level for the new power level in roughly 40 to 50 hours.
It should be noted that the magnitude and the rate of change of xenon concentration during the
initial 4 to 6 hours following the power change is dependent upon the initial power level and on
the amount of change in power level. The xenon concentration change is greater for a larger
change in power level.
Figure 6
NP-03
Xenon-135 Variations During Power Changes
Page 40
Rev. 0
DOE-HDBK-1019/2-93
XENON
When reactor power is decreased from 100% to 50% power (t = 55 hours), the process is
reversed. There is an immediate decrease in xenon burnup, which results in an increase in
xenon-135 concentration. The iodine-135 concentration is still at the higher equilibrium level
for 100% power and is therefore still producing xenon-135 at the higher rate. The xenon-135
concentration continues to rise until the rate of production of xenon-135 becomes equal to the
rate of removal (roughly 7 to 8 hours after the initial reduction in power level). The xenon-135
concentration then gradually decreases to the new equilibrium level in about 50 to 60 hours. The
magnitude of the xenon peak is greatest if the initial power level is very high.
Maximum peak xenon occurs when a reactor that is operating at 100% equilibrium xenon
concentration is suddenly shut down. The most rapid possible burnout of xenon occurs when
a reactor is started up and operated at full power while this maximum peak xenon condition
exists.
Summary
Xenon Summary
Xenon-135 is produced directly as a fission product and by the decay of iodine-135
during reactor operation. Xenon-135 is removed from the core by radioactive
decay and by neutron absorption during reactor operation.
The equilibrium concentration for xenon-135 is determined by the following
equation.
N Xe (eq)
Xe fuel
f
Xe
I NI
Xe
a
or NXe (eq)
Xe
Xe
I fuel
f
Xe
a
The xenon-135 concentration increases with increasing power level in a non-linear

manner. Equilibrium xenon-135 concentration reaches a maximum at a flux of
about 1015 neutrons/cm2-sec.
After a power increase, xenon-135 concentration will initially decrease due to the
increased removal by burnout. Xenon-135 will reach a minimum about 5 hours
after the power increase and then increase to a new, higher equilibrium value as the
production from iodine decay increases.
NP-03
Page 41
Rev. 0
XENON
DOE-HDBK-1019/2-93
Xenon Summary (Cont.)

A xenon-135 oscillation may be caused by a rapid perturbation in the core power
distribution. The xenon-135 oscillation can change local power levels in the core
by a factor of three or more.
Following a reactor shutdown, xenon-135 concentration will increase due to the
decay of the iodine inventory of the core. Xenon-135 will peak approximately
10 hours after the shutdown (from 100%) and then decrease as xenon-135 decay
becomes greater than the iodine-135 decay.
The greater the pre-shutdown power level, the greater the peak value of xenon.
The core can be considered xenon-free about 3 days after shutdown.
A xenon precluded startup occurs when there is insufficient reactivity in the control
rods to overcome the negative reactivity of xenon-135.
Xenon dead time is the period of time where the reactor is unable to override the
effects of xenon.
After a power decrease, xenon-135 concentration will initially increase due to
production by iodine decay being greater than the burnout. Xenon-135 will reach a
maximum about 8 hours after the power decrease and then decrease to a new,
lower equilibrium value.
NP-03
Page 42
Rev. 0
DOE-HDBK-1019/2-93
SAMARIUM AND OTHER FISSION PRODUCT POISONS

The fission product poison that has the most significant effect on reactor
operations other than xenon-135 is samarium-149. Samarium-149 behaves
significantly different from xenon-135 due to its different nuclear properties.
EO 4.10
DESCRIBE how samarium-149 is produced and removed from

the reactor core during reactor operation.
EO 4.11
STATE the
concentration.
EO 4.12
DESCRIBE how equilibrium samarium-149 concentration

varies with reactor power level.
EO 4.13
DESCRIBE how samarium-149 concentration changes following

a reactor shutdown from steady-state conditions.
EO 4.14
DESCRIBE how samarium-149 concentration changes following

a reactor startup.
EO 4.15
STATE the conditions under which helium-3 will have a

significant effect on the reactivity of a reactor.
equation
for
equilibrium
samarium-149
Production and Removal of Samarium-149

Samarium-149 is the second most important fission-product poison because of its high thermal
neutron absorption cross section of 4.1 x 104 barns. Samarium-149 is produced from the decay
of the neodymium-149 fission fragment as shown in the decay chain below.
149
Nd
60
Rev. 0
149
149
Pm
Sm (stable)
61
62
1.72 hr
53.1 hr
Page 43
NP-03
DOE-HDBK-1019/2-93
For the purpose of examining the behavior of samarium-149, the 1.73 hour half-life of
neodymium-149 is sufficiently shorter than the 53.1 hour value for promethium-149 that the
promethium-149 may be considered as if it were formed directly from fission. This assumption,
and neglecting the small amount of promethium burnup, allows the situation to be described as
follows.
Rate of change of
149
Pm = yield from fission - decay
149
Pm concentration
therefore:
dNPm
dt
Pm fuel
Pm NPm
where:
NPm
149
Pm concentration
Pm
149
Pm fission yield
Pm
decay constant for
149
Pm
Solving for the equilibrium value of promethium-149 gives the following.

Pm fuel
N Pm(eq)
Pm
The rate of samarium-149 formation is described as follows.

Rate of change of
149
Sm = yield from fission +
149
Pm decay -
149
Sm burnup
therefore:
dNSm
dt
Sm fuel
Pm NPm
NSm Sm
where:
NP-03
NSm
149
Sm concentration
Sm
149
Sm fission yield
aSm
microscopic absorption cross section of
Page 44
149
Sm
Rev. 0
DOE-HDBK-1019/2-93
The fission yield of samarium-149, however, is nearly zero; therefore, the equation becomes the
following.
dNSm
dt
Pm N Pm
N Sm Sm
Solving this equation for the equilibrium concentration of samarium-149 and substituting
Pmffuel / Pm for NPm(eq) yields the following.
N Sm(eq)
Pm fuel
f
Sm
a
This expression for equilibrium samarium-149 concentration during reactor operation illustrates
that equilibrium samarium-149 concentration is independent of neutron flux and power level. The
samarium concentration will undergo a transient following a power level change, but it will return
to its original value.
Samarium-149 Response to Reactor Shutdown

Since the neutron flux drops to essentially zero after reactor shutdown, the rate of samarium-149
production becomes the following.
dNSm
dt
Pm N Pm
Because samarium-149 is not radioactive and is not removed by decay, it presents problems
somewhat different from those encountered with xenon-135, as illustrated in Figure 7. The
equilibrium concentration and the poisoning effect build to an equilibrium value during reactor
operation. This equilibrium is reached in approximately 20 days (500 hours), and since
samarium-149 is stable, the concentration remains essentially constant during reactor operation.
When the reactor is shutdown, the samarium-149 concentration builds up as a result of the decay
of the accumulated promethium-149. The buildup of samarium-149 after shutdown depends
upon the power level before shutdown. Samarium-149 does not peak as xenon-135 does, but
increases slowly to a maximum value as shown in Figure 7. After shutdown, if the reactor is
then operated at power, samarium-149 is burned up and its concentration returns to the
equilibrium value. Samarium poisoning is minor when compared to xenon poisoning. Although
samarium-149 has a constant poisoning effect during long-term sustained operation, its behavior
during initial startup and during post-shutdown and restart periods requires special considerations
in reactor design.
Rev. 0
Page 45
NP-03
DOE-HDBK-1019/2-93
Figure 7
Behavior of Samarium-149 in a Typical Light Water Reactor
The xenon-135 and samarium-149 mechanisms are dependent on their very large thermal neutron
cross sections and only affect thermal reactor systems. In fast reactors, neither these nor any
other fission products have a major poisoning influence.
Other Neutron Poisons

There are numerous other fission products that, as a result of their concentration and thermal
neutron absorption cross section, have a poisoning effect on reactor operation. Individually, they
are of little consequence, but "lumped" together they have a significant impact. These are often
characterized as "lumped fission product poisons" and accumulate at an average rate of 50 barns
per fission event in the reactor.
In addition to fission product poisons, other materials in the reactor decay to materials that act
as neutron poisons. An example of this is the decay of tritium to helium-3. Since tritium has
a half-life of 12.3 years, normally this decay does not significantly affect reactor operations
because the rate of decay of tritium is so slow. However, if tritium is produced in a reactor and
then allowed to remain in the reactor during a prolonged shutdown of several months, a
NP-03
Page 46
Rev. 0
DOE-HDBK-1019/2-93
sufficient amount of tritium may decay to helium-3 to add a significant amount of negative
reactivity. Any helium-3 produced in the reactor during a shutdown period will be removed
during subsequent operation by a neutron-proton reaction.
Summary
Samarium and Other Fission Product Poisons Summary

Samarium-149 is produced directly from fission and from the decay of
promethium-149 during reactor operation. Samarium-149 is removed from the
core by neutron absorption.
The equation for equilibrium samarium-149 concentration is stated below.
N Sm(eq)
Pm fuel
f
Sm
a
The equilibrium samarium-149 concentration is independent of power level.

Following a reactor shutdown, the samarium-149 concentration increases due to the
decay of the promethium-149 inventory of the core and the loss of the burnup
factor.
If the reactor is restarted following a shutdown, the samarium-149 concentration
decreases as samarium is burned up and returns to its equilibrium operating value.
Helium-3 will become a significant neutron poison if significant amounts of tritium
are left in a reactor during a shutdown period that lasts longer than several
months.
Rev. 0
Page 47
NP-03
CONTROL RODS
DOE-HDBK-1019/2-93
CONTROL RODS
Most reactors contain control rods made of neutron absorbing materials that are
used to adjust the reactivity of the core. Control rods can be designed and used
for coarse control, fine control, or fast shutdowns.
EO 5.1
DESCRIBE the difference between a "grey" neutron absorbing

m aterial and a "black" neutron absorbing material.
EO 5.2
EXPLAIN why a "grey" neutron absorbing material may be

preferable to a "black" neutron absorbing material for use in
control rods.
EO 5.3
EXPLAIN why resonance absorbers are sometimes preferred

over therm al absorbers as a control rod material.
EO 5.4

a.
b.
Integral control rod worth

Differential control rod worth
EO 5.5
DESCRIBE the shape of a typical differential control rod

worth curve and explain the reason for the shape.
EO 5.6
DESCRIBE the shape of a typical integral control rod worth

curve and explain the reason for the shape.
EO 5.7
Given an integral or differential control rod worth curve,

CALCULATE the reactivity change due to a control rod
m ovem ent between two positions.
EO 5.8
Given differential control rod worth data, PLOT differential

and integral control rod worth curves.
Selection of Control Rod Materials

Rods of neutron-absorbing material are installed in most reactors to provide precise, adjustable
control of reactivity. These rods are able to be moved into or out of the reactor core and
typically contain elements such as silver, indium, cadmium, boron, or hafnium.
NP-03
Page 48
Rev. 0
DOE-HDBK-1019/2-93
CONTROL RODS
The material used for the control rods varies depending on reactor design. Generally, the
material selected should have a good absorption cross section for neutrons and have a long
lifetime as an absorber (not burn out rapidly). The ability of a control rod to absorb neutrons
can be adjusted during manufacture. A control rod that is referred to as a "black" absorber
absorbs essentially all incident neutrons. A "grey" absorber absorbs only a part of them. While
it takes more grey rods than black rods for a given reactivity effect, the grey rods are often
preferred because they cause smaller depressions in the neutron flux and power in the vicinity
of the rod. This leads to a flatter neutron flux profile and more even power distribution in the
core.
If grey rods are desired, the amount of material with a high absorption cross section that is
loaded in the rod is limited. Material with a very high absorption cross section may not be
desired for use in a control rod, because it will burn out rapidly due to its high absorption cross
section. The same amount of reactivity worth can be achieved by manufacturing the control rod
from material with a slightly lower cross section and by loading more of the material. This also
results in a rod that does not burn out as rapidly.
Another factor in control rod material selection is that materials that resonantly absorb neutrons
are often preferred to those that merely have high thermal neutron absorption cross sections.
Resonance neutron absorbers absorb neutrons in the epithermal energy range. The path length
traveled by the epithermal neutrons in a reactor is greater than the path length traveled by
thermal neutrons. Therefore, a resonance absorber absorbs neutrons that have their last collision
farther (on the average) from the control rod than a thermal absorber. This has the effect of
making the area of influence around a resonance absorber larger than around a thermal absorber
and is useful in maintaining a flatter flux profile.
Types of Control Rods

There are several ways to classify the types of control rods. One classification method is by the
purpose of the control rods. Three purposes of control rods are listed below.
Shim rods
used for coarse control and/or to remove reactivity in relatively large

amounts.
Regulating rods -
used for fine adjustments and to maintain desired power or temperature.
Safety rods
provide a means for very fast shutdown in the event of an unsafe condition.
Addition of a large amount of negative reactivity by rapidly inserting the
safety rods is referred to as a "scram" or "trip."
Rev. 0
Page 49
NP-03
CONTROL RODS
DOE-HDBK-1019/2-93
Not all reactors have different control rods to serve the purposes mentioned above. Depending
upon the type of reactor and the controls necessary, it is possible to use dual-purpose or even
triple-purpose rods. For example, consider a set of control rods that can insert enough reactivity
to be used as shim rods. If the same rods can be operated at slow speeds, they will function as
regulating rods. Additionally, these same rods can be designed for rapid insertion, or scram.
These rods serve a triple function yet meet other specifications such as precise control, range of
control, and efficiency.
Control Rod Effectiveness

The effectiveness of a control rod depends largely upon the value of the ratio of the neutron flux
at the location of the rod to the average neutron flux in the reactor. The control rod has
maximum effect (inserts the most negative reactivity) if it is placed in the reactor where the flux
is maximum. If a reactor has only one control rod, the rod should be placed in the center of the
reactor core. The effect of such a rod on the flux is illustrated in Figure 8.
Figure 8
Effect of Control Rod on Radial Flux Distribution
If additional rods are added to this simple reactor, the most effective location is where the flux
is maximum, that is, at point A. Numerous control rods are required for a reactor that has a
large amount of excess reactivity (that amount of reactivity in excess of that needed to be
critical). The exact amount of reactivity that each control rod inserts depends upon the reactor
design. The change in reactivity caused by control rod motion is referred to as control rod
worth.
NP-03
Page 50
Rev. 0
DOE-HDBK-1019/2-93
CONTROL RODS
Integral and Differential Control Rod Worth

The exact effect of control rods on reactivity can be determined experimentally. For example,
a control rod can be withdrawn in small increments, such as 0.5 inch, and the change in
reactivity can be determined following each increment of withdrawal. By plotting the resulting
reactivity versus the rod position, a graph similar to Figure 9 is obtained. The graph depicts
integral control rod worth over the full range of withdrawal. The integral control rod worth is
the total reactivity worth of the rod at that particular degree of withdrawal and is usually defined
to be the greatest when the rod is fully withdrawn.
Figure 9
Rev. 0
Integral Control Rod Worth
Page 51
NP-03
CONTROL RODS
DOE-HDBK-1019/2-93
The slope of the curve (/x), and therefore the amount of reactivity inserted per unit of
withdrawal, is greatest when the control rod is midway out of the core. This occurs because the
area of greatest neutron flux is near the center of the core; therefore, the amount of change in
neutron absorption is greatest in this area. If the slope of the curve for integral rod worth in
Figure 9 is taken, the result is a value for rate of change of control rod worth as a function of
control rod position. A plot of the slope of the integral rod worth curve, also called the
differential control rod worth, is shown in Figure 10. At the bottom of the core, where there are
few neutrons, rod movement has little effect so the change in rod worth per inch varies little.
As the rod approaches the center of the core its effect becomes greater, and the change in rod
worth per inch is greater. At the center of the core the differential rod worth is greatest and
varies little with rod motion. From the center of the core to the top, the rod worth per inch is
basically the inverse of the rod worth per inch from the center to the bottom.
Differential control rod worth is the reactivity change per unit movement of a rod and is
normally expressed as /inch, k/k per inch, or pcm/inch. The integral rod worth at a given
withdrawal is merely the summation of all the differential rod worths up to that point of
withdrawal. It is also the area under the differential rod worth curve at any given withdrawal
position.
Figure 10 Differential Control Rod Worth
NP-03
Page 52
Rev. 0
DOE-HDBK-1019/2-93
CONTROL RODS
The following exercises are intended to reinforce an understanding of the concepts of integral
and differential rod worth.
Example 1:
Using the integral rod worth curve provided in Figure 11, find the reactivity inserted by
moving the rod from 12 inches withdrawn out to 18 inches withdrawn.
Figure 11 Rod Worth Curves for Example Problems
Solution:
The integral rod worth at 12 inches is 40 pcm and the integral rod worth at 18 inches is
80 pcm.
final
18
initial
12
80 pcm
40 pcm
40 pcm
Rev. 0
Page 53
NP-03
CONTROL RODS
DOE-HDBK-1019/2-93
Example 2:
Using the differential rod worth curve provided in Figure 11, calculate the reactivity
inserted by moving the rod from 10 inches withdrawn to 6 inches withdrawn.
Solution:
The solution is basically given by the area under the curve for the interval. The answers
obtained in the following approximation may vary slightly depending upon the degree of
approximation.
Method 1.
Treating the range from 10 inches to 6 inches as a trapezoid, that is,

taking the end values of pcm/inch and multiplying their average by the
4 inches moved yields the following.
pcm
inch
pcm
inch
4 inches
22 pcm
This is negative because the rod was inserted.

Method 2.
Using the central value of rod position at 8 inches yields an average rod
worth of 5.5 pcm/inch. Multiplying by the 4 inches of rod travel yields
the answer.
(5.5 pcm/in.)(4 in.) = -22 pcm
Method 3.
Breaking the rod travel total into two parts (10 inches to 8 inches and
8 inches to 6 inches) yields:
8 pcm
inch
5.5 pcm
inch
2 inches
13.5 pcm
3 pcm
inch
2 inches
8.5 pcm
2
5.5 pcm
inch
2
( - 13.5 pcm) + ( - 8.5 pcm) = -22 pcm
NP-03
Page 54
Rev. 0
DOE-HDBK-1019/2-93
CONTROL RODS
In this example the various approximations used did not cause any difference because the
problem deals with a section of the curve with an approximately constant slope. To
obtain the value over the interval between 8 inches and 20 inches, however, would require
the use of several subintervals (as in the last approximation) to obtain an accurate
answer.
Example 3:
For the differential rod worth data given below, construct differential and integral rod
worth curves.
Interval (inches)
0 to 2
2 to 4
4 to 6
6 to 8
8 to 10
10 to 12
12 to 14
14 to 16
Reactivity Inserted (pcm)

10
20
40
60
60
40
20
10
Solution:
Differential rod worth:
For each interval, the number of pcm/inch must be determined. For example, in
the first interval (0 inches to 2 inches), 10 pcm is added. Therefore, the
differential rod worth equals an average 5 pcm/inch. This value of differential
rod worth is plotted at the center of each interval. The center of the interval
0 inches to 2 inches is 1 inch. The values of pcm/inch for each interval are then
listed as shown below and plotted on Figure 12.
Interval Center
1
3
5
7
9
11
13
15
Rev. 0
Page 55
pcm/inch
5
10
20
30
30
20
10
5
NP-03
CONTROL RODS
DOE-HDBK-1019/2-93
Integral rod worth:

To plot the integral rod worth, merely develop a cumulative total of the reactivity
added after each interval and plot the summed reactivity insertion vs. rod position
as shown in Figure 12.
Interval Endpoint
2
4
6
8
10
12
14
16
Summed Reactivity
10
30
70
130
190
230
250
260
Figure 12 Rod Worth Curves From Example 3
If an integral rod worth curve is supplied, a differential rod worth curve can be generated from
the integral rod worth data. Merely select a convenient interval of rod withdrawal, such as
1 inch or 2 inches. Then, determine from the curve the amount of reactivity added for each
constant interval of rod withdrawal. A plot of this reactivity addition versus rod withdrawal
represents differential rod worth.
NP-03
Page 56
Rev. 0
DOE-HDBK-1019/2-93
CONTROL RODS
Rod Control M echanisms

The control rod insertion rates on a scram are designed to be sufficient to protect the reactor
against damage in all transients that are expected to occur during the life of the reactor.
During normal rod motion, the control rods must be able to move rapidly enough to compensate
for the most rapid rate at which positive reactivity is expected to build within the reactor in
order to provide positive control. The transient that is normally considered when setting this
minimum rod speed is the burnout of maximum peak xenon while at full power. Xenon burnout
is usually the most rapid, non-accident transient expected. The maximum rod speed is normally
limited in order to reduce the severity of an accident involving the continuous withdrawal of
control rods.
Summary
Rev. 0
Page 57
NP-03
CONTROL RODS
DOE-HDBK-1019/2-93
Control Rods Summary

A black neutron-absorbing material absorbs essentially all incident neutrons. A
grey neutron-absorbing material absorbs only part of the incident neutrons.
A grey neutron-absorbing material may be preferable to a black neutronabsorbing material in the construction of control rods because the grey absorber
causes smaller depressions in neutron flux and power in the vicinity of the rod.
Resonance absorbers are sometimes preferred to thermal absorbers as control
rod materials because they have a larger area of influence and result in a flatter
flux profile.
Integral control rod worth is the total reactivity worth of the control rod at a
particular degree of withdrawal from the core.
Differential control rod worth is the reactivity change per unit movement of a
control rod.
The typical differential control rod worth curve has a bell shape. It has very
low values at the top and bottom of the core and a maximum value at the center
of the core. The curve has this shape because rod worth is related to neutron
flux, and flux is highest in the center of the core.
The typical integral control rod worth curve has an "S" shape. It has a
relatively flat slope at the top and bottom of the core and a maximum slope at
the center of the core.
Integral or differential control rod worth curves can be used to determine the
reactivity change due to a control rod movement between two positions.
Integral or differential control rod worth curves can be plotted based on
measured control rod worth data.
NP-03
Page 58
Rev. 0
NUCLEAR PHYSICS
AND REACTOR THEORY
M odule 4
Reactor Theory (Reactor Operations)
DOE-HDBK-1019/2-93
TABLE OF CONTENTS
TABLE OF CONTENTS
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ii
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
SUBCRITICAL MULTIPLICATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Subcritical Multiplication Factor . . . . . . . . . . . . . . . . . .

Effect of Reactivity Changes on Subcritical Multiplication
Use of 1/M Plots . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
REACTOR KINETICS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Reactor Period () . . . . . . . . . . . . . . . . . . . . . . . .
Effective Delayed Neutron Fraction . . . . . . . . . . . . .
Effective Delayed Neutron Precursor Decay Constant
Prompt Criticality . . . . . . . . . . . . . . . . . . . . . . . . .
Stable Period Equation . . . . . . . . . . . . . . . . . . . . .
Reactor Startup Rate (SUR) . . . . . . . . . . . . . . . . . .
Doubling Time . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
REACTOR OPERATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
23
Rev. 0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Page i
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
10
11
11
13
15
16
17
17
21
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
3
6
9
.
.
.
.
.
.
.
.
Startup . . . . . . . . . . . . .
Estimated Critical Position
Core Power Distribution .
Power Tilt . . . . . . . . . . .
Shutdown Margin . . . . . .
Operation . . . . . . . . . . .
Temperature . . . . . . . . .
Pressure . . . . . . . . . . . .
Power Level . . . . . . . . .
Flow . . . . . . . . . . . . . . .
Core Burnup . . . . . . . . .
Shutdown . . . . . . . . . . .
Decay Heat . . . . . . . . . .
Summary . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
24
24
25
27
28
28
28
29
29
30
30
31
33
33
NP-04
LIST OF FIGURES
DOE-HDBK-1019/2-93
LIST OF FIGURES
Figure 1 1/M Plot vs. Rod Withdrawal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Figure 2 Reactor Power Response to Positive Reactivity Addition . . . . . . . . . . . . . . . . 14
Figure 3 Reactor Power Response to Negative Reactivity Addition . . . . . . . . . . . . . . . . 15
Figure 4 Neutron Radial Flux Shapes for Bare and Reflected Cores . . . . . . . . . . . . . . . 26
Figure 5 Effect of Non-Uniform Enrichment on Radial Flux Shape . . . . . . . . . . . . . . . 26
Figure 6 Effect of Control Rod Position on Axial Flux Distribution . . . . . . . . . . . . . . . 27
NP-04
Page ii
Rev. 0
DOE-HDBK-1019/2-93
LIST OF TABLES
LIST OF TABLES
Table 1 Delayed Neutron Fractions for Various Fuels . . . . . . . . . . . . . . . . . . . . . . . .
Rev. 0
Page iii
12
NP-04
REFERENCES
DOE-HDBK-1019/2-93
REFERENCES
1972.
NP-04
Page iv
Rev. 0
DOE-HDBK-1019/2-93
OBJECTIVES
TERMINAL OBJECTIVE
1.0
Given the necessary information and equations, EXPLAIN how subcritical multiplication
occurs.
ENABLING OBJECTIVES
1.1
a.
b.
Subcritical multiplication
Subcritical multiplication factor
1.2
Given a neutron source strength and a subcritical system of known keff, CALCULATE
the steady-state neutron level.
1.3
Given an initial count rate and keff, CALCULATE the final count rate that will result
from the addition of a known amount of reactivity.
1.4
Given count rates vs. the parameter being adjusted, ESTIMATE the value of the
parameter at which the reactor will become critical through the use of a 1/M plot.
Rev. 0
Page v
NP-04
OBJECTIVES
DOE-HDBK-1019/2-93
TERMINAL OBJECTIVE
2.0
Given the necessary information and equations, DESCRIBE how power changes in a
reactor that is near criticality.
ENABLING OBJECTIVES
2.1
a.
b.
c.
2.2
Reactor period
Doubling time
Reactor startup rate
DESCRIBE the relationship between the delayed neutron fraction, average delayed
neutron fraction, and effective delayed neutron fraction.

2.3
W RITE the period equation and IDENTIFY each symbol.
2.4
Given the reactivity of the core and values for the effective average delayed neutron
fraction and decay constant, CALCULATE the reactor period and the startup rate.
2.5
Given the initial power level and either the doubling or halving time, CALCULATE the
power at any later time.
2.6
Given the initial power level and the reactor period, CALCULATE the power at any
later time.
2.7
EXPLAIN what is meant by the terms prompt drop and prompt jump.
2.8
DEFINE the term prompt critical.
2.9
DESCRIBE reactor behavior during the prompt critical condition.
2.10
EXPLAIN the use of measuring reactivity in units of dollars.
NP-04
Page vi
Rev. 0
DOE-HDBK-1019/2-93
OBJECTIVES
TERMINAL OBJECTIVE
3.0
Without references, EXPLAIN the concepts concerning reactor startup, operation, and
shutdown.
ENABLING OBJECTIVES
3.1
EXPLAIN why a startup neutron source may be required for a reactor.
3.2
LIST four variables typically involved in a reactivity balance.
3.3
EXPLAIN how a reactivity balance may be used to predict the conditions under which
the reactor will become critical.

3.4
LIST three methods used to shape or flatten the core power distribution.
3.5
DESCRIBE the concept of power tilt.
3.6
DEFINE the term shutdown margin.
3.7
EXPLAIN the rationale behind the one stuck rod criterion.
3.8
IDENTIFY five changes that will occur during and after a reactor shutdown that will
affect the reactivity of the core.

3.9
EXPLAIN why decay heat is present following reactor operation.
3.10
LIST three variables that will affect the amount of decay heat present following reactor
shutdown.
3.11
ESTIMATE the approximate amount of decay heat that will exist one hour after a
shutdown from steady state conditions.
Rev. 0
Page vii
NP-04
OBJECTIVES
DOE-HDBK-1019/2-93
NP-04
Page viii
Rev. 0
DOE-HDBK-1019/2-93
SUBCRITICAL MULTIPLICATION
Subcritical multiplication is the phenomenon that accounts for the changes in
neutron flux that takes place in a subcritical reactor due to reactivity changes.
It is important to understand subcritical multiplication in order to understand
reactor response to changes in conditions.
EO 1.1

a.
b.
Subcritical multiplication
Subcritical multiplication factor
EO 1.2
Given a neutron source strength and a subcritical system of

known k eff, CALCULATE the steady-state neutron level.
EO 1.3
Given an initial count rate and k eff, CALCULATE the final

count rate that will result from the addition of a known amount
of reactivity.
EO 1.4
Given count rates vs. the parameter being adjusted,

ESTIMATE the value of the param eter at which the reactor
will becom e critical through the use of a 1/M plot.
Subcritical M ultiplication Factor

When a reactor is in a shutdown condition, neutrons are still present to interact with the fuel.
These source neutrons are produced by a variety of methods that were discussed in Module 2.
If neutrons and fissionable material are present in the reactor, fission will take place. Therefore,
a reactor will always be producing a small number of fissions even when it is shutdown.
Consider a reactor in which keff is 0.6. If 100 neutrons are suddenly introduced into the reactor,
these 100 neutrons that start the current generation will produce 60 neutrons (100 x 0.6) from
fission to start the next generation. The 60 neutrons that start the second generation will
produce 36 neutrons (60 x 0.6) to start the third generation. The number of neutrons produced
by fission in subsequent generations due to the introduction of 100 source neutrons into the
reactor is shown below.
Generation
1st
2nd
3rd
4th
5th
6th
7th
8th
9th
10th
11th
12th
Neutrons
100
60
36
22
13
Rev. 0
Page 1
NP-04
DOE-HDBK-1019/2-93
Because the reactor is subcritical, neutrons introduced in the reactor will have a decreasing effect
on each subsequent generation. The addition of source neutrons to the reactor containing
fissionable material has the effect of maintaining a much higher stable neutron level due to the
fissions occurring than the neutron level that would result from the source neutrons alone. The
effects of adding source neutrons at a rate of 100 neutrons per generation to a reactor with a keff
of 0.6 are shown below.
Generation
1st
2nd
3rd
4th
5th
6th
7th
8th
9th
10th
11th
12th
100
60
36
22
13
100
60
36
22
13
100
60
36
22
13
100
60
36
22
13
100
60
36
22
13
100
60
36
22
13
100
60
36
22
13
100
60
36
22
13
100
60
36
22
100
60
36
100
60
100
Total n
100
160
196
218
231
239
244
247
249
250
250
...
A neutron source strength of 100 neutrons per generation will result in 250 neutrons per
generation being produced from a combination of sources and fission in a shutdown reactor with
a keff of 0.6. If the value of keff were higher, the source neutrons would produce a greater
number of fission neutrons and their effects would be felt for a larger number of subsequent
generations after their addition to the reactor.
The effect of fissions in the fuel increasing the effective source strength of a reactor with a keff
of less than one is subcritical multiplication. For a given value of keff there exists a subcritical
multiplication factor (M) that relates the source level to the steady-state neutron level of the
core. If the value of keff is known, the amount that the neutron source strength will be multiplied
(M) can easily be determined by Equation (4-1).
M
NP-04
1
1
(4-1)
keff
Page 2
Rev. 0
DOE-HDBK-1019/2-93
Example:
Calculate the subcritical multiplication factors for the following values of keff.
1)
2)
keff = 0.6
keff = 0.986
Solution:
1)
1
keff
1
1
1
0.6
2.5
2)
1
keff
1
0.986
71.4
The example above illustrates that the subcritical multiplication factor will increase as positive
reactivity is added to a shutdown reactor, increasing the value of keff. If the source strength of
this reactor were 1000 neutrons/sec, the neutron level would increase from 2500 neutrons/second
at a keff of 0.6 to a neutron level of 71,400 neutrons/sec at a keff of 0.986.
Effect of Reactivity Changes on Subcritical M ultiplication

In a subcritical reactor, the neutron level is related to the source strength by Equation (4-2).
N
(S) (M)
(4-2)
where:
N
S
M
Rev. 0
=
=
=
neutron level
neutron source strength
subcritical multiplication factor
Page 3
NP-04
DOE-HDBK-1019/2-93
If the term M in Equation (4-2) is replaced by the expression 1/1-keff from Equation (4-1), the
following expression results.
N
(4-3)
keff
Example:
A reactor contains a neutron source that produces 110,000 neutrons per second. The
reactor has a keff of 0.986. Calculate the stable total neutron production rate in the
reactor.
Solution:
The neutron production rate is calculated using Equation (4-3).
N
1
1
keff
110,000
neutrons
second
1
0.986
7.86 x 106 neutrons

second
To this point it has been necessary to know the neutron source strength of the reactor in order
to use the concept of subcritical multiplication. In most reactors the actual strength of the
neutron sources is difficult, if not impossible, to determine. Even though the actual source
strength may not be known, it is still possible to relate the change in reactivity to a change in
neutron level.
Consider a reactor at two different times when keff is two different values, k1 and k2. The
neutron level at each time can be determined based on the neutron source strength and the
subcritical multiplication factor using Equation (4-3).
N1
NP-04
1
1
k1
N2
1
1
Page 4
k2
Rev. 0
DOE-HDBK-1019/2-93
The equation for N1 can be divided by the equation for N2.

S
N1
N2
1
1
k1
1
N1
k2
N2
k1
k2
Because the source strength appears in both the numerator and denominator, it cancels out of
the equation. Therefore, the neutron level at any time can be determined based on the neutron
level present at any other time provided the values of keff or reactivity for both times are known.
The neutron level in a shutdown reactor is typically monitored using instruments that measure
the neutron leakage out of the reactor. The neutron leakage is proportional to the neutron level
in the reactor. Typical units for displaying the instrument reading are counts per second (cps).
Because the instrument count rate is proportional to the neutron level, the above equation can
be restated as shown in Equation (4-4).
CR1
k2
CR2
k1
(4-4)
where:
CR1
CR2
k1
k2
=
=
=
=
count
count
keff at
keff at
rate at time 1
rate at time 2
time 1
time 2
Equation (4-4) is very useful during the shutdown operation of a reactor. Before adding positive
reactivity to a reactor, it is possible to predict the effect the reactivity addition will have on the
neutron level.
Example:
A reactor that has a reactivity of -1000 pcm has a count rate of 42 counts per second
(cps) on the neutron monitoring instrumentation. Calculate what the neutron level should
be after a positive reactivity insertion of 500 pcm from the withdrawal of control rods.
Rev. 0
Page 5
NP-04
DOE-HDBK-1019/2-93
Solution:
Step 1:
Determine the initial value of keff for the core.

k1
Step 2:
1
( 0.01000)
0.9901
Determine the final value of keff for the core. The final value of reactivity
will be -500 pcm (-1000 + 500).
k2
Step 3:
1
1
1
( 0.00500)
0.9950
Use Equation (4-4) to determine the final count rate.
CR1
k2
CR2
k1
CR2
CR1
k1
k2
42 cps
1
1
0.9901
0.9950
83 cps
Notice from this example that the count rate doubled as the reactivity was halved (e.g., reactivity
was changed from -1000 pcm to -500 pcm).
Use of 1/M Plots

Because the subcritical multiplication factor is related to the value of keff, it is possible to
monitor the approach to criticality through the use of the subcritical multiplication factor. As
positive reactivity is added to a subcritical reactor, keff will get nearer to one. As keff gets nearer
to one, the subcritical multiplication factor (M) gets larger. The closer the reactor is to
criticality, the faster M will increase for equal step insertions of positive reactivity. When the
reactor becomes critical, M will be infinitely large. For this reason, monitoring and plotting M
during an approach to criticality is impractical because there is no value of M at which the
reactor clearly becomes critical.
NP-04
Page 6
Rev. 0
DOE-HDBK-1019/2-93
Instead of plotting M directly, its inverse (1/M) is plotted on a graph of 1/M versus rod height.
M
1
M
1
1
keff
keff
As control rods are withdrawn and keff approaches one and M approaches infinity, 1/M
approaches zero. For a critical reactor, 1/M is equal to zero. A true 1/M plot requires
knowledge of the neutron source strength. Because the actual source strength is usually
unknown, a reference count rate is substituted, and the calculation of the factor 1/M is through
the use of Equation (4-5).
1
M
CR o
(4-5)
CR
where:
1/M
CRo
CR
=
=
=
inverse multiplication factor

reference count rate
current count rate
In practice, the reference count rate used is the count rate prior to the beginning of the reactivity
change. The startup procedures for many reactors include instructions to insert positive
reactivity in incremental steps with delays between the reactivity insertions to allow time for
subcritical multiplication to increase the steady-state neutron population to a new, higher level
and allow more accurate plotting of 1/M. The neutron population will typically reach its new
steady-state value within 1-2 minutes, but the closer the reactor is to criticality, the longer the
time will be to stabilize the neutron population.
Example:
Given the following rod withdrawal data, construct a 1/M plot and estimate the rod
position when criticality would occur. The initial count rate on the nuclear
instrumentation prior to rod withdrawal is 50 cps.
Rod Withdrawal
(inches)
2
4
6
8
10
12
Rev. 0
Page 7
Count Rate
(cps)
55
67
86
120
192
500
NP-04
DOE-HDBK-1019/2-93
Solution:
Step 1:
Calculate 1/M for each of the rod positions using equation (4-5). The
reference count rate is 50 cps at a rod position of zero.
Rod Withdrawal
(inches)
0
2
4
6
8
10
12
Step 2:
CRo/CR
1
0.909
0.746
0.581
0.417
0.260
0.100
Plotting these values, as shown in Figure 1, and extrapolating to a 1/M

value of 0 reveals that the reactor will go critical at approximately 13
inches of rod withdrawal.
Figure 1
NP-04
Count Rate
(cps)
50
55
67
86
120
192
500
1/M Plot vs. Rod Withdrawal
Page 8
Rev. 0
DOE-HDBK-1019/2-93
Summary
Subcritical M ultiplication Summary

Subcritical multiplication is the effect of fissions in the fuel increasing the
effective source strength of a reactor with a keff less than one.
Subcritical multiplication factor is the factor that relates the source level to the
steady-state neutron level of the core.
The steady-state neutron level of a subcritical reactor can be calculated based on
the source strength and keff using Equation (4-3).
N
1
1
keff
The count rate expected in a subcritical reactor following a change in reactivity

can be calculated based on the initial count rate, initial keff, and amount of
reactivity addition using Equation (4-4).
CR1
k2
CR2
k1
1/M plots can be used to predict the point of criticality.
Rev. 0
Page 9
NP-04
REACTOR KINETICS
DOE-HDBK-1019/2-93
REACTOR KINETICS
The response of neutron flux and reactor power to changes in reactivity is much
different in a critical reactor than in a subcritical reactor. The reliance of the chain
reaction on delayed neutrons makes the rate of change of reactor power
controllable.
EO 2.1

a.
b.
c.
NP-04
Reactor period
Doubling time
Reactor startup rate
EO 2.2
DESCRIBE the relationship between the delayed neutron

fraction, average delayed neutron fraction, and effective delayed
neutron fraction.
EO 2.3
WRITE the period equation and IDENTIFY each symbol.
EO 2.4
Given the reactivity of the core and values for the effective
average delayed neutron fraction and decay constant,
CALCULATE the reactor period and the startup rate.
EO 2.5
Given the initial power level and either the doubling or halving
time, CALCULATE the power at any later time.
EO 2.6
Given the initial power level and the reactor period,

CALCULATE the power at any later time.
EO 2.7
EXPLAIN what is meant by the terms prompt drop and

prompt jump.
EO 2.8
DEFINE the term prompt critical.
EO 2.9
DESCRIBE reactor behavior during the prompt critical

condition.
EO 2.10
EXPLAIN the use of measuring reactivity in units of dollars.
Page 10
Rev. 0
DOE-HDBK-1019/2-93
REACTOR KINETICS
Reactor Period ( )
The reactor period is defined as the time required for reactor power to change by a factor of
"e," where "e" is the base of the natural logarithm and is equal to about 2.718. The reactor
period is usually expressed in units of seconds. From the definition of reactor period, it is
possible to develop the relationship between reactor power and reactor period that is expressed
by Equation (4-6).
Po e t /
P
Po
=
=
=
=
(4-6)
where:
transient reactor power

initial reactor power
reactor period (seconds)
time during the reactor transient (seconds)
The smaller the value of , the more rapid the change in reactor power. If the reactor period is
positive, reactor power is increasing. If the reactor period is negative, reactor power is
decreasing.
There are numerous equations used to express reactor period, but Equation (4-7) shown below,
or portions of it, will be useful in most situations. The first term in Equation (4-7) is the prompt
term and the second term is the delayed term.
eff
(4-7)
eff
where:
*
eff
eff
= prompt generation lifetime

= effective delayed neutron fraction
= reactivity
= effective delayed neutron precursor decay constant
= rate of change of reactivity
Effective Delayed Neutron Fraction

Recall that , the delayed neutron fraction, is the fraction of all fission neutrons that are born
as delayed neutrons. The value of depends upon the actual nuclear fuel used. As discussed
in Module 1, the delayed neutron precursors for a given type of fuel are grouped on the basis
of half-life. The following table lists the fractional neutron yields for each delayed neutron
group of three common types of fuel.
Rev. 0
Page 11
NP-04
REACTOR KINETICS
DOE-HDBK-1019/2-93
TABLE 1
Delayed Neutron Fractions for Various Fuels
Group
Half-Life (sec)
Uranium-235
Uranium-238
Plutonium-239
55.6
0.00021
0.0002
0.00021
22.7
0.00141
0.0022
0.00182
6.22
0.00127
0.0025
0.00129
2.30
0.00255
0.0061
0.00199
0.61
0.00074
0.0035
0.00052
0.23
0.00027
0.0012
0.00027
0.00650
0.0157
0.00200
TOTAL
The term (pronounced beta-bar) is the average delayed neutron fraction. The value of is
the weighted average of the total delayed neutron fractions of the individual types of fuel. Each
total delayed neutron fraction value for each type of fuel is weighted by the percent of total
neutrons that the fuel contributes through fission. If the percentage of fissions occurring in the
different types of fuel in a reactor changes over the life of the core, the average delayed neutron
fraction will also change. For a light water reactor using low enriched fuel, the average delayed
neutron fraction can change from 0.0070 to 0.0055 as uranium-235 is burned out and
plutonium-239 is produced from uranium-238.
Delayed neutrons do not have the same properties as prompt neutrons released directly from
fission. The average energy of prompt neutrons is about 2 MeV. This is much greater than the
average energy of delayed neutrons (about 0.5 MeV). The fact that delayed neutrons are born
at lower energies has two significant impacts on the way they proceed through the neutron life
cycle. First, delayed neutrons have a much lower probability of causing fast fissions than
prompt neutrons because their average energy is less than the minimum required for fast fission
to occur. Second, delayed neutrons have a lower probability of leaking out of the core while
they are at fast energies, because they are born at lower energies and subsequently travel a
shorter distance as fast neutrons. These two considerations (lower fast fission factor and higher
fast non-leakage probability for delayed neutrons) are taken into account by a term called the
importance factor (I). The importance factor relates the average delayed neutron fraction to the
effective delayed neutron fraction.
The effective delayed neutron fraction eff is defined as the fraction of neutrons at thermal
energies which were born delayed. The effective delayed neutron fraction is the product of the
average delayed neutron fraction and the importance factor.
NP-04
Page 12
Rev. 0
DOE-HDBK-1019/2-93
eff
eff
effective delayed neutron fraction
=
=
average delayed neutron fraction

importance factor
REACTOR KINETICS
where:
In a small reactor with highly enriched fuel, the increase in fast non-leakage probability will
dominate the decrease in the fast fission factor, and the importance factor will be greater than
one. In a large reactor with low enriched fuel, the decrease in the fast fission factor will
dominate the increase in the fast non-leakage probability and the importance factor will be less
than one (about 0.97 for a commercial PWR).
Effective Delayed Neutron Precursor Decay Constant

Another new term has been introduced in the reactor period ( ) equation. That term is eff
(pronounced lambda effective), the effective delayed neutron precursor decay constant. The
decay rate for a given delayed neutron precursor can be expressed as the product of precursor
concentration and the decay constant ( ) of that precursor. The decay constant of a precursor
is simply the fraction of an initial number of the precursor atoms that decays in a given unit
time. A decay constant of 0.1 sec-1, for example, implies that one-tenth, or ten percent, of a
sample of precursor atoms decays within one second. The value for the effective delayed
neutron precursor decay constant, eff, varies depending upon the balance existing between the
concentrations of the precursor groups and the nuclide(s) being used as the fuel.
If the reactor is operating at a constant power, all the precursor groups reach an equilibrium
value. During an up-power transient, however, the shorter-lived precursors decaying at any
given instant were born at a higher power level (or flux level) than the longer-lived precursors
decaying at the same instant. There is, therefore, proportionately more of the shorter-lived and
fewer of the longer-lived precursors decaying at that given instant than there are at constant
power. The value of eff is closer to that of the shorter-lived precursors.
During a down-power transient the longer-lived precursors become more significant. The
longer-lived precursors decaying at a given instant were born at a higher power level (or flux
level) than the shorter-lived precursors decaying at that instant. Therefore, proportionately
more of the longer-lived precursors are decaying at that instant, and the value of eff approaches
the values of the longer-lived precursors.
Approximate values for eff are 0.08 sec-1 for steady-state operation, 0.1 sec-1 for a power
increase, and 0.05 sec-1 for a power decrease. The exact values will depend upon the materials
used for fuel and the value of the reactivity of the reactor core.
Rev. 0
Page 13
NP-04
REACTOR KINETICS
DOE-HDBK-1019/2-93
Returning now to Equation (4-7) for reactor period.
eff
eff
prompt
term
delayed
term
If the positive reactivity added is less than the value of eff , the emission of prompt fission
neutrons alone is not sufficient to overcome losses to non-fission absorption and leakage. If
delayed neutrons were not being produced, the neutron population would decrease as long as
the reactivity of the core has a value less than the effective delayed neutron fraction. The
positive reactivity insertion is followed immediately by a small immediate power increase called
the prompt jump. This power increase occurs because the rate of production of prompt neutrons
changes abruptly as the reactivity is added. Recall from an earlier module that the generation
time for prompt neutrons is on the order of 10 -13 seconds. The effect can be seen in Figure 2.
After the prompt jump, the rate of change of power cannot increase any more rapidly than the
built-in time delay the precursor half-lives allow. Therefore, the power rise is controllable, and
the reactor can be operated safely.
Figure 2 Reactor Power Response to Positive Reactivity Addition
NP-04
Page 14
Rev. 0
DOE-HDBK-1019/2-93
REACTOR KINETICS
Conversely, in the case where negative reactivity is added to the core there will be a prompt
drop in reactor power. The prompt drop is the small immediate decrease in reactor power
caused by the negative reactivity addition. The prompt drop is illustrated in Figure 3. After the
prompt drop, the rate of change of power slows and approaches the rate determined by the
delayed term of Equation (4-7).
Figure 3 Reactor Power Response to Negative Reactivity Addition
Prompt Criticality
It can be readily seen from Equation (4-7) that if the amount of positive reactivity added equals
the value of eff , the reactor period equation becomes the following.
Rev. 0
Page 15
NP-04
REACTOR KINETICS
DOE-HDBK-1019/2-93
In this case, the production of prompt neutrons alone is enough to balance neutron losses and
increase the neutron population. The condition where the reactor is critical on prompt neutrons,
and the neutron population increases as rapidly as the prompt neutron generation lifetime allows
is known as prompt critical. The prompt critical condition does not signal a dramatic change
in neutron behavior. The reactor period changes in a regular manner between reactivities above
and below this reference. Prompt critical is, however, a convenient condition for marking the
transition from delayed neutron to prompt neutron time scales. A reactor whose reactivity even
approaches prompt critical is likely to suffer damage due to the rapid rise in power to a very
high level. For example, a reactor which has gone prompt critical could experience a several
thousand percent power increase in less than one second.
Because the prompt critical condition is so important, a specific unit of reactivity has been
defined that relates to it. The unit of reactivity is the dollar ($), where one dollar of reactivity
is equivalent to the effective delayed neutron fraction eff . A reactivity unit related to the
dollar is the cent, where one cent is one-hundredth of a dollar. If the reactivity of the core is one
dollar, the reactor is prompt critical. Because the effective delayed neutron fraction is
dependent upon the nuclides used as fuel, the value of the dollar is also dependent on the
nuclides used as fuel.
Stable Period Equation

For normal reactor operating conditions, the value of positive reactivity in the reactor is never
permitted to approach the effective delayed neutron fraction, and the reactor period equation is
normally written as follows.
eff
(4-8)
eff
Equation (4-8) is referred to as the transient period equation since it incorporates the term
to account for the changing amount of reactivity in the core. The */ term (prompt period) is
normally negligible with respect to the remainder of the equation and is often not included.
0 ), and the reactor

For conditions when the amount of reactivity in the core is constant (
period is unchanging, Equation (4-8) can be simplified further to Equation (4-9) which is known
as the stable period equation.
eff
(4-9)
eff
NP-04
Page 16
Rev. 0
DOE-HDBK-1019/2-93
REACTOR KINETICS
Reactor Startup Rate (SUR)

The reactor startup rate (SUR) is defined as the number of factors of ten that power changes
in one minute. The units of SUR are powers of ten per minute, or decades per minute (DPM).
Equation (4-10) shows the relationship between reactor power and startup rate.
SUR (t)
Po 10
(4-10)
where:
SUR
t
= reactor startup rate (DPM)

= time during reactor transient (minutes)
The relationship between reactor period and startup rate can be developed by considering
Equations (4-6) and (4-10).
Po e t /
P
P
Po
and P
e t/
10
Po 10 SUR (t)
SUR (t)
Changing the base of the exponential term on the right side to "e" (10 = e 2.303) and solving the
result yields the following.
e t (sec)/
t (sec)
60
e 2.303
SUR (t (min))
2.303 SUR(t (min))

2.303 SUR
SUR
26.06
(4-11)
Doubling Time
Sometimes it is useful to discuss the rate of change of reactor power in terms similar to those
used in radioactive decay calculations. Doubling or halving time are terms that relate to the
amount of time it takes reactor power to double or be reduced to one-half the initial power level.
If the stable reactor period is known, doubling time can be determined as follows.
Rev. 0
Page 17
NP-04
REACTOR KINETICS
DOE-HDBK-1019/2-93
Doubling time (DT) =
(ln 2)
where:
= stable reactor period
= natural logarithm of 2
ln 2
When the doubling time is known, the power level change from P o is given by the following
equation.
Po 2t /DT
(4-12)
where:
t
DT
= time interval of transient

= doubling time
The following example problems reinforce the concepts of period and startup rate.
Example 1:
A reactor has a eff of 0.10 sec-1 and an effective delayed neutron fraction of 0.0070. If
keff is equal to 1.0025, what is the stable reactor period and the SUR?
Solution:
Step 1:
First solve for reactivity using Equation (3-5).
keff
keff
1.0025 1
1.0025
0.00249
Step 2:
k/k
Use this value of reactivity in Equation (4-9) to calculate reactor period.
eff
eff
0.0070
0.10 sec
0.00249
1
0.00249
18.1 sec
NP-04
Page 18
Rev. 0
Step 3:
DOE-HDBK-1019/2-93
REACTOR KINETICS
The startup rate can be calculated from the reactor period using
Equation (4-11).
26.06
SUR
26.06
18.1 sec
1.44 DPM
Example 2:
130 pcm of negative reactivity is added to a reactor that is initially critical at a power of
100 watts. eff for the reactor is 0.05 sec-1 and the effective delayed neutron fraction is
0.0068. Calculate the steady state period and startup rate. Also calculate the power
level 2 minutes after the reactivity insertion.
Solution:
Step 1:
Use Equation (4-9) to calculate the reactor period.
eff
eff
0.0068
0.05 sec
( 0.00130)
1
( 0.00130)
124.6 sec
Step 2:
The startup rate can be calculated from the reactor period using
Equation (4-11).
SUR
26.06
26.06
124.6 sec
0.2091 DPM
Step 3:
Use either Equation (4-1) or Equation (4-10) to calculate the reactor

power two minutes after the reactivity insertion.
Po e t /
100 W e (120 s/
P
124.6 s)
SUR (t)
(100 W) 10(
38.2 W
Rev. 0
Po 10
0.2091 DPM) (2 min)
38.2 W
Page 19
NP-04
REACTOR KINETICS
DOE-HDBK-1019/2-93
Example 3:
A reactor has a power level of 1000 watts and a doubling time of 2 minutes. What is the
reactor power level 10 minutes later?
Solution:
Use Equation (4-12) to calculate the final power level.
Po (2)t /DT
(1,000 W) (2)10 min /2
min
32,000 W
NP-04
Page 20
Rev. 0
DOE-HDBK-1019/2-93
REACTOR KINETICS
Summary
Reactor Kinetics Summary

Reactor period is the time required for reactor power to change by a factor of e
(2.718).
Doubling time is the time required for reactor power to double.
Reactor startup rate is the number of factors of ten that reactor power changes in
one minute.
The delayed neutron fraction ( ) is the fraction of all fission neutrons that are
born as delayed neutrons for a particular type of fuel (that is, uranium-235 and
plutonium-239).
The average delayed neutron fraction ( ) is the weighted average of the total
delayed neutron fractions of the different types of fuel used in a particular reactor.
The effective delayed neutron fraction ( eff ) is the average delayed neutron
fraction multiplied by an Importance Factor which accounts for the fact that
delayed neutrons are born at lower average energies than fast neutrons.
The reactor period equation is stated below.
eff
eff
prompt
term
delayed
term
where:
eff
eff
Rev. 0
=
=
=
=
=
=
reactor period
prompt generation lifetime
effective delayed neutron fraction
reactivity
effective delayed neutron precursor decay constant
rate of change of reactivity
Page 21
NP-04
REACTOR KINETICS
DOE-HDBK-1019/2-93
Reactor Kinetics Summary (Cont.)

Equations (4-9) and (4-11) can be used to calculate the stable reactor period and
startup rate.
26.06
eff
SUR
eff
The concept of doubling time can be used in a similar manner to reactor period to
calculate changes in reactor power using Equation (4-12).
Po 2t /DT
The reactor period or the startup rate can be used to determine the reactor power
using Equations (4-6) and (4-10).
Po e t /
Po 10
SUR (t)
Prompt jump is the small, immediate power increase that follows a positive
reactivity insertion related to an increase in the prompt neutron population.
Prompt drop is the small, immediate power decrease that follows a negative
reactivity insertion related to a decrease in the prompt neutron population.
Prompt critical is the condition when the reactor is critical on prompt neutrons
alone.
When a reactor is prompt critical, the neutron population, and hence power, can
increase as quickly as the prompt neutron generation time allows.
Measuring reactivity in units of dollars is useful when determining if a reactor is
prompt critical. A reactor that contains one dollar of positive reactivity is prompt
critical since one dollar of reactivity is equivalent to eff.
NP-04
Page 22
Rev. 0
DOE-HDBK-1019/2-93
REACTOR OPERATION
REACTOR OPERATION
It is important to understand the principles that determine how a reactor responds
during all modes of operation. Special measures must be taken during the startup
of a reactor to ensure that expected responses are occurring. During power
operation, control of the flux shape is necessary to ensure operation within limits
and maximum core performance. Even when a reactor is shut down, the fact that
the fission products created by the fission process continue to generate heat
results in a need to monitor support systems to ensure adequate cooling of the
core.
Rev. 0
EO 3.1
EXPLAIN why a startup neutron source may be required for

a reactor.
EO 3.2
LIST four variables typically involved in a reactivity balance.
EO 3.3
EXPLAIN how a reactivity balance may be used to predict the

conditions under which the reactor will become critical.
EO 3.4
LIST three methods used to shape or flatten the core power

distribution.
EO 3.5
DESCRIBE the concept of power tilt.
EO 3.6
DEFINE the term shutdown margin.
EO 3.7
EXPLAIN the rationale behind the one stuck rod criterion.
EO 3.8
IDENTIFY five changes that will occur during and after a

reactor shutdown that will affect the reactivity of the core.
EO 3.9
EXPLAIN why decay heat is present following reactor

operation.
EO 3.10
LIST three variables that will affect the amount of decay heat
present following reactor shutdown.
EO 3.11
ESTIMATE the approxim ate am ount of decay heat that will

exist one hour after a shutdown from steady state conditions.
Page 23
NP-04
REACTOR OPERATION
DOE-HDBK-1019/2-93
Startup
When a reactor is started up with unirradiated fuel, or on those occasions when the reactor is
restarted following a long shutdown period, the source neutron population will be very low. In
some reactors, the neutron population is frequently low enough that it cannot be detected by the
nuclear instrumentation during the approach to criticality. Installed neutron sources, such as
those discussed in Module 2, are frequently used to provide a safe, easily monitored reactor
startup. The neutron source, together with the subcritical multiplication process, provides a
sufficiently large neutron population to allow monitoring by the nuclear instruments throughout
the startup procedure. Without the installed source, it may be possible to withdraw the control
rods to the point of criticality, and then continue withdrawal without detecting criticality because
the reactor goes critical below the indicating range. Continued withdrawal of control rods at this
point could cause reactor power to rise at an uncontrollable rate before neutron level first
becomes visible on the nuclear instruments.
An alternative to using a startup source is to limit the rate of rod withdrawal, or require waiting
periods between rod withdrawal increments. By waiting between rod withdrawal increments,
the neutron population is allowed to increase through subcritical multiplication. Subcritical
multiplication is the process where source neutrons are used to sustain the chain reaction in a
reactor with a multiplication factor (keff) of less than one. The chain reaction is not
"self-sustaining," but if the neutron source is of sufficient magnitude, it compensates for the
neutrons lost through absorption and leakage. This process can result in a constant, or
increasing, neutron population even though keff is less than one.
Estimated Critical Position

In the first chapter of this module, 1/M plots were discussed. These plots were useful for
monitoring the approach to criticality and predicting when criticality will occur based on
indications received while the startup is actually in progress. Before the reactor startup is
initiated, the operator calculates an estimate of the amount of rod withdrawal that will be
necessary to achieve criticality. This process provides an added margin of safety because a large
discrepancy between actual and estimated critical rod positions would indicate that the core was
not performing as designed. Depending upon a reactor's design or age, the buildup of xenon
within the first several hours following a reactor shutdown may introduce enough negative
reactivity to cause the reactor to remain shutdown even with the control rods fully withdrawn.
In this situation it is important to be able to predict whether criticality can be achieved, and if
criticality cannot be achieved, the startup should not be attempted.
For a given set of conditions (such as time since shutdown, temperature, pressure, fuel burnup,
samarium and xenon poisoning) there is only one position of the control rods (and boron
concentrations for a reactor with chemical shim) that results in criticality, using the normal rod
withdrawal sequence. Identification of these conditions allows accurate calculation of control
rod position at criticality. The calculation of an estimated critical position (ECP) is simply a
mathematical procedure that takes into account all of the changes in factors that significantly
affect reactivity that have occurred between the time of reactor shutdown and the time that the
reactor is brought critical again.
NP-04
Page 24
Rev. 0
DOE-HDBK-1019/2-93
REACTOR OPERATION
For most reactor designs, the only factors that change significantly after the reactor is shut down
are the average reactor temperature and the concentration of fission product poisons. The
reactivities normally considered when calculating an ECP include the following.
Basic Reactivity of the Core-
The reactivity associated with the critical control rod

position for a xenon-free core at normal operating
temperature. This reactivity varies with the age of the core
(amount of fuel burnup).
Direct Xenon Reactivity -
The reactivity related to the xenon that was actually present

in the core at the time it was shutdown. This reactivity is
corrected to allow for xenon decay.
Indirect Xenon Reactivity -
The reactivity related to the xenon produced by the decay

of iodine that was present in the core at the time of
shutdown.
Temperature Reactivity -
The reactivity related to the difference between the actual

reactor temperature during startup and the normal operating
temperature.
To arrive at an ECP of the control rods, the basic reactivity, direct and indirect xenon reactivity,
and temperature reactivity are combined algebraically to determine the amount of positive control
rod reactivity that must be added by withdrawing control rods to attain criticality. A graph of
control rod worth versus rod position is used to determine the estimated critical position.
Core Power Distribution

In order to ensure predictable temperatures and uniform depletion of the fuel installed in a
reactor, numerous measures are taken to provide an even distribution of flux throughout the
power producing section of the reactor. This shaping, or flattening, of the neutron flux is
normally achieved through the use of reflectors that affect the flux profile across the core, or
by the installation of poisons to suppress the neutron flux where desired. The last method,
although effective at shaping the flux, is the least desirable since it reduces neutron economy by
absorbing the neutrons.
A reactor core is frequently surrounded by a "reflecting" material to reduce the ratio of peak
flux to the flux at the edge of the core fuel area. Reflector materials are normally not
fissionable, have a high scattering cross section, and have a low absorption cross section.
Essentially, for thermal reactors a good moderator is a good reflector. Water, heavy water,
beryllium, zirconium, or graphite are commonly used as reflectors. In fast reactor systems,
reflectors are not composed of moderating materials because it is desired to keep neutron energy
high. The reflector functions by scattering some of the neutrons, which would have leaked from
a bare (unreflected) core, back into the fuel to produce additional fissions.
Rev. 0
Page 25
NP-04
REACTOR OPERATION
DOE-HDBK-1019/2-93
Figure 4 shows the general effect of reflection in the thermal reactor system where core power
is proportional to the thermal flux. Notice that a reflector can raise the power density of the
core periphery and thus increase the core average power level without changing the peak power.
As illustrated in Figure 4, the thermal flux in the reflector may actually be higher than that in
the outermost fuel since there are very few absorptions in the reflector.
Figure 4
Neutron Radial Flux Shapes for Bare and Reflected Cores
Varying the fuel enrichment or fuel concentrations in the core radially, axially, or both, can
readily be used to control power distribution. The simplified example illustrated in Figure 5
shows the effect of using a higher enrichment in the outer regions of the core. Varying fuel
concentrations or poison loading for flux shaping is frequently referred to as zoning. In the
example illustrated the large central peak is reduced, but the average power level remains the
same.
Figure 5
NP-04
Effect of Non-Uniform Enrichment on Radial Flux Shape
Page 26
Rev. 0
DOE-HDBK-1019/2-93
REACTOR OPERATION
The previous examples discuss changes in radial power distribution. Large variations also exist
in axial power distribution. Figure 6(A) illustrates the power distribution that may exist for a
reactor with a cylindrical geometry. The control rods in this reactor are inserted from the top,
and the effect of inserting control rods further is shown in Figure 6(B). The thermal flux is
largely suppressed in the vicinity of the control rods, and the majority of the power is generated
low in the core. This flux profile can be flattened by the use of axial fuel and/or poison zoning.
Figure 6
Effect of Control Rod Position on Axial Flux Distribution
Power Tilt
A power tilt, or flux tilt, is a specific type of core power distribution problem. It is a
non-symmetrical variation of core power in one quadrant of the core relative to the others. The
power in one portion might be suppressed by over-insertion of control rods in that portion of the
core, which, for a constant overall power level, results in a relatively higher flux in the
remainder of the core. This situation can lead to xenon oscillations, which were previously
discussed.
Rev. 0
Page 27
NP-04
REACTOR OPERATION
DOE-HDBK-1019/2-93
Shutdown Margin
Shutdown margin is the instantaneous amount of reactivity by which a reactor is subcritical or
would be subcritical from its present condition assuming all control rods are fully inserted except
for the single rod with the highest integral worth, which is assumed to be fully withdrawn.
Shutdown margin is required to exist at all times, even when the reactor is critical. It is
important that there be enough negative reactivity capable of being inserted by the control rods
to ensure complete shutdown at all times during the core lifetime. A shutdown margin in the
range of one to five percent reactivity is typically required.
The stuck rod criterion refers to the fact that the shutdown margin does not take credit for the
insertion of the highest worth control rod. The application of the stuck rod criterion ensures that
the failure of a single control rod will not prevent the control rod system from shutting down
the reactor.
Operation
During reactor operation, numerous parameters such as temperature, pressure, power level, and
flow are continuously monitored and controlled to ensure safe and stable operation of the reactor.
The specific effects of variations in these parameters vary greatly depending upon reactor design,
but generally the effects for thermal reactors are as follows.
Temperature
The most significant effect of a variation in temperature upon reactor operation is the addition
of positive or negative reactivity. As previously discussed, reactors are generally designed with
negative temperature coefficients of reactivity (moderator and fuel temperature coefficients) as
a self-limiting safety feature. A rise in reactor temperature results in the addition of negative
reactivity. If the rise in temperature is caused by an increase in reactor power, the negative
reactivity addition slows, and eventually turns the increase in reactor power. This is a highly
desirable effect because it provides a negative feedback in the event of an undesired power
excursion.
Negative temperature coefficients can also be utilized in water cooled and moderated power
reactors to allow reactor power to automatically follow energy demands that are placed upon the
system. For example, consider a reactor operating at a stable power level with the heat
produced being transferred to a heat exchanger for use in an external closed cycle system. If
the energy demand in the external system increases, more energy is removed from reactor system
causing the temperature of the reactor coolant to decrease.
As the reactor temperature
decreases, positive reactivity is added and a corresponding increase in reactor power level
results.
NP-04
Page 28
Rev. 0
DOE-HDBK-1019/2-93
REACTOR OPERATION
As reactor power increases to a level above the level of the new energy demand, the temperature
of the moderator and fuel increases, adding negative reactivity and decreasing reactor power
level to near the new level required to maintain system temperature. Some slight oscillations
above and below the new power level occur before steady state conditions are achieved. The
final result is that the average temperature of the reactor system is essentially the same as the
initial temperature, and the reactor is operating at the new higher required power level. The
same inherent stability can be observed as the energy demand on the system is decreased.
If the secondary system providing cooling to the reactor heat exchanger is operated as an open
system with once-through cooling, the above discussion is not applicable. In these reactors, the
temperature of the reactor is proportional to the power level, and it is impossible for the reactor
to be at a higher power level and the same temperature.
Pressure
The pressure applied to the reactor system can also affect reactor operation by causing changes
in reactivity. The reactivity changes result from changes in the density of the moderator in
response to the pressure changes. For example, as the system pressure rises, the moderator
density increases and results in greater moderation, less neutron leakage, and therefore the
insertion of positive reactivity. A reduction in system pressure results in the addition of negative
reactivity. Typically, in pressurized water reactors (PWR), the magnitude of this effect is
considerably less than that of a change in temperature. In two-phase systems such as boiling
water reactors (BWR), however, the effects of pressure changes are more noticeable because
there is a greater change in moderator density for a given change in system pressure.
Power Level
A change in reactor power level can result in a change in reactivity if the power level change
results in a change in system temperature.
The power level at which the reactor is producing enough energy to make up for the energy lost
to ambient is commonly referred to as the point of adding heat. If a reactor is operating well
below the point of adding heat, then variations in power level produce no measurable variations
in temperature. At power levels above the point of adding heat, temperature varies with power
level, and the reactivity changes will follow the convention previously described for temperature
variations.
The inherent stability and power turning ability of a negative temperature coefficient are
ineffective below the point of adding heat. If a power excursion is initiated from a very low
power level, power will continue to rise unchecked until the point of adding heat is reached, and
the subsequent temperature rise adds negative reactivity to slow, and turn, the rise of reactor
power. In this region, reactor safety is provided by automatic reactor shutdown systems and
operator action.
Rev. 0
Page 29
NP-04
REACTOR OPERATION
DOE-HDBK-1019/2-93
Flow
At low reactor power levels, changing the flow rate of the coolant through the reactor does not
result in a measurable reactivity change because fuel and moderator temperatures and the fraction
of steam voids occurring in the core are not changed appreciably.
When the flow rate is varied, however, the change in temperature that occurs across the core
(outlet versus inlet temperature) will vary inversely with the flow rate. At higher power levels,
on liquid cooled systems, increasing flow will lower fuel and coolant temperatures slightly,
resulting in a small positive reactivity insertion. A positive reactivity addition also occurs when
flow is increased in a two-phase (steam-water) cooled system. Increasing the flow rate decreases
the fraction of steam voids in the coolant and results in a positive reactivity addition. This
property of the moderator in a two-phase system is used extensively in commercial BWRs.
Normal power variations required to follow load changes on BWRs are achieved by varying the
coolant/moderator flow rate.
Core Burnup
As a reactor is operated, atoms of fuel are constantly consumed, resulting in the slow depletion
of the fuel frequently referred to as core burnup. There are several major effects of this fuel
depletion. The first, and most obvious, effect of the fuel burnup is that the control rods must
be withdrawn or chemical shim concentration reduced to compensate for the negative reactivity
effect of this burnup.
Some reactor designs incorporate the use of supplemental burnable poisons in addition to the
control rods to compensate for the reactivity associated with excess fuel in a new core. These
fixed burnable poisons burn out at a rate that approximates the burnout of the fuel and they
reduce the amount of control rod movement necessary to compensate for fuel depletion early in
core life.
As control rods are withdrawn to compensate for fuel depletion, the effective size of the reactor
is increased. By increasing the effective size of the reactor, the probability that a neutron slows
down and is absorbed while it is still in the reactor is also increased. Therefore, neutron leakage
decreases as the effective reactor size is increased. The magnitude of the moderator negative
temperature coefficient is determined in part by the change in neutron leakage that occurs as the
result of a change in moderator temperature. Since the fraction of neutrons leaking out is less
with the larger core, a given temperature change will have less of an effect on the leakage.
Therefore, the magnitude of the moderator negative temperature coefficient decreases with fuel
burnup.
NP-04
Page 30
Rev. 0
DOE-HDBK-1019/2-93
REACTOR OPERATION
There is also another effect that is a consideration only on reactors that use dissolved boron in
the moderator (chemical shim). As the fuel is burned up, the dissolved boron in the moderator
is slowly removed (concentration diluted) to compensate for the negative reactivity effects of fuel
burnup. This action results in a larger (more negative) moderator temperature coefficient of
reactivity in a reactor using chemical shim. This is due to the fact that when water density is
decreased by rising moderator temperature in a reactor with a negative temperature coefficient,
it results in a negative reactivity addition because some moderator is forced out of the core.
With a coolant containing dissolved poison, this density decrease also results in some poison
being forced out of the core, which is a positive reactivity addition, thereby reducing the
magnitude of the negative reactivity added by the temperature increase. Because as fuel burnup
increases the concentration of boron is slowly lowered, the positive reactivity added by the above
poison removal process is lessened, and this results in a larger negative temperature coefficient
of reactivity.
The following effect of fuel burnup is most predominant in a reactor with a large concentration
of uranium-238. As the fission process occurs in a thermal reactor with low or medium
enrichment, there is some conversion of uranium-238 into plutonium-239. Near the end of core
life in certain reactors, the power contribution from the fission of plutonium-239 may be
comparable to that from the fission of uranium-235. The value of the delayed neutron fraction
() for uranium-235 is 0.0064 and for plutonium-239 is 0.0021. Consequently, as core burnup
progresses, the effective delayed neutron fraction for the fuel decreases appreciably. It follows
then that the amount of reactivity insertion needed to produce a given reactor period decreases
with burnup of the fuel.
Shutdown
A reactor is considered to be shut down when it is subcritical and sufficient shutdown reactivity
exists so there is no immediate probability of regaining criticality. Shutdown is normally
accomplished by insertion of some (or all) of the control rods, or by introduction of soluble
neutron poison into the reactor coolant.
The rate at which the reactor fission rate decays immediately following shutdown is similar for
all reactors provided a large amount of negative reactivity is inserted. After a large negative
reactivity addition the neutron level undergoes a rapid decrease of about two decades (prompt
drop) until it is at the level of production of delayed neutrons. Then the neutron level slowly
drops off as the delayed neutron precursors decay, and in a short while only the longest-lived
precursor remains in any significant amount. This precursor determines the final rate of
decrease in reactor power until the neutron flux reaches the steady state level corresponding to
the subcritical multiplication of the neutron source.
Rev. 0
Page 31
NP-04
REACTOR OPERATION
DOE-HDBK-1019/2-93
The half-life of the longest lived delayed neutron precursor results in a reactor period of around
-80 seconds or a startup rate of -1/3 DPM for most reactors after a reactor shutdown. One
noticeable exception to this is a heavy water reactor. In a heavy water reactor, the photoneutron source is extremely large after shutdown due to the amount of deuterium in the
moderator and the large number of high energy gammas from short-lived fission product decay.
The photo-neutron source is large enough to have a significant impact on neutron population
immediately after shutdown. The photo-neutron source has the result of flux levels decreasing
more slowly so that a heavy water reactor will have a significantly larger negative reactor period
after a shutdown.
Throughout the process of reactor shutdown the nuclear instrumentation is closely monitored to
observe that reactor neutron population is decreasing as expected, and that the instrumentation
is functioning properly to provide continuous indication of neutron population. Instrumentation
is observed for proper overlap between ranges, comparable indication between multiple
instrument channels, and proper decay rate of neutron population.
A distinction should be made between indicated reactor power level after shutdown and the
actual thermal power level. The indicated reactor power level is the power produced directly
from fission in the reactor core, but the actual thermal power drops more slowly due to decay
heat production as previously discussed. Decay heat, although approximately 5 to 6% of the
steady state reactor power prior to shutdown, diminishes to less than 1% of the pre-shutdown
power level after about one hour.
After a reactor is shutdown, provisions are provided for the removal of decay heat. If the
reactor is to be shut down for only a short time, operating temperature is normally maintained.
If the shutdown period will be lengthy or involves functions requiring cooldown of the reactor,
the reactor temperature can be lowered by a number of methods. The methods for actually
conducting cooldown of the reactor vary depending on plant design, but in all cases limitations
are imposed on the maximum rate at which the reactor systems may be cooled. These limits are
provided to reduce the stress applied to system materials, thereby reducing the possibility of stress
induced failure.
Although a reactor is shut down, it must be continuously monitored to ensure the safety of the
reactor. Automatic monitoring systems are employed to continuously collect and assess the data
provided by remote sensors. It is ultimately the operator who must ensure the safety of the
reactor.
NP-04
Page 32
Rev. 0
DOE-HDBK-1019/2-93
REACTOR OPERATION
Decay Heat
About 7 percent of the 200 MeV produced by an average fission is released at some time after
the instant of fission. This energy comes from the decay of the fission products. When a
reactor is shut down, fission essentially ceases, but decay energy is still being produced. The
energy produced after shutdown is referred to as decay heat. The amount of decay heat
production after shutdown is directly influenced by the power history of the reactor prior to
shutdown. A reactor operated at full power for 3 to 4 days prior to shutdown has much higher
decay heat generation than a reactor operated at low power for the same period. The decay heat
produced by a reactor shutdown from full power is initially equivalent to about 5 to 6% of the
thermal rating of the reactor. This decay heat generation rate diminishes to less than 1%
approximately one hour after shutdown. However, even at these low levels, the amount of heat
generated requires the continued removal of heat for an appreciable time after shutdown. Decay
heat is a long-term consideration and impacts spent fuel handling, reprocessing, waste
management, and reactor safety.
Summary
Reactor Operation Summary

An installed neutron source, together with the subcritical multiplication process,
may be needed to increase the neutron population to a level where it can be
monitored throughout the startup procedure.
Reactivity balances, such as Estimated Critical Position calculations, typically
consider the basic reactivity of the core and the reactivity effects of temperature,
direct xenon, and indirect xenon.
A reactivity balance called an Estimated Critical Position is used to predict the
position of the control rods at which criticality will be achieved during a startup.
To arrive at an ECP of the control rods, the basic reactivity, direct and indirect
xenon reactivity, and temperature reactivity are added together to determine the
amount of positive reactivity that must be added by withdrawing control rods to
attain criticality. A graph of control rod worth versus rod position is used to
determine the estimated critical position.
Rev. 0
Page 33
NP-04
REACTOR OPERATION
DOE-HDBK-1019/2-93
Reactor Operation Summary (Cont.)

Three methods are used to shape or flatten the core power distribution.
Use of reflectors
Installation of neutron poisons
Axial or radial variation of fuel enrichment
Power tilt is a non-symmetrical variation of core power in one quadrant of the
core relative to the other quadrants.
Shutdown margin is the instantaneous amount of reactivity by which a reactor
is subcritical or would be subcritical from its present condition assuming all
control rods are fully inserted except for the single rod with the highest integral
worth, which is assumed to be fully withdrawn.
The stuck rod criterion is applied to the shutdown margin to ensure that the
failure of a single control rod will not prevent the control rod system from
shutting down the reactor.
Several factors may change during and after the shutdown of the reactor that
affect the reactivity of the core.
Control rod position
Soluble neutron poison concentration
Temperature of the fuel and coolant
Xenon
Samarium
Decay heat is always present following reactor operation due to energy resulting
from the decay of fission products.
The amount of decay heat present in the reactor is dependent on three factors.
The pre-shutdown power level
How long the reactor operated
The amount of time since reactor shutdown
Decay heat immediately after shutdown is approximately 5-6% of the preshutdown power level. Decay heat will decrease to approximately 1% of the
pre-shutdown power level within one hour of reactor shutdown.
NP-04
Page 34
Rev. 0
DOE-HDBK-1019/2-93
REACTOR OPERATION
end of text.
CONCLUDING MATERIAL
Review activities:
Preparing activity:

DOE - NE-73
Project Number 6910-0025
Rev. 0
Page 35
NP-04
REACTOR OPERATION
DOE-HDBK-1019/2-93
NP-04
Page 36
Rev. 0
DOE-HDBK-1012/1-92
JUNE 1992

THERMODYNAMICS, HEAT TRANSFER,
AND FLUID FLOW
Volume 1 of 3
FSC-6910

Available to DOE and DOE contractors from the Office of Scientific and Technical Information.
P. O. Box 62, Oak Ridge, TN 37831; (615) 576-8401.
Available to the public from the National Technical Information Service, U.S. Department of
Commerce, 5285 Port Royal Rd., Springfield, VA 22161.
THERMODYNAMICS, HEAT TRANSFER, AND FLUID FLOW
ABSTRACT
The Thermodynamics, Heat Transfer, and Fluid Flow Fundamentals Handbook was
developed to assist nuclear facility operating contractors provide operators, maintenance
personnel, and the technical staff with the necessary fundamentals training to ensure a basic
understanding of the thermal sciences. The handbook includes information on thermodynamics
and the properties of fluids; the three modes of heat transfer - conduction, convection, and
radiation; and fluid flow, and the energy relationships in fluid systems. This information will
provide personnel with a foundation for understanding the basic operation of various types of DOE
nuclear facility fluid systems.
Key Words: Training Material, Thermodynamics, Heat Transfer, Fluid Flow, Bernoulli's
Equation
Rev. 0
HT
FOREWORD
subjects, which include Mathematics; Classical Physics; Thermodynamics, Heat Transfer, and Fluid
Flow; Instrumentation and Control; Electrical Science; Material Science; Mechanical Science;
Chemistry; Engineering Symbology, Prints, and Drawings; and Nuclear Physics and Reactor
Theory. The handbooks are provided as an aid to DOE nuclear facility contractors.
for use by DOE Category A reactors. The subject areas, subject matter content, and level of detail
of the Reactor Operator Fundamentals Manuals was determined from several sources. DOE
Category A reactor training managers determined which materials should be included, and served
as a primary reference in the initial development phase. Training guidelines from the commercial
nuclear power industry, results of job and task analyses, and independent input from contractors
and operations-oriented personnel were all considered and included to some degree in developing
the text material and learning objectives.
fundamentals training requirements. To increase their applicability to nonreactor nuclear facilities,
of each of these handbooks was then reviewed by these two groups. This approach has resulted
material, and is divided into modules so that content and order may be modified by individual DOE
contractors to suit their specific training needs. Each subject area is supported by a separate
Nuclear Energy, Office of Nuclear Safety Policy and Standards, by the DOE Training Coordination
Program. This program is managed by EG&G Idaho, Inc.
Rev. 0
HT
OVERVIEW
The Department of Energy Fundamentals Handbook entitled Thermodynamics, Heat
Transfer, and Fluid Flow was prepared as an information resource for personnel who are
responsible for the operation of the Department's nuclear facilities. A basic understanding of the
thermal sciences is necessary for DOE nuclear facility operators, maintenance personnel, and the
technical staff to safely operate and maintain the facility and facility support systems. The
information in the handbook is presented to provide a foundation for applying engineering
concepts to the job. This knowledge will help personnel more fully understand the impact that
their actions may have on the safe and reliable operation of facility components and systems.
The Thermodynamics, Heat Transfer, and Fluid Flow handbook consists of three modules
that are contained in three volumes. The following is a brief description of the information
presented in each module of the handbook.
Volume 1 of 3
Module 1 - Thermodynamics
This module explains the properties of fluids and how those properties are
affected by various processes. The module also explains how energy balances can
be performed on facility systems or components and how efficiency can be
calculated.
Volume 2 of 3
Module 2 - Heat Transfer
This module describes conduction, convection, and radiation heat transfer. The
module also explains how specific parameters can affect the rate of heat transfer.
Volume 3 of 3
Module 3 - Fluid Flow
This module describes the relationship between the different types of energy in a
fluid stream through the use of Bernoulli's equation. The module also discusses
the causes of head loss in fluid systems and what factors affect head loss.
Rev. 0
HT
The information contained in this handbook is by no means all encompassing. An

attempt to present the entire subject of thermodynamics, heat transfer, and fluid flow would be
impractical. However, the Thermodynamics, Heat Transfer, and Fluid Flow handbook does
present enough information to provide the reader with a fundamental knowledge level sufficient
to understand the advanced theoretical concepts presented in other subject areas, and to better
understand basic system and equipment operations.
Rev. 0
HT

AND FLUID FLOW
Module 1
Thermodynamics
Thermodynamics
TABLE OF CONTENTS
TABLE OF CONTENTS
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
iv
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . viii
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . x
THERMODYNAMIC PROPERTIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Mass and Weight . . . . . . . . . . . .
Specific Volume . . . . . . . . . . . .
Density . . . . . . . . . . . . . . . . . .
Specific Gravity . . . . . . . . . . . .
Humidity . . . . . . . . . . . . . . . . .
Intensive and Extensive Properties
Summary . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
3
3
4
4
4
5
TEMPERATURE AND PRESSURE MEASUREMENTS . . . . . . . . . . . . . . . . . . . . . . . . 6

Temperature . . . . .
Temperature Scales
Pressure . . . . . . . .
Pressure Scales . . .
Summary . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
6
6
9
9
12
ENERGY, WORK, AND HEAT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

Energy . . . . . . . . . . . . . . . . . .
Potential Energy . . . . . . . . . . .
Kinetic Energy . . . . . . . . . . . .
Specific Internal Energy . . . . . .
Specific P-V Energy . . . . . . . .
Specific Enthalpy . . . . . . . . . .
Work . . . . . . . . . . . . . . . . . . .
Heat . . . . . . . . . . . . . . . . . . . .
Entropy . . . . . . . . . . . . . . . . .
Energy and Power Equivalences
Summary . . . . . . . . . . . . . . . .
Rev. 0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Page i
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
14
14
15
16
17
18
18
19
22
23
25
HT-01
TABLE OF CONTENTS
Thermodynamics

THERMODYNAMIC SYSTEMS AND PROCESSES . . . . . . . . . . . . . . . . . . . . . . . . . 26
Thermodynamic Systems and Surroundings
Types of Thermodynamic Systems . . . . . .
Thermodynamic Equilibrium . . . . . . . . . . .
Control Volume . . . . . . . . . . . . . . . . . . .
Steady State . . . . . . . . . . . . . . . . . . . . . .
Thermodynamic Process . . . . . . . . . . . . . .
Cyclic Process . . . . . . . . . . . . . . . . . . . . .
Reversible Process . . . . . . . . . . . . . . . . . .
Irreversible Process . . . . . . . . . . . . . . . . .
Adiabatic Process . . . . . . . . . . . . . . . . . .
Isentropic Process . . . . . . . . . . . . . . . . . .
Polytropic Process . . . . . . . . . . . . . . . . . .
Throttling Process . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
26
27
27
27
27
28
28
28
28
29
29
29
29
30
CHANGE OF PHASE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Classification of Properties . . . . .
Saturation . . . . . . . . . . . . . . . . .
Saturated and Subcooled Liquids .
Quality . . . . . . . . . . . . . . . . . . .
Moisture Content . . . . . . . . . . . .
Saturated and Superheated Vapors
Constant Pressure Heat Addition .
Critical Point . . . . . . . . . . . . . .
Fusion . . . . . . . . . . . . . . . . . . .
Sublimation . . . . . . . . . . . . . . .
Triple Point . . . . . . . . . . . . . . .
Condensation . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
31
33
33
34
35
35
35
36
36
37
37
38
39
PROPERTY DIAGRAMS AND STEAM TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

Property Diagrams . . . . . . . . . . . . . . . .
Pressure-Temperature (P-T) Diagram . . .
Pressure-Specific Volume (P-v) Diagram
Pressure-Enthalpy (P-h) Diagram . . . . . .
Enthalpy-Temperature (h-T) Diagram . . .
HT-01
.
.
.
.
.
Page ii
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
41
42
43
44
45
Rev. 0
Thermodynamics
TABLE OF CONTENTS

Temperature-Entropy (T-s) Diagram . . . .
Enthalpy-Entropy (h-s) or Mollier Diagram
Steam Tables . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . .
..
.
..
..
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
46
47
47
52
FIRST LAW OF THERMODYNAMICS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

First Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
SECOND LAW OF THERMODYNAMICS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
Second Law of Thermodynamics . . . .
Entropy . . . . . . . . . . . . . . . . . . . . .
Carnots Principle . . . . . . . . . . . . . .
Carnot Cycle . . . . . . . . . . . . . . . . . .
Diagrams of Ideal and Real Processes
Power Plant Components . . . . . . . . .
Heat Rejection . . . . . . . . . . . . . . . .
Typical Steam Cycle . . . . . . . . . . . .
Causes of Inefficiency . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
69
70
71
71
77
78
85
90
95
96
COMPRESSION PROCESSES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Boyles and Charles Laws . . . . . . . . . . . . . . . . . .
Ideal Gas Law . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Compressibility of Fluids . . . . . . . . . . . . . . . . . . .
Constant Pressure Process . . . . . . . . . . . . . . . . . . .
Constant Volume Process . . . . . . . . . . . . . . . . . . .
Effects of Pressure Changes on Fluid Properties . . .
Effects of Temperature Changes on Fluid Properties
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
97
98
99
99
100
100
100
101
102
APPENDIX A Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-1
Rev. 0
Page iii
HT-01
LIST OF FIGURES
Thermodynamics
LIST OF FIGURES
Figure 1
Comparison of Temperature Scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Figure 2
Pressure Relationships . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Figure 3
Intensive Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Figure 4
Piston-Cylinder Arrangement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Figure 5
Vapor Pressure Curve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Figure 6
T-V Diagram Showing the Saturation Region . . . . . . . . . . . . . . . . . . . . . . . 34
Figure 7
T-V Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Figure 8
Pressure-Temperature Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Figure 9
P-T Diagram for Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Figure 10 P-v Diagram for Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

Figure 11 P-h Diagram for Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Figure 12 h-T Diagram for Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Figure 13 T-s Diagram for Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Figure 14 First Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Figure 15 Control Volume Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
Figure 16 Open System Control Volumes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
Figure 17 Open System Control Volumes (Cont.) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Figure 18 Mulitple Control Volumes in Same System . . . . . . . . . . . . . . . . . . . . . . . . . 58
Figure 19 T-s Diagram with Rankine Cycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
HT-01
Page iv
Rev. 0
Thermodynamics
LIST OF FIGURES
LIST OF FIGURES (Cont.)

Figure 20 Typical Steam Plant Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
Figure 21 Carnot Cycle Representation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
Figure 22 Real Process Cycle Compared to Carnot Cycle . . . . . . . . . . . . . . . . . . . . . . 75
Figure 23 Control Volume for Second Law Analysis . . . . . . . . . . . . . . . . . . . . . . . . . 76
Figure 24 Expansion and Compression Processes on T-s Diagram . . . . . . . . . . . . . . . . 78
Figure 25 Expansion and Compression Processes on h-s Diagram . . . . . . . . . . . . . . . . 78
Figure 26 Steam Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
Figure 27 Comparison of Ideal and Actual Turbine Performances . . . . . . . . . . . . . . . . . 80
Figure 28 Carnot Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
Figure 29 Carnot Cycle vs. Typical Power Cycle Available Energy . . . . . . . . . . . . . . . 86
Figure 30 Ideal Carnot Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
Figure 31 Rankine Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Figure 32 Rankine Cycle with Real v.s. Ideal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Figure 33 Rankine Cycle Efficiencies T-s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Figure 34 h-s Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Figure 35 Typical Steam Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
Figure 36 Steam Cycle (Ideal) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
Figure 37 Steam Cycle (Real) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
Figure 38 Mollier Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
Figure 39 Ideal Gas Constant Values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Figure 40 Pressure-Volume Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Rev. 0
Page v
HT-01
LIST OF FIGURES
Thermodynamics
LIST OF FIGURES (Cont.)

Figure A-1 Mollier Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-1
Figure A-2 Sample Steam Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . A-3
Figure A-3 Thermodynamic Properties of Mercury . . . . . . . . . . . . . . . . . . . . . . . . . . A-5
Figure A-4 Thermodynamic Properties of CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . .
HT-01
Page vi
A-7
Rev. 0
Thermodynamics
LIST OF TABLES
LIST OF TABLES
NONE
Rev. 0
Page vii
HT-01
REFERENCES
Thermodynamics
REFERENCES
VanWylen, G. J. and Sonntag, R. E., Fundamentals of Classical Thermodynamics
SI Version, 2nd Edition, John Wiley and Sons, New York, ISBN 0-471-04188-2.
Kreith, Frank, Principles of Heat Transfer, 3rd Edition, Intext Press, Inc., New
York, ISBN 0-7002-2422-X.
Holman, J. P., Thermodynamics, McGraw-Hill, New York.
Streeter, Victor, L., Fluid Mechanics, 5th Edition, McGraw-Hill, New York, ISBN
07-062191-9.
Rynolds, W. C. and Perkins, H. C., Engineering Thermodynamics, 2nd Edition,
McGraw-Hill, New York, ISBN 0-07-052046-1.
Meriam, J. L., Engineering Mechanics Statics and Dynamics, John Wiley and
Sons, New York, ISBN 0-471-01979-8.
Schneider, P. J. Conduction Heat Transfer, Addison-Wesley Pub. Co., California.
Holman, J. P., Heat Transfer, 3rd Edition, McGraw-Hill, New York.
Knudsen, J. G. and Katz, D. L., Fluid Dynamics and Heat Transfer, McGraw-Hill,
New York.
Kays, W. and London, A. L., Compact Heat Exchangers, 2nd Edition, McGrawHill, New York.
Weibelt, J. A., Engineering Radiation Heat Transfer, Holt, Rinehart and Winston
Publish., New York.
Sparrow, E. M. and Cess, R. E., Radiation Heat Transfer, Brooks/Cole Publish.
Co., Belmont, California.
Hamilton, D. C. and Morgan, N. R., Radiant-Interchange Configuration Factors,
Tech. Note 2836, National Advisory Committee for Aeronautics.
HT-01
Page viii
Rev. 0
Thermodynamics
REFERENCES
REFERENCES (Cont.)
McDonald, A. T. and Fox, R. W., Introduction to Fluid mechanics, 2nd Edition,
John Wiley and Sons, New York, ISBN 0-471-01909-7.
Zucrow, M. J. and Hoffman, J. D., Gas Dynamics Vol.b1, John Wiley and Sons,
New York, ISBN 0-471-98440-X.
Crane Company, Flow of Fluids Through Valves, Fittings, and Pipe, Crane Co.
Technical Paper No. 410, Chicago, Illinois, 1957.
Esposito, Anthony, Fluid Power with Applications, Prentice-Hall, Inc., New
Jersey, ISBN 0-13-322701-4.
Beckwith, T. G. and Buck, N. L., Mechanical Measurements, Addison-Wesley
Publish Co., California.
Wallis, Graham, One-Dimensional Two-Phase Flow, McGraw-Hill, New York,
1969.
Kays, W. and Crawford, M. E., Convective Heat and Mass Transfer, McGrawHill, New York, ISBN 0-07-03345-9.
Collier, J. G., Convective Boiling and Condensation, McGraw-Hill, New York,
ISBN 07-084402-X.
Academic Program for Nuclear Power Plant Personnel, Volumes III and IV,
Columbia, MD: General Physics Corporation, Library of Congress Card
#A326517, 1982.
Faires, Virgel Moring and Simmang, Clifford Max, Thermodynamics, MacMillan
Publishing Co. Inc., New York.
Rev. 0
Page ix
HT-01
OBJECTIVES
Thermodynamics
TERMINAL OBJECTIVE
1.0
Given operating conditions of a system, EVALUATE the thermodynamic state of the

system.
ENABLING OBJECTIVES
1.1
DEFINE the following properties:

a.
Specific volume
b.
Density
c.
Specific gravity
d.
Humidity
1.2
DESCRIBE the following classifications of thermodynamic properties:

a.
Intensive properties
b.
Extensive properties
1.3
DEFINE the thermodynamic properties temperature and pressure.
1.4
DESCRIBE the Fahrenheit, Celsius, Kelvin, and Rankine temperature scales including:
a.
Absolute zero temperature
b.
The freezing point of water at atmospheric pressure
c.
The boiling point of water at atmospheric pressure
1.5
CONVERT temperatures between the Fahrenheit, Celsius, Kelvin, and Rankine scales.
1.6
DESCRIBE the relationship between absolute pressure, gauge pressure, and vacuum.
1.7
CONVERT pressures between the following units:

a.
Pounds per square inch
b.
Inches of water
c.
Inches of mercury
d.
Millimeters of mercury
e.
Microns of mercury
1.8
DEFINE the following:

a.
Heat
b.
Latent heat
c.
Sensible heat
d.
Unit used to measure heat
HT-01
Page x
Rev. 0
Thermodynamics
OBJECTIVES

1.9
DEFINE the following thermodynamic properties:

a.
Specific enthalpy
b.
Entropy
1.10
DESCRIBE the following types of thermodynamic systems:

a.
Isolated system
b.
Closed system
c.
Open system
1.11
DEFINE the following terms concerning thermodynamic systems:

a.
Thermodynamic surroundings
b.
Thermodynamic equilibrium
c.
Control volume
d.
Steady-state
1.12
DESCRIBE the following terms concerning thermodynamic processes:

a.
Thermodynamic process
b.
Cyclic process
c.
Reversible process
d.
Irreversible process
e.
Adiabatic process
f.
Isentropic process
g.
Throttling process
h.
Polytropic process
1.13
DISTINGUISH between intensive and extensive properties.
1.14

a.
Saturation
b.
Subcooled liquid
c.
Superheated vapor
d.
Critical Point
e.
Triple Point
f.
Vapor pressure curve
g.
Quality
h.
Moisture content
1.15
DESCRIBE the processes of sublimation, vaporization, condensation, and fusion.
Rev. 0
Page xi
HT-01
OBJECTIVES
Thermodynamics

1.16
Given a Mollier diagram and sufficient information to indicate the state of the fluid,
DETERMINE any unknown properties for the fluid.
1.17
Given a set of steam tables and sufficient information to indicate the state of the fluid,
DETERMINE any unknown properties for the fluid.
1.18
DETERMINE the change in the enthalpy of a fluid as it passes through a system

component, given the state of the fluid at the inlet and outlet of the component and either
steam tables or a Mollier diagram.
1.19
STATE the First Law of Thermodynamics.
1.20
Using the First Law of Thermodynamics, ANALYZE an open system including all
energy transfer processes crossing the boundaries.
1.21
Using the First Law of Thermodynamics, ANALYZE cyclic processes for a

thermodynamic system.
1.22
Given a defined system, PERFORM energy balances on all major components in the
system.
1.23
Given a heat exchanger, PERFORM an energy balance across the two sides of the heat
exchanger.
1.24
IDENTIFY the path(s) on a T-s diagram that represents the thermodynamic processes
occurring in a fluid system.
1.25
STATE the Second Law of Thermodynamics.
1.26
Using the Second Law of Thermodynamics, DETERMINE the maximum possible

efficiency of a system.
1.27
Given a thermodynamic system, CONDUCT an analysis using the Second Law of

Thermodynamics.
1.28
Given a thermodynamic system, DESCRIBE the method used to determine:

a.
The maximum efficiency of the system
b.
The efficiency of the components within the system
HT-01
Page xii
Rev. 0
Thermodynamics
OBJECTIVES

1.29
DIFFERENTIATE between the path for an ideal process and that for a real process on
a T-s or h-s diagram.
1.30
Given a T-s or h-s diagram for a system EVALUATE:

a.
System efficiencies
b.
Component efficiencies
1.31
DESCRIBE how individual factors affect system or component efficiency.
1.32
Apply the ideal gas laws to SOLVE for the unknown pressure, temperature, or volume.
1.33
DESCRIBE when a fluid may be considered to be incompressible.
1.34
CALCULATE the work done in constant pressure and constant volume processes.
1.35
DESCRIBE the effects of pressure changes on confined fluids.
1.36
DESCRIBE the effects of temperature changes on confined fluids.
Rev. 0
Page xiii
HT-01
Thermodynamics
HT-01
Page xiv
Rev. 0
Thermodynamics
THERMODYNAMIC PROPERTIES
Thermodynamic properties describe measurable characteristics of a substance.
A knowledge of these properties is essential to the understanding of
thermodynamics.
EO 1.1
DEFINE the following properties:

a.
Specific volume
b.
Density
c.
Specific gravity
d.
Humidity
EO 1.2
DESCRIBE the following classifications of

thermodynamic properties:
a.
Intensive properties
b.
Extensive properties
Mass and Weight

The mass (m) of a body is the measure of the amount of material present in that body. The
weight (wt) of a body is the force exerted by that body when its mass is accelerated in a
gravitational field. Mass and weight are related as shown in Equation 1-1.
wt =
mg
gc
(1-1)
where:
wt
m
g
gc
=
=
=
=
weight (lbf)
mass (lbm)
acceleration of gravity = 32.17 ft/sec2
gravitational constant = 32.17 lbm-ft/lbf-sec2
Note that gc has the same numerical value as the acceleration of gravity at sea level, but is not
the acceleration of gravity. Rather, it is a dimensional constant employed to facilitate the use of
Newtons Second Law of Motion with the English system of units.
The weight of a body is a force produced when the mass of the body is accelerated by a
gravitational acceleration. The mass of a certain body will remain constant even if the
gravitational acceleration acting upon that body changes.
Rev. 0
Page 1
HT-01
Thermodynamics
According to Newtons Second Law of Motion, force (F) = ma, where a is acceleration. For
example, on earth an object has a certain mass and a certain weight. When the same object is
placed in outer space, away from the earths gravitational field, its mass is the same, but it is
now in a "weightless" condition (that is, gravitational acceleration and, thus, force equal zero).
The English system uses the pound-force (lbf) as the unit of weight. Knowing that acceleration
has the units of ft/sec2 and using Newtons second law, we can determine that the units of mass
are lbf-sec2/ft. For simplification, 1 lbf-sec2/ft is called a slug. The basic unit of mass in the
English system is the slug. However, the slug is an almost meaningless unit for the average
individual. The unit of mass generally used is the pound-mass (lbm). In order to allow lbm to
be used as a unit of mass, we must divide Newtons second law by the gravitational constant (gc).
32.17 lbm ft
lbf sec2
gc
Newtons second law can be expressed by Equation 1-2.

F
ma
gc
(1-2)
Use of the gravitational constant, gc, adapts Newtons second law such that 1 lbf = 1 lbm at the
surface of the earth. It is important to note that this relationship is only true at the surface of the
earth, where the acceleration due to gravity is 32.17 ft/sec2. However, because all of our
discussions will be based upon experiences and observations on earth, we will use the lbm as the
unit of mass.
NOTE:
In Equation 1-2, acceleration "a" is often written as "g" because, in this case, the
acceleration is the gravitational acceleration due to the earths gravitational field
(g = 32.17 ft/sec2).
Example:
Using Equation 1-2, prove that 1 lbf = l lbm on earth.
Solution:
F
1 lbf
1 lbf
HT-01
mg
gc
(1 lbm) (32.17 ft/sec2)
(lbm ft)
32.17
(lbf sec2)
1 lbf ( an equality)
Page 2
Rev. 0
Thermodynamics
Specific Volume
The specific volume () of a substance is the total volume (V) of that substance divided by the
total mass (m) of that substance (volume per unit mass). It has units of cubic feet per
pound-mass (ft3/lbm).
V
m
(1-3)
where:
specific volume (ft3/lbm)
volume (ft3)
mass (lbm)
Density
The density ( ) of a substance is the total mass (m) of that substance divided by the total
volume (V) occupied by that substance (mass per unit volume). It has units of pound-mass per
cubic feet (lbm/ft3). The density ( ) of a substance is the reciprocal of its specific volume ().
m
V
(1-4)
where:
Rev. 0
density (lbm/ft3)
mass (lbm)
volume (ft3)
Page 3
HT-01
Thermodynamics
Specific Gravity
Specific gravity (S.G.) is a measure of the relative density of a substance as compared to the
density of water at a standard temperature. Physicists use 39.2F (4C) as the standard, but
engineers ordinarily use 60F. In the International System of Units (SI Units), the density of
water is 1.00 g/cm3 at the standard temperature. Therefore, the specific gravity (which is
dimensionless) for a liquid has the same numerical value as its density in units of g/cm3. Since
the density of a fluid varies with temperature, specific gravities must be determined and specified
at particular temperatures.
Humidity
Humidity is the amount of moisture (water vapor) in the air. It can be expressed as absolute
humidity or relative humidity. Absolute humidity is the mass of water vapor divided by a unit
volume of air (grams of water/cm3 of air). Relative humidity is the amount of water vapor
present in the air divided by the maximum amount that the air could contain at that temperature.
Relative humidity is expressed as a percentage. The relative humidity is 100% if the air is
saturated with water vapor and 0% if no water vapor is present in the air at all.
Intensive and Extensive Properties

Thermodynamic properties can be divided into two general classes, intensive and extensive
properties. An intensive property is independent of the amount of mass. The value of an
extensive property varies directly with the mass. Thus, if a quantity of matter in a given state
is divided into two equal parts, each part will have the same value of intensive property as the
original and half the value of the extensive property. Temperature, pressure, specific volume,
and density are examples of intensive properties. Mass and total volume are examples of
extensive properties.
HT-01
Page 4
Rev. 0
Thermodynamics
Summary
Thermodynamic Properties Summary

The following properties were defined:
Specific volume () is the total volume (V) of a substance divided by the

total mass (m) of that substance.
Density () is the total mass (m) of a substance divided by the total

volume (V) occupied by that substance.
Specific gravity (S.G.) is a measure of the relative density of a substance

as compared to the density of water at a standard temperature.
Humidity is the amount of moisture (water vapor) in the air. It can be

measured in absolute or relative units.
The following classifications of thermodynamic properties were described:
Intensive properties are those that are independent of the amount of mass.
Extensive properties are those that vary directly with the mass.
Rev. 0
Page 5
HT-01
TEMPERATURE AND PRESSURE MEASUREMENTS
Thermodynamics

Several types of temperature and pressure measurements are used during
discussions of thermodynamics. Operators must recognize the different types and
their interrelationships in order to understand thermodynamics.
EO 1.3
DEFINE the thermodynamic properties temperature

and pressure.
EO 1.4
DESCRIBE the Fahrenheit, Celsius, Kelvin, and

Rankine temperature scales including:
a.
Absolute zero temperature
b.
The freezing point of water at atmospheric pressure
c.
The boiling point of water at atmospheric pressure
EO 1.5
CONVERT temperatures between the Fahrenheit,

Celsius, Kelvin, and Rankine scales.
EO 1.6
DESCRIBE the relationship between absolute

pressure, gauge pressure, and vacuum.
EO 1.7
CONVERT pressures between the following units:

a.
Pounds per square inch
b.
Inches of water
c.
Inches of mercury
d.
Millimeters of mercury
e.
Microns of mercury
Temperature
Temperature is a measure of the molecular activity of a substance. The greater the movement
of molecules, the higher the temperature. It is a relative measure of how "hot" or "cold" a
substance is and can be used to predict the direction of heat transfer.
Temperature Scales
The two temperature scales normally employed for measurement purposes are the Fahrenheit (F)
and Celsius (C) scales. These scales are based on a specification of the number of increments
between the freezing point and boiling point of water at standard atmospheric pressure. The
Celsius scale has 100 units between these points, and the Fahrenheit scale has 180 units. The
zero points on the scales are arbitrary.
HT-01
Page 6
Rev. 0
Thermodynamics
The freezing point of water was selected as the zero point of the Celsius scale. The coldest
temperature achievable with a mixture of ice and salt water was selected as the zero point of the
Fahrenheit scale. The temperature at which water boils was set at 100 on the Celsius scale and
212 on the Fahrenheit scale. The relationship between the scales is represented by the following
equations.
F = 32.0 + (9/5)C
(1-5)
C = (F - 32.0)(5/9)
(1-6)
It is necessary to define an absolute temperature scale having only positive values. The absolute
temperature scale that corresponds to the Celsius scale is called the Kelvin (K) scale, and the
absolute scale that corresponds to the Fahrenheit scale is called the Rankine (R) scale. The zero
points on both absolute scales represent the same physical state. This state is where there is no
molecular motion of individual atoms. The relationships between the absolute and relative
temperature scales are shown in the following equations.
R = F + 460
(1-7)
K = C + 273
(1-8)
Figure 1
Rev. 0
Comparison of Temperature Scales
Page 7
HT-01
Thermodynamics
The conversion of one temperature scale to another is sometimes required at nuclear facilities,
and the operator should be acquainted with the process. The following two examples will be
helpful.
Example 1: Temperature Scale Conversion
What is the Rankine equivalent of 80C?
Solution:
F
= (9/5) C + 32
= (9/5)(80) + 32
= 176 F
= F + 460
= 176 + 460
= 636 R
Example 2: Temperature Scale Conversion

What is the Kelvin equivalent of 80F?
Solution:
C
= (5/9) (F - 32)
= (5/9) (80 - 32)
= 26.7C
= C + 273
= 26.7 + 273
= 299.7 K
HT-01
Page 8
Rev. 0
Thermodynamics
Pressure
Pressure is a measure of the force exerted per unit area on the boundaries of a substance (or
system). It is caused by the collisions of the molecules of the substance with the boundaries of
the system. As molecules hit the walls, they exert forces that try to push the walls outward. The
forces resulting from all of these collisions cause the pressure exerted by a system on its
surroundings. Pressure is frequently measured in units of lbf/in2 (psi).
Pressure Scales
When pressure is measured relative to a perfect vacuum, it is called absolute pressure (psia);
when measured relative to atmospheric pressure (14.7 psi), it is called gauge pressure (psig). The
latter pressure scale was developed because almost all pressure gauges register zero when open
to the atmosphere. Therefore, pressure gauges measure the difference between the pressure of
the fluid to which they are connected and that of the surrounding air.
If the pressure is below that of the atmosphere, it is designated as a vacuum. A perfect vacuum
would correspond to absolute zero pressure. All values of absolute pressure are positive, because
a negative value would indicate tension, which is considered impossible in any fluid. Gauge
pressures are positive if they are above atmospheric pressure and negative if they are below
atmospheric pressure. Figure 2 shows the relationships between absolute, gauge, vacuum, and
atmospheric pressures, as do Equations 1-9 and 1-10.
Figure 2
Rev. 0
Pressure Relationships
Page 9
HT-01
Thermodynamics
Pabs = Patm + Pgauge
(1-9)
Pabs = Patm - Pvac
(1-10)
Patm is atmospheric pressure, which is also called the barometric pressure. Pgauge is the gauge
pressure, and Pvac is vacuum. Once again, the following examples relating the various pressures
will be helpful in understanding the idea of gauge versus absolute pressures.
Example 1: Pressure Relationships

How deep can a diver descend in ocean water (density = 64 lbm/ft3) without damaging
his watch, which will withstand an absolute pressure of 80 psia? (P = density height)
Solution:
Assume:
Patm
= 14.7 psia
Pabs
= Patm + Pgauge
80 psia
= 14.7 + Pgauge
Pgauge
= (80 - 14.7) = 65.3 psig
Pgauge
= density
(65.3)(144 in2/ft2)
HT-01
height = H
= (64 lbm/ft3)H
= (65.3)(144)/(64)
= 146.9 ft
Page 10
Rev. 0
Thermodynamics
Example 2: Pressure Relationships

What is the absolute pressure at the bottom of a swimming pool 6 feet deep that is filled
with fresh water? Patm = 14.7 psia
Solution:
Pabs
= Patm + Pgauge
= 14.7 + H
= 14.7 + [(62.4 lbm/ft3)(6 ft)/(144 in.2/ft2)]
= 14.7 + 2.6
Pabs
= 17.3 psia
In addition to pounds per square inch, pressure can be measured with reference to the force that
exists in a column of fluid at a certain height. The most common of these are inches of water,
inches of mercury, millimeters of mercury, and microns of mercury. Conversion factors are listed
below.
14.7 psia = 408 inches of water
14.7 psia = 29.9 inches of mercury
1 inch of mercury = 25.4 millimeters of mercury
1 millimeter of mercury = 103 microns of mercury
Rev. 0
Page 11
HT-01
Thermodynamics
Summary
Temperature and Pressure Scales Summary

The following properties were defined as follows.
Temperature is a measure of the molecular activity of a substance.
Pressure is a measure of the force per unit area exerted on the boundaries of a
substance (or system).
The relationship between the Fahrenheit, Celsius, Kelvin, and Rankine temperature scales
was described.
Absolute zero
= -460 F or -273 C
Freezing point of water = 32 F or 0 C
Boiling point of water
= 212 F or 100 C
Conversions between the different scales can be made using the following formulas.
F = 32 + (9/5)C
C = (F - 32)(5/9)
R = F + 460
K = C + 273
Relationships between absolute pressure, gauge pressure, and vacuum can be shown
using the following formulas.
HT-01
Pabs
Pabs
= Patm + Pgauge
= Patm - Pvac
Page 12
Rev. 0
Thermodynamics
Temperature and Pressure Scales Summary (Cont.)

Converting between the different pressure units can be done using the following
conversions.
14.7 psia
= 408 inches of water
14.7 psia
= 29.9 inches of mercury
1 inch of mercury
1 millimeter of mercury
Rev. 0
= 25.4 millimeters of mercury

= 103 microns of mercury
Page 13
HT-01
ENERGY, WORK, AND HEAT
Thermodynamics

Heat and work are the two ways in which energy can be transferred across the
boundary of a system. One of the most important discoveries in thermodynamics
was that work could be converted into an equivalent amount of heat and that heat
could be converted into work.
EO 1.8
DEFINE the following:

a.
Heat
b.
Latent heat
c.
Sensible heat
d.
Units used to measure heat
EO 1.9
DEFINE the following thermodynamic properties:

a.
Specific enthalpy
b.
Entropy
Energy
Energy is defined as the capacity of a system to perform work or produce heat.
Potential Energy
Potential energy (PE) is defined as the energy of position. Using English system units, it is
defined by Equation 1-11.
PE
mgz
gc
PE
potential energy (ft-lbf)
mass (lbm)
height above some reference level (ft)
acceleration due to gravity (ft/sec2)
gc
gravitational constant = 32.17 ft-lbm/lbf-sec2
(1-11)
where:
HT-01
Page 14
Rev. 0
Thermodynamics
In most practical engineering calculations, the acceleration due to gravity (g) is numerically equal
to the gravitational constant (gc); thus, the potential energy (PE) in foot-pounds-force is
numerically equal to the product of the mass (m) in pounds-mass times the height (z) in feet
above some reference level.
Example:
Determine the potential energy of 50 lbm of water in a storage tank 100 ft above the
ground.
Solution:
Using Equation 1-11
PE
mgz
gc
PE
(50 lbm) (32.17 ft/sec2) (100 ft)

32.17 ft lbm/lbf sec2
PE
5000 ft lbf
Kinetic Energy
Kinetic energy (KE) is the energy of motion. Using English system units, it is defined by
Equation 1-12.
KE
mv 2
2gc
KE
kinetic energy (ft-lbf)
mass (lbm)
velocity (ft/sec)
gc
gravitational constant = 32.17 ft-lbm/lbf-sec2
(1-12)
where:
Rev. 0
Page 15
HT-01
Thermodynamics
Example:
Determine the kinetic energy of 7 lbm of steam flowing through a pipe at a velocity of
100 ft/sec.
Solution:
Using Equation 1-12.
mv 2
KE
2gc
KE
(7 lbm) (100 ft/sec)2

2(32.17 ft lbm/lbf sec2)
KE
(7 lbm) (10,000 ft 2/sec2)

(64.34 ft lbm/lbf sec2)
KE
1088 ft lbf
Specific Internal Energy

Potential energy and kinetic energy are macroscopic forms of energy. They can be visualized
in terms of the position and the velocity of objects. In addition to these macroscopic forms of
energy, a substance possesses several microscopic forms of energy. Microscopic forms of energy
include those due to the rotation, vibration, translation, and interactions among the molecules of
a substance. None of these forms of energy can be measured or evaluated directly, but
techniques have been developed to evaluate the change in the total sum of all these microscopic
forms of energy. These microscopic forms of energy are collectively called internal energy,
customarily represented by the symbol U. In engineering applications, the unit of internal energy
is the British thermal unit (Btu), which is also the unit of heat.
The specific internal energy (u) of a substance is its internal energy per unit mass. It equals the
total internal energy (U) divided by the total mass (m).
U
u
(1-13)
m
where:
HT-01
specific internal energy (Btu/lbm)
internal energy (Btu)
mass (lbm)
Page 16
Rev. 0
Thermodynamics
Example:
Determine the specific internal energy of 12 lbm of steam if the total internal energy is
23,000 Btu.
Solution:
Using Equation 1-13.
U
u
m
u
23,000 Btu
12 lbm
1916.67 Btu/lbm
Specific P-V Energy

In addition to the internal energy (U), another form of energy exists that is important in
understanding energy transfer systems. This form of energy is called P-V energy because it
arises from the pressure (P) and the volume (V) of a fluid. It is numerically equal to PV, the
product of pressure and volume. Because energy is defined as the capacity of a system to
perform work, a system where pressure and volume are permitted to expand performs work on
its surroundings. Therefore, a fluid under pressure has the capacity to perform work. In
engineering applications, the units of P-V energy, also called flow energy, are the units of
pressure times volume (pounds-force per square foot times cubic feet), which equals foot-pounds
force (ft-lbf).
The specific P-V energy of a substance is the P-V energy per unit mass. It equals the total P-V
divided by the total mass m, or the product of the pressure P and the specific volume , and is
written as P.
PV
P
(1-14)
m
where:
Rev. 0
pressure (lbf/ft2)
volume (ft3)
mass (lbm)
Page 17
V
m
HT-01
Thermodynamics
Example:
Determine the specific P-V energy of 15 lbm of steam at 1000 psi in an 18 ft3 tank.
Solution:
Using Equation 1-14
P
PV
m
(1000 lbf/in.2) (144 in.2/ft 2) (18 ft 3)

15 lbm
172,800 ft lbf/lbm
Specific Enthalpy
Specific enthalpy (h) is defined as h = u + P, where u is the specific internal energy (Btu/lbm)
of the system being studied, P is the pressure of the system (lbf/ft2), and is the specific volume
(ft3/lbm) of the system. Enthalpy is usually used in connection with an "open" system problem
in thermodynamics. Enthalpy is a property of a substance, like pressure, temperature, and
volume, but it cannot be measured directly. Normally, the enthalpy of a substance is given with
respect to some reference value. For example, the specific enthalpy of water or steam is given
using the reference that the specific enthalpy of water is zero at .01C and normal atmospheric
pressure. The fact that the absolute value of specific enthalpy is unknown is not a problem,
however, because it is the change in specific enthalpy (h) and not the absolute value that is
important in practical problems. Steam tables include values of enthalpy as part of the
information tabulated.
Work
Kinetic energy, potential energy, internal energy, and P-V energy are forms of energy that are
properties of a system. Work is a form of energy, but it is energy in transit. Work is not a
property of a system. Work is a process done by or on a system, but a system contains no work.
This distinction between the forms of energy that are properties of a system and the forms of
energy that are transferred to and from a system is important to the understanding of energy
transfer systems.
HT-01
Page 18
Rev. 0
Thermodynamics
Work is defined for mechanical systems as the action of a force on an object through a distance.
It equals the product of the force (F) times the displacement (d).
W = Fd
(1-15)
where:
W
work (ft-lbf)
force (lbf)
displacement (ft)
Example:
Determine the amount of work done if a force of 150 lbf is applied to an object until it
has moved a distance of 30 feet.
Solution:
Using Equation 1-15
W = Fd
W = (150 lbf)(30 ft)
W = 4500 ft-lbf
In dealing with work in relation to energy transfer systems, it is important to distinguish between
work done by the system on its surroundings and work done on the system by its surroundings.
Work is done by the system when it is used to turn a turbine and thereby generate electricity in
a turbine-generator. Work is done on the system when a pump is used to move the working fluid
from one location to another. A positive value for work indicates that work is done by the
system on its surroundings; a negative value indicates that work is done on the system by its
surroundings.
Heat
Heat, like work, is energy in transit. The transfer of energy as heat, however, occurs at the
molecular level as a result of a temperature difference. The symbol Q is used to denote heat.
In engineering applications, the unit of heat is the British thermal unit (Btu). Specifically, this
is called the 60 degree Btu because it is measured by a one degree temperature change from 59.5
to 60.5F.
Rev. 0
Page 19
HT-01
Thermodynamics
As with work, the amount of heat transferred depends upon the path and not simply on the initial
and final conditions of the system. Also, as with work, it is important to distinguish between
heat added to a system from its surroundings and heat removed from a system to its
surroundings. A positive value for heat indicates that heat is added to the system by its
surroundings. This is in contrast to work that is positive when energy is transferred from the
system and negative when transferred to the system. The symbol q is sometimes used to indicate
the heat added to or removed from a system per unit mass. It equals the total heat (Q) added
or removed divided by the mass (m). The term "specific heat" is not used for q since specific
heat is used for another parameter. The quantity represented by q is referred to simply as the
heat transferred per unit mass.
q
Q
m
(1-16)
where:
q
heat transferred per unit mass (Btu/lbm)
heat transferred (Btu)
mass (lbm)
Example:
Determine the heat transferred per unit mass if 1500 Btus are transferred to 40 lbm of
water.
Solution:
Using Equation 1-16
q
Q
m
1500 Btu
40 lbm
37.5 Btu/lbm
The best way to quantify the definition of heat is to consider the relationship between the amount
of heat added to or removed from a system and the change in the temperature of the system.
Everyone is familiar with the physical phenomena that when a substance is heated, its
temperature increases, and when it is cooled, its temperature decreases. The heat added to or
removed from a substance to produce a change in its temperature is called sensible heat. The
units of heat are often defined in terms of the changes in temperature it produces.
HT-01
Page 20
Rev. 0
Thermodynamics
Another type of heat is called latent heat. Latent heat is the amount of heat added to or removed
from a substance to produce a change in phase. When latent heat is added, no temperature
change occurs. There are two types of latent heat. The first is the latent heat of fusion. This
is the amount of heat added or removed to change phase between solid and liquid. The second
type of latent heat is the latent heat of vaporization. This is the amount of heat added or
removed to change phase between liquid and vapor. The latent heat of vaporization is sometimes
called the latent heat of condensation.
Different substances are affected to different magnitudes by the addition of heat. When a given
amount of heat is added to different substances, their temperatures increase by different amounts.
The ratio of the heat (Q) added to or removed from a substance to the change in temperature
(T) produced is called the heat capacity (Cp) of the substance. The heat capacity of a substance
per unit mass is called the specific heat (cp) of the substance. The subscript p indicates that the
heat capacity and specific heat apply when the heat is added or removed at constant pressure.
Cp
Q
T
cp
Q
mT
cp
q
T
Cp
heat capacity at constant pressure (Btu/F)
cp
specific heat at constant pressure (Btu/lbm-F)
heat transferred (Btu)
heat transferred per unit mass (Btu/lbm)
mass (lbm)
temperature change (F)
(1-17)
where:
One lbm of water is raised 1F and one Btu of heat is added. This implies that the specific heat
(cp) of water is one Btu/lbm-F. The cp of water is equal to one Btu/lbm-F only at 39.1F.
By rearranging Equation 1-17 we obtain Q = mcpT, which is used to calculate latent heat. By
substituting mass flow rate in lbm/hr, m

, for m, we obtain Q
mc
pT . This equation is used
to calculate heat transfer in Btu/hr and will be useful in later chapters.
Rev. 0
Page 21
HT-01
Thermodynamics
Example:
How much heat is required to raise the temperature of 5 lbm of water from 50F to
150F? (Assume the specific heat (cp) for water is constant at 1.0 Btu/lbm-F.)
Solution:
Q
mT
cp
= cpmT
= (1.0 Btu/lbm-F)(5 lbm)(150F - 50F)
= (1.0 Btu/lbm-F)(5 lbm)(100F)
= 500 Btu
From the previous discussions on heat and work, it is evident that there are many similarities
between them. Heat and work are both transient phenomena. Systems never possess heat or
work, but either or both may occur when a system undergoes a change of energy state. Both heat
and work are boundary phenomena in that both are observed at the boundary of the system. Both
represent energy crossing the system boundary.
Entropy
Entropy (S) is a property of a substance, as are pressure, temperature, volume, and enthalpy.
Because entropy is a property, changes in it can be determined by knowing the initial and final
conditions of a substance. Entropy quantifies the energy of a substance that is no longer
available to perform useful work. Because entropy tells so much about the usefulness of an
amount of heat transferred in performing work, the steam tables include values of specific
entropy (s = S/m) as part of the information tabulated. Entropy is sometimes referred to as a
measure of the inability to do work for a given heat transferred. Entropy is represented by the
letter S and can be defined as S in the following relationships.
S
Q
Tabs
(1-18)
q
Tabs
(1-19)
where:
HT-01
the change in entropy of a system during some process (Btu/R)
Page 22
Rev. 0
Thermodynamics
the amount of heat transferred to or from the system during the process
(Btu)
Tabs
the absolute temperature at which the heat was transferred (R)
the change in specific entropy of a system during some process

(Btu/lbm -oR)
the amount of heat transferred to or from the system during the process
(Btu/lbm)
Like enthalpy, entropy cannot be measured directly. Also, like enthalpy, the entropy of a
substance is given with respect to some reference value. For example, the specific entropy of
water or steam is given using the reference that the specific entropy of water is zero at 32F.
The fact that the absolute value of specific entropy is unknown is not a problem because it is the
change in specific entropy (s) and not the absolute value that is important in practical problems.
Energy and Power Equivalences

The various forms of energy involved in energy transfer systems (such as potential energy,
kinetic energy, internal energy, P-V energy, work and heat) may be measured in numerous basic
units. In general, three types of units are used to measure energy: (1) mechanical units, such
as the foot-pound-force (ft-lbf); (2) thermal units, such as the British thermal unit (Btu); and (3)
electrical units, such as the watt-second (W-sec). In the mks and cgs systems, the mechanical
units of energy are the joule (j) and the erg, the thermal units are the kilocalorie (kcal) and the
calorie (cal), and the electrical units are the watt-second (W-sec) and the erg. Although the units
of the various forms of energy are different, they are equivalent.
Some of the most important experiments in science were those conducted by J. P. Joule in 1843,
who showed quantitatively that there was a direct correspondence between mechanical and
thermal energy. These experiments showed that one kilocalorie equals 4,186 joules. These same
experiments, when performed using English system units, show that one British thermal unit
(Btu) equals 778.3 ft-lbf. These experiments established the equivalence of mechanical and
thermal energy. Other experiments established the equivalence of electrical energy with both
mechanical and thermal energy. For engineering applications, these equivalences are expressed
by the following relationships.
1 ft-lbf = 1.286 x 10-3 Btu = 3.766 x 10-7 kW-hr
1 Btu = 778.3 ft-lbf = 2.928 x 10-4 kW-hr
1 kW-hr = 3.413 x 103 Btu = 2.655 x 106 ft-lbf
Rev. 0
Page 23
HT-01
Thermodynamics
There is one additional unit of energy encountered in engineering applications. It is the

horsepower-hour (hp-hr). It is a mechanical unit of energy defined by the following relationship:
1 hp-hr = 1.980 x 106 ft-lbf
These relationships can be used to convert between the various English system units for the
various forms of energy.
Most computations involving the energy of the working fluid in an energy transfer system are
performed in Btus. Forms of mechanical energy (such as potential energy, kinetic energy, and
mechanical work) and other forms of energy (such as P-V energy) are usually given in
foot-pounds-force. These are converted to Btus by using 1 Btu = 778.3 ft-lbf.
This conversion factor is often used. In fact, a constant called the mechanical equivalent of heat,
usually denoted by the symbol J and sometimes referred to as Joules constant, is defined as:
J
778
ft lbf
.
Btu
Power is defined as the time rate of doing work. It is equivalent to the rate of the energy
transfer. Power has units of energy per unit time. As with energy, power may be measured in
numerous basic units, but the units are equivalent. In the English system, the mechanical units
of power are foot-pounds-force per second or per hour (ft-lbf/sec or ft-lbf/hr) and horsepower
(hp). The thermal units of power are British thermal units per hour (Btu/hr), and the electrical
units of power are watts (W) or kilowatts (kW). For engineering applications, the equivalence
of these units is expressed by the following relationships.
1 ft-lbf/sec = 4.6263 Btu/hr = 1.356 x 10-3 kW
1 Btu/hr = 0.2162 ft-lbf/sec = 2.931 x 10-4 kW
1 kW = 3.413 x 103 Btu/hr = 737.6 ft-lbf/sec
Horsepower is related to foot-pounds-force per second (ft-lbf/sec) by the following relationship:
1 hp = 550.0 ft-lbf/sec
These relationships can be used to convert the English system units for power.
HT-01
Page 24
Rev. 0
Thermodynamics
Summary
Energy, Work, and Heat Summary
Heat is described as energy in transit. This transfer occurs

on a molecular level as a result of temperature differences.
The unit of heat is the British thermal unit (Btu).
Latent heat
the amount of heat added or

removed to produce only a
phase change.
Sensible heat =
the heat added or removed

that causes a temperature
change.
The following properties were defined:

Specific enthalpy (h) is defined as h = u +
P, where u is the specific internal energy
(Btu/lbm) of the system being studied, P is
the pressure of the system (lbf/ft2), and is
the specific volume (ft3/lbm) of the system.
Entropy is sometimes referred to as a
measure of the inability to do work for a
given heat transferred.
Rev. 0
Page 25
HT-01
THERMODYNAMIC SYSTEMS AND PROCESSES
Thermodynamics

Defining an appropriate system can greatly simplify a thermodynamic analysis.
A thermodynamic system is any three-dimensional region of space that is bounded
by one or more surfaces. The bounding surfaces may be real or imaginary and
may be at rest or in motion. The boundary may change its size or shape. The
region of physical space that lies outside the selected boundaries of the system is
called the surroundings or the environment.
EO 1.10
DESCRIBE the following types of thermodynamic

systems:
a.
Isolated system
b.
Closed system
c.
Open system
EO 1.11
DEFINE the following terms concerning

thermodynamic systems:
a.
Thermodynamic surroundings
b.
Thermodynamic equilibrium
c.
Control volume
d.
Steady-state
EO 1.12
DESCRIBE the following terms concerning

thermodynamic processes:
a.
Thermodynamic process
b.
Cyclic process
c.
Reversible process
d.
Irreversible process
e.
Adiabatic process
f.
Isentropic process
g.
Throttling process
h.
Polytropic process
Thermodynamic Systems and Surroundings

Thermodynamics involves the study of various systems. A system in thermodynamics is nothing
more than the collection of matter that is being studied. A system could be the water within one
side of a heat exchanger, the fluid inside a length of pipe, or the entire lubricating oil system for
a diesel engine. Determining the boundary to solve a thermodynamic problem for a system will
depend on what information is known about the system and what question is asked about the
system.
HT-01
Page 26
Rev. 0
Thermodynamics
Everything external to the system is called the thermodynamic surroundings, and the system is
separated from the surroundings by the system boundaries. These boundaries may either be fixed
or movable. In many cases, a thermodynamic analysis must be made of a device, such as a heat
exchanger, that involves a flow of mass into and/or out of the device. The procedure that is
followed in such an analysis is to specify a control surface, such as the heat exchanger tube
walls. Mass, as well as heat and work (and momentum), may flow across the control surface.
Types of Thermodynamic Systems

Systems in thermodynamics are classified as isolated, closed, or open based on the possible
transfer of mass and energy across the system boundaries. An isolated system is one that is not
influenced in any way by the surroundings. This means that no energy in the form of heat or
work may cross the boundary of the system. In addition, no mass may cross the boundary of the
system.
A thermodynamic system is defined as a quantity of matter of fixed mass and identity upon
which attention is focused for study. A closed system has no transfer of mass with its
surroundings, but may have a transfer of energy (either heat or work) with its surroundings.
An open system is one that may have a transfer of both mass and energy with its surroundings.
Thermodynamic Equilibrium
When a system is in equilibrium with regard to all possible changes in state, the system is in
thermodynamic equilibrium. For example, if the gas that comprises a system is in thermal
equilibrium, the temperature will be the same throughout the entire system.
Control Volume
A control volume is a fixed region in space chosen for the thermodynamic study of mass and
energy balances for flowing systems. The boundary of the control volume may be a real or
imaginary envelope. The control surface is the boundary of the control volume.
Steady State
Steady state is that circumstance in which there is no accumulation of mass or energy within the
control volume, and the properties at any point within the system are independent of time.
Rev. 0
Page 27
HT-01
Thermodynamics
Thermodynamic Process
Whenever one or more of the properties of a system change, a change in the state of the system
occurs. The path of the succession of states through which the system passes is called the
thermodynamic process. One example of a thermodynamic process is increasing the temperature
of a fluid while maintaining a constant pressure. Another example is increasing the pressure of
a confined gas while maintaining a constant temperature. Thermodynamic processes will be
discussed in more detail in later chapters.
Cyclic Process
When a system in a given initial state goes through a number of different changes in state (going
through various processes) and finally returns to its initial values, the system has undergone a
cyclic process or cycle. Therefore, at the conclusion of a cycle, all the properties have the same
value they had at the beginning. Steam (water) that circulates through a closed cooling loop
undergoes a cycle.
Reversible Process
A reversible process for a system is defined as a process that, once having taken place, can be
reversed, and in so doing leaves no change in either the system or surroundings. In other words
the system and surroundings are returned to their original condition before the process took place.
In reality, there are no truly reversible processes; however, for analysis purposes, one uses
reversible to make the analysis simpler, and to determine maximum theoretical efficiencies.
Therefore, the reversible process is an appropriate starting point on which to base engineering
study and calculation.
Although the reversible process can be approximated, it can never be matched by real processes.
One way to make real processes approximate reversible process is to carry out the process in a
series of small or infinitesimal steps. For example, heat transfer may be considered reversible
if it occurs due to a small temperature difference between the system and its surroundings. For
example, transferring heat across a temperature difference of 0.00001 F "appears" to be more
reversible than for transferring heat across a temperature difference of 100 F. Therefore, by
cooling or heating the system in a number of infinitesamally small steps, we can approximate a
reversible process. Although not practical for real processes, this method is beneficial for
thermodynamic studies since the rate at which processes occur is not important.
Irreversible Process
An irreversible process is a process that cannot return both the system and the surroundings to
their original conditions. That is, the system and the surroundings would not return to their
HT-01
Page 28
Rev. 0
Thermodynamics
original conditions if the process was reversed. For example, an automobile engine does not give
back the fuel it took to drive up a hill as it coasts back down the hill.
There are many factors that make a process irreversible. Four of the most common causes of
irreversibility are friction, unrestrained expansion of a fluid, heat transfer through a finite
temperature difference, and mixing of two different substances. These factors are present in real,
irreversible processes and prevent these processes from being reversible.
Adiabatic Process
An adiabatic process is one in which there is no heat transfer into or out of the system. The
system can be considered to be perfectly insulated.
Isentropic Process
An isentropic process is one in which the entropy of the fluid remains constant. This will be true
if the process the system goes through is reversible and adiabatic. An isentropic process can also
be called a constant entropy process.
Polytropic Process
When a gas undergoes a reversible process in which there is heat transfer, the process frequently
takes place in such a manner that a plot of the Log P (pressure) vs. Log V (volume) is a straight
line. Or stated in equation form PVn = a constant. This type of process is called a polytropic
process. An example of a polytropic process is the expansion of the combustion gasses in the
cylinder of a water-cooled reciprocating engine.
Throttling Process
A throttling process is defined as a process in which there is no change in enthalpy from state
one to state two, h1 = h2; no work is done, W = 0; and the process is adiabatic, Q = 0. To better
understand the theory of the ideal throttling process lets compare what we can observe with the
above theoretical assumptions.
An example of a throttling process is an ideal gas flowing through a valve in midposition. From
experience we can observe that: Pin > Pout, velin < velout (where P = pressure and vel = velocity).
These observations confirm the theory that hin = hout. Remember h = u + Pv (v = specific
volume), so if pressure decreases then specific volume must increase if enthalpy is to remain
constant (assuming u is constant). Because mass flow is constant, the change in specific volume
is observed as an increase in gas velocity, and this is verified by our observations.
Rev. 0
Page 29
HT-01
Thermodynamics
The theory also states W = 0. Our observations again confirm this to be true as clearly no
"work" has been done by the throttling process. Finally, the theory states that an ideal throttling
process is adiabatic. This cannot clearly be proven by observation since a "real" throttling
process is not ideal and will have some heat transfer.
Summary
Thermodynamic Systems and Processes Summary
A thermodynamic system is a collection of matter and space with its boundaries

defined in such a way that the energy transfer across the boundaries can be best
understood.
Surroundings are everything not in the system being studied.
Systems are classified into one of three groups:

Isolated system Closed system
Open system
neither mass nor energy can cross the

boundaries
only energy can cross the boundaries
both mass and energy can cross the
boundaries
A control volume is a fixed region of space that is studied as a thermodynamic

system.
Steady state refers to a condition where the properties at any given point within the
system are constant over time. Neither mass nor energy are accumulating within the
system.
A thermodynamic process is the succession of states that a system passes through.

Processes can be described by any of the following terms:
Cyclic process
Reversible process Irreversible process Adiabatic process
Isentropic process
Polytropic process Throttling process
HT-01
a series of processes that results in the system

returning to its original state
a process that can be reversed resulting in no change
in the system or surroundings
a process that, if reversed, would result in a change to
the system or surroundings
a process in which there is no heat transfer across the
system boundaries
a process in which the entropy of the system remains
unchanged
the plot of Log P vs. Log V is a straight line, PVn =
constant
a process in which enthalpy is constant h1 = h2, work
= 0, and which is adiabatic, Q=0.
Page 30
Rev. 0
Thermodynamics
CHANGE OF PHASE
CHANGE OF PHASE
The phase change of materials in a system is very important to thermodynamics.
It is possible to design systems to take advantage of the phase changes between
solid and liquid or between liquid and vapor to enhance the performance of the
system.
EO 1.13
DISTINGUISH between intensive and extensive

properties.
EO 1.14

a.
Saturation
b.
Subcooled liquid
c.
Superheated vapor
d.
Critical Point
e.
Triple Point
f.
Vapor pressure curve
g.
Quality
h.
Moisture Content
EO 1.15
DESCRIBE the processes of sublimation, vaporization,

condensation, and fusion.
Classification of Properties
As discussed earlier in this module, properties are classified as either intensive or extensive.
Properties are intensive if independent of the amount of mass present and extensive if a function
of the amount of mass present. Properties such as pressure, temperature, and density are
intensive, whereas volume and mass are extensive. An extensive property may be made intensive
by dividing the particular property by the total mass. Total volume (V), which is an extensive
property, can be changed to specific volume, which is an intensive property, by dividing by the
mass of the system, = V/m. Any specific property (specific volume, specific enthalpy, specific
entropy), is an intensive property, as indicated in Figure 3.
The use of intensive and extensive properties is demonstrated in the following discussion.
Consider as a system 1 lbm of water contained in the piston-cylinder arrangement of Figure 4.
Suppose that the piston and weight maintain a pressure of 14.7 psia in the cylinder and that the
initial temperature is 60F, part (a) of Figure 4. As heat is transferred to the water, the
temperature increases. The specific volume increases slightly, and the pressure remains constant.
When the temperature reaches 212F, additional heat transfer results in a change in phase
(boiling), as indicated in part (b).
Rev. 0
Page 31
HT-01
CHANGE OF PHASE
Thermodynamics
That is, some of the liquid becomes vapor and both the temperature and pressure remain constant,
but the specific volume increases considerably. When the last drop of liquid is vaporized, further
transfer of heat results in an increase in both temperature and specific volume of the vapor, part
(c). In this example, temperature and pressure are intensive, and therefore do not depend upon
the amount of mass present. By examining the specific volume (an intensive property) of the
water in the piston instead of the volume (an extensive property), we can examine how any
portion of the water in the piston changes. Volume by itself tells us nothing about the water in
the piston. However, by knowing the specific volume we can tell if the water is a liquid or
steam.
It is customary to define some intensive properties

associated with extensive properties. For example, the
volume per unit mass is called the specific volume,
v
V
M
and the internal energy per unit mass is called the

specific internal energy.
u
U
M
Intensive properties are useful because they can be

tabulated or graphed without reference to the amount
of material under study.
Figure 3 Intensive Properties
HT-01
Page 32
Rev. 0
Thermodynamics
CHANGE OF PHASE
Figure 4
Piston-cylinder Arrangement
Saturation
The term saturation defines a condition in which
a mixture of vapor and liquid can exist together
at a given temperature and pressure.
The
temperature at which vaporization (boiling) starts
to occur for a given pressure is called the
saturation temperature or boiling point. The
pressure at which vaporization (boiling) starts to
occur for a given temperature is called the
saturation pressure. For water at 212F, the
saturation pressure is 14.7 psia and, for water at
14.7 psia, the saturation temperature is 212F.
For a pure substance there is a definite
relationship between saturation pressure and
saturation temperature. The higher the pressure,
the higher the saturation temperature. The
graphical representation of this relationship
Figure 5 Vapor Pressure Curve
between temperature and pressure at saturated
conditions is called the vapor pressure curve. A
typical vapor pressure curve is shown in Figure 5. The vapor/liquid mixture is at saturation when
the conditions of pressure and temperature fall on the curve.
Saturated and Subcooled Liquids

If a substance exists as a liquid at the saturation temperature and pressure, it is called a saturated
liquid.
Rev. 0
Page 33
HT-01
CHANGE OF PHASE
Thermodynamics
If the temperature of the liquid is lower than the saturation temperature for the existing pressure,
it is called either a subcooled liquid (implying that the temperature is lower than the saturation
temperature for the given pressure) or a compressed liquid (implying that the pressure is greater
than the saturation pressure for the given temperature). Both terms have the same meaning, so
either term may be used.
Quality
When a substance exists as part liquid and part vapor at saturation conditions, its quality (x) is
defined as the ratio of the mass of the vapor to the total mass of both vapor and liquid. Thus,
if the mass of vapor is 0.2 lbm and the mass of the liquid is 0.8 lbm, the quality is 0.2 or 20%.
Quality is an intensive property. Quality has meaning when the substance is in a saturated state
only, at saturation pressure and temperature. The area under the bell-shaped curve on figure 6
shows the region in which quality is important.
x
mvapor
(mliquid
(1-20)
mvapor)
Figure 6 T-V Diagram Showing the Saturation Region
HT-01
Page 34
Rev. 0
Thermodynamics
CHANGE OF PHASE
Moisture Content
The moisture content of a substance is the opposite of its quality. Moisture (M) is defined as
the ratio of the mass of the liquid to the total mass of both liquid and vapor. The moisture of
the mixture in the previous paragraph would be 0.8 or 80%. The following equations show how
to calculate the moisture of a mixture and the relationship between quality and moisture.
mliquid
M
(1-21)
(mliquid mvapor)
M=1-x
Saturated and Superheated Vapors

If a substance exists entirely as vapor at saturation temperature, it is called saturated vapor.
Sometimes the term dry saturated vapor is used to emphasize that the quality is 100%. When
the vapor is at a temperature greater than the saturation temperature, it is said to exist as
superheated vapor. The pressure and temperature of superheated vapor are independent
properties, since the temperature may increase while the pressure remains constant. Actually, the
substances we call gases are highly superheated vapors.
Constant Pressure Heat Addition

Consider the plot on the
temperature-volume diagram of
Figure 7, viewing the
constant-pressure line that
represents the states through
which the water of the
previous discussion passes as it
is heated from the initial state
of 14.7 psia and 60F. Let
state A represent the initial
state and state B represent the
start of the saturated liquid line
(212F). Therefore, line AB
represents the process in which
the liquid is heated from the
initial temperature to the
saturation temperature.
Figure 7 T-V Diagram
Rev. 0
Page 35
HT-01
CHANGE OF PHASE
Thermodynamics
Point C is the saturated vapor state, and line BC is the constant-temperature process in which the
change of phase from liquid to vapor occurs. Line CD represents the process in which the steam
is super-heated at constant pressure. Temperature and volume both increase during the process.
Now let the process take place at a constant pressure of 100 psia, beginning from an initial
temperature of 60F. Point E represents the initial state, the specific volume being slightly less
than 14.7 psia and 60F. Vaporization now begins at point F, where the temperature is 327.8F.
Point G is the saturated-vapor state, and line GH is the constant-pressure process in which the
steam is superheated.
In a similar manner, a constant pressure of 1000 psia is represented by line IJKL, the saturation
temperature being 544.6F.
Critical Point
At a pressure of 3206.2 psia, represented by line MNO, there is no constant-temperature
vaporization process. Rather, point N is a point of inflection, with the slope being zero. This
point is called the critical point, and at the critical point the saturated-liquid and saturated-vapor
states are identical. The temperature, pressure, and specific volume at the critical point are called
the critical temperature, critical pressure, and critical volume.
A constant pressure process greater than the critical pressure is represented by line PQ. There
is no definite change in phase from liquid to vapor and no definite point at which there is a
change from the liquid phase to the vapor phase. For pressures greater than the critical pressure,
the substance is usually called a liquid when the temperature is less than the critical temperature
(705.47F) and a vapor or gas when the temperature is greater than the critical temperature. In
the figure, line NJFB represents the saturated liquid line, and the line NKGC represents the
saturated vapor line.
Fusion
Consider one further experiment with the piston-cylinder arrangement of Figure 4. Suppose the
cylinder contained 1 lbm of ice at 0F, 14.7 psia. When heat is transferred to the ice, the
pressure remains constant, the specific volume increases slightly, and the temperature increases
until it reaches 32F, at which point the ice melts while the temperature remains constant. In this
state the ice is called a saturated solid. For most substances, the specific volume increases during
this melting process, but for water the specific volume of the liquid is less than the specific
volume of the solid. This causes ice to float on water. When all the ice is melted, any further
heat transfer causes an increase in temperature of the liquid. The process of melting is also
referred to as fusion. The heat added to melt ice into a liquid is called the latent heat of fusion.
HT-01
Page 36
Rev. 0
Thermodynamics
CHANGE OF PHASE
Sublimation
If the initial pressure of the ice at 0F is 0.0505 psia, heat transfer to the ice first results in an
increase in temperature to 20F. At this point, however, the ice passes directly from the solid
phase to the vapor phase in the process known as sublimation. Sublimation is a special term
used for cases in which the transition between the solid phase and the vapor phase occurs
directly, without passing through the liquid phase. Further heat transfer would result in
superheating the vapor.
Triple Point
Finally, consider an initial pressure of the ice of 0.08854 psia. Again, as a result of heat transfer,
the temperature will increase until it reaches 32F. At this point, however, further heat transfer
may result in some of the ice becoming vapor and some becoming liquid because it is possible
to have the three phases in equilibrium. This is called the triple point, defined as the state in
which all three phases may be present in equilibrium.
Figure 8 is a pressure-temperature diagram for water that shows how the solid, liquid, and vapor
phases may exist together in equilibrium. Along the sublimation line, the solid and vapor phases
are in equilibrium, along the fusion line, the solid and liquid phases are in equilibrium; and along
the vaporization line, the liquid and vapor phases are in equilibrium. The only point at which
all three phases may exist in equilibrium is the triple point. The temperature and pressure for
the triple point of water are 32.02F and 0.08865 psia. The vaporization line ends at the critical
point because there is no distinct change from the liquid phase to the vapor phase above the
critical point.
Rev. 0
Page 37
HT-01
CHANGE OF PHASE
Thermodynamics
Figure 8 Pressure-Temperature Diagram
Condensation
All the processes discussed on the preceding pages (vaporization, sublimation, and fusion) occur
during a heat addition to a substance. If heat is removed from a substance, the opposite of the
described processes will occur.
As previously described, a heat addition at a constant pressure to a saturated liquid will cause
the liquid to evaporate (change phase from liquid to vapor). If heat is removed at a constant
pressure from a saturated vapor, condensation will occur and the vapor will change phase to
liquid. So the processes of vaporization and condensation are the exact opposite of each other.
Similarly, freezing is the opposite process of melting and fusion. Sublimation also has an
opposite process in which a gas goes directly to solid, but this process is not normally referred
to with a unique term.
Summary
The important information from this chapter is summarized on the following page.
HT-01
Page 38
Rev. 0
Thermodynamics
CHANGE OF PHASE
Change of Phase Summary
Classification of Properties
Intensive properties are independent of mass (temperature,
pressure, or any specific property)
Extensive properties are a function of the mass of the system
(mass, volume)
Rev. 0
The following terms were defined in this chapter:

Saturation
combination of temperature and pressure

at which a mixture of vapor and liquid
can exist at equilibrium
Subcooled liquid
a liquid at a temperature below saturation

temperature for its pressure
Superheated vapor -
a vapor at a temperature above saturation

temperature for its pressure
Critical point
the temperature and pressure above which

there is no distinction between the liquid
and vapor phases
Triple point
the temperature and pressure at which all

three phases can exist in equilibrium
Vapor pressure curve -
a graphical representation of the

relationship between temperature and
pressure at saturated conditions
Quality
the fraction of the total mass of

a mixture that is in the vapor
phase
Moisture Content -
the fraction of the total mass of

a mixture that is in the liquid
phase
Page 39
HT-01
CHANGE OF PHASE
Thermodynamics
Change of Phase Summary (Cont.)
The following terms are labels for processes that occur when a substance changes
between the three phases of matter: solid, liquid, and vapor.
Sublimation
change of phase from solid to vapor
Vaporization
change of phase from liquid to vapor
Condensation
change of phase from vapor to liquid
Fusion or melting -
HT-01
change of phase from solid to liquid
Page 40
Rev. 0
Thermodynamics
PROPERTY DIAGRAMS AND STEAM TABLES

Property diagrams and steam tables are used in studying the theoretical and
actual properties and efficiencies of a given system.
EO 1.16
Given a Mollier diagram and sufficient information to

indicate the state of the fluid, DETERMINE any
unknown properties for the fluid.
EO 1.17
Given a set of steam tables and sufficient information

to indicate the state of the fluid, DETERMINE any
unknown properties for the fluid.
EO 1.18
DETERMINE the change in the enthalpy of a fluid as

it passes through a system component, given the state
of the fluid at the inlet and outlet of the component
and either steam tables or a Mollier diagram.
Property Diagrams
The phases of a substance and the relationships between its properties are most commonly shown
on property diagrams. A large number of different properties have been defined, and there are
some dependencies between properties. For example, at standard atmospheric pressure and
temperature above 212F, water exists as steam and not a liquid; it exists as a liquid at
temperatures between 32F and 212F; and, it exists as ice at temperatures below 32F. In
addition, the properties of ice, water, and steam are related. Saturated steam at 212F and
standard atmospheric pressure has a specific volume of 26.8 ft3/lbm. At any other temperature
and pressure, saturated steam has a different specific volume. For example, at 544F and 1000
psia pressure, its specific volume is 0.488 ft3/lbm.
There are five basic properties of a substance that are usually shown on property diagrams.
These are: pressure (P), temperature (T), specific volume (), specific enthalpy (h), and specific
entropy (s). When a mixture of two phases, such as water and steam, is involved, a sixth
property, quality (x), is also used.
There are six different types of commonly encountered property diagrams. These are: PressureTemperature (P-T) diagrams, Pressure-Specific Volume (P-) diagrams, Pressure-Enthalpy (P-h)
diagrams, Enthalpy-Temperature (h-T) diagrams, Temperature-entropy (T-s) diagrams, and
Enthalpy-Entropy (h-s) or Mollier diagrams.
Rev. 0
Page 41
HT-01
Thermodynamics
Pressure-Temperature (P-T) Diagram

A P-T diagram is the most common way to show the phases of a substance. Figure 9 is the P-T
diagram for pure water. A P-T diagram can be constructed for any pure substance. The line that
separates the solid and vapor phases is called the sublimation line. The line that separates the
solid and liquid phases is called the fusion line. The line that separates the liquid and vapor
phases is called the vaporization line. The point where the three lines meet is called the triple
point. The triple point is the only point at which all three phases can exist in equilibrium. The
point where the vaporization line ends is called the critical point. At temperatures and pressures
greater than those at the critical point, no substance can exist as a liquid no matter how great a
pressure is exerted upon it.
Figure 9 P-T Diagram for Water
HT-01
Page 42
Rev. 0
Thermodynamics
Pressure-Specific Volume (P-) Diagram

A P- diagram is another common
type of property diagram. Figure
10 is the P- diagram for pure
water. A P- diagram can be
constructed for any pure substance.
A P- diagram is different from a
P-T diagram in one particularly
important way. There are regions
on a P- diagram in which two
phases exist together.
In the
liquid-vapor region in Figure 10,
water and steam exist together.
For example, at point A, water
with a specific volume (f), given
by point B, exists together with
steam with a specific volume (g),
given by point C. The dotted lines
Figure 10 P-v Diagram for Water
on Figure 10 are lines of constant
temperature. The quality of the
mixture at any point in the liquid-vapor region can be found because the specific volumes of
water, steam, and the mixture are all known. The quality can be found using the following
relationship.
= xg + (1 - x)f
x
specific volume of the mixture (ft3/lbm)
quality of the mixture (no units)
specific volume of the vapor (ft3/lbm)
specific volume of the liquid (ft3/lbm)
fg
specific volume change of vaporization (ft3/lbm) or vfg = vg - vf
fg
where:
Rev. 0
Page 43
HT-01
Thermodynamics
Pressure-Enthalpy (P-h) Diagram

A P-h diagram exhibits the same
features as a P- diagram. Figure
11 is the P-h diagram for pure
water. A P-h diagram can be
constructed for any pure substance.
Like the P- diagram, there are
regions on a P-h diagram in which
two phases exist together. In the
liquid-vapor region in Figure 11,
water and steam exist together.
For example, at point A, water
with an enthalpy (hf), given by
point B, exists together with steam
with an enthalpy (hg), given by
point C.
The quality of the
mixture at any point in the
liquid-vapor region can be found
using the following relationship.
Figure 11 P-h Diagram for Water
h = xhg + (1 - x)hf
x
hf
hfg
where:
HT-01
specific enthalpy of the mixture (Btu/lbm)
hg
specific enthalpy of the saturated vapor (Btu/lbm)
hf
specific enthalpy of the saturated liquid (Btu/lbm)
hfg
specific enthalpy change of vaporization (Btu/lbm) or hfg = hg - hf
Page 44
Rev. 0
Thermodynamics
Enthalpy-Temperature (h-T) Diagram

An h-T diagram exhibits the same features as on the previous property diagrams. Figure 12 is
the h-T diagram for pure water. An h-T diagram can be constructed for any pure substance. As
in the previous property diagrams, there are regions on the h-T diagram in which two phases
exist together. The region between the saturated liquid line and the saturated vapor line
represents the area of two phases existing at the same time. The vertical distance between the
two saturation lines represents the latent heat of vaporization. If pure water existed at point A
on the saturated liquid line and an amount of heat was added equal to the latent heat of
vaporization, then the water would change phase from a saturated liquid to a saturated vapor
(point B), while maintaining a constant temperature. As shown in Figure 12, operation outside
the saturation lines results in a subcooled liquid or superheated steam.
Figure 12
h-T Diagram for Water
The quality of the mixture at any point in the liquid-vapor region can be found using the same
relationship as shown for the P-h diagram.
x
Rev. 0
h hf
hfg
Page 45
HT-01
Thermodynamics
Temperature-Entropy (T-s) Diagram

A T-s diagram is the type of diagram most frequently used to analyze energy transfer system
cycles. This is because the work done by or on the system and the heat added to or removed
from the system can be visualized on the T-s diagram. By the definition of entropy, the heat
transferred to or from a system equals the area under the T-s curve of the process. Figure 13 is
the T-s diagram for pure water. A T-s diagram can be constructed for any pure substance. It
exhibits the same features as P- diagrams.
Figure 13 T-s Diagram for Water
In the liquid-vapor region in Figure 13, water and steam exist together. For example, at point
A, water with an entropy (sf) given by point B, exists together with steam with an entropy (sg)
given by point C. The quality of the mixture at any point in the liquid-vapor region can be found
using the following relationship.
s = xsg + (1 - x)sf
x
HT-01
sf
sfg
Page 46
Rev. 0
Thermodynamics
where:
s
specific entropy of the mixture (Btu/lbm-R)
sg
specific entropy of the saturated vapor (Btu/lbm-R)
sf
specific entropy of the saturated liquid

(Btu/lbm-R)
sfg
specific entropy change of vaporization (Btu/lbm-R) or sfg = sg - sf
Enthalpy-Entropy (h-s) or Mollier Diagram

The Mollier diagram, shown in Figure A-1 of Appendix A, is a chart on which enthalpy (h)
versus entropy (s) is plotted. It is sometimes known as the h-s diagram and has an entirely
different shape from the T-s diagrams. The chart contains a series of constant temperature lines,
a series of constant pressure lines, a series of constant moisture or quality lines, and a series of
constant superheat lines. The Mollier diagram is used only when quality is greater than 50% and
for superheated steam.
Steam Tables
Steam tables consist of two sets of tables of the energy transfer properties of water and steam:
saturated steam tables and superheated steam tables. Portions of the tables are shown in Figure
A-2 of Appendix A. Both sets of tables are tabulations of pressure (P), temperature (T), specific
volume (), specific enthalpy (h), and specific entropy (s). The following notation is used in
steam tables. Some tables use v for (specific volume) because there is little possibility of
confusing it with velocity.
Rev. 0
temperature (F)
pressure (psi)
specific volume of saturated liquid (ft3/lbm)
specific volume of saturated vapor (ft3/lbm)
Page 47
HT-01
Thermodynamics
fg
specific volume change of vaporization (ft3/lbm)
specific enthalpy (Btu/lbm)
hf
specific enthalpy of saturated liquid (Btu/lbm)
hg
specific enthalpy of saturated vapor (Btu/lbm)
hfg
specific enthalpy change of vaporization (Btu/lbm)
specific entropy (Btu/lbm-R)
sf
specific entropy of saturated liquid (Btu/lbm-R)
sg
specific entropy of saturated vapor (Btu/lbm-R)
sfg
specific entropy change of vaporization (Btu/lbm-R)
Sh
number of degrees of superheat (F)
The saturated steam tables give the energy transfer properties of saturated water and saturated
steam for temperatures from 32 to 705.47F (the critical temperature) and for the corresponding
pressure from 0.08849 to 3208.2 psi. Normally, the saturated steam tables are divided into two
parts: temperature tables, which list the properties according to saturation temperature (Tsat); and
pressure tables, which list them according to saturation pressure (Psat). Figure A-2 shows a
portion of a typical saturated steam temperature table and a portion of a typical saturated steam
pressure table. The values of enthalpy and entropy given in these tables are measured relative
to the properties of saturated liquid at 32F. Hence, the enthalpy (hf) of saturated liquid and the
entropy (sf) of saturated liquid have values of approximately zero at 32F.
Most practical applications using the saturated steam tables involve steam-water mixtures. The
key property of such mixtures is steam quality (x), defined as the mass of steam present per unit
mass of steam-water mixture, or steam moisture content (y), defined as the mass of water present
per unit mass of steam-water mixture. The following relationships exist between the quality of
a liquid-vapor mixture and the specific volumes, enthalpies, or entropies of both phases and of
the mixture itself. These relationships are used with the saturated steam tables.
HT-01
Page 48
Rev. 0
Thermodynamics
x g
(1
x) f
f
fg
xhg
h
(1
x) hf
hf
hfg
xsg
s
(1
x) sf
sf
sfg
In order to solve problems in Thermodynamics, information concerning the "state" of the

substance studied must be obtained. Usually, two properties (for example, v, p, T, h, s) of the
substance must be known in order to determine the other needed properties. These other
properties are usually obtained utilizing either the Mollier diagram (if the substance is steam) or
the saturated and superheated steam tables, as shown in the Figures A-1 and A-2.
The following two examples illustrate the use of the Mollier diagram and the steam tables.
Example 1: Use of Mollier Chart.

Superheated steam at 700 psia and 680F is expanded at constant entropy to 140 psia.
What is the change in enthalpy?
Solution:
Use the Mollier Chart. Locate point 1 at the intersection of the 700 psia and the 680F
line. Read h = 1333 Btu/lbm.
Follow the entropy line downward vertically to the 140 psia line and read h = 1178
Btu/lbm.
h = 1178 - 1333 = -155 Btu/lbm
Rev. 0
Page 49
HT-01
Thermodynamics
Example 2: Use of steam tables

What are the specific volume, enthalpy, and entropy of steam having a quality of 90%
at 400 psia?
Solution:
From the steam tables at 400 psia:
f = 0.01934
g = 1.14162
hf = 424.2
hfg = 780.4
sf = 0.6217
sfg = 0.8630
= f + x (fg)
= 0.01934 + (0.9)(1.14162) = 1.0468 lbm/ft3
= hf + x(hfg)
= 424.2 + (0.90)(780.4) = 1126.56 Btu/lbm
= sf + x(sfg)
= 0.6217 + (0.9)(0.8630) = 1.3984 Btu/lbm-R
If the substance is not water vapor, the "state" of the substance is usually obtained through the
use of T-s (temperature-entropy) and h-s (enthalpy-entropy) diagrams, available in most
thermodynamics texts for common substances. The use of such diagrams is demonstrated by the
following two examples.
Example 3: Use of the h-s diagram

Mercury is used in a nuclear facility. What is the enthalpy of the mercury if its pressure
is 100 psia and its quality is 70%?
Solution:
From the mercury diagram, Figure A-3 of Appendix A, locate the pressure of 100 psia.
Follow that line until reaching a quality of 70%. The intersection of the two lines gives
an enthalpy that is equal to h = 115 Btu/lbm.
HT-01
Page 50
Rev. 0
Thermodynamics
Example 4: Use of the T-s diagram

Carbon dioxide is used in a particular process in which the pressure is 100 psia and the
temperature is 100F. What is the enthalpy value of the gas?
Solution:
From the carbon dioxide diagram, Figure A-4 of Appendix A, locate the pressure of 100
psia. Follow that line until reaching a temperature of 100F. The intersection of the two
lines gives an enthalpy that is equal to h = 316 Btu/lbm.
Once the various states have been fixed for the particular process the substance has passed
through (for example, going from a saturated liquid state to a compressed liquid state across a
pump), energy exchanges may be determined as was shown in Example 1. The energy exchanges
are never 100 percent efficient, as already discussed. The degree of efficiency obtained by the
system depends upon the process through which the system has passed. Generally, the efficiency
of a component depends upon how much friction exists in the flow of the substance, the pressure
drops within the system, the inlet and outlet temperatures, and various other factors. The
properties affecting the efficiency of the system are determined by use of the charts and diagrams
mentioned in this section.
When power cycles are utilized for large systems, the efficiency of each component should be
maximized in order to have the highest possible overall efficiency for the system. Each
component affects the system efficiency in a different manner. To maximize efficiency, the
practical approach to large systems is to have multistage expansion with reheat between stages
and regenerators in the system where applicable.
Rev. 0
Page 51
HT-01
Thermodynamics
Summary
Property Diagrams and Steam Tables Summary
The Mollier diagram can be used to determine various properties of a fluid.

Mollier diagram is an h versus s plot.
Can only be used when quality is greater than 50% and for superheated
steam.
Contains a series of constant temperature, constant pressure, constant
moisture content, and constant superheat lines.
The steam tables can be used to determine various properties of water using the
following equations.
v = xvg + (1 - x)vf
h = xhg + (1 - x)hf
s = xsg + (1 - x)sf
x=
x=
x=
HT-01
vf
vfg
hf
hfg
sf
sfg
The change in enthalpy of a fluid as it passes through a component can be

determined using a Mollier diagram on steam tables.
Page 52
Rev. 0
Thermodynamics
FIRST LAW OF THERMODYNAMICS

The First Law of Thermodynamics is a balance of the various forms of energy as
they pertain to the specified thermodynamic system (control volume) being studied.
EO 1.19
STATE the First Law of Thermodynamics.
EO 1.20
Using the First Law of Thermodynamics, ANALYZE

an open system including all energy transfer processes
crossing the boundaries.
EO 1.21
Using the First Law of Thermodynamics, ANALYZE

cyclic processes for a thermodynamic system.
EO 1.22
Given a defined system, PERFORM energy balances

on all major components in the system.
EO 1.23
Given a heat exchanger, PERFORM an energy

balance across the two sides of the heat exchanger.
EO 1.24
IDENTIFY the path(s) on a T-s diagram that

represents the thermodynamic processes occurring in
a fluid system.
First Law of Thermodynamics

The First Law of Thermodynamics states:
Energy can neither be created nor destroyed, only altered in form.
For any system, energy transfer is associated with mass and energy crossing the control
boundary, external work and/or heat crossing the boundary, and the change of stored energy
within the control volume. The mass flow of fluid is associated with the kinetic, potential,
internal, and "flow" energies that affect the overall energy balance of the system. The exchange
of external work and/or heat complete the energy balance.
Rev. 0
Page 53
HT-01
Thermodynamics
The First Law of Thermodynamics is referred to as the Conservation of Energy principle,

meaning that energy can neither be created nor destroyed, but rather transformed into various
forms as the fluid within the control volume is being studied. The energy balance spoken of here
is maintained within the system being studied. The system is a region in space (control volume)
through which the fluid passes. The various energies associated with the fluid are then observed
as they cross the boundaries of the system and the balance is made.
As discussed in previous chapters of this module, a system may be one of three types: isolated,
closed, or open. The open system, the most general of the three, indicates that mass, heat, and
external work are allowed to cross the control boundary. The balance is expressed in words as:
all energies into the system are equal to all energies leaving the system plus the change in storage
of energies within the system. Recall that energy in thermodynamic systems is composed of
kinetic energy (KE), potential energy (PE), internal energy (U), and flow energy (PL); as well as
heat and work processes.
(all energies in) = (all energies out) + (energy stored in system)
Ein
Eout
E storage
For most industrial plant applications that most frequently use cycles, there is no change in
storage (i.e. heat exchangers do not swell while in operation).
In equation form, the balance appears as indicated on Figure 14.
where:
heat flow into the system (Btu/hr)
m
in
mass flow rate into the system (lbm/hr)
uin
specific internal energy into the system (Btu/lbm)
Pinin =
pressure-specific volume energy into the system (ft-lbf/lbm)
Vin
2gc
kinetic energy into the system (ft-lbf /lbm) where

Vin = average velocity of fluid (ft/sec)
gc = the gravitational constant (32.17 ft-lbm/lbf-sec2)
g
Z
gc in
=
Zin
g
gc
HT-01
potential energy of the fluid entering the system (ft-lbf/lbm) where

= height above reference level (ft)
= acceleration due to gravity (ft/sec2)
= the gravitational constant (32.17 ft-lbm/lbf-sec2)
Page 54
Rev. 0
Thermodynamics
= work flow out of the system (ft-lbf/hr)
m
out
= mass flow rate out of the system (lbm/hr)
uout
= specific internal energy out of the system (Btu/lbm)
Poutout
= pressure-specific volume energy out of the system

(ft-lbf/lbm)
Vout
2gc
g
Z
gc out
= kinetic energy out the system (ft-lbf/lbm)
= potential energy out of the system (ft-lbf/lbm)
Figure 14
Rev. 0
First Law of Thermodynamics
Page 55
HT-01
Thermodynamics
Heat and/or work can be directed into or out of the control volume. But, for convenience and
as a standard convention, the net energy exchange is presented here with the net heat exchange
assumed to be into the system and the net work assumed to be out of the system. If no mass
crosses the boundary, but work and/or heat do, then the system is referred to as a "closed"
system. If mass, work and heat do not cross the boundary (that is, the only energy exchanges
taking place are within the system), then the system is referred to as an isolated system. Isolated
and closed systems are nothing more than specialized cases of the open system. In this text, the
open system approach to the First Law of Thermodynamics will be emphasized because it is
more general. Also, almost all practical applications of the first law require an open system
analysis.
An understanding of the control volume concept is essential in analyzing a thermodynamic
problem or constructing an energy balance. Two basic approaches exist in studying
Thermodynamics: the control mass approach and the control volume approach. The former is
referred to as the LeGrange approach and the latter as the Eulerian approach. In the control mass
concept, a "clump" of fluid is studied with its associated energies. The analyzer "rides" with the
clump wherever it goes, keeping a balance of all energies affecting the clump.
Figure 15
HT-01
Control Volume Concepts
Page 56
Rev. 0
Thermodynamics
The control volume approach is one in which a fixed region in space is established with specified
control boundaries, as shown in Figure 15. The energies that cross the boundary of this control
volume, including those with the mass crossing the boundary, are then studied and the balance
performed. The control volume approach is usually used today in analyzing thermodynamic
systems. It is more convenient and requires much less work in keeping track of the energy
balances. Examples of control volume applications are included in Figures 16-18.
Figure 16 Open System Control Volumes
Rev. 0
Page 57
HT-01
Figure 17
Figure 18
HT-01
Thermodynamics
Open System Control Volumes (Cont.)
Multiple Control Volumes in Same System
Page 58
Rev. 0
Thermodynamics
The forms of energy that may cross the control volume boundary include those associated with
the mass (m) crossing the boundary. Mass in motion has potential (PE), kinetic (KE), and
internal energy (U). In addition, since the flow is normally supplied with some driving power
(a pump for example), there is another form of energy associated with the fluid caused by its
pressure. This form of energy is referred to as flow energy (P-work). The thermodynamic
terms thus representing the various forms of energy crossing the control boundary with the mass
are given as m (u + P + ke + pe).
In open system analysis, the u and P terms occur so frequently that another property, enthalpy,
has been defined as h = u + P. This results in the above expression being written as m (h +
ke + pe). In addition to the mass and its energies, externally applied work (W), usually
designated as shaft work, is another form of energy that may cross the system boundary.
In order to complete and satisfy the conservation of energy relationship, energy that is caused
by neither mass nor shaft work is classified as heat energy (Q). Then we can describe the
relationship in equation form as follows.
m(h
in
pein
kein)
m(h
out
peout
keout)
(1-22)
where:
Rev. 0
mass flow rate of working fluid (lbm/hr)
hin
specific enthalpy of the working fluid entering the system (Btu/lbm)
hout
specific enthalpy of the working fluid leaving the system (Btu/lbm)
pein
specific potential energy of working fluid entering the system (ft-lbf/lbm)
peout
specific potential energy of working fluid leaving the system (ft-lbf/lbm)
kein
specific kinetic energy of working fluid entering the system (ft-lbf/lbm)
keout
specific kinetic energy of working fluid leaving the system (ft-lbf/lbm)
rate of work done by the system (ft-lbf/hr)
heat rate into the system (Btu/hr)
Page 59
HT-01
Thermodynamics
Example 1 illustrates the use of the control volume concept while solving a first law problem
involving most of the energy terms mentioned previously.
Example 1: Open System Control Volume
The enthalpies of steam entering and leaving a steam turbine are 1349 Btu/lbm and 1100
Btu/lbm, respectively. The estimated heat loss is 5 Btu/lbm of steam. The flow enters
the turbine at 164 ft/sec at a point 6.5 ft above the discharge and leaves the turbine at 262
ft/sec. Determine the work of the turbine.
Solution:
m
in(hin
pein
kein)
1) Divide by m
since, m
in
Q
m
out
mout (hout
peout
keout)
m.
(hin + pein + kein) + q = (hout + peout + keout) + w

where:
q
= heat added to the system per pound (Btu/lbm)
= work done by the system per pound (ft-lbf/lbm)
2) Use Joules constant J = 778 ft-lbf/Btu for conversions and substitute known values.
1349 Btu/lbm + (6.5/778) Btu/lbm + [(164)2/2(32.17)(778)] Btu/lbm +
(-5 Btu/lbm) = 1100 Btu/lbm + 0 peout + [(262)2/2(32.17)(778)] Btu/lbm + w
Note: The minus sign indicates heat out of the turbine.
3) Solve for work, w.
1349 Btu/lbm + 8.3548 x 10-3 Btu/lbm + 0.5368 Btu/lbm - 5 Btu/lbm = 1100
Btu/lbm + 1.37 Btu/lbm + w
1344.54 Btu/lbm = 1101.37 Btu/lbm + w
w = 1344.54 Btu/lbm - 1101.37 Btu/lbm
w = 243.17 Btu/lbm
HT-01
Page 60
Rev. 0
Thermodynamics
This example demonstrates that

potential and kinetic energy terms are
insignificant for a turbine, since the
pe and ke values are less than 1
Btu/lbm.
When the system (the fluid being
studied) changes its properties
(temperature, pressure, volume) from
one value to another as a consequence
of work or heat or internal energy
exchange, then it is said that the fluid
has gone through a "process." In
some processes, the relationships
between pressure, temperature, and
volume are specified as the fluid goes
from one thermodynamic state to
another. The most common processes
are those in which the temperature,
pressure, or volume is held constant
during the process. These would be
classified as isothermal, isobaric, or
isovolumetric processes, respectively.
Iso means "constant or one." If the
fluid passes through various processes
and then eventually returns to the
same state it began with, the system is
said to have undergone a cyclic
process. One such cyclic process used
is the Rankine cycle, two examples of
which are shown in Figure 19.
The processes that comprise the cycle
are described below.
Figure 19
Rev. 0
T-s Diagram with Rankine Cycles
ab:
Liquid is compressed
with no change in
entropy (by ideal pump).
bc:
Constant pressure transfer of heat in the boiler. Heat is added to the compressed
liquid, two-phase, and superheat states.
cd:
Constant entropy expansion with shaft work output (in ideal turbine).
da:
Constant pressure transfer of heat in the sink. Unavailable heat is rejected to the
heat sink (condenser).
Page 61
HT-01
Thermodynamics
Note the individual processes the fluid must go through before completing the complete cycle.
Rankine cycles will be discussed in greater detail later in this module. Figure 20 shows a typical
steam plant cycle. Heat is supplied to the steam generator (boiler) where liquid is converted to
steam or vapor. The vapor is then expanded adiabatically in the turbine to produce a work
output. Vapor leaving the turbine then enters the condenser where heat is removed and the vapor
is condensed into the liquid state. The condensation process is the heat-rejection mechanism for
the cycle. Saturated liquid is delivered to the condensate pump and then the feed pump where
its pressure is raised to the saturation pressure corresponding to the steam generator temperature,
and the high pressure liquid is delivered to the steam generator where the cycle repeats itself.
Figure 20
Typical Steam Plant Cycle
With the example complete, it seems appropriate to discuss the various components of a typical
steam plant system. Although such a system is extremely complex, only the major components
will be discussed. A typical steam plant system consists of: a heat source to produce the thermal
energy (e.g. nuclear or fossil fuel); a steam generator to change the thermal energy into steam
energy (a complete steam plant usually exists in connection with the steam generator in
converting the steam into eventual electrical energy); pumps to transfer the fluid back to the heat
source (reactor coolant pumps in a nuclear reactor); a pressurizer to ensure that the primary
system maintains its desired pressure; and the necessary piping to ensure the fluid passes through
each stage of its cyclic process. Of necessity, the steam plant is a large "closed" system.
However, each component of the system is thermodynamically analyzed as an open system as
the fluid passes through it. Of primary importance is the process of dissipating the energy
created by the heat source. This process takes place in the steam generator, which acts as a giant
two-phase heat generator.
HT-01
Page 62
Rev. 0
Thermodynamics
The hot fluid from the heat source passes through the primary side of the steam generator where
its energy is passed to the secondary side of the heat exchanger in such a manner as to create
steam. The fluid, with its energy removed from the primary side, leaves the steam generator at
a lower temperature, and is pumped back to the heat source to be "re-heated." Each major
component of a steam plant can be treated as a separate open system problem. A thermodynamic
analysis, using the various forms of energies discussed, can be applied to the particular
component in studying its behavior. A simplified example of the thermodynamics involved in
the steam generator is shown below.
Example 2: Open System - Steam Plant Component
Primary fluid enters the heat exchanger of a nuclear facility at 610F and leaves at 540F.
The flow rate is approximately 1.38 x 108 lbm/hr. If the specific heat of the fluid is taken
as 1.5 Btu/lbmF, what is the heat transferred out of the steam generator?
Solution:
m
in(h
pe
kein)
m
out(h
pe
keout)
1) Neglecting pe and ke and assuming no work is done on the system.
m(h
in)
m(h
out
2) Substituting Q
m(h
out)
hin)
mc
pT where cp = specific heat capacity (Btu/lbm-F).
m
(cp) (Tout - Tin)
1.38 x 108 lbm/hr (1.5 Btu/lbm-oF) (540 - 610oF)
-1.45 x 1010 Btu/hr
The minus sign indicating heat out of the heat exchanger, which is consistent with the
physical case. This example demonstrates that for a heat exchanger, the heat transfer rate
can be calculated using the equation Q

m
(hout-hin), or Q
mc
pT. It is important
to note that the later equation can only be used when no phase change occurs since T
= 0 during a phase change. The first equation can be used for a phase change heat
transfer process as well as for latent heat calculations.
Rev. 0
Page 63
HT-01
Thermodynamics
The pumps used for returning the fluid to the heat source can be analyzed as a thermodynamic
system also. One such example is illustrated in Example 3.
Example 3: Open System - Coolant
A power pump is used to return the fluid from the heat exchanger back to the core. The
flow rate through the pump is about 3.0 x 107 lbm/hr with the fluid entering the pump as
saturated liquid at 540F. The pressure rise across the pump is 90 psia. What is the
work of the pump, neglecting heat losses and changes in potential and kinetic energy?
Solution:
m
(hin
1)
pein
Assume Q
m(h
in)
2)
W
hin
hout
m
(hout
peout
keout)
0 and neglect changes in pe and ke
m(h
out)
is the rate of doing work by the pump

m
(hin - hout) where W
uin
Pin
uout Pout
(hin - hout)
3)
kein)
(uin - uout)
(Pin - Pout) = u
(Pin - Pout)
Since no heat is transferred, u = 0 and the specific volume out of the pump is
the same as the specific volume entering since water is incompressible.
(hin - hout) = (Pin - Pout)
4)
Substituting the expression for work, W
5)
m
(Pin
m
(hin-hout) we have:
Pout) .
Using 0.01246 for specific volume.

= 3.0 x 107 lbm/hr (0.01246 ft3/lbm) (-90psia) (144 in2/ft2)/778 ft-lbf/Btu
W
= -6.23 x 106 Btu/hr or -2446 hp
W
Note: The minus sign indicating work put into the fluid by the pump. 1 hp = 2545
Btu/hr.
HT-01
Page 64
Rev. 0
Thermodynamics
A thermodynamic balance across the reactor core gives an indication of the amount of
heat removed by the coolant that is given off by the fuel rods.
Example 4: Thermodynamic Balance across Heat Source
In a particular facility, the temperature leaving the reactor core is 612F, while that
entering the core is 542F. The coolant flow through the heat source is 1.32 x 108
lbm/hr. The cp of the fluid averages 1.47 Btu/lbmF. How much heat is being removed
from the heat source? The pe and ke energies are small compared to other terms and
may be neglected.
Solution:
m(h
pe
ke) in
m(h
out
hin)
1) Substituting Q
m(h
pe
ke) out
mc
pT where cp = specific heat capacity.
m(c
p) (Tout
1.32 x 108 lbm/hr (1.47 Btu/lbm -oF) (612 - 542oF)
1.36 x 1010 Btu/hr
Tin)
mc
pT has been used to calculate the heat transfer rate since no
phase change has occurred. However, Q

m
(hout-hin) could also have been used had
the problem data included inlet and outlet enthalpies.
For this example Q
The individual principal components of a reactor system have been thermodynamically

analyzed. If all components were combined into an overall system, the system could be
analyzed as a "closed" system problem. Such an analysis is illustrated in the following
example.
Rev. 0
Page 65
HT-01
Thermodynamics
Example 5: Overall Thermodynamic Balance

A nuclear facility (primary side) is to be studied as a complete system. The heat
produced by the heat source is 1.36 x 1010 Btu/hr. The heat removed by the heat
exchanger (steam generator) is 1.361 x 1010 Btu/hr. What is the required pump power to
maintain a stable temperature?
Solution:
= pump work, Q
= heat produced by the heat source, Q
W
p
c
into steam generator
m(h
1)
pe
ke)
W
p
Q
c
Q
sg
m(h
pe
heat transferred
ke)
For a closed system, the mass entering and leaving the system is zero, therefore,
m
is constant. The energy entering and leaving the system is zero, and you can
assume that the ke and pe are constant so that:
c+ W
p= Q
sg
Q
2)
W
p
= Q
sg
Q
c
= 1.361 x 1010 Btu/hr - 1.36 x 1010 Btu/hr

= 1.0 x 107 Btu/hr
W
p
= 4007 hp
Of the examples just completed, emphasis should be placed on the heat exchanger analysis. Both
the primary side and the secondary side have their own energy balances as the heat energy is
transferred from one fluid to the other. In calculating heat exchanger heat transfer rates, we
found that we could use the equations Q

mc
h .
p
Perhaps a short analysis of the secondary side of the heat exchanger will aid in understanding
the heat exchangers importance in the energy conversion process.
HT-01
Page 66
Rev. 0
Thermodynamics
Example 6: Secondary Side of Heat Exchanger

Steam flows through a condenser at 2.0 x 106 kg/hr, entering as saturated vapor at 40C
(h = 2574 kj/kg), and leaving at the same pressure as subcooled liquid at 30C (h = 125.8
kJ/kg). Cooling water is available at 18C (h = 75.6 kJ/kg). Environmental requirements
limit the exit temperature to 25C (h = 104.9 kJ/kg). Determine the required cooling
water flow rate.
Solution:
Thermal balance gives the following:
Q
stm
Q
cw
m
stm(hout
m
cw
hin) stm
m
cw(hout
hin) cw
m
stm(hout hin) stm/(hout hin) cw
= -2.0 x 106 kg/hr (125.8 - 2574 kj/kg)/(104.9 - 75.6 kj/kg)

m
cw
1.67 x 108 kg/hr
In this example, we calculated the flow rate using the equation Q

mh
since a phase change
occurred when the steam was condensed to liquid water. Q

mc
pT would not have worked
mc
pT , we
since T=0 for a phase change. Had we attempted to solve the problem using Q
o
would have discovered that an error occurs since the T = 10 C is the T needed to subcool the
liquid from saturation at 40oC to a subcooled value of 30oC. Therefore, the heat transfer process
to condense the steam to a saturated liquid has not been taken into account.
Rev. 0
Page 67
HT-01
Thermodynamics
Summary
First Law of Thermodynamics Summary
The First Law of Thermodynamics states that energy can neither be

created nor destroyed, only altered in form.
In analyzing an open system using the First Law of Thermodynamics, the

energy into the system is equal to the energy leaving the system.
If the fluid passes through various processes and then eventually returns
to the same state it began with, the system is said to have undergone a
cyclic process. The first law is used to analyze a cyclic process.
The energy entering any component is equal to the energy leaving that
component at steady state.
The amount of energy transferred across a heat exchanger is dependent

upon the temperature of the fluid entering the heat exchanger from both
sides and the flow rates of thse fluids.
A T-s diagram can be used to represent thermodynamic processes.
HT-01
Page 68
Rev. 0
Thermodynamics
SECOND LAW OF THERMODYNAMICS

The Second Law of Thermodynamics is used to determine the maximum efficiency
of any process. A comparison can then be made between the maximum possible
efficiency and the actual efficiency obtained.
EO 1.25
STATE the Second Law of Thermodynamics.
EO 1.26
Using the Second Law of Thermodynamics,

DETERMINE the maximum possible efficiency of a
system.
EO 1.27
Given a thermodynamic system, CONDUCT an

analysis using the Second Law of Thermodynamics.
EO 1.28
Given a thermodynamic system, DESCRIBE the

method used to determine:
a.
The maximum efficiency of the system
b.
The efficiency of the components within the system
EO 1.29
DIFFERENTIATE between the path for an ideal

process and that for a real process on a T-s or h-s
diagram.
EO 1.30
Given a T-s or h-s diagram for a system EVALUATE:

a.
System efficiencies
b.
Component efficiencies
EO 1.31
DESCRIBE how individual factors affect system or

component efficiency.
Second Law of Thermodynamics

One of the earliest statements of the Second Law of Thermodynamics was made by R. Clausius
in 1850. He stated the following.
It is impossible to construct a device that operates in a cycle and produces no
effect other than the removal of heat from a body at one temperature and the
absorption of an equal quantity of heat by a body at a higher temperature.
Rev. 0
Page 69
HT-01
Thermodynamics
With the Second Law of Thermodynamics, the limitations imposed on any process can be studied
to determine the maximum possible efficiencies of such a process and then a comparison can be
made between the maximum possible efficiency and the actual efficiency achieved. One of the
areas of application of the second law is the study of energy-conversion systems. For example,
it is not possible to convert all the energy obtained from a nuclear reactor into electrical energy.
There must be losses in the conversion process. The second law can be used to derive an
expression for the maximum possible energy conversion efficiency taking those losses into
account. Therefore, the second law denies the possibility of completely converting into work all
of the heat supplied to a system operating in a cycle, no matter how perfectly designed the
system may be. The concept of the second law is best stated using Max Plancks description:
It is impossible to construct an engine that will work in a complete cycle and
produce no other effect except the raising of a weight and the cooling of a heat
reservoir.
The Second Law of Thermodynamics is needed because the First Law of Thermodynamics does
not define the energy conversion process completely. The first law is used to relate and to
evaluate the various energies involved in a process. However, no information about the direction
of the process can be obtained by the application of the first law. Early in the development of
the science of thermodynamics, investigators noted that while work could be converted
completely into heat, the converse was never true for a cyclic process. Certain natural processes
were also observed always to proceed in a certain direction (e.g., heat transfer occurs from a hot
to a cold body). The second law was developed as an explanation of these natural phenomena.
Entropy
One consequence of the second law is the development of the physical property of matter termed
entropy (S). Entropy was introduced to help explain the Second Law of Thermodynamics. The
change in this property is used to determine the direction in which a given process will proceed.
Entropy can also be explained as a measure of the unavailability of heat to perform work in a
cycle. This relates to the second law since the second law predicts that not all heat provided to
a cycle can be transformed into an equal amount of work, some heat rejection must take place.
The change in entropy is defined as the ratio of heat transferred during a reversible process to
the absolute temperature of the system.
HT-01
Page 70
Rev. 0
Thermodynamics
Q
Tabs
(For a reversible process)
the change in entropy of a system during some process (Btu/R)
the amount of heat added to the system during the process (Btu)
Tabs
the absolute temperature at which the heat was transferred (R)
where
The second law can also be expressed as SO for a closed cycle. In other words, entropy must
increase or stay the same for a cyclic system; it can never decrease.
Entropy is a property of a system. It is an extensive property that, like the total internal energy
or total enthalpy, may be calculated from specific entropies based on a unit mass quantity of the
system, so that S = ms. For pure substances, values of the specific entropy may be tabulated
along with specific enthalpy, specific volume, and other thermodynamic properties of interest.
One place to find this tabulated information is in the steam tables described in a previous chapter
(refer back to Figure 19).
Specific entropy, because it is a property, is advantageously used as one of the coordinates when
representing a reversible process graphically. The area under a reversible process curve on the
T-s diagram represents the quantity of heat transferred during the process.
Thermodynamic problems, processes, and cycles are often investigated by substitution of
reversible processes for the actual irreversible process to aid the student in a second law analysis.
This substitution is especially helpful because only reversible processes can be depicted on the
diagrams (h-s and T-s, for example) used for the analysis. Actual or irreversible processes cannot
be drawn since they are not a succession of equilibrium conditions. Only the initial and final
conditions of irreversible processes are known; however, some thermodynamics texts represent
an irreversible process by dotted lines on the diagrams.
Rev. 0
Page 71
HT-01
Thermodynamics
Carnots Principle
With the practice of using reversible processes, Sadi Carnot in 1824 advanced the study of the
second law by disclosing a principle consisting of the following propositions.
1.
No engine can be more efficient than a reversible engine operating between the
same high temperature and low temperature reservoirs. Here the term heat
reservoir is taken to mean either a heat source or a heat sink.
2.
The efficiencies of all reversible engines operating between the same constant
temperature reservoirs are the same.
3.
The efficiency of a reversible engine depends only upon the temperatures of the
heat source and heat receiver.
Carnot Cycle
The above principle is best demonstrated with a simple cycle (shown in Figure 21) and an
example of a proposed heat power cycle. The cycle consists of the following reversible
processes.
HT-01
1-2:
adiabatic compression from TC to TH due to work performed on fluid.
2-3:
isothermal expansion as fluid expands when heat is added to the fluid at

temperature TH.
3-4:
adiabatic expansion as the fluid performs work during the expansion process and
temperature drops from TH to TC.
4-1:
isothermal compression as the fluid contracts when heat is removed from the fluid
at temperature TC.
Page 72
Rev. 0
Thermodynamics
This cycle is known as a Carnot Cycle. The heat input (QH) in a Carnot Cycle is graphically
represented on Figure 21 as the area under line 2-3. The heat rejected (QC) is graphically
represented as the area under line 1-4. The difference between the heat added and the heat
rejected is the net work (sum of all work processes), which is represented as the area of rectangle
1-2-3-4.
Figure 21
Carnot Cycle Representation
The efficiency () of the cycle is the ratio of the net work of the cycle to the heat input to the
cycle. This ratio can be expressed by the following equation.
where:
Rev. 0
(QH - QC)/QH = (TH - TC)/TH
1 - (TC/TH)
cycle efficiency
TC
designates the low-temperature reservoir (R)
TH
designates the high-temperature reservoir (R)
(1-23)
Page 73
HT-01
Thermodynamics
Equation 1-23 shows that the maximum possible efficiency exists when TH is at its largest
possible value or when TC is at its smallest value. Since all practical systems and processes are
really irreversible, the above efficiency represents an upper limit of efficiency for any given
system operating between the same two temperatures. The systems maximum possible
efficiency would be that of a Carnot efficiency, but because Carnot efficiencies represent
reversible processes, the actual system will not reach this efficiency value. Thus, the Carnot
efficiency serves as an unattainable upper limit for any real systems efficiency. The following
example demonstrates the above principles.
Example 1: Carnot Efficiency
An inventor claims to have an engine that receives 100 Btu of heat and produces 25 Btu
of useful work when operating between a source at 140F and a receiver at 0F. Is the
claim a valid claim?
Solution:
TH
= 140oF + 460 = 600R
TC
= 0oF + 460 = 460R
= (600-460)/600 x 100 = 23.3%
Claimed efficiency = 25/100 = 25%

Therefore, the claim is invalid.
The most important aspect of the second law for our practical purposes is the determination of
maximum possible efficiencies obtained from a power system. Actual efficiencies will always
be less than this maximum. The losses (friction, for example) in the system and the fact that
systems are not truly reversible preclude us from obtaining the maximum possible efficiency.
An illustration of the difference that may exist between the ideal and actual efficiency is
presented in Figure 22 and the following example.
Example 2: Actual vs. Ideal Efficiency
The actual efficiency of a steam cycle is 18.0%. The facility operates from a steam
source at 340F and rejects heat to atmosphere at 60F. Compare the Carnot efficiency
to the actual efficiency.
HT-01
Page 74
Rev. 0
Thermodynamics
Figure 22
Real Process Cycle Compared to Carnot Cycle
Solution:
1 - (Tc / Th)
1 - (60 + 460)/(340 + 460)
1 - 520/800
35%
as compared to 18.0% actual efficiency.
An open system analysis was performed using the First Law of Thermodynamics in the previous
chapter. The second law problems are treated in much the same manner; that is, an isolated,
closed, or open system is used in the analysis depending upon the types of energy that cross the
boundary. As with the first law, the open system analysis using the second law equations is the
more general case, with the closed and isolated systems being "special" cases of the open system.
The solution to second law problems is very similar to the approach used in the first law analysis.
Figure 23 illustrates the control volume from the viewpoint of the second law. In this diagram,
the fluid moves through the control volume from section in to section out while work is delivered
external to the control volume. We assume that the boundary of the control volume is at some
environmental temperature and that all of the heat transfer (Q) occurs at this boundary. We have
already noted that entropy is a property, so it may be transported with the flow of the fluid into
and out of the control volume, just like enthalpy or internal energy. The entropy flow into the
control volume resulting from mass transport is, therefore, m
insin, and the entropy flow out of the
control volume is m
outsout, assuming that the properties are uniform at
Rev. 0
Page 75
HT-01
Thermodynamics
sections in and out. Entropy may also be added to the control volume because of heat transfer
at the boundary of the control volume.
Figure 23 Control Volume for Second Law Analysis
A simple demonstration of the use of this form of system in second law analysis will give the
student a better understanding of its use.
Example 3: Open System Second Law
Steam enters the nozzle of a steam turbine with a velocity of 10 ft/sec at a pressure of
100 psia and temperature of 500F at the nozzle discharge. The pressure and temperature
are 1 atm at 300F. What is the increase in entropy for the system if the mass flow rate
is 10,000 lbm/hr?
HT-01
Page 76
Rev. 0
Thermodynamics
Solution:
ms
in
ms
out where p = entropy added to the system
m
(sout
sin)
sin
1.7088 Btu/lbm -R (from steam tables)
sout
1.8158 Btu/lbmR (from steam tables)
p /m
sout
p /m
0.107 Btu/lbm -R
10,000 (0.107)
1070 Btu/lbm -R. = entropy added to the system
sin
1.8158
1.7088 Btu/lbm-oR
It should always be kept in mind that the Second Law of Thermodynamics gives an upper limit
(which is never reached in physical systems) to how efficiently a thermodynamic system can
perform. A determination of that efficiency is as simple as knowing the inlet and exit
temperatures of the overall system (one that works in a cycle) and applying Carnots efficiency
equation using these temperatures in absolute degrees.
Diagrams of Ideal and Real Processes

Any ideal thermodynamic process can be drawn as a path on a property diagram, such as a T-s
or an h-s diagram. A real process that approximates the ideal process can also be represented
on the same diagrams (usually with the use of dashed lines).
In an ideal process involving either a reversible expansion or a reversible compression, the
entropy will be constant. These isentropic processes will be represented by vertical lines on
either T-s or h-s diagrams, since entropy is on the horizontal axis and its value does not change.
A real expansion or compression process operating between the same pressures as the ideal
process will look much the same, but the dashed lines representing the real process will slant
slightly towards the right since the entropy will increase from the start to the end of the process.
Figures 24 and 25 show ideal and real expansion and compression processes on T-s and h-s
diagrams.
Rev. 0
Page 77
HT-01
Thermodynamics
Figure 24 Expansion and Compression Processes

on T-s Diagram
Figure 25 Expansion and Compression Processes

on h-s Diagram
Power Plant Components

In order to analyze a complete power plant steam power cycle, it is first necessary to analyze the
elements which make up such cycles. (See Figure 26) Although specific designs differ, there are
three basic types of elements in power cycles, (1) turbines, (2) pumps and (3) heat exchangers.
Associated with each of these three types of elements is a characteristic change in the properties
of the working fluid.
Previously we have calculated
system efficiency by knowing the
temperature of the heat source and
the heat sink. It is also possible to
calculate the efficiencies of each
individual component.
The efficiency of each type of
component can be calculated by
comparing the actual work
produced by the component to the
work that would have been
produced by an ideal component
operating isentropically between
the same inlet and outlet
conditions.
HT-01
Figure 26
Page 78
Steam Cycle
Rev. 0
Thermodynamics
A steam turbine is designed to extract energy from the working fluid (steam) and use it to do
work in the form of rotating the turbine shaft. The working fluid does work as it expands
through the turbine. The shaft work is then converted to electrical energy by the generator. In
the application of the first law, general energy equation to a simple turbine under steady flow
conditions, it is found that the decrease in the enthalpy of the working fluid Hin - Hout equals the
work done by the working fluid in the turbine (Wt).
Hin
m
(hin
where:
Hout
hout)
(1-24)
Wt
w
t
(1-25)
Hin = enthalpy of the working fluid entering the turbine (Btu)

Hout = enthalpy of the working fluid leaving the turbine (Btu)
Wt = work done by the turbine (ft-lbf)
m
= mass flow rate of the working fluid (lbm/hr)
hin = specific enthalpy of the working fluid entering the turbine (Btu/lbm)
hout = specific enthalpy of the working fluid leaving the turbine (Btu/lbm)
w
t = power of turbine (Btu/hr)
These relationships apply when the kinetic and potential energy changes and the heat losses of
the working fluid while in the turbine are negligible. For most practical applications, these are
valid assumptions. However, to apply these relationships, one additional definition is necessary.
The steady flow performance of a turbine is idealized by assuming that in an ideal case the
working fluid does work reversibly by expanding at a constant entropy. This defines the socalled ideal turbine. In an ideal turbine, the entropy of the working fluid entering the turbine Sin
equals the entropy of the working fluid leaving the turbine.
Sin = Sout
sin = sout
where:
Sin
Sout
sin
sout
=
=
=
=
entropy of the working fluid entering the turbine (Btu/oR)

entropy of the working fluid leaving the turbine (Btu/oR)
specific entropy of the working fluid entering the turbine (Btu/lbm -oR)
specific entropy of the working fluid leaving the turbine (Btu/lbm -oR)
The reason for defining an ideal turbine is to provide a basis for analyzing the performance of
turbines. An ideal turbine performs the maximum amount of work theoretically possible.
Rev. 0
Page 79
HT-01
Thermodynamics
An actual turbine does less work because of friction losses in the blades, leakage past the blades
and, to a lesser extent, mechanical friction. Turbine efficiency t , sometimes called isentropic
turbine efficiency because an ideal turbine is defined as one which operates at constant entropy,
is defined as the ratio of the actual work done by the turbine Wt, actual to the work that would be
done by the turbine if it were an ideal turbine Wt,ideal.
Wt,actual
t
(1-26)
Wt,ideal
(hin
hout) actual
(hin
hout) ideal
(1-27)
where:
t
= turbine efficiency (no units)
Wt,actual
Wt,ideal
(hin - hout)actual
(hin - hout)ideal
=
=
=
=
actual work done by the turbine (ft-lbf)

work done by an ideal turbine (ft-lbf)
actual enthalpy change of the working fluid (Btu/lbm)
actual enthalpy change of the working fluid in an ideal turbine
(Btu/lbm)
In many cases, the turbine

efficiency t has been determined
independently. This permits the
actual work done to be calculated
directly by multiplying the turbine
efficiency t by the work done by
an ideal turbine under the same
conditions. For small turbines, the
turbine efficiency is generally 60%
to 80%; for large turbines, it is
generally about 90%.
The actual and idealized
performances of a turbine may be
compared conveniently using a T-s
diagram. Figure 27 shows such a
Figure 27 Comparison of Ideal and Actual Turbine Performances
comparison. The ideal case is a
constant entropy. It is represented
by a vertical line on the T-s diagram. The actual turbine involves an increase in entropy. The
smaller the increase in entropy, the closer the turbine efficiency t is to 1.0 or 100%.
HT-01
Page 80
Rev. 0
Thermodynamics
A pump is designed to move the working fluid by doing work on it. In the application of the
first law general energy equation to a simple pump under steady flow conditions, it is found that
the increase in the enthalpy of the working fluid Hout - Hin equals the work done by the pump,
Wp, on the working fluid.
Hout Hin Wp
(1-28)
m
(hout
hin)
w
p
(1-29)
where:
Hout
Hin
Wp
= enthalpy of the working fluid leaving the pump (Btu)

= enthalpy of the working fluid entering the pump (Btu)
= work done by the pump on the working fluid (ft-lbf)
hout
hin
= specific enthalpy of the working fluid leaving the pump (Btu/lbm)

= specific enthalpy of the working fluid entering the pump (Btu/lbm)
w
p
= power of pump (Btu/hr)
These relationships apply when the kinetic and potential energy changes and the heat losses of
the working fluid while in the pump are negligible. For most practical applications, these are
valid assumptions. It is also assumed that the working fluid is incompressible. For the ideal
case, it can be shown that the work done by the pump Wp is equal to the change in enthalpy
across the ideal pump.
Wp ideal = (Hout - Hin)ideal
(1-30)
w
p
(1-31)
ideal
= m
(hout - hin)ideal
where:
Wp
Hout
Hin
= work done by the pump on the working fluid (ft-lbf)

= enthalpy of the working fluid leaving the pump (Btu)
= enthalpy of the working fluid entering the pump (Btu)
w
p
= power of pump (Btu/hr)
hout
hin
= specific enthalpy of the working fluid leaving the pump (Btu/lbm)

= specific enthalpy of the working fluid entering the pump (Btu/lbm)
The reason for defining an ideal pump is to provide a basis for analyzing the performance of
actual pumps. A pump requires more work because of unavoidable losses due to friction and
fluid turbulence. The work done by a pump Wp is equal to the change in enthalpy across the
actual pump.
Rev. 0
Page 81
HT-01
Thermodynamics
Wp actual = (Hout - Hin)actual
(1-32)
w
p
(1-33)
actual
= m
(hout - hin)actual
Pump efficiency, p , is defined as the ratio of the work required by the pump if it were an ideal
pump wp, ideal to the actual work required by the pump wp, actual.
Wp, ideal
(1-34)
Wp, actual
Example:
A pump operating at 75% efficiency has an inlet specific enthalpy of 200 Btu/lbm. The
exit specific enthalpy of the ideal pump is 600 Btu/lbm. What is the exit specific
enthalpy of the actual pump?
Solution:
Using Equation 1-34:
p
wp, ideal
wp, actual
wp, ideal
wp, actual
(hout
p
hin) actual
hout, actual
hout, actual
(hout
(hout
hin) ideal
p
hin) ideal
hin, actual
p
(600 Btu/lbm
200 Btu/lbm)
.75
200 Btu/lbm
hout, actual = 533.3 Btu/lbm + 200 Btu/lbm

hout, actual = 733.3 Btu/lbm
HT-01
Page 82
Rev. 0
Thermodynamics
Pump efficiency, p , relates the work required by an ideal pump to the actual work required by
the pump; it relates the minimum amount of work theoretically possible to the actual work
required by the pump. However, the work required by a pump is normally only an intermediate
form of energy. Normally a motor or turbine is used to run the pump. Pump efficiency does
not account for losses in this motor or turbine. An additional efficiency factor, motor efficiency
m , is defined as the ratio of the actual work required by the pump to the electrical energy input
to the pump motor, when both are expressed in the same units.
Wp, actual
Wm, inC
where:
m
Wp, actual
Wm, in
C
=
=
=
=
motor efficiency (no units)

actual work required by the pump (ft-lbf)
electrical energy input to the pump motor (kw-hr)
conversion factor = 2.655 x 106 ft-lbf/kw-hr
Like pump efficiency p , motor efficiency m is always less than 1.0 or 100% for an actual
pump motor. The combination of pump efficiency p and motor efficiency m relates the ideal
pump to the electrical energy input to the pump motor.
m p
Wp, ideal
(1-35)
Wm, inC
where:
m
= motor efficiency (no units)
= pump efficiency (no units)
Wp, ideal
Wm, in
C
= ideal work required by the pump (ft-lbf)

= electrical energy input to the pump motor (kw-hr)
= conversion factor = 2.655 x 106 ft-lbf/kw-hr
A heat exchanger is designed to transfer heat between two working fluids. There are several heat
exchangers used in power plant steam cycles. In the steam generator or boiler, the heat source
(e.g., reactor coolant) is used to heat and vaporize the feedwater. In the condenser, the steam
exhausting from the turbine is condensed before being returned to the steam generator. In
addition to these two major heat exchangers, numerous smaller heat exchangers are used
throughout the steam cycle. Two primary factors determine the rate of heat transfer and the
temperature difference between the two fluids passing through the heat exchanger.
Rev. 0
Page 83
HT-01
Thermodynamics
In the application of the first law general energy equation to a simple heat exchanger under
steady flow conditions, it is found that the mass flow rates and enthalpies of the two fluids are
related by the following relationship.
m
1 (hout, 1
hin, 1)
m
2 (hout, 2
hin, 2)
(1-36)
where:
m
1
= mass flow rate of the working fluid 1 (lbm/hr)
m
2
= mass flow rate of the working fluid 2 (lbm/hr)
hout, 1
hin, 1
hout, 2
hin, 2
=
=
=
=
specific enthalpy of the working fluid 1 leaving the heat exchanger (Btu/lbm)
specific enthalpy of the working fluid 1 entering the heat exchanger (Btu/lbm)
specific enthalpy of the working fluid 2 leaving the heat exchanger (Btu/lbm)
specific enthalpy of the working fluid 2 entering the heat exchanger (Btu/lbm)
In the preceding sections we have discussed the Carnot cycle, cycle efficiencies, and component
efficiencies. In this section we will apply this information to allow us to compare and evaluate
various ideal and real cycles. This will allow us to determine how modifying a cycle will affect
the cycles available energy that can be extracted for work.
Since the efficiency of a Carnot cycle is solely dependent on the temperature of the heat source
and the temperature of the heat sink, it follows that to improve a cycles efficiency all we have
to do is increase the temperature of the heat source and decrease the temperature of the heat sink.
In the real world the ability to do this is limited by the following constraints.
1. For a real cycle the heat sink is limited by the fact that the "earth" is our final heat
sink. And therefore, is fixed at about 60F (520R).
2. The heat source is limited to the combustion temperatures of the fuel to be burned or
the maximum limits placed on nuclear fuels by their structural components (pellets,
cladding etc.). In the case of fossil fuel cycles the upper limit is ~3040F (3500R).
But even this temperature is not attainable due to the metallurgical restraints of the
boilers, and therefore they are limited to about 1500F (1960R) for a maximum heat
source temperature.
Using these limits to calculate the maximum efficiency attainable by an ideal Carnot cycle gives
the following.
HT-01
TSOURCE
TSINK
TSOURCE
1960 oR 520 oR
1960 oR
Page 84
73.5%
Rev. 0
Thermodynamics
This calculation indicates that the Carnot cycle, operating with ideal components under real world
constraints, should convert almost 3/4 of the input heat into work. But, as will be shown, this
ideal efficiency is well beyond the present capabilities of any real systems.
Heat Rejection
To understand why an efficiency of 73% is not possible we must analyze the Carnot cycle, then
compare the cycle using real and ideal components. We will do this by looking at the T-s
diagrams of Carnot cycles using both real and ideal components.
The energy added to a working fluid during the Carnot isothermal expansion is given by qs. Not
all of this energy is available for use by the heat engine since a portion of it (q r) must be rejected
to the environment. This is given by:
qr = To s in units of Btu/lbm,
(1-37)
where To is the average heat sink temperature of 520R. The available energy (A.E.) for the
Carnot cycle may be given as:
A.E. = qs - qr.
(1-38)
Substituting equation 1-37 for qr gives:

A.E. = qs - To s
in units of Btu/lbm.
(1-39)
and is equal to the area of the shaded

region labeled available energy in
Figure 28 between the temperatures
1962 and 520R. From Figure 28 it
can been seen that any cycle operating
at a temperature of less than 1962R
will be less efficient. Note that by
developing materials capable of
withstanding the stresses above
1962R, we could greatly add to the
energy available for use by the plant
cycle.
From equation 1-37, one can see why
the change in entropy can be defined
as a measure of the energy unavailable
to do work. If the temperature of the
heat sink is known, then the change in
entropy does correspond to a measure
of the heat rejected by the engine.
Rev. 0
Figure 28
Page 85
Carnot Cycle
HT-01
Thermodynamics
Figure 29 Carnot Cycle vs. Typical Power Cycle Available Energy
HT-01
Page 86
Rev. 0
Thermodynamics
Figure 29 is a typical power cycle employed by a fossil fuel plant. The working fluid is water,
which places certain restrictions on the cycle. If we wish to limit ourselves to operation at or
below 2000 psia, it is readily apparent that constant heat addition at our maximum temperature
of 1962R is not possible (Figure 29, 2 to 4). In reality, the nature of water and certain
elements of the process controls require us to add heat in a constant pressure process instead
(Figure 29, 1-2-3-4). Because of this, the average temperature at which we are adding heat is
far below the maximum allowable material temperature.
As can be seen, the actual available energy (area under the 1-2-3-4 curve, Figure 29) is less than
half of what is available from the ideal Carnot cycle (area under 1-2-4 curve, Figure 29)
operating between the same two temperatures. Typical thermal efficiencies for fossil plants are
on the order of 40% while nuclear plants have efficiencies of the order of 31%. Note that these
numbers are less than 1/2 of the maximum thermal efficiency of the ideal Carnot cycle calculated
earlier.
Figure 30 shows a proposed Carnot steam cycle superimposed on a T-s diagram. As shown, it
has several problems which make it undesirable as a practical power cycle. First a great deal of
pump work is required to compress a two phase mixture of water and steam from point 1 to the
saturated liquid state at point 2. Second, this same isentropic compression will probably result
in some pump cavitation in the feed system. Finally, a condenser designed to produce a twophase mixture at the outlet (point 1) would pose technical problems.
Figure 30 Ideal Carnot Cycle
Rev. 0
Page 87
HT-01
Thermodynamics
Early thermodynamic developments were centered around improving the performance of

contemporary steam engines. It was desirable to construct a cycle that was as close to being
reversible as possible and would better lend itself to the characteristics of steam and process
control than the Carnot cycle did. Towards this end, the Rankine cycle was developed.
The main feature of the Rankine cycle, shown in Figure 31, is that it confines the isentropic
compression process to the liquid phase only (Figure 31 points 1 to 2). This minimizes the
amount of work required to attain operating pressures and avoids the mechanical problems
associated with pumping a two-phase mixture. The compression process shown in figure 31
between points 1 and 2 is greatly exaggerated*. In reality, a temperature rise of only 1F occurs
in compressing water from 14.7 psig at a saturation temperature of 212F to 1000 psig.
Figure 31 Rankine Cycle
* The constant pressure lines converge rapidly in the subcooled or compressed

liquid region and it is difficult to distinguish them from the saturated liquid line
without artificially expanding them away from it.
In a Rankine cycle available and unavailable energy on a T-s diagram, like a T-s diagram of a
Carnot cycle, is represented by the areas under the curves. The larger the unavailable energy,
the less efficient the cycle.
HT-01
Page 88
Rev. 0
Thermodynamics
Figure 32
Rankine Cycle With Real v.s. Ideal
From the T-s diagram (Figure 32) it can also be seen that if an ideal component, in this case the
turbine, is replaced with a non-ideal component, the efficiency of the cycle will be reduced. This
is due to the fact that the non-ideal turbine incurs an increase in entropy which increases the area
under the T-s curve for the cycle. But the increase in the area of available energy (3-2-3,
Figure 32) is less than the increase in area for unavailable energy (a-3-3-b, Figure 32).
Figure 33 Rankine Cycle Efficiencies T-s
Rev. 0
Page 89
HT-01
Thermodynamics
The same loss of cycle efficiency can be seen when two Rankine cycles are compared (see Figure
33). Using this type of comparison, the amount of rejected energy to available energy of one
cycle can be compared to another cycle to determine which cycle is the most efficient, i.e. has
the least amount of unavailable energy.
An h-s diagram can also be
used to compare systems and
help determine their
efficiencies.
Like the T-s
diagram, the h-s diagram will
show (Figure 34) that
substituting non-ideal
components in place of ideal
components in a cycle, will
result in the reduction in the
cycles efficiency.
This is
because a change in enthalpy
(h) always occurs when work
is done or heat is added or
removed in an actual cycle
(non-ideal).
This deviation
Figure 34 h-s Diagram
from an ideal constant enthalpy
(vertical line on the diagram)
allows the inefficiencies of the cycle to be easily seen on a h-s diagram.
Typical Steam Cycle

Figure 35 shows a simplified version of the major components of a typical steam plant cycle.
This is a simplified version and does not contain the exact detail that may be found at most
power plants. However, for the purpose of understanding the basic operation of a power cycle,
further detail is not necessary.
The following are the processes that comprise the cycle:
HT-01
1-2:
Saturated steam from the steam generator is expanded in the high pressure (HP)
turbine to provide shaft work output at a constant entropy.
2-3:
The moist steam from the exit of the HP turbine is dried and superheated in the
moisture separator reheater (MSR).
3-4:
Superheated steam from the MSR is expanded in the low pressure (LP) turbine to
provide shaft work output at a constant entropy.
Page 90
Rev. 0
Thermodynamics
4-5:
Steam exhaust from the turbine is condensed in the condenser in which heat is
transferred to the cooling water under a constant vacuum condition.
5-6:
The feedwater is compressed as a liquid by the condensate and feedwater pump

and the feedwater is preheated by the feedwater heaters.
6-1:
Heat is added to the working fluid in the steam generator under a constant
pressure condition.
Figure 35
Typical Steam Cycle
The previous cycle can also be represented on a T-s diagram as was done with the ideal Carnot
and Rankine cycles. This is shown in Figure 36. The numbered points on the cycle correspond
to the numbered points on Figure 36.
It must be pointed out that the cycle we have just shown is an ideal cycle and does not exactly
represent the actual processes in the plant. The turbine and pumps in an ideal cycle are ideal
pumps and turbines and therefore do not exhibit an increase in entropy across them. Real pumps
and turbines would exhibit an entropy increase across them.
Rev. 0
Page 91
HT-01
Figure 36
Thermodynamics
Steam Cycle (Ideal)
Figure 37 is a T-s diagram of a cycle which more closely approximates actual plant processes.
The pumps and turbines in this cycle more closely approximate real pumps and turbines and thus
exhibit an entropy increase across them. Additionally, in this cycle, a small degree of subcooling
is evident in the condenser as shown by the small dip down to point 5. This small amount of
subcooling will decrease cycle efficiency since additional heat has been removed from the cycle
to the cooling water as heat rejected. This additional heat rejected must then be made up for in
the steam generator. Therefore, it can be seen that excessive condenser subcooling will decrease
cycle efficiency. By controlling the temperature or flow rate of the cooling water to the
condenser, the operator can directly effect the overall cycle efficiency.
Figure 37
HT-01
Steam Cycle (Real)
Page 92
Rev. 0
Thermodynamics
It is sometimes useful to plot on the Mollier diagram the processes that occur during the cycle.
This is done on Figure 38. The numbered points on Figure 38 correspond to the numbered points
on Figures 35 and 36. Because the Mollier diagram is a plot of the conditions existing for water
in vapor form, the portions of the plot which fall into the region of liquid water do not show up
on the Mollier diagram. The following conditions were used in plotting the curves on Figure 38.
Point 1:
Saturated steam at 540oF
Point 2:
82.5% quality at exit of HP turbine
Point 3:
Temperature of superheated steam is 440oF
Point 4:
Condenser vacuum is 1 psia
The solid lines on Figure 38 represent the conditions for a cycle which uses ideal turbines as
verified by the fact that no entropy change is shown across the turbines. The dotted lines on
Figure 38 represent the path taken if real turbines were considered, in which case an increase in
entropy is evident.
HT-01
Page 94
Rev. 0
Thermodynamics
Causes of Inefficiency
In the preceeding sections, cycle and component efficiencies have been discussed, but the actual
causes or reasons for the inefficiencies have not been explained. In this section we will compare
some of the types and causes for the inefficiencies of real components and cycles to that of their
"ideal" counterparts.
Components
In real systems, a percentage of the overall cycle inefficiency is due to the losses by the
individual components. Turbines, pumps, and compressors all behave non-ideally due to
heat losses, friction and windage losses. All of these losses contribute to the nonisentropic behavior of real equipment. As explained previously (Figures 24, 25) these
losses can be seen as an increase in the systems entropy or amount of energy that is
unavailable for use by the cycle.
Cycles
In real systems, a second source of inefficiencies is from the compromises made due to
cost and other factors in the design and operation of the cycle. Examples of these types
of losses are: In a large power generating station the condensers are designed to subcool
the liquid by 8-10F. This subcooling allows the condensate pumps to pump the water
forward without cavitation. But, each degree of subcooling is energy that must be put
back by reheating the water, and this heat (energy) does no useful work and therefore
increases the inefficiency of the cycle. Another example of a loss due to a systems
design is heat loss to the environment, i.e. thin or poor insulation. Again this is energy
lost to the system and therefore unavailable to do work. Friction is another real world
loss, both resistance to fluid flow and mechanical friction in machines. All of these
contribute to the systems inefficiency.
Rev. 0
Page 95
HT-01
Thermodynamics
Summary
Second Law of Thermodynamics Summary
Plancks statement of the Second Law of Thermodynamics is:

It is impossible to construct an engine that will work in a
complete cycle and produce no other effect except the raising of
a weight and the cooling of a heat reservoir.
The Second Law of Thermodynamics demonstrates that the maximum possible

efficiency of a system is the Carnot efficiency written as:
= (TH - TC)/TH
The maximum efficiency of a closed cycle can be determined by calculating the

efficiency of a Carnot cycle operating between the same value of high and low
temperatures.
The efficiency of a component can be calculated by comparing the work

produced by the component to the work that would have been produced by an
ideal component operating isentropically between the same inlet and outlet
conditions.
An isentropic expansion or compression process will be represented as a vertical

line on a T-s or h-s diagram. A real expansion or compression process will look
similar, but will be slanted slightly to the right.
Efficiency will be decreased by:

Presence of friction
Heat losses
Cycle inefficiencies
HT-01
Page 96
Rev. 0
Thermodynamics
COMPRESSION PROCESSES
C OMPRESSION PROCESSES
Compression and pressurization processes are very common in many types of
industrial plants. These processes vary from being the primary function of a
piece of equipment, such as an air compressor, to an incidental result of another
process, such as filling a tank with water without first opening the valve.
EO 1.32
Apply the ideal gas laws to SOLVE for the unknown

pressure, temperature, or volume.
EO 1.33
DESCRIB E when a fluid may be considered to be

incompressible.
EO 1.34
CALCULATE the work done in constant pressure and

constant volume processes.
EO 1.35
DESCRIB E the effects of pressure changes on confined

fluids.
EO 1.36
DESCRIB E the effects of temperature changes on

confined fluids.
Boyle's and Charles' Laws

The results of certain experiments with gases at relatively low pressure led Robert Boyle to
formulate a well-known law. It states that:
the pressure of a gas expanding at constant temperature varies inversely to the
volume, or
(P1)(V1) = (P2)(V2) = (P3)(V3) = constant.
(1-40)
Charles, also as the result of experimentation, concluded that:

the pressure of a gas varies directly with temperature when the volume is held
constant, and the volume varies directly with temperature when the pressure is
held constant, or
Rev. 0
V1
T1
V2
T2
or
P1
T1
P2
T2
(1-41)
Page 97
HT-01
Thermodynamics
Ideal Gas Law

By combining the results of Charles' and Boyle's experiments, the relationship
Pv
T
constant
(1-42)
may be obtained. The constant in the above equation is called the ideal gas constant and is
designated by R; thus the ideal gas equation becomes
Pv = RT
(1-43)
where the pressure and temperature are absolute values. The values of the ideal gas constant
(R) for several of the more common gases are given in Figure 39.
Figure 39
Ideal Gas Constant Values
The individual gas constant (R) may be obtained by dividing the universal gas constant (Ro) by
Ro
the molecular weight (MW) of the gas, R
. The units of R must always be consistent
MW
with the units of pressure, temperature, and volume used in the gas equation. No real gases
follow the ideal gas law or equation completely. At temperatures near a gases boiling point,
increases in pressure will cause condensation to take place and drastic decreases in volume. At
very high pressures, the intermolecular forces of a gas are significant. However, most gases are
in approximate agreement at pressures and temperatures above their boiling point.
HT-01
Page 98
Rev. 0
Thermodynamics
The ideal gas law is utilized by engineers working with gases because it is simple to use and
approximates real gas behavior. Most physical conditions of gases used by man fit the above
description. Perhaps the most common use of gas behavior studied by engineers is that of the
compression process using ideal gas approximations. Such a compression process may occur
at constant temperature (pV = constant), constant volume, or adiabatic (no heat transfer).
Whatever the process, the amount of work that results from it depends upon the process, as
brought out in the discussion on the First Law of Thermodynamics. The compression process
using ideal gas considerations results in work performed on the system and is essentially the area
under a P-V curve. As can be seen in Figure 40, different amounts of work result from different
ideal gas processes such as constant temperature and constant pressure.
Figure 40
Pressure-Volume Diagram
Fluid
A fluid is any substance that conforms to the shape of its container. It may be either a liquid
or a gas.
Compressibility of Fluids
Usually a fluid may be considered incompressible when the velocity of the fluid is greater than
one-third of the speed of sound for the fluid, or if the fluid is a liquid. The treatment of a fluid
that is considered incompressible is easy because the density is assumed to be constant, giving
a simple relationship for the state of the substance. The variation of density of the fluid with
changes in pressure is the primary factor considered in deciding whether a fluid is
incompressible.
Rev. 0
Page 99
HT-01
Thermodynamics
Fluids that are compressible have much more complex equations to deal with, due to density
changes, and have property relationships that vary more rapidly than incompressible fluids. In
addition, fixing the state of a liquid can be done easily by knowing its temperature and pressure.
Once the substance becomes a gas, the process becomes more difficult.
Constant Pressure Process

To determine the work done in a constant pressure process, the following equation is used:
W1-2 = P(V)
(1-44)
Constant Volume Process

The solution of Equation 1-45 for a constant volume process is also not difficult. The work
done in a constant volume process is the product of the volume and the change in pressure.
W1-2 = V(P)
(1-45)
In addition to gases, Equation 1-45 also applies to liquids. The power requirement for pumps
that move incompressible liquids (such as water) can be determined from Equation 1-44.
Replacing the volume (V) with the product of the specific volume and the mass yields Equation
1-45.
W1-2 = mv (P)
(1-46)
Taking the time rate of change of both sides of Equation 1-46 determines the power
requirements of the pump.
W1 2
mv(P)
(1-47)
Effects of Pressure Changes on Fluid Properties

The predominant effect of an increase in pressure in a compressible fluid, such as a gas, is an
increase in the density of the fluid. An increase in the pressure of an incompressible fluid will
not have a significant effect on the density. For example, increasing the pressure of 100 F
water from 15 psia to 15,000 psia will only increase the density by approximately 6%.
Therefore, in engineering calculations, it is assumed that incompressible fluids' density remain
constant.
HT-01
Page 100
Rev. 0
Thermodynamics
Effects of Temperature Changes on Fluid Properties

An increase in temperature will tend to decrease the density of any fluid. If the fluid is confined
in a container of fixed volume, the effect of a temperature change will depend on whether the
fluid is compressible.
If the fluid is a gas, it will respond to a temperature change in a manner predicted by the ideal
gas laws. A 5% increase in absolute temperature will result in a 5% increase in the absolute
pressure.
If the fluid is an incompressible liquid in a closed container, an increase in the temperature will
have a tremendously greater and potentially catastrophic effect. As the fluid temperature
increases, it tries to expand, but expansion is prevented by the walls of the container. Because
the fluid is incompressible, this results in a tremendous increase in pressure for a relatively
minor temperature change. The change in specific volume for a given change in temperature
is not the same at various beginning temperatures. Resultant pressure changes will vary. A
useful thumb rule for water is that pressure in a water-solid system will increase about 100 psi
for every 1 F increase in temperature.
Rev. 0
Page 101
HT-01
Thermodynamics
Summary
Compression Processes Summary
The ideal gas law can be used to determine how the properties of pressure,
temperature, and volume will be related during compression processes.
Pv = R T
A fluid may be considered incompressible if one of two conditions is true:

The fluid is a liquid.
The fluid is a gas with a velocity greater than one-third of the speed of
sound in the gas.
The work for certain types of processes can be determined as follows:

Constant pressure process
Constant volume process
HT-01
Page 102
W1-2 = P(V)
W1-2 = V(P)
Rev. 0
Appendix A
Therm odynam ics
Thermodynamics
APPENDIX A
Rev. 0
Page A-2
HT-01
Thermodynamics
APPENDIX A
Rev. 0
Page A-4
HT-01
Thermodynamics
APPENDIX A
Rev. 0
Page A-6
HT-01
Thermodynamics
APPENDIX A
Rev. 0
Page A-8
HT-01
DOE-HDBK-1012/2-92
JUNE 1992

AND FLUID FLOW
Volume 2 of 3
FSC-6910

Available to DOE and DOE contractors from the Office of Scientific and Technical
Information. P. O. Box 62, Oak Ridge, TN 37831; prices available from (615) 5768401. FTS 626-8401.
Department of Commerce, 5285 Port Royal Rd., Springfield, VA 22161.
ABSTRACT
Equation
Rev. 0
HT
FOREWORD
Rev. 0
HT
OVERVIEW
Volume 1 of 3
calculated.
Volume 2 of 3
Volume 3 of 3
Rev. 0
HT

Rev. 0
HT

AND FLUID FLOW,
Module 2
Heat Transfer
Heat Transfer
TABLE OF CONTENTS
TABLE OF CONTENTS
LIST OF FIGURES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iv
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
HEAT TRANSFER TERMINOLOGY . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Heat and Temperature . . . . . . . . . .
Heat and Work . . . . . . . . . . . . . . .
Modes of Transferring Heat . . . . . .
Heat Flux . . . . . . . . . . . . . . . . . . .
Thermal Conductivity . . . . . . . . . . .
Log Mean Temperature Difference .
Convective Heat Transfer Coefficient
Overall Heat Transfer Coefficient . .
Bulk Temperature . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
2
2
3
3
3
4
4
4
5
CONDUCTION HEAT TRANSFER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Conduction . . . . . . . . . . . . . . . . . .
Conduction-Rectangular Coordinates
Equivalent Resistance Method . . . . .
Electrical Analogy . . . . . . . . . . . . .
Conduction-Cylindrical Coordinates .
Summary . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 6
. 7
. 9
10
11
17
CONVECTION HEAT TRANSFER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

Convection . . . . . . . . . . . . . . . .
Overall Heat Transfer Coefficient
Convection Heat Transfer . . . . . .
Summary . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
18
20
23
25
RADIANT HEAT TRANSFER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

Thermal Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Black Body Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Emissivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Rev. 0
Page i
HT-02
TABLE OF CONTENTS
Heat Transfer

Radiation Configuration Factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
HEAT EXCHANGERS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Heat Exchangers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Parallel and Counter-Flow Designs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Non-Regenerative Heat Exchanger . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Regenerative Heat Exchanger . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Cooling Towers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Log Mean Temperature Difference Application to Heat Exchangers . . . . . . . . .
Overall Heat Transfer Coefficient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
30
31
34
34
35
36
37
39
BOILING HEAT TRANSFER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40

Boiling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nucleate Boiling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Bulk Boiling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Film Boiling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Departure from Nucleate Boiling and Critical Heat Flux . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
40
40
41
41
42
43
HEAT GENERATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Heat Generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Flux Profiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Thermal Limits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Average Linear Power Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Maximum Local Linear Power Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Temperature Profiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Volumetric Thermal Source Strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Fuel Changes During Reactor Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
44
46
47
47
48
48
50
50
51
DECAY HEAT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Reactor Decay Heat Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Calculation of Decay heat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Decay Heat Limits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Decay Heat Removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
HT-02
Page ii
52
53
55
56
57
Rev. 0
Heat Transfer
LIST OF FIGURES
LIST OF FIGURES
Figure 1
Conduction Through a Slab . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Figure 2
Equivalent Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Figure 3
Cross-sectional Surface Area of a Cylindrical Pipe . . . . . . . . . . . . . . . . 11
Figure 4
Composite Cylindrical Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Figure 5
Pipe Insulation Problem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Figure 6
Overall Heat Transfer Coefficient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Figure 7
Combined Heat Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Figure 8
Typical Tube and Shell Heat Exchanger . . . . . . . . . . . . . . . . . . . . . . . . 31
Figure 9
Fluid Flow Direction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
Figure 10
Heat Exchanger Temperature Profiles . . . . . . . . . . . . . . . . . . . . . . . . . . 33
Figure 11
Non-Regenerative Heat Exchanger . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Figure 12
Regenerative Heat Exchanger . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Figure 13
Boiling Heat Transfer Curve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Figure 14
Axial Flux Profile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Figure 15
Radial Flux Profile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Figure 16
Axial Temperature Profile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Figure 17
Radial Temperature Profile Across a Fuel Rod and

Coolant Channel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Rev. 0
Page iii
HT-02
LIST OF TABLES
Heat Transfer
LIST OF TABLES
NONE
HT-02
Page iv
Rev. 0
Heat Transfer
REFERENCES
REFERENCES
VanWylen, G. J. and Sonntag, R. E., Fundamentals of Classical Thermodynamics
SI Version, 2nd Edition, John Wiley and Sons, New York, ISBN 0-471-04188-2.
Kreith, Frank, Principles of Heat Transfer, 3rd Edition, Intext Press, Inc., New
York, ISBN 0-7002-2422-X.
Holman, J. P., Thermodynamics, McGraw-Hill, New York.
Streeter, Victor, L., Fluid Mechanics, 5th Edition, McGraw-Hill, New York, ISBN
07-062191-9.
Rynolds, W. C. and Perkins, H. C., Engineering Thermodynamics, 2nd Edition,
McGraw-Hill, New York, ISBN 0-07-052046-1.
Meriam, J. L., Engineering Mechanics Statics and Dynamics, John Wiley and
Sons, New York, ISBN 0-471-01979-8.
Schneider, P. J. Conduction Heat Transfer, Addison-Wesley Pub. Co., California.
Holman, J. P., Heat Transfer, 3rd Edition, McGraw-Hill, New York.
Knudsen, J. G. and Katz, D. L., Fluid Dynamics and Heat Transfer, McGraw-Hill,
New York.
Kays, W. and London, A. L., Compact Heat Exchangers, 2nd Edition, McGrawHill, New York.
Weibelt, J. A., Engineering Radiation Heat Transfer, Holt, Rinehart and Winston
Publish., New York.
Sparrow, E. M. and Cess, R. E., Radiation Heat Transfer, Brooks/Cole Publish.
Co., Belmont, California.
Hamilton, D. C. and Morgan, N. R., Radiant-Interchange Configuration Factors,
Tech. Note 2836, National Advisory Committee for Aeronautics.
McDonald, A. T. and Fox, R. W., Introduction to Fluid mechanics, 2nd Edition,
John Wiley and Sons, New York, ISBN 0-471-01909-7.
Rev. 0
Page v
HT-02
REFERENCES
Heat Transfer
REFERENCES (Cont.)
Zucrow, M. J. and Hoffman, J. D., Gas Dynamics Vol.b1, John Wiley and Sons,
New York, ISBN 0-471-98440-X.
Crane Company, Flow of Fluids Through Valves, Fittings, and Pipe, Crane Co.
Technical Paper No. 410, Chicago, Illinois, 1957.
Esposito, Anthony, Fluid Power with Applications, Prentice-Hall, Inc., New
Jersey, ISBN 0-13-322701-4.
Beckwith, T. G. and Buck, N. L., Mechanical Measurements, Addison-Wesley
Publish Co., California.
Wallis, Graham, One-Dimensional Two-Phase Flow, McGraw-Hill, New York,
1969.
Kays, W. and Crawford, M. E., Convective Heat and Mass Transfer, McGrawHill, New York, ISBN 0-07-03345-9.
Collier, J. G., Convective Boiling and Condensation, McGraw-Hill, New York,
ISBN 07-084402-X.
Academic Program for Nuclear Power Plant Personnel, Volumes III and IV,
Columbia, MD: General Physics Corporation, Library of Congress Card #A
326517, 1982.
Faires, Virgel Moring and Simmang, Clifford Max, Thermodynamics, MacMillan
Publishing Co. Inc., New York.
HT-02
Page vi
Rev. 0
Heat Transfer
OBJECTIVES
TERMINAL OBJECTIVE
1.0
Given the operating conditions of a thermodynamic system and the necessary

formulas, EVALUATE the heat transfer processes which are occurring.
ENABLING OBJECTIVES
1.1
DESCRIBE the difference between heat and temperature.
1.2
DESCRIBE the difference between heat and work.
1.3
DESCRIBE the Second Law of Thermodynamics and how it relates to heat transfer.
1.4
DESCRIBE the three modes of heat transfer.
1.5
DEFINE the following terms as they relate to heat transfer:

a.
Heat flux
b.
Thermal conductivity
c.
Log mean temperature difference
d.
Convective heat transfer coefficient
e.
Overall heat transfer coefficient
f.
Bulk temperature
1.6
Given Fouriers Law of Conduction, CALCULATE the conduction heat flux in a

rectangular coordinate system.
1.7
Given the formula and the necessary values, CALCULATE the equivalent thermal
resistance.
1.8
Given Fouriers Law of Conduction, CALCULATE the conduction heat flux in a

cylindrical coordinate system.
1.9
Given the formula for heat transfer and the operating conditions of the system,
CALCULATE the rate of heat transfer by convection.
1.10
DESCRIBE how the following terms relate to radiant heat transfer:

a.
Black body radiation
b.
Emissivity
c.
Radiation configuration factor
Rev. 0
Page vii
HT-02
OBJECTIVES
Heat Transfer

1.11
DESCRIBE the difference in the temperature profiles for counter-flow and parallel flow
heat exchangers.
1.12
DESCRIBE the differences between regenerative and non-regenerative heat exchangers.
1.13
Given the temperature changes across a heat exchanger, CALCULATE the log mean
temperature difference for the heat exchanger.
1.14
Given the formulas for calculating the conduction and convection heat transfer
coefficients, CALCULATE the overall heat transfer coefficient of a system.
1.15
DESCRIBE the process that occurs in the following regions of the boiling heat transfer
curve:
a.
Nucleate boiling
b.
Partial film boiling
c.
Film boiling
d.
Departure from nucleate boiling (DNB)
e.
Critical heat flux
HT-02
Page viii
Rev. 0
Heat Transfer
OBJECTIVES
TERMINAL OBJECTIVE
2.0
Given the operating conditions of a typical nuclear reactor, DESCRIBE the heat transfer
processes which are occurring.
ENABLING OBJECTIVES
2.1
DESCRIBE the power generation process in a nuclear reactor core and the factors that
affect the power generation.
2.2
DESCRIBE the relationship between temperature, flow, and power during operation of
a nuclear reactor.
2.3

a.
Nuclear enthalpy rise hot channel factor
b.
Average linear power density
c.
Nuclear heat flux hot channel factor
d.
Heat generation rate of a core
e.
Volumetric thermal source strength
2.4
CALCULATE the average linear power density for an average reactor core fuel rod.
2.5
DESCRIBE a typical reactor core axial and radial flux profile.
2.6
DESCRIBE a typical reactor core fuel rod axial and radial temperature profile.
2.7
DEFINE the term decay heat.
2.8
Given the operating conditions of a reactor core and the necessary formulas,
CALCULATE the core decay heat generation.
2.9
DESCRIBE two categories of methods for removing decay heat from a reactor core.
Rev. 0
Page ix
HT-02
Heat Transfer
HT-02
Page x
Rev. 0
Heat Transfer
HEAT TRANSFER TERMINOLOGY

To understand and communicate in the thermal science field, certain terms and
expressions must be learned in heat transfer.
EO 1.1
DESCRIBE the difference between heat and temperature.
EO 1.2
DESCRIBE the difference between heat and work.
EO 1.3
DESCRIBE the Second Law of Thermodynamics and

how it relates to heat transfer.
EO 1.4
DESCRIBE the three modes of heat transfer.
EO 1.5
DEFINE the following terms as they relate to heat

transfer:
a.
Heat flux
b.
Thermal conductivity
c.
Log mean temperature difference
d.
Convective heat transfer coefficient
e.
Overall heat transfer coefficient
f.
Bulk temperature
Heat and Temperature

In describing heat transfer problems, students often make the mistake of interchangeably using
the terms heat and temperature. Actually, there is a distinct difference between the two.
Temperature is a measure of the amount of energy possessed by the molecules of a substance.
It is a relative measure of how hot or cold a substance is and can be used to predict the direction
of heat transfer. The symbol for temperature is T. The common scales for measuring
temperature are the Fahrenheit, Rankine, Celsius, and Kelvin temperature scales.
Heat is energy in transit. The transfer of energy as heat occurs at the molecular level as a result
of a temperature difference. Heat is capable of being transmitted through solids and fluids by
conduction, through fluids by convection, and through empty space by radiation. The symbol
for heat is Q. Common units for measuring heat are the British Thermal Unit (Btu) in the
English system of units and the calorie in the SI system (International System of Units).
Rev. 0
Page 1
HT-02
Heat Transfer
Heat and Work

Distinction should also be made between the energy terms heat and work. Both represent energy
in transition. Work is the transfer of energy resulting from a force acting through a distance.
Heat is energy transferred as the result of a temperature difference. Neither heat nor work are
thermodynamic properties of a system. Heat can be transferred into or out of a system and work
can be done on or by a system, but a system cannot contain or store either heat or work. Heat
into a system and work out of a system are considered positive quantities.
When a temperature difference exists across a boundary, the Second Law of Thermodynamics
indicates the natural flow of energy is from the hotter body to the colder body. The Second Law
of Thermodynamics denies the possibility of ever completely converting into work all the heat
supplied to a system operating in a cycle. The Second Law of Thermodynamics, described by
Max Planck in 1903, states that:
It is impossible to construct an engine that will work in a complete cycle and
produce no other effect except the raising of a weight and the cooling of a
reservoir.
The second law says that if you draw heat from a reservoir to raise a weight, lowering the weight
will not generate enough heat to return the reservoir to its original temperature, and eventually
the cycle will stop. If two blocks of metal at different temperatures are thermally insulated from
their surroundings and are brought into contact with each other the heat will flow from the hotter
to the colder. Eventually the two blocks will reach the same temperature, and heat transfer will
cease. Energy has not been lost, but instead some energy has been transferred from one block
to another.
Modes of Transferring Heat

Heat is always transferred when a temperature difference exists between two bodies. There are
three basic modes of heat transfer:
Conduction involves the transfer of heat by the interactions of atoms or molecules of a
material through which the heat is being transferred.
Convection involves the transfer of heat by the mixing and motion of macroscopic
portions of a fluid.
Radiation, or radiant heat transfer, involves the transfer of heat by electromagnetic
radiation that arises due to the temperature of a body.
The three modes of heat transfer will be discussed in greater detail in the subsequent chapters
of this module.
HT-02
Page 2
Rev. 0
Heat Transfer
Heat Flux
. Common units for heat
The rate at which heat is transferred is represented by the symbol Q
transfer rate is Btu/hr. Sometimes it is important to determine the heat transfer rate per unit area,
. Units for heat flux are Btu/hr-ft2. The heat flux can be
or heat flux, which has the symbol Q
determined by dividing the heat transfer rate by the area through which the heat is being
transferred.
Q
(2-1)
A
where:
= heat flux (Btu/hr-ft2)
= heat transfer rate (Btu/hr)
= area (ft2)
Thermal Conductivity
The heat transfer characteristics of a solid material are measured by a property called the thermal
conductivity (k) measured in Btu/hr-ft-oF. It is a measure of a substances ability to transfer heat
through a solid by conduction. The thermal conductivity of most liquids and solids varies with
temperature. For vapors, it depends upon pressure.
Log Mean Temperature Difference

In heat exchanger applications, the inlet and outlet temperatures are commonly specified based
on the fluid in the tubes. The temperature change that takes place across the heat exchanger from
the entrance to the exit is not linear. A precise temperature change between two fluids across
the heat exchanger is best represented by the log mean temperature difference (LMTD or Tlm),
defined in Equation 2-2.
T1m
(T2
T1)
(2-2)
ln(T2 / T1)
where:
T2 =
T1 =
Rev. 0
the
the
the
the
larger temperature difference between the two fluid streams at either

entrance or the exit to the heat exchanger
smaller temperature difference between the two fluid streams at either
entrance or the exit to the heat exchanger
Page 3
HT-02
Heat Transfer
Convective Heat Transfer Coefficient

The convective heat transfer coefficient (h), defines, in part, the heat transfer due to convection.
The convective heat transfer coefficient is sometimes referred to as a film coefficient and
represents the thermal resistance of a relatively stagnant layer of fluid between a heat transfer
surface and the fluid medium. Common units used to measure the convective heat transfer
coefficient are Btu/hr - ft2 - oF.

In the case of combined heat transfer, it is common practice to relate the total rate of heat
), the overall cross-sectional area for heat transfer (Ao), and the overall temperature
transfer ( Q
difference (To) using the overall heat transfer coefficient (Uo). The overall heat transfer
coefficient combines the heat transfer coefficient of the two heat exchanger fluids and the thermal
conductivity of the heat exchanger tubes. Uo is specific to the heat exchanger and the fluids that
are used in the heat exchanger.
UoAoT0
(2-3)
where:
the rate heat of transfer (Btu/hr)
Uo
the overall heat transfer coefficient (Btu/hr - ft2 - oF)
Ao
the overall cross-sectional area for heat transfer (ft2)
To
the overall temperature difference (oF)
Bulk Temperature
The fluid temperature (Tb), referred to as the bulk temperature, varies according to the details of
the situation. For flow adjacent to a hot or cold surface, Tb is the temperature of the fluid that
is "far" from the surface, for instance, the center of the flow channel. For boiling or
condensation, Tb is equal to the saturation temperature.
HT-02
Page 4
Rev. 0
Heat Transfer
Summary
Heat Transfer Terminology Summary

Heat is energy transferred as a result of a temperature difference.
Temperature is a measure of the amount of molecular energy contained
in a substance.
Work is a transfer of energy resulting from a force acting through a
distance.
The Second Law of Thermodynamics implies that heat will not transfer
from a colder to a hotter body without some external source of energy.
Conduction involves the transfer of heat by the interactions of atoms or
molecules of a material through which the heat is being transferred.
Convection involves the transfer of heat by the mixing and motion of
macroscopic portions of a fluid.
Radiation, or radiant heat transfer, involves the transfer of heat by
electromagnetic radiation that arises due to the temperature of a body.
Heat flux is the rate of heat transfer per unit area.
Thermal conductivity is a measure of a substances ability to transfer heat
through itself.
Log mean temperature difference is the T that most accurately represents the
T for a heat exchanger.
The local heat transfer coefficient represents a measure of the ability to transfer
heat through a stagnant film layer.
The overall heat transfer coefficient is the measure of the ability of a heat
exchanger to transfer heat from one fluid to another.
The bulk temperature is the temperature of the fluid that best represents the
majority of the fluid which is not physically connected to the heat transfer site.
Rev. 0
Page 5
HT-02
CONDUCTION HEAT TRANSFER
Heat Transfer

Conduction heat transfer is the transfer of thermal energy by interactions between
adjacent atoms and molecules of a solid.
EO 1.6
Given Fouriers Law of Conduction, CALCULATE the

conduction heat flux in a rectangular coordinate system.
EO 1.7
Given the formula and the necessary values,

CALCULATE the equivalent thermal resistance.
EO 1.8
Given Fouriers Law of Conduction, CALCULATE the

conduction heat flux in a cylindrical coordinate system.
Conduction
Conduction involves the transfer of heat by the interaction between adjacent molecules of a
material. Heat transfer by conduction is dependent upon the driving "force" of temperature
difference and the resistance to heat transfer. The resistance to heat transfer is dependent upon
the nature and dimensions of the heat transfer medium. All heat transfer problems involve the
temperature difference, the geometry, and the physical properties of the object being studied.
In conduction heat transfer problems, the object being studied is usually a solid. Convection
problems involve a fluid medium. Radiation heat transfer problems involve either solid or fluid
surfaces, separated by a gas, vapor, or vacuum. There are several ways to correlate the geometry,
physical properties, and temperature difference of an object with the rate of heat transfer through
the object. In conduction heat transfer, the most common means of correlation is through
Fouriers Law of Conduction. The law, in its equation form, is used most often in its rectangular
or cylindrical form (pipes and cylinders), both of which are presented below.
HT-02
Rectangular
T
k A
(2-4)
Cylindrical
T
k A
(2-5)
Page 6
Rev. 0
Heat Transfer
where:
Q
A
x
r
T
k
=
=
=
=
=
=
rate of heat transfer (Btu/hr)

cross-sectional area of heat transfer (ft2)
thickness of slab (ft)
thickness of cylindrical wall (ft)
temperature difference (F)
thermal conductivity of slab (Btu/ft-hr-F)
The use of Equations 2-4 and 2-5 in determining the amount of heat transferred by conduction
is demonstrated in the following examples.
Conduction-Rectangular Coordinates
Example:
1000 Btu/hr is conducted through a section of insulating material shown in Figure 1 that
measures 1 ft2 in cross-sectional area. The thickness is 1 in. and the thermal conductivity
is 0.12 Btu/hr-ft-F. Compute the temperature difference across the material.
Figure 1
Rev. 0
Conduction Through a Slab
Page 7
HT-02
Heat Transfer
Solution:
Using Equation 2-4:
T
k A
Solving for T:
T
x
Q
k A
Btu 1
ft
1000

hr 12
Btu
2
0.12
1 ft
hr ft F
694 F
Example:
A concrete floor with a conductivity of 0.8 Btu/hr-ft-F measures 30 ft by 40 ft with a
thickness of 4 inches. The floor has a surface temperature of 70F and the temperature
beneath it is 60F. What is the heat flux and the heat transfer rate through the floor?
Solution:
Using Equations 2-1 and 2-4:
Q
A
T
k
Btu 10 F
0.8

hr ft F 0.333 ft
24
HT-02
Btu
hr ft 2
Page 8
Rev. 0
Heat Transfer
Using Equation 2-3:
T
k A
A
Q
24 Btu (1200 ft 2)
hr ft 2
28,800
Btu
hr
Equivalent Resistance Method

It is possible to compare heat transfer to current flow in electrical circuits. The heat transfer rate
may be considered as a current flow and the combination of thermal conductivity, thickness of
material, and area as a resistance to this flow. The temperature difference is the potential or
driving function for the heat flow, resulting in the Fourier equation being written in a form
similar to Ohms Law of Electrical Circuit Theory. If the thermal resistance term x/k is written
as a resistance term where the resistance is the reciprocal of the thermal conductivity divided by
the thickness of the material, the result is the conduction equation being analogous to electrical
systems or networks. The electrical analogy may be used to solve complex problems involving
both series and parallel thermal resistances. The student is referred to Figure 2, showing the
equivalent resistance circuit. A typical conduction problem in its analogous electrical form is
given in the following example, where the "electrical" Fourier equation may be written as
follows.
T
Rth
/A) (Btu/hr-ft2)
= Heat Flux ( Q
= Temperature Difference (oF)
Rth
= Thermal Resistance (x/k) (hr-ft2-oF/Btu)
(2-6)
where:
Rev. 0
Page 9
HT-02
Heat Transfer
Figure 2
Equivalent Resistance
Electrical Analogy
Example:
A composite protective wall is formed of a 1 in. copper plate, a 1/8 in. layer of asbestos,
and a 2 in. layer of fiberglass. The thermal conductivities of the materials in units of
Btu/hr-ft-oF are as follows: kCu = 240, kasb = 0.048, and kfib = 0.022. The overall
temperature difference across the wall is 500F. Calculate the thermal resistance of each
layer of the wall and the heat transfer rate per unit area (heat flux) through the composite
structure.
Solution:
RCu
xCu
Rasb
kCu
1 ft
1 in
12 in
Btu
240
hr ft F
0.000347
HT-02
hr ft 2 F
Btu
xasb
Rfib
kasb
1 ft
0.125 in
12 in
Btu
0.048
hr ft F
0.2170
hr ft 2 F
Btu
Page 10
xfib
kfib
1 ft
2 in
12 in
Btu
0.022
hr ft F
7.5758
hr ft 2 F
Btu
Rev. 0
Heat Transfer
Q
A
(Ti
(RCu
To )
Rasb
Rfib)
500F
(0.000347
64.2
0.2170
7.5758)
hr ft 2 F
Btu
Btu
hr ft 2
Conduction-Cylindrical Coordinates
Heat transfer across a rectangular solid is the most direct application of Fouriers law. Heat
transfer across a pipe or heat exchanger tube wall is more complicated to evaluate. Across a
cylindrical wall, the heat transfer surface area is continually increasing or decreasing. Figure 3
is a cross-sectional view of a pipe constructed of a homogeneous material.
Figure 3
Rev. 0
Cross-sectional Surface Area of a Cylindrical Pipe
Page 11
HT-02
Heat Transfer
The surface area (A) for transferring heat through the pipe (neglecting the pipe ends) is directly
proportional to the radius (r) of the pipe and the length (L) of the pipe.
A = 2rL
As the radius increases from the inner wall to the outer wall, the heat transfer area increases.
The development of an equation evaluating heat transfer through an object with cylindrical
geometry begins with Fouriers law Equation 2-5.
T
k A
From the discussion above, it is seen that no simple expression for area is accurate. Neither the
area of the inner surface nor the area of the outer surface alone can be used in the equation. For
a problem involving cylindrical geometry, it is necessary to define a log mean cross-sectional
area (Alm).
Alm
Aouter
Ainner
(2-7)
A
ln outer
Ainner
Substituting the expression 2rL for area in Equation 2-7 allows the log mean area to be
calculated from the inner and outer radius without first calculating the inner and outer area.
Alm
2 router L
2 rinner L
2 r
L
outer
ln
2 rinner L
r
rinner
outer
2 L
ln router
rinner
This expression for log mean area can be inserted into Equation 2-5, allowing us to calculate the
heat transfer rate for cylindrical geometries.
HT-02
Page 12
Rev. 0
Heat Transfer
T
k Alm
r
ri
k 2 L o
ln ro
ri
T
o
r
o
Ti
ri
2 k L (T)
ln (ro / ri)
(2-8)
where:
L
= length of pipe (ft)
ri
= inside pipe radius (ft)
ro
= outside pipe radius (ft)
Example:
A stainless steel pipe with a length of 35 ft has an inner diameter of 0.92 ft and an outer
diameter of 1.08 ft. The temperature of the inner surface of the pipe is 122oF and the
temperature of the outer surface is 118oF. The thermal conductivity of the stainless steel
is 108 Btu/hr-ft-oF.
Calculate the heat transfer rate through the pipe.
Calculate the heat flux at the outer surface of the pipe.
Solution:
2 k L (Th
Tc)
ln (ro/ri)
Btu
6.28 108
(35 ft) (122F
hr ft F
0.54 ft
ln
0.46 ft
5.92 x 105
Rev. 0
118F)
Btu
hr
Page 13
HT-02
Heat Transfer
Q
A
Q
2 ro L
Btu
hr
2 (3.14) (0.54 ft) (35 ft)
5.92 x 105
4985
Btu
hr ft 2
Example:
A 10 ft length of pipe with an inner radius of 1 in and an outer radius of 1.25 in has an
outer surface temperature of 250F. The heat transfer rate is 30,000 Btu/hr. Find the
interior surface temperature. Assume k = 25 Btu/hr-ft-F.
Solution:
2 k L (Th
Tc )
ln (ro / ri )
Solving for Th:

Th
ln (r / r )
Q
o i
2 k L
Tc
Btu 1.25 in
30,000
ln
hr
1 in
Btu
2 (3.14) 25
(10 ft)
hr ft F
250F
254F
The evaluation of heat transfer through a cylindrical wall can be extended to include a composite
body composed of several concentric, cylindrical layers, as shown in Figure 4.
HT-02
Page 14
Rev. 0
Heat Transfer
Figure 4
Rev. 0
Composite Cylindrical Layers
Page 15
HT-02
Heat Transfer
Example:
A thick-walled nuclear coolant pipe (ks = 12.5 Btu/hr-ft-F) with 10 in. inside diameter
(ID) and 12 in. outside diameter (OD) is covered with a 3 in. layer of asbestos insulation
(ka = 0.14 Btu/hr-ft-oF) as shown in Figure 5. If the inside wall temperature of the pipe
is maintained at 550F, calculate the heat loss per foot of length. The outside temperature
is 100F.
Figure 5
HT-02
Pipe Insulation Problem
Page 16
Rev. 0
Heat Transfer
Solution:
Q
L
2 (Tin
r
ln 2
r
1
k
s
To )
r
ln 3
r2
ka
2 (5500F
ln 6 in
5 in
12.5 Btu
hr ft oF
971
100 oF)
9 in
ln
6 in
Btu
0.14
hr ft oF
Btu
hr ft
Summary
Conduction Heat Transfer Summary
Conduction heat transfer is the transfer of thermal energy by interactions between

adjacent molecules of a material.
Fouriers Law of Conduction can be used to solve for rectangular and cylindrical
coordinate problems.
) is the heat transfer rate ( Q

) divided by the area (A).
Heat flux ( Q
Heat conductance problems can be solved using equivalent resistance formulas

analogous to electrical circuit problems.
Rev. 0
Page 17
HT-02
CONVECTION HEAT TRANSFER
Heat Transfer

Heat transfer by the motion and mixing of the molecules of a liquid or gas is
called convection.
EO 1.9
Given the formula for heat transfer and the operating

conditions of the system, CALCULATE the rate of heat
transfer by convection.
Convection
Convection involves the transfer of heat by the motion and mixing of "macroscopic" portions of
a fluid (that is, the flow of a fluid past a solid boundary). The term natural convection is used
if this motion and mixing is caused by density variations resulting from temperature differences
within the fluid. The term forced convection is used if this motion and mixing is caused by an
outside force, such as a pump. The transfer of heat from a hot water radiator to a room is an
example of heat transfer by natural convection. The transfer of heat from the surface of a heat
exchanger to the bulk of a fluid being pumped through the heat exchanger is an example of
forced convection.
Heat transfer by convection is more difficult to analyze than heat transfer by conduction because
no single property of the heat transfer medium, such as thermal conductivity, can be defined to
describe the mechanism. Heat transfer by convection varies from situation to situation (upon the
fluid flow conditions), and it is frequently coupled with the mode of fluid flow. In practice,
analysis of heat transfer by convection is treated empirically (by direct observation).
Convection heat transfer is treated empirically because of the factors that affect the stagnant film
thickness:
Fluid velocity
Fluid viscosity
Heat flux
Surface roughness
Type of flow (single-phase/two-phase)
Convection involves the transfer of heat between a surface at a given temperature (Ts) and fluid
at a bulk temperature (Tb). The exact definition of the bulk temperature (Tb) varies depending
on the details of the situation. For flow adjacent to a hot or cold surface, Tb is the temperature
of the fluid "far" from the surface. For boiling or condensation, Tb is the saturation temperature
of the fluid. For flow in a pipe, Tb is the average temperature measured at a particular crosssection of the pipe.
HT-02
Page 18
Rev. 0
Heat Transfer
The basic relationship for heat transfer by convection has the same form as that for heat transfer
by conduction:
(2-9)
Q
h A T
where:
= rate of heat transfer (Btu/hr)
= convective heat transfer coefficient (Btu/hr-ft2-F)
= surface area for heat transfer (ft2)
T = temperature difference (F)

The convective heat transfer coefficient (h) is dependent upon the physical properties of the fluid
and the physical situation. Typically, the convective heat transfer coefficient for laminar flow
is relatively low compared to the convective heat transfer coefficient for turbulent flow. This is
due to turbulent flow having a thinner stagnant fluid film layer on the heat transfer surface.
Values of h have been measured and tabulated for the commonly encountered fluids and flow
situations occurring during heat transfer by convection.
Example:
A 22 foot uninsulated steam line crosses a room. The outer diameter of the steam line
is 18 in. and the outer surface temperature is 280oF. The convective heat transfer
coefficient for the air is 18 Btu/hr-ft2-oF. Calculate the heat transfer rate from the pipe
into the room if the room temperature is 72oF.
Solution:
h A T
h (2 r L) T
Btu
18
2 (3.14) (0.75 ft) (22 ft) (280F

hr ft 2 F
3.88 x 105
72F)
Btu
hr
Many applications involving convective heat transfer take place within pipes, tubes, or some
similar cylindrical device. In such circumstances, the surface area of heat transfer normally given
in the convection equation ( Q

h A T ) varies as heat passes through the cylinder. In addition,
the temperature difference existing between the inside and the outside of the pipe, as well as the
temperature differences along the pipe, necessitates the use of some average temperature value
in order to analyze the problem. This average temperature difference is called the log mean
temperature difference (LMTD), described earlier.
Rev. 0
Page 19
HT-02
Heat Transfer
It is the temperature difference at one end of the heat exchanger minus the temperature difference
at the other end of the heat exchanger, divided by the natural logarithm of the ratio of these two
temperature differences. The above definition for LMTD involves two important assumptions:
(1) the fluid specific heats do not vary significantly with temperature, and (2) the convection heat
transfer coefficients are relatively constant throughout the heat exchanger.

Many of the heat transfer processes encountered in nuclear facilities involve a combination of
both conduction and convection. For example, heat transfer in a steam generator involves
convection from the bulk of the reactor coolant to the steam generator inner tube surface,
conduction through the tube wall, and convection from the outer tube surface to the secondary
side fluid.
In cases of combined heat transfer for a heat exchanger, there are two values for h. There is the
convective heat transfer coefficient (h) for the fluid film inside the tubes and a convective heat
transfer coefficient for the fluid film outside the tubes. The thermal conductivity (k) and
thickness (x) of the tube wall must also be accounted for. An additional term (Uo), called the
overall heat transfer coefficient, must be used instead. It is common practice to relate the total
) to the cross-sectional area for heat transfer (Ao) and the overall heat
rate of heat transfer ( Q
transfer coefficient (Uo). The relationship of the overall heat transfer coefficient to the individual
conduction and convection terms is shown in Figure 6.
Figure 6
HT-02
Page 20
Rev. 0
Heat Transfer
Recalling Equation 2-3:
UoAoTo
where Uo is defined in Figure 6.

An example of this concept applied to cylindrical geometry is illustrated by Figure 7, which
shows a typical combined heat transfer situation.
Figure 7
Combined Heat Transfer
Using the figure representing flow in a pipe, heat transfer by convection occurs between
temperatures T1 and T2; heat transfer by conduction occurs between temperatures T2 and T3; and
heat transfer occurs by convection between temperatures T3 and T4. Thus, there are three
processes involved. Each has an associated heat transfer coefficient, cross-sectional area for heat
transfer, and temperature difference. The basic relationships for these three processes can be
expressed using Equations 2-5 and 2-9.
Rev. 0
h1 A1 ( T1
T2 )
Page 21
HT-02
k
A (T
r lm 2
h2 A2 ( T3
Heat Transfer
T3 )
T4 )
To can be expressed as the sum of the T of the three individual processes.

To
( T1
T2 )
( T2
T3 )
( T3
T4 )
If the basic relationship for each process is solved for its associated temperature difference and
substituted into the expression for To above, the following relationship results.
To
Q
h1 A1
1
h2 A2
r
k Alm
This relationship can be modified by selecting a reference cross-sectional area Ao.

To
Q
Ao
A
o
h A
1 1
r Ao
k Alm
Ao
h2 A2
results in an equation in the form Q
Solving for Q
1
A
o
h A
1 1
r Ao
k Alm
Ao
h2 A2
Uo Ao To .
Ao To
where:
Uo
1
A
o
h A
1 1
r Ao
k Alm
(2-10)
Ao
h2 A2
Equation 2-10 for the overall heat transfer coefficient in cylindrical geometry is relatively
difficult to work with. The equation can be simplified without losing much accuracy if the tube
that is being analyzed is thin-walled, that is the tube wall thickness is small compared to the tube
diameter. For a thin-walled tube, the inner surface area (A1), outer surface area (A2), and log
mean surface area (A1m), are all very close to being equal. Assuming that A1, A2, and A1m are
equal to each other and also equal to Ao allows us to cancel out all the area terms in the
denominator of Equation 2-11.
HT-02
Page 22
Rev. 0
Heat Transfer
This results in a much simpler expression that is similar to the one developed for a flat plate heat
exchanger in Figure 6.
Uo
1
h1
1
r
k
(2-11)
1
h2
The convection heat transfer process is strongly dependent upon the properties of the fluid being
considered. Correspondingly, the convective heat transfer coefficient (h), the overall coefficient
(Uo), and the other fluid properties may vary substantially for the fluid if it experiences a large
temperature change during its path through the convective heat transfer device. This is especially
true if the fluids properties are strongly temperature dependent. Under such circumstances, the
temperature at which the properties are "looked-up" must be some type of average value, rather
than using either the inlet or outlet temperature value.
For internal flow, the bulk or average value of temperature is obtained analytically through the
use of conservation of energy. For external flow, an average film temperature is normally
calculated, which is an average of the free stream temperature and the solid surface temperature.
In any case, an average value of temperature is used to obtain the fluid properties to be used in
the heat transfer problem. The following example shows the use of such principles by solving
a convective heat transfer problem in which the bulk temperature is calculated.
Convection Heat Transfer

Example:
A flat wall is exposed to the environment. The wall is covered with a layer of insulation
1 in. thick whose thermal conductivity is 0.8 Btu/hr-ft-F. The temperature of the wall
on the inside of the insulation is 600F. The wall loses heat to the environment by
convection on the surface of the insulation. The average value of the convection heat
transfer coefficient on the insulation surface is 950 Btu/hr-ft2-F. Compute the bulk
temperature of the environment (Tb) if the outer surface of the insulation does not exceed
105F.
Rev. 0
Page 23
HT-02
Heat Transfer
Solution:
a.
) through the insulation.

Find heat flux ( Q
T
k A
Q
A
0.8
Btu 600F 105F
hr ft F
1 ft
1 in
12 in
4752
b.
Btu
hr ft 2
Find the bulk temperature of the environment.
Q
(Tins
Tb)
Tb
h A (Tins
Tb)
Q
h A
Tins
Q
h
Btu
hr ft 2
Btu
950
hr ft 2 F
4752
HT-02
Tb
105F
Tb
100 F
Page 24
Rev. 0
Heat Transfer
Summary
Convection Heat Transfer Summary
Convection heat transfer is the transfer of thermal energy by the mixing and
motion of a fluid or gas.
Whether convection is natural or forced is determined by how the medium

is placed into motion.
When both convection and conduction heat transfer occurs, the overall heat
transfer coefficient must be used to solve problems.
The heat transfer equation for convection heat transfer is Q
Rev. 0
Page 25
hAT .
HT-02
RADIATION HEAT TRANSFER
Heat Transfer
RADIANT HEAT TRANSFER

Radiant heat transfer is thermal energy transferred by means of electromagnetic
waves or particles.
EO 1.10
DESCRIBE how the following terms relate to radiant

heat transfer:
a.
Black body radiation
b.
Emissivity
c.
Radiation configuration factor
Thermal Radiation
Radiant heat transfer involves the transfer of heat by electromagnetic radiation that arises due to
the temperature of a body. Most energy of this type is in the infra-red region of the
electromagnetic spectrum although some of it is in the visible region. The term thermal radiation
is frequently used to distinguish this form of electromagnetic radiation from other forms, such
as radio waves, x-rays, or gamma rays. The transfer of heat from a fireplace across a room in
the line of sight is an example of radiant heat transfer.
Radiant heat transfer does not need a medium, such as air or metal, to take place. Any material
that has a temperature above absolute zero gives off some radiant energy. When a cloud covers
the sun, both its heat and light diminish. This is one of the most familiar examples of heat
transfer by thermal radiation.
Black Body Radiation

A body that emits the maximum amount of heat for its absolute temperature is called a black
body. Radiant heat transfer rate from a black body to its surroundings can be expressed by the
following equation.
Q
AT 4
(2-12)
where:
HT-02
=
Q
heat transfer rate (Btu/hr)
Stefan-Boltzman constant (0.174 Btu/hr-ft2-R4)
surface area (ft2)
temperature (R)
Page 26
Rev. 0
Heat Transfer
Two black bodies that radiate toward each other have a net heat flux between them. The net
flow rate of heat between them is given by an adaptation of Equation 2-12.
4
4
Q
A ( T1
T2 )
where:
A
surface area of the first body (ft2)
T1
temperature of the first body (R)
T2
temperature of the second body (R)
All bodies above absolute zero temperature radiate some heat. The sun and earth both radiate
heat toward each other. This seems to violate the Second Law of Thermodynamics, which states
that heat cannot flow from a cold body to a hot body. The paradox is resolved by the fact that
each body must be in direct line of sight of the other to receive radiation from it. Therefore,
whenever the cool body is radiating heat to the hot body, the hot body must also be radiating
heat to the cool body. Since the hot body radiates more heat (due to its higher temperature) than
the cold body, the net flow of heat is from hot to cold, and the second law is still satisfied.
Emissivity
Real objects do not radiate as much heat as a perfect black body. They radiate less heat than a
black body and are called gray bodies. To take into account the fact that real objects are gray
bodies, Equation 2-12 is modified to be of the following form.
AT 4
where:
= emissivity of the gray body (dimensionless)
Emissivity is simply a factor by which we multiply the black body heat transfer to take into
account that the black body is the ideal case. Emissivity is a dimensionless number and has a
maximum value of 1.0.
Radiation Configuration Factor

Radiative heat transfer rate between two gray bodies can be calculated by the equation stated
below.
Rev. 0
fa fe A ( T1
T2 )
Page 27
HT-02
Heat Transfer
where:
fa =
is the shape factor, which depends on the spatial arrangement of the two objects
(dimensionless)
fe =
is the emissivity factor, which depends on the emissivities of both objects

(dimensionless)
The two separate terms fa and fe can be combined and given the symbol f. The heat flow
between two gray bodies can now be determined by the following equation:
fA (T1
T2 )
(2-13)
The symbol (f) is a dimensionless factor sometimes called the radiation configuration factor,
which takes into account the emissivity of both bodies and their relative geometry. The radiation
configuration factor is usually found in a text book for the given situation. Once the
configuration factor is obtained, the overall net heat flux can be determined. Radiant heat flux
should only be included in a problem when it is greater than 20% of the problem.
Example:
Calculate the radiant heat between the floor (15 ft x 15 ft) of a furnace and the roof, if
the two are located 10 ft apart. The floor and roof temperatures are 2000F and 600F,
respectively. Assume that the floor and the roof have black surfaces.
Solution:
A1 = A2 = (15 ft) (15 ft) = 225 ft2
T1 = 2000oF + 460 = 2460R
T2 = 600oF + 460 = 1060R
Tables from a reference book, or supplied by the instructor, give:
f1-2
= f2-1 = 0.31
Q1-2
= Af(T14 - T24)
= (0.174
Btu
) (225 ft 2) (0.31) [ (2460 oR)4
2 o 4
hr ft R
(1060 oR)4]
= 4.29 x 1014 Btu/hr
HT-02
Page 28
Rev. 0
Heat Transfer
Summary
Radiant Heat Transfer Summary

Black body radiation is the maximum amount of heat that can be
transferred from an ideal object.
Emissivity is a measure of the departure of a body from the ideal black
body.
Radiation configuration factor takes into account the emittance and
relative geometry of two objects.
Rev. 0
Page 29
HT-02
HEAT EXCHANGERS
Heat Transfer
HEAT EXCHANGERS
Heat exchangers are devices that are used to transfer thermal energy
from one fluid to another without mixing the two fluids.
EO 1.11
DESCRIBE the difference in the temperature profiles

for counter-flow and parallel flow heat exchangers.
EO 1.12
DESCRIBE the differences between regenerative and

non-regenerative heat exchangers.
EO 1.13
Given the temperature changes across a heat exchanger,

CALCULATE the log mean temperature difference for
the heat exchanger.
EO 1.14
Given the formulas for calculating the conduction and

convection heat transfer coefficients, CALCULATE the
overall heat transfer coefficient of a system.
Heat Exchangers
The transfer of thermal energy between fluids is one of the most important and frequently used
processes in engineering. The transfer of heat is usually accomplished by means of a device
known as a heat exchanger. Common applications of heat exchangers in the nuclear field include
boilers, fan coolers, cooling water heat exchangers, and condensers.
The basic design of a heat exchanger normally has two fluids of different temperatures separated
by some conducting medium. The most common design has one fluid flowing through metal
tubes and the other fluid flowing around the tubes. On either side of the tube, heat is transferred
by convection. Heat is transferred through the tube wall by conduction.
Heat exchangers may be divided into several categories or classifications. In the most commonly
used type of heat exchanger, two fluids of different temperature flow in spaces separated by a
tube wall. They transfer heat by convection and by conduction through the wall. This type is
referred to as an "ordinary heat exchanger," as compared to the other two types classified as
"regenerators" and "cooling towers."
An ordinary heat exchanger is single-phase or two-phase. In a single-phase heat exchanger, both
of the fluids (cooled and heated) remain in their initial gaseous or liquid states. In two-phase
exchangers, either of the fluids may change its phase during the heat exchange process. The
steam generator and main condenser of nuclear facilities are of the two-phase, ordinary heat
exchanger classification.
HT-02
Page 30
Rev. 0
Heat Transfer
HEAT EXCHANGERS
Single-phase heat exchangers are usually of the tube-and-shell type; that is, the exchanger
consists of a set of tubes in a container called a shell (Figure 8). At the ends of the heat
exchanger, the tube-side fluid is separated from the shell-side fluid by a tube sheet. The design
of two-phase exchangers is essentially the same as that of single-phase exchangers.
Figure 8
Typical Tube and Shell Heat Exchanger
Parallel and Counter-Flow Designs

Although ordinary heat exchangers may be extremely different in design and construction and
may be of the single- or two-phase type, their modes of operation and effectiveness are largely
determined by the direction of the fluid flow within the exchanger.
The most common arrangements for flow paths within a heat exchanger are counter-flow and
parallel flow. A counter-flow heat exchanger is one in which the direction of the flow of one
of the working fluids is opposite to the direction to the flow of the other fluid. In a parallel flow
exchanger, both fluids in the heat exchanger flow in the same direction.
Figure 9 represents the directions of fluid flow in the parallel and counter-flow exchangers. Under
comparable conditions, more heat is transferred in a counter-flow arrangement than in a parallel
flow heat exchanger.
Rev. 0
Page 31
HT-02
HEAT EXCHANGERS
Heat Transfer
Figure 9
Fluid Flow Direction
The temperature profiles of the two heat exchangers indicate two major disadvantages in the
parallel-flow design. First, the large temperature difference at the ends (Figure 10) causes large
thermal stresses. The opposing expansion and contraction of the construction materials due to
diverse fluid temperatures can lead to eventual material failure. Second, the temperature of the
cold fluid exiting the heat exchanger never exceeds the lowest temperature of the hot fluid. This
relationship is a distinct disadvantage if the design purpose is to raise the temperature of the cold
fluid.
HT-02
Page 32
Rev. 0
Heat Transfer
HEAT EXCHANGERS
Figure 10
Heat Exchanger Temperature Profiles
The design of a parallel flow heat exchanger is advantageous when two fluids are required to be
brought to nearly the same temperature.
The counter-flow heat exchanger has three significant advantages over the parallel flow design.
First, the more uniform temperature difference between the two fluids minimizes the thermal
stresses throughout the exchanger. Second, the outlet temperature of the cold fluid can approach
the highest temperature of the hot fluid (the inlet temperature). Third, the more uniform
temperature difference produces a more uniform rate of heat transfer throughout the heat
exchanger.
Whether parallel or counter-flow, heat transfer within the heat exchanger involves both
conduction and convection. One fluid (hot) convectively transfers heat to the tube wall where
conduction takes place across the tube to the opposite wall. The heat is then convectively
transferred to the second fluid. Because this process takes place over the entire length of the
exchanger, the temperature of the fluids as they flow through the exchanger is not generally
constant, but varies over the entire length, as indicated in Figure 10. The rate of heat transfer
varies along the length of the exchanger tubes because its value depends upon the temperature
difference between the hot and the cold fluid at the point being viewed.
Rev. 0
Page 33
HT-02
HEAT EXCHANGERS
Heat Transfer
Non-Regenerative Heat Exchanger

Applications of heat exchangers may be classified as either regenerative or non-regenerative. The
non-regenerative application is the most frequent and involves two separate fluids. One fluid
cools or heats the other with no interconnection between the two fluids. Heat that is removed
from the hotter fluid is usually rejected to the environment or some other heat sink (Figure 11).
Figure 11
Non-Regenerative Heat Exchanger
Regenerative Heat Exchanger

A regenerative heat exchanger typically uses the fluid from a different area of the same system
for both the hot and cold fluids. An example of both regenerative and non-regenerative heat
exchangers working in conjunction is commonly found in the purification system of a reactor
facility. The primary coolant to be purified is drawn out of the primary system, passed through
a regenerative heat exchanger, non-regenerative heat exchanger, demineralizer, back through the
regenerative heat exchanger, and returned to the primary system (Figure 12).
In the regenerative heat exchanger, the water returning to the primary system is pre-heated by
the water entering the purification system. This accomplishes two objectives. The first is to
minimize the thermal stress in the primary system piping due to the cold temperature of the
purified coolant being returned to the primary system.
HT-02
Page 34
Rev. 0
Heat Transfer
HEAT EXCHANGERS
The second is to reduce the temperature of the water entering the purification system prior to
reaching the non-regenerative heat exchanger, allowing use of a smaller heat exchanger to
achieve the desired temperature for purification. The primary advantage of a regenerative heat
exchanger application is conservation of system energy (that is, less loss of system energy due
to the cooling of the fluid).
Figure 12 Regenerative Heat Exchanger
Cooling Towers
The typical function of a cooling tower is to cool the water of a steam power plant by air that
is brought into direct contact with the water. The water is mixed with vapor that diffuses from
the condensate into the air. The formation of the vapor requires a considerable removal of
internal energy from the water; the internal energy becomes "latent heat" of the vapor. Heat and
mass exchange are coupled in this process, which is a steady-state process like the heat exchange
in the ordinary heat exchanger.
Wooden cooling towers are sometimes employed in nuclear facilities and in factories of various
industries. They generally consists of large chambers loosely filled with trays or similar wooden
elements of construction. The water to be cooled is pumped to the top of the tower where it is
distributed by spray or wooden troughs. It then falls through the tower, splashing down from
deck to deck. A part of it evaporates into the air that passes through the tower. The enthalpy
needed for the evaporation is taken from the water and transferred to the air, which is heated
while the water cools. The air flow is either horizontal due to wind currents (cross flow) or
vertically upward in counter-flow to the falling water. The counter-flow is caused by the
Rev. 0
Page 35
HT-02
HEAT EXCHANGERS
Heat Transfer
chimney effect of the warm humid air in the tower or by fans at the bottom (forced draft) or at
the top (induced flow) of the tower. Mechanical draft towers are more economical to construct
and smaller in size than natural-convection towers of the same cooling capacity.
Log Mean Temperature Difference Application To Heat Exchangers

In order to solve certain heat exchanger problems, a log mean temperature difference (LMTD
or )Tlm) must be evaluated before the heat removal from the heat exchanger is determined. The
following example demonstrates such a calculation.
Example:
A liquid-to-liquid counterflow heat exchanger is used as part of an auxiliary system at
a nuclear facility. The heat exchanger is used to heat a cold fluid from 120EF to 310EF.
Assuming that the hot fluid enters at 500EF and leaves at 400EF, calculate the LMTD
for the exchanger.
Solution:
)T2 '
400EF
& 120EF ' 280EF
)T 1 '
500EF
& 310EF ' 190EF
)Tlm '
()T2
ln
& )T 1 )
)T2
)T1
' (280EF & 190EF)

ln
280EF
190EF
' 232EF
The solution to the heat exchanger problem may be simple enough to be represented by a
straight-forward overall balance or may be so detailed as to require integral calculus. A steam
generator, for example, can be analyzed by an overall energy balance from the feedwater inlet
to the steam outlet in which the amount of heat transferred can be expressed simply as
0 ' m
Q
0 )h , where m
0 is the mass flow rate of the secondary coolant and )h is the change in
enthalpy of the fluid. The same steam generator can also be analyzed by an energy balance on
0 ' m
the primary flow stream with the equation Q
0 cp )T , where m
0 , cp , and )T are the mass
flow rate, specific heat capacity, and temperature change of the primary coolant. The heat
HT-02
Page 36
Rev. 0
Heat Transfer
HEAT EXCHANGERS
transfer rate of the steam generator can also be determined by comparing the temperatures on
the primary and secondary sides with the heat transfer characteristics of the steam generator
0 ' U A )T .
using the equation Q
o
o
lm
Condensers are also examples of components found in nuclear facilities where the concept of
LMTD is needed to address certain problems. When the steam enters the condenser, it gives up
its latent heat of vaporization to the circulating water and changes phase to a liquid. Because
condensation is taking place, it is appropriate to term this the latent heat of condensation. After
the steam condenses, the saturated liquid will continue to transfer some heat to the circulating
water system as it continues to fall to the bottom (hotwell) of the condenser. This continued
cooling is called subcooling and is necessary to prevent cavitation in the condensate pumps.
The solution to condenser problems is approached in the same manner as those for steam
generators, as shown in the following example.

When dealing with heat transfer across heat exchanger tubes, an overall heat transfer coefficient,
Uo, must be calculated. Earlier in this module we looked at a method for calculating Uo for both
rectangular and cylindrical coordinates. Since the thickness of a condenser tube wall is so small
and the cross-sectional area for heat transfer is relatively constant, we can use Equation 2-11 to
calculate Uo.
Uo
'
1
h1
1
)r
k
% 1
h2
Example:
Referring to the convection section of this manual, calculate the heat rate per foot of
tube from a condenser under the following conditions. )Tlm = 232EF. The outer
diameter of the copper condenser tube is 0.75 in. with a wall thickness of 0.1 in. Assume
the inner convective heat transfer coefficient is 2000 Btu/hr-ft2-EF, and the thermal
conductivity of copper is 200 Btu/hr-ft-EF. The outer convective heat transfer
coefficient is 1500 Btu/hr-ft2-EF.
Rev. 0
Page 37
HT-02
HEAT EXCHANGERS
Heat Transfer
Solution:
Uo
'
'
1
h1
1
)r
k
% 1
h2
1
1
2000
' 827.6
% 0.1 in
200
1 ft
12 in
1
1500
Btu
hr&ft 2&EF
0
Q
' U o Ao )Tlm
0
Q
L
'
Uo Ao
)Tlm
' U o 2B r )Tlm
' 827.6
Btu
hr&ft 2&EF
(2B) (0.375 in)
1 ft
12 in
(232EF)
' 37,700 Btu

hr&ft
HT-02
Page 38
Rev. 0
Heat Transfer
HEAT EXCHANGERS
Summary
Heat Exchangers Summary

Heat exchangers remove heat from a high-temperature fluid by
convection and conduction.
Counter-flow heat exchangers typically remove more heat than
parallel flow heat exchangers.
Parallel flow heat exchangers have a large temperature difference at
the inlet and a small temperature difference at the outlet.
Counter-flow heat exchangers have an even temperature difference
across the heat transfer length.
Regenerative heat exchangers improve system efficiency by
returning energy to the system. A non-regenerative heat exchanger
rejects heat to the surroundings.
The heat transfer rate for a heat exchanger can be calculated using
the equation below.
Rev. 0
Uo Ao Tlm
Page 39
HT-02
BOILING HEAT TRANSFER
Heat Transfer

The formation of steam bubbles along a heat transfer surface has a
significant effect on the overall heat transfer rate.
EO 1.15
DESCRIBE the process that occurs in the following

regions of the boiling heat transfer curve:
a.
Nucleate boiling
b.
Partial film boiling
c.
Film boiling
d.
Departure from nucleate boiling (DNB)
e.
Critical heat flux
Boiling
In a nuclear facility, convective heat transfer is used to remove heat from a heat transfer surface.
The liquid used for cooling is usually in a compressed state, (that is, a subcooled fluid) at
pressures higher than the normal saturation pressure for the given temperature. Under certain
conditions, some type of boiling (usually nucleate boiling) can take place. It is advisable,
therefore, to study the process of boiling as it applies to the nuclear field when discussing
convection heat transfer.
More than one type of boiling can take place within a nuclear facility, especially if there is a
rapid loss of coolant pressure. A discussion of the boiling processes, specifically local and bulk
boiling, will help the student understand these processes and provide a clearer picture of why
bulk boiling (specifically film boiling) is to be avoided in nuclear facility operations.
Nucleate Boiling
The most common type of local boiling encountered in nuclear facilities is nucleate boiling. In
nucleate boiling, steam bubbles form at the heat transfer surface and then break away and are
carried into the main stream of the fluid. Such movement enhances heat transfer because the heat
generated at the surface is carried directly into the fluid stream. Once in the main fluid stream,
the bubbles collapse because the bulk temperature of the fluid is not as high as the heat transfer
surface temperature where the bubbles were created. This heat transfer process is sometimes
desirable because the energy created at the heat transfer surface is quickly and efficiently
"carried" away.
HT-02
Page 40
Rev. 0
Heat Transfer
Bulk Boiling
As system temperature increases or system pressure drops, the bulk fluid can reach saturation
conditions. At this point, the bubbles entering the coolant channel will not collapse. The bubbles
will tend to join together and form bigger steam bubbles. This phenomenon is referred to as bulk
boiling. Bulk boiling can provide adequate heat transfer provided that the steam bubbles are
carried away from the heat transfer surface and the surface is continually wetted with liquid
water. When this cannot occur film boiling results.
Film Boiling
When the pressure of a system drops or the flow decreases, the bubbles cannot escape as quickly
from the heat transfer surface. Likewise, if the temperature of the heat transfer surface is
increased, more bubbles are created. As the temperature continues to increase, more bubbles are
formed than can be efficiently carried away. The bubbles grow and group together, covering
small areas of the heat transfer surface with a film of steam. This is known as partial film
boiling. Since steam has a lower convective heat transfer coefficient than water, the steam
patches on the heat transfer surface act to insulate the surface making heat transfer more difficult.
As the area of the heat transfer surface covered with steam increases, the temperature of the
surface increases dramatically, while the heat flux from the surface decreases. This unstable
situation continues until the affected surface is covered by a stable blanket of steam, preventing
contact between the heat transfer surface and the liquid in the center of the flow channel. The
condition after the stable steam blanket has formed is referred to as film boiling.
The process of going from nucleate boiling to film boiling is graphically represented in Figure
13. The figure illustrates the effect of boiling on the relationship between the heat flux and the
temperature difference between the heat transfer surface and the fluid passing it.
Rev. 0
Page 41
HT-02
Heat Transfer
Figure 13
Boiling Heat Transfer Curve
Four regions are represented in Figure 13. The first and second regions show that as heat flux
increases, the temperature difference (surface to fluid) does not change very much. Better heat
transfer occurs during nucleate boiling than during natural convection. As the heat flux increases,
the bubbles become numerous enough that partial film boiling (part of the surface being
blanketed with bubbles) occurs. This region is characterized by an increase in temperature
difference and a decrease in heat flux. The increase in temperature difference thus causes total
film boiling, in which steam completely blankets the heat transfer surface.
Departure from Nucleate Boiling and Critical Heat Flux

In practice, if the heat flux is increased, the transition from nucleate boiling to film boiling occurs
suddenly, and the temperature difference increases rapidly, as shown by the dashed line in the
figure. The point of transition from nucleate boiling to film boiling is called the point of
departure from nucleate boiling, commonly written as DNB. The heat flux associated with DNB
is commonly called the critical heat flux (CHF). In many applications, CHF is an important
parameter.
HT-02
Page 42
Rev. 0
Heat Transfer
For example, in a reactor, if the critical heat flux is exceeded and DNB occurs at any location
in the core, the temperature difference required to transfer the heat being produced from the
surface of the fuel rod to the reactor coolant increases greatly. If, as could be the case, the
temperature increase causes the fuel rod to exceed its design limits, a failure will occur.
The amount of heat transfer by convection can only be determined after the local heat transfer
coefficient is determined. Such determination must be based on available experimental data.
After experimental data has been correlated by dimensional analysis, it is a general practice to
write an equation for the curve that has been drawn through the data and to compare
experimental results with those obtained by analytical means. In the application of any empirical
equation for forced convection to practical problems, it is important for the student to bear in
mind that the predicted values of heat transfer coefficient are not exact. The values of heat
transfer coefficients used by students may differ considerably from one student to another,
depending on what source "book" the student has used to obtain the information. In turbulent
and laminar flow, the accuracy of a heat transfer coefficient predicted from any available
equation or graph may be no better than 30%.
Summary
Boiling Heat Transfer Summary
Nucleate boiling is the formation of small bubbles at a heat transfer surface. The
bubbles are swept into the coolant and collapse due to the coolant being a
subcooled liquid. Heat transfer is more efficient than for convection.
Bulk boiling occurs when the bubbles do not collapse due to the coolant being
at saturation conditions.
Film boiling occurs when the heat transfer surface is blanketed with steam
bubbles and the heat transfer coefficient rapidly decreases.
Departure from nucleate boiling (DNB) occurs at the transition from nucleate to
film boiling.
Critical heat flux (CHF) is the heat flux that causes DNB to occur.
Rev. 0
Page 43
HT-02
HEAT GENERATION
Heat Transfer
HEAT GENERATION
Heat generation and power output in a reactor are related. Reactor
power is related to the mass flow rate of the coolant and the
temperature difference across the reactor core.
EO 2.1
DESCRIBE the power generation process in a nuclear

reactor core and the factors that affect the power
generation.
EO 2.2
DESCRIBE the relationship between temperature, flow,

and power during operation of a nuclear reactor.
EO 2.3

a.
Nuclear enthalpy rise hot channel factor
b.
c.
Nuclear heat flux hot channel factor
d.
Heat generation rate of a core
e.
Volumetric thermal source strength
EO 2.4
CALCULATE the average linear power density for an

average reactor core fuel rod.
EO 2.5
DESCRIBE a typical reactor core axial and radial flux

profile.
EO 2.6
DESCRIBE a typical reactor core fuel rod axial and

radial temperature profile.
Heat Generation
The heat generation rate in a nuclear core is directly proportional to the fission rate of the fuel
and the thermal neutron flux present. On a straight thermodynamic basis, this same heat
generation is also related to the fluid temperature difference across the core and the mass flow
rate of the fluid passing through the core. Thus, the size of the reactor core is dependent upon
and limited by how much liquid can be passed through the core to remove the generated thermal
energy. Many other factors affect the amount of heat generated within a reactor core, but its
limiting generation rate is based upon how much energy can safely be carried away by the
coolant.
HT-02
Page 44
Rev. 0
Heat Transfer
HEAT GENERATION
The fission rate within a nuclear reactor is controlled by several factors. The density of the fuel,
the neutron flux, and the type of fuel all affect the fission rate and, therefore, the heat generation
) is
rate. The following equation is presented here to show how the heat generation rate ( Q
related to these factors. The terms will be discussed in more detail in the Nuclear Science
modules.
G N f Vf
(2-14)
where:
=
Q
heat generation rate (Btu/sec)
energy produced per fission (Btu/fission)
number of fissionable fuel nuclei/unit volume (atoms/cm3)
f =
microscopic fission cross-section of the fuel (cm2)
neutron flux (n/cm2-sec)
Vf =
volume of the fuel (cm3)
The thermal power produced by a reactor is directly related to the mass flow rate of the reactor
coolant and the temperature difference across the core. The relationship between power, mass
flow rate, and temperature is given in Equation 2-14.
m
cp T
(2-15)
where:
Q
m
cp
T
=
=
=
=
heat generation rate (Btu/hr)

mass flow rate (lbm/hr)
specific heat capacity of reactor coolant system (Btu/lbm-F)
temperature difference across core (F)
For most types of reactors (boiling water reactor excluded), the temperature of the coolant is
dependent upon reactor power and coolant flow rate. If flow rate is constant, temperature will
vary directly with power. If power is constant, temperature will vary inversely with flow rate.
Rev. 0
Page 45
HT-02
HEAT GENERATION
Heat Transfer
Flux Profiles
Once the type and amount of fuel
is determined, the shape of the
neutron flux distribution along the
core is established. Both radial
and axial flux distributions must
be determined. A radial
distribution looks at flux from the
center of the core out to the edges.
An axial distribution looks at flux
from the bottom to the top of the
core. As seen in Equation 2-14,
the fission rate directly affects the
heat generation rate within a
reactor core. In the core regions
of highest flux, the highest heat
generation rate will be present.
Many factors affect the axial and
Figure 14 Axial Flux Profile
radial flux distributions, including
the number and type of control
rods, the geometry and size of core, the concentration of fission product poisons, and reflector
properties. The peak power production regions within each distribution normally occurs near the
center of the core, as indicated in Figures 14 and 15, but can vary during transients or as the core
ages.
The above figures represent the
neutron flux profiles without
considering the effects of control
rods.
Once control rods and
reflectors are taken into account,
the flux profiles become much
flatter although the peak still
occurs near the center.
The shape of the profiles can be
determined by measuring the ratio
of the peak flux to the average
flux in the distribution.
This
peaking factor is referred to as the
hot channel factor. A hot channel
factor of 1.0 would imply a flat
flux profile.
HT-02
Figure 15
Page 46
Radial Flux Profile
Rev. 0
Heat Transfer
HEAT GENERATION
Thermal Limits
Hot channel factors are calculated values used to take into account various uncertainties in
tolerances used in core manufacturing. For example, consider a coolant channel of the minimum
acceptable width and length, that happens to be adjacent to a fuel plate with the maximum
acceptable fuel loading. In this channel, we would now have less water than in the average
channel, receiving more heat than the normal coolant channel. For any given values of core
power and flow, this hypothetical channel would be closest to a thermal limit. Therefore, all
design considerations are based upon the hot channel factor for each core. The nuclear heat flux
hot channel factor (HFHCF) is the ratio of the maximum heat flux expected at any area to the
average heat flux for the core. The nuclear enthalpy rise hot channel factor is the ratio of the
total kW heat generation along the fuel rod with the highest total kW to the total kW of the
average fuel rod.
Thus the limitation of the peak flux value in a core is directly related to the hot channel factor.
However, in discussing flux profiles, "average" values of flux in the core are usually referred to
rather than peaks.
Average Linear Power Density

In nuclear reactors, the fuel is usually distributed in individual components which sometimes
resemble rods, tubes, or plates. It is possible to determine the average power produced per unit
length of fuel component by dividing the total thermal output of the core by the total length of
all the fuel components in the core. This quantity is called the average linear power density.
Common units for measuring average linear power density are kW/ft.
Example:
Calculate the average linear power density for an entire core if a 3400 MW reactor is
operating at full power.
Core data is:
each fuel rod is 12 ft long

264 rods/fuel assembly
193 fuel assemblies in the core
Solution:
Rev. 0
total thermal power

total fuel rod length
3.4 x 106 kW
12 (264) (193)
5.56 kW/ft
Page 47
HT-02
HEAT GENERATION
Heat Transfer
Maximum Local Linear Power Density

The maximum local linear power density when compared to the average linear power density
results in the definition of the nuclear heat flux hot channel factor. The nuclear heat flux hot
channel factor can be looked at as having axial and radial components that are dependent upon
the power densities and, thus, the flux in the radial and axial planes of the core. Once the hot
channel factor is known, the maximum local linear power density anywhere in the core can be
determined, as demonstrated in the following example.
Example:
If the nuclear heat flux hot channel factor is 1.83, calculate the maximum local linear
power density in the core for the previous example (the average linear power density
problem).
Solution:
Maximum linear power density
= HFHCF (Av linear power density)

= 1.83 (5.56) kW/ft
= 10.18 kW/ft
Normally, nuclear facility operators

are provided with the above core
power and heat generation
distributions, rather than having to
calculate them. In addition, various
monitoring systems are always
employed to provide the operator with
a means of monitoring core
performance and the proximity of the
existing operating conditions to core
operational limitations.
Temperature Profiles
Additional areas of interest are the
temperature profiles found within the
core. A typical axial temperature
profile along a coolant channel for a
pressurized water reactor (PWR) is
Figure 16 Axial Temperature Profile
shown in Figure 16. As would be
expected, the temperature of the
coolant will increase throughout the entire length of the channel.
HT-02
Page 48
Rev. 0
Heat Transfer
HEAT GENERATION
However, the rate of increase will vary along with the linear heat flux of the channel. The power
density and linear heat rate will follow the neutron flux shape. However, the temperature
distributions are skewed by the changing capacity of the coolant to remove the heat energy.
Since the coolant increases in temperature as it flows up the channel, the fuel cladding and, thus,
the fuel temperatures are higher in the upper axial region of the core.
A radial temperature profile across a reactor core (assuming all channel coolant flows are equal)
will basically follow the radial power distribution. The areas with the highest heat generation
rate (power) will produce the most heat and have the highest temperatures. A radial temperature
profile for an individual fuel rod and coolant channel is shown in Figure 17. The basic shape
of the profile will be dependent upon the heat transfer coefficient of the various materials
involved. The temperature differential across each material will have to be sufficient to transfer
the heat produced. Therefore, if we know the heat transfer coefficient for each material and the
heat flux, we can calculate peak fuel temperatures for a given coolant temperature.
Figure 17 Radial Temperature Profile Across a

Fuel Rod and Coolant Channel
Rev. 0
Page 49
HT-02
HEAT GENERATION
Heat Transfer
Volumetric Thermal Source Strength

The total heat output of a reactor core is called the heat generation rate. The heat generation
rate divided by the volume of fuel will give the average volumetric thermal source strength. The
volumetric thermal source strength may be used to calculate the heat output of any section of fuel
rod, provided the volume of the section is known.
Volumetric Thermal Source Strength
Q
core
Vfuel
Fuel Changes During Reactor Operation

During the operation of a nuclear reactor, physical changes occur to the fuel that affect its ability
to transfer heat to the coolant. The exact changes that occur are dependant on the type and form
of fuel. Some reactors use fuel assemblies that consist of zircalloy tubes containing cylindrical
ceramic pellets of uranium dioxide. During manufacture, a small space or gap is left between
the fuel pellets and the zircalloy tube (clad). This gap is filled with pressurized helium. As the
reactor is operated at power, several physical changes occur in the fuel that affect the gap
between the pellets and clad. One change occurs due to high pressure in the coolant outside the
clad and the relatively high temperature of the clad during reactor operation. The high
temperature and high pressure causes the clad to be pushed in on the pellets by a process referred
to as creep. Another physical change is caused by the fission process. Each fission event creates
two fission product atoms from a fuel atom. Even though each fission product atom is roughly
half the mass of the fuel atom, the fission products take up more volume than the original fuel
atom. Fission products that are gases can collect together and form small gas bubbles within the
fuel pellet. These factors cause the fuel pellets to swell, expanding them out against the clad.
So the two processes of pellet swell and clad creep both work to reduce the gap between the fuel
and clad.
This change in the gap between the pellet and clad has significant impact on heat transfer from
the fuel and operating fuel temperatures. Initially a significant temperature difference exists
across the gap to cause heat transfer to take place by convection through the helium gas. As the
size of the gap is reduced, a smaller temperature difference can maintain the same heat flux.
When the fuel pellets and clad come in contact, heat transfer by conduction replaces convection
and the temperature difference between the fuel surface and clad decreases even more. Due to
the processes of pellet swell and clad creep, the fuel temperatures of some reactors decrease
slightly over time while the heat flux from the fuel and therefore the power of the reactor remain
constant.
Not all changes that occur to the fuel during reactor operation work to enhance heat transfer.
If the chemistry of the coolant is not carefully controlled within appropriate limits, chemical
reactions can take place on the surface of the clad, resulting in the formation of a layer of
corrosion products or crud between the metal of the clad and the coolant. Typically, this layer
will have a lower thermal conductivity than that of the clad material, so it will act as an
insulating blanket, reducing heat transfer.
HT-02
Page 50
Rev. 0
Heat Transfer
HEAT GENERATION
If this corrosion layer is allowed to form, a larger temperature difference will be required
between the coolant and fuel to maintain the same heat flux. Therefore, operation at the same
power level will cause higher fuel temperatures after the buildup of corrosion products and crud.
Summary
The important information in this chapter is summarized below:
Heat Generation Summary
The power generation process in a nuclear core is directly proportional to the

fission rate of the fuel and the thermal neutron flux present.
The thermal power produced by a reactor is directly related to the mass flow rate
of the reactor coolant and the temperature difference across the core.
The nuclear enthalpy rise hot channel factor is the ratio of the total kW heat
generation along a fuel rod with the highest total kW, to the total kW of the
average fuel rod.
The average linear power density in the core is the total thermal power divided
by the active length of the fuel rods.
The nuclear heat flux hot channel factor is the ratio of the maximum heat flux
expected at any area to the average heat flux for the core.
The total heat output of a reactor core is called the heat generation rate.
The heat generation rate divided by the volume of fuel will give the average
volumetric thermal source strength.
Rev. 0
Page 51
HT-02
DECAY HEAT
Heat Transfer
DECAY HEAT
Decay heat production is a particular problem associated with nuclear
reactors. Even though the reactor is shut down, heat is produced from
the decay of fission fragments. Limits for each particular reactor are
established to prevent damage to fuel assemblies due to decay heat.
EO 2.7
DEFINE the term decay heat.
EO 2.8
Given the operating conditions of a reactor core and the

necessary formulas, CALCULATE the core decay heat
generation.
EO 2.9
DESCRIBE two categories of methods for removing

decay heat from a reactor core.
Reactor Decay Heat Production

A problem peculiar to power generation by nuclear reactors is that of decay heat. In fossil fuel
facilities, once the combustion process is halted, there is no further heat generation, and only a
relatively small amount of thermal energy is stored in the high temperature of plant components.
In a nuclear facility, the fission of heavy atoms such as isotopes of uranium and plutonium results
in the formation of highly radioactive fission products. These fission products radioactively
decay at a rate determined by the amount and type of radioactive nuclides present. Some
radioactive atoms will decay while the reactor is operating and the energy released by their decay
will be removed from the core along with the heat produced by the fission process. All
radioactive materials that remain in the reactor at the time it is shut down and the fission process
halted will continue to decay and release energy. This release of energy by the decay of fission
products is called decay heat.
The amount of radioactive materials present in the reactor at the time of shutdown is dependent
on the power levels at which the reactor operated and the amount of time spent at those power
levels. The amount of decay heat is very significant. Typically, the amount of decay heat that
will be present in the reactor immediately following shutdown will be roughly 7% of the power
level that the reactor operated at prior to shutdown. A reactor operating at 1000 MW will
produce 70 MW of decay heat immediately after a shutdown. The amount of decay heat
produced in the reactor will decrease as more and more of the radioactive material decays to
some stable form. Decay heat may decrease to about 2% of the pre-shutdown power level within
the first hour after shutdown and to 1% within the first day. Decay heat will continue to
decrease after the first day, but it will decrease at a much slower rate. Decay heat will be
significant weeks and even months after the reactor is shutdown.
HT-02
Page 52
Rev. 0
Heat Transfer
DECAY HEAT
The design of the reactor must allow for the removal of this decay heat from the core by some
means. If adequate heat removal is not available, decay heat will increase the temperatures in
the core to the point that fuel melting and core damage will occur. Fuel that has been removed
from the reactor will also require some method of removing decay heat if the fuel has been
exposed to a significant neutron flux. Each reactor facility will have its own method of removing
decay heat from both the reactor core and also any irradiated fuel removed from the core.
Calculation of Decay Heat

The amount of decay heat being generated in a fuel assembly at any time after shutdown can be
calculated in two ways. The first way is to calculate the amount of fission products present at
the time of shutdown. This is a fairly detailed process and is dependent upon power history.
For a given type of fuel, the concentrations, decay energies, and half lives of fission products are
known. By starting from a known value, based on power history at shutdown, the decay heat
generation rate can be calculated for any time after shutdown.
An exact solution must take into account the fact that there are hundreds of different
radionuclides present in the core, each with its own concentration and decay half-life. It is
possible to make a rough approximation by using a single half-life that represents the overall
decay of the core over a certain period of time. An equation that uses this approximation is
Equation 2-16.
time
life
1 half
Q
o
2
(2-16)
where:
= decay heat generation rate at some time after shutdown
Q
o
= initial decay heat immediately after shutdown
time
half-life
Rev. 0
= amount of time since shutdown

= overall decay half-life of the core
Page 53
HT-02
DECAY HEAT
Heat Transfer
Example:
A 250 MW reactor has an unexpected shutdown. From data supplied by the vendor, we
know that decay heat at time of shutdown will be 7% of the effective power at time of
shutdown and will decrease with a 1 hr half life. Effective power at time of shutdown
was calculated to be 120 MW. How much heat removal capability (in units of Btu/hr)
will be required 12 hours after shutdown?
Solution:
(a)
First determine the decay heat immediately following shutdown.

(120 MW)(.07) = 8.4 MW decay heat at shutdown
(b)
Then use Equation 2-15 to determine the decay heat 12 hours later.
time
life
1 half
Q
o
2
1
8.4 MW
2
2.05 x 10
7000
12 hr
1 hr
3.413 x 106 Btu/hr

MW
1 MW
Btu
hr
The second method is much simpler to use, but is not useful for forecasting heat loads in the
future. To calculate the decay heat load at a given point after shutdown, secure any heat removal
components from the primary system or spent fuel pool and plot the heatup rate. If the mass of
the coolant and the specific heat of the coolant are known, the heat generation rate can be
accurately calculated.
HT-02
m cp
T
t
(2-17)
Page 54
Rev. 0
Heat Transfer
DECAY HEAT
where:
= decay heat (Btu/hr)
= mass of coolant (lbm)
cp
= specific heat capacity of coolant (Btu/lbm-oF)
T = temperature change of coolant (oF)

t
= time over which heatup takes place (hr)
Example:
Three days after a planned reactor shutdown, it is desired to perform maintenance on one
of two primary heat exchangers. Each heat exchanger is rated at 12,000 Btu/hr. To
check the current heat load on the primary system due to decay heat, cooling is secured
to both heat exchangers. The primary system heats up at a rate of 0.8F/hr. The primary
system contains 24,000 lbm of coolant with a specific heat capacity of 0.8 Btu/lbm-F.
Will one heat exchanger be sufficient to remove the decay heat?
Solution:
m cp
T
t
Btu 0.8F
(24,000 lbm) 0.8

lbm F 1 hr
15,360
Btu
hr
One heat exchanger removes 12,000 Btu/hr.

One heat exchanger will not be sufficient.
Decay Heat Limits

Reactor decay heat can be a major concern. In the worst case scenarios, it can cause melting of
and/or damage to the reactor core, as in the case of Three Mile Island. The degree of concern
with decay heat will vary according to reactor type and design. There is little concern about core
temperature due to decay heat for low power, pool-type reactors.
Rev. 0
Page 55
HT-02
DECAY HEAT
Heat Transfer
Each reactor will have some limits during shutdown that are based upon decay heat
considerations. These limits may vary because of steam generator pressure, core temperature,
or any other parameter that may be related to decay heat generation. Even during refueling
processes, heat removal from expended fuel rods is a controlling factor. For each limit
developed, there is usually some safety device or protective feature established.
Decay Heat Removal

Methods for removing decay heat from a reactor core can be grouped into two general categories.
One category includes methods which circulate fluid through the reactor core in a closed loop,
using some type of heat exchanger to transfer heat out of the system. The other category
includes methods which operate in an open system, drawing in cool fluid from some source and
discharging warmer fluid to some storage area or the environment.
In most reactors, decay heat is normally removed by the same methods used to remove heat
generated by fission during reactor operation. Additionally, many reactors are designed such that
natural circulation between the core and either its normal heat exchanger or an emergency heat
exchanger can remove decay heat. These are examples of the first category of methods for decay
heat removal.
If a reactor design is such that decay heat removal is required for core safety, but accidents are
possible that will make the closed loop heat transfer methods described above unavailable, then
an emergency cooling system of some sort will be included in the reactor design. Generally,
emergency cooling systems consist of some reliable source of water that is injected into the core
at a relatively low temperature. This water will be heated by the decay heat of the core and exit
the reactor via some path where it will either be stored in some structure or released to the
environment. Use of this type of system is almost always less desirable than the use of the
closed loop systems described above.
Students should research systems, limits, and protective features applicable to their own specific
facilities.
HT-02
Page 56
Rev. 0
Heat Transfer
DECAY HEAT
Summary
Decay Heat Summary

Decay heat is the amount of heat generated by decay of fission
products after shutdown of the facility.
The amount of decay heat is dependent on the reactors power
history.
Methods for removing decay heat usually fall into one of the
following categories.
-
Closed loop systems, where coolant is circulated between the

reactor and a heat exchanger in a closed loop. The heat
exchanger transfers the decay heat to the fluid in the secondary
side of the heat exchanger.
Once through systems, where coolant from a source is injected

into the reactor core. The decay heat is transferred from the fuel
assemblies into the coolant, then the coolant leaves the reactor and
is either collected in a storage structure or released to the
environment.
The limits for decay heat are calculated to prevent damage to the
reactor core.
end of text.
CONCLUDING MATERIAL
Review activities:
Preparing activity:

DOE - NE-73
Project Number 6910-0018/2
Rev. 0
Page 57
HT-02
DECAY HEAT
Heat Transfer
HT-02
Page 58
Rev. 0
DOE-HDBK-1012/3-92
JUNE 1992

AND FLUID FLOW
Volume 3 of 3
FSC-6910

Available to DOE and DOE contractors from the Office of Scientific and Technical
Information. P. O. Box 62, Oak Ridge, TN 37831; prices available from (615) 5768401. FTS 626-8401.
Department of Commerce, 5285 Port Royal Rd., Springfield, VA 22161.
ABSTRACT
Equation
Rev. 0
HT
FOREWORD
Rev. 0
HT
OVERVIEW
Volume 1 of 3
calculated.
Volume 2 of 3
Volume 3 of 3
Rev. 0
HT

Rev. 0
HT

AND FLUID FLOW,
Module 3
Fluid Flow
blank
Fluid Flow
TABLE OF CONTENTS
TABLE OF CONTENTS
LIST OF TABLES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vi
OBJECTIVES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
CONTINUITY EQUATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Introduction . . . . . . . . . . . . . . . . . . . .
Properties of Fluids . . . . . . . . . . . . . . .
Buoyancy . . . . . . . . . . . . . . . . . . . . . .
Compressibility . . . . . . . . . . . . . . . . . .
Relationship Between Depth and Pressure
Pascals Law . . . . . . . . . . . . . . . . . . . .
Control Volume . . . . . . . . . . . . . . . . .
Volumetric Flow Rate . . . . . . . . . . . . .
Mass Flow Rate . . . . . . . . . . . . . . . . .
Conservation of Mass . . . . . . . . . . . . . .
Steady-State Flow . . . . . . . . . . . . . . . .
Continuity Equation . . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
2
2
3
3
7
8
9
9
10
10
11
16
LAMINAR AND TURBULENT FLOW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

Flow Regimes . . . . . . .
Laminar Flow . . . . . . .
Turbulent Flow . . . . . .
Flow Velocity Profiles .
Average (Bulk) Velocity
Viscosity . . . . . . . . . .
Ideal Fluid . . . . . . . . .
Reynolds Number . . . .
Summary . . . . . . . . . .
Rev. 0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Page i
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
17
17
17
18
19
19
19
19
20
HT-03
TABLE OF CONTENTS
Fluid Flow

BERNOULLIS EQUATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
General Energy Equation . . . . . . . . . . . . . . . . .
Simplified Bernoulli Equation . . . . . . . . . . . . . .
Head . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Energy Conversions in Fluid Systems . . . . . . . .
Restrictions on the Simplified Bernoulli Equation
Extended Bernoulli . . . . . . . . . . . . . . . . . . . . .
Application of Bernoullis Equation to a Venturi .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
21
22
23
23
25
25
27
30
HEAD LOSS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
Head Loss . . . . . . . . . .
Friction Factor . . . . . . .
Darcys Equation . . . . . .
Minor Losses . . . . . . . .
Equivalent Piping Length
Summary . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
31
31
32
34
34
36
NATURAL CIRCULATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
Forced and Natural Circulation . . . . . . . . .
Thermal Driving Head . . . . . . . . . . . . . . .
Conditions Required for Natural Circulation
Example of Natural Circulation Cooling . . .
Flow Rate and Temperature Difference . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
37
37
38
39
39
40
TWO-PHASE FLUID FLOW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

Two-Phase Fluid Flow . . .
Flow Instability . . . . . . . .
Pipe Whip . . . . . . . . . . .
Water Hammer . . . . . . . .
Pressure spike . . . . . . . . .
Steam Hammer . . . . . . . .
Operational Considerations
Summary . . . . . . . . . . . .
HT-03
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Page ii
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
41
42
43
43
43
45
45
46
Rev. 0
Fluid Flow
TABLE OF CONTENTS

CENTRIFUGAL PUMPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Energy Conversion in a Centrifugal Pump . . . .
Operating Characteristics of a Centrifugal Pump
Cavitation . . . . . . . . . . . . . . . . . . . . . . . . . . .
Net Positive Suction Head . . . . . . . . . . . . . . .
Pump Laws . . . . . . . . . . . . . . . . . . . . . . . . . .
System Characteristic Curve . . . . . . . . . . . . . .
System Operating Point . . . . . . . . . . . . . . . . .
System Use of Multiple Centrifugal Pumps . . .
Centrifugal Pumps in Parallel . . . . . . . . . . . . .
Centrifugal Pumps in Series . . . . . . . . . . . . . .
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
47
48
48
49
49
52
52
53
53
54
56
APPENDIX B Fluid Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B-1
Rev. 0
Page iii
HT-03
LIST OF FIGURES
Fluid Flow
LIST OF FIGURES
Figure 1
Pressure Versus Depth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Figure 2
Pascals Law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Figure 3
Continuity Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Figure 4
"Y" Configuration for Example Problem . . . . . . . . . . . . . . . . . . . . . . . . 14
Figure 5
Laminar and Turbulent Flow Velocity Profiles . . . . . . . . . . . . . . . . . . . . 18
Figure 6
Venturi Meter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Figure 7
Typical Centrifugal Pump Characteristic Curve . . . . . . . . . . . . . . . . . . . . 48
Figure 8
Changing Speeds for Centrifugal Pump . . . . . . . . . . . . . . . . . . . . . . . . . 51
Figure 9
Typical System Head Loss Curve . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
Figure 10
Operating Point for a Centrifugal Pump . . . . . . . . . . . . . . . . . . . . . . . . . 52
Figure 11
Pump Characteristic Curve for Two Identical

Centrifugal Pumps Used in Parallel . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Figure 12
Operating Point for Two Parallel Centrifugal Pumps . . . . . . . . . . . . . . . . 54
Figure 13
Pump Characteristic Curve for Two Identical

Centrifugal Pumps Used in Series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
Figure 14
Operating Point for Two Centrifugal Pumps in Series . . . . . . . . . . . . . . . 55
Figure B-1
Moody Chart . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B-1
HT-03
Page iv
Rev. 0
Fluid Flow
LIST OF TABLES
LIST OF TABLES
Table 1
Rev. 0
Typical Values of
Leq
D
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Page v
HT-03
REFERENCES
Fluid Flow
REFERENCES
Streeter, Victor L., Fluid Mechanics, 5th Edition, McGraw-Hill, New York,
ISBN 07-062191-9.
Knudsen, J. G. and Katz, D. L., Fluid Dynamics and Heat Transfer, McGraw-Hill, New
York.
McDonald, A. T. and Fox, R. W., Introduction to Fluid Mechanics, 2nd Edition, John
Wiley and Sons, New York, ISBN 0-471-98440-X.
Crane Company, Flow of Fluids Through Valves, Fittings, and Pipe, Crane Co. Technical
Paper No. 410, Chicago, Illinois, 1957.
Esposito, Anthony, Fluid Power with Applications, Prentice-Hall, Inc., New Jersey, ISBN
0-13-322701-4.
Wallis, Graham, One-Dimensional Two-Phase Flow, McGraw-Hill, New York, 1969.
Academic Program for Nuclear Power Plant Personnel, Volume III and IV,
General Physics Corporation, Library of Congress Card #A 397747, June 1982 and
April 1982.
HT-03
Page vi
Rev. 0
Fluid Flow
OBJECTIVES
TERMINAL OBJECTIVE
1.0
Given conditions affecting the fluid flow in a system, EVALUATE the effects on
the operation of the system.
ENABLING OBJECTIVES
1.1
DESCRIBE how the density of a fluid varies with temperature.
1.2
DEFINE the term buoyancy.
1.3
DESCRIBE the relationship between the pressure in a fluid column and the density and
depth of the fluid.
1.4
STATE Pascals Law.
1.5
DEFINE the terms mass flow rate and volumetric flow rate.
1.6
CALCULATE either the mass flow rate or the volumetric flow rate for a fluid system.
1.7
STATE the principle of conservation of mass.
1.8
CALCULATE the fluid velocity or flow rate in a specified fluid system using the
continuity equation.
1.9
DESCRIBE the characteristics and flow velocity profiles of laminar flow and turbulent
flow.
1.10
DEFINE the property of viscosity.
1.11
DESCRIBE how the viscosity of a fluid varies with temperature.
1.12
DESCRIBE the characteristics of an ideal fluid.
1.13
DESCRIBE the relationship between the Reynolds number and the degree of turbulence
of the flow.
1.14
DESCRIBE the relationship between Bernoullis equation and the First Law of
Thermodynamics.
Rev. 0
Page vii
HT-03
OBJECTIVES
Fluid Flow

1.15
DEFINE the term head with respect to its use in fluid flow.
1.16
EXPLAIN the energy conversions that take place in a fluid system between the velocity,
elevation, and pressure heads as flow continues through a piping system.
1.17
Given the initial and final conditions of the system, CALCULATE the unknown fluid
properties using the simplified Bernoulli equation.
1.18
DESCRIBE the restrictions applied to Bernoullis equation when presented in its simplest
form.
1.19
EXPLAIN how to extend the Bernoulli equation to more general applications.
1.20
RELATE Bernoullis principle to the operation of a venturi.
1.21
DEFINE the terms head loss, frictional loss, and minor losses.
1.22
DETERMINE friction factors for various flow situations using the Moody chart.
1.23
CALCULATE the head loss in a fluid system due to frictional losses using Darcys
equation.
1.24
CALCULATE the equivalent length of pipe that would cause the same head loss as the
minor losses that occur in individual components.
1.25
DEFINE natural circulation and forced circulation.
1.26
DEFINE thermal driving head.
1.27
DESCRIBE the conditions necessary for natural circulation to exist.
1.28
EXPLAIN the relationship between flow rate and temperature difference in natural
circulation flow.
1.29
DESCRIBE how the operator can determine whether natural circulation exists in the
reactor coolant system and other heat removal systems.
1.30
DESCRIBE how to enhance natural circulation flow.
1.31
DEFINE two-phase flow.
HT-03
Page viii
Rev. 0
Fluid Flow
OBJECTIVES

1.32
DESCRIBE two-phase flow including such phenomena as bubbly, slug, and annular flow.
1.33
DESCRIBE the problems associated with core flow oscillations and flow instability.
1.34
DESCRIBE the conditions that could lead to core flow oscillation and instability.
1.35
DESCRIBE the phenomenon of pipe whip.
1.36
DESCRIBE the phenomenon of water hammer.
1.37
DEFINE the terms net positive suction head and cavitation.
1.38
CALCULATE the new volumetric flow rate, head, or power for a variable speed
centrifugal pump using the pump laws.
1.39
DESCRIBE the effect on system flow and pump head for the following changes:
a.
Changing pump speeds
b.
Adding pumps in parallel
c.
Adding pumps in series
Rev. 0
Page ix
HT-03
Fluid Flow
HT-03
Page x
Rev. 0
Fluid Flow
CONTINUITY EQUATION
CONTINUITY EQUATION
Understanding the quantities measured by the volumetric flow rate
and mass flow rate is crucial to understanding other fluid flow topics.
The continuity equation expresses the relationship between mass flow
rates at different points in a fluid system under steady-state flow
conditions.
EO 1.1
DESCRIBE how the density of a fluid varies with temperature.
EO 1.2
DEFINE the term buoyancy.
EO 1.3
DESCRIBE the relationship between the pressure in a

fluid column and the density and depth of the fluid.
EO 1.4
STATE Pascals Law.
EO 1.5
DEFINE the terms mass flow rate and volumetric flow

rate.
EO 1.6
CALCULATE either the mass flow rate or the

volumetric flow rate for a fluid system.
EO 1.7
STATE the principle of conservation of mass.
EO 1.8
CALCULATE the fluid velocity or flow rate in a

specified fluid system using the continuity equation.
Introduction
Fluid flow is an important part of most industrial processes; especially those involving the
transfer of heat. Frequently, when it is desired to remove heat from the point at which it is
generated, some type of fluid is involved in the heat transfer process. Examples of this are the
cooling water circulated through a gasoline or diesel engine, the air flow past the windings of
a motor, and the flow of water through the core of a nuclear reactor. Fluid flow systems are also
commonly used to provide lubrication.
Fluid flow in the nuclear field can be complex and is not always subject to rigorous mathematical
analysis. Unlike solids, the particles of fluids move through piping and components at different
velocities and are often subjected to different accelerations.
Rev. 0
Page 1
HT-03
CONTINUITY EQUATION
Fluid Flow
Even though a detailed analysis of fluid flow can be extremely difficult, the basic concepts
involved in fluid flow problems are fairly straightforward. These basic concepts can be applied
in solving fluid flow problems through the use of simplifying assumptions and average values,
where appropriate. Even though this type of analysis would not be sufficient in the engineering
design of systems, it is very useful in understanding the operation of systems and predicting the
approximate response of fluid systems to changes in operating parameters.
The basic principles of fluid flow include three concepts or principles; the first two of which the
student has been exposed to in previous manuals. The first is the principle of momentum
(leading to equations of fluid forces) which was covered in the manual on Classical Physics. The
second is the conservation of energy (leading to the First Law of Thermodynamics) which was
studied in thermodynamics. The third is the conservation of mass (leading to the continuity
equation) which will be explained in this module.
Properties of Fluids
A fluid is any substance which flows because its particles are not rigidly attached to one another.
This includes liquids, gases and even some materials which are normally considered solids, such
as glass. Essentially, fluids are materials which have no repeating crystalline structure.
Several properties of fluids were discussed in the Thermodynamics section of this text. These
included temperature, pressure, mass, specific volume and density. Temperature was defined as
the relative measure of how hot or cold a material is. It can be used to predict the direction that
heat will be transferred. Pressure was defined as the force per unit area. Common units for
pressure are pounds force per square inch (psi). Mass was defined as the quantity of matter
contained in a body and is to be distinguished from weight, which is measured by the pull of
gravity on a body. The specific volume of a substance is the volume per unit mass of the
substance. Typical units are ft3/lbm. Density, on the other hand, is the mass of a substance per
unit volume. Typical units are lbm/ft3. Density and specific volume are the inverse of one
another. Both density and specific volume are dependant on the temperature and somewhat on
the pressure of the fluid. As the temperature of the fluid increases, the density decreases and the
specific volume increases. Since liquids are considered incompressible, an increase in pressure
will result in no change in density or specific volume of the liquid. In actuality, liquids can be
slightly compressed at high pressures, resulting in a slight increase in density and a slight
decrease in specific volume of the liquid.
Buoyancy
Buoyancy is defined as the tendency of a body to float or rise when submerged in a fluid. We
all have had numerous opportunities of observing the buoyant effects of a liquid. When we go
swimming, our bodies are held up almost entirely by the water. Wood, ice, and cork float on
water. When we lift a rock from a stream bed, it suddenly seems heavier on emerging from the
water. Boats rely on this buoyant force to stay afloat. The amount of this buoyant effect was
first computed and stated by the Greek philosopher Archimedes. When a body is placed in a
fluid, it is buoyed up by a force equal to the weight of the water that it displaces.
HT-03
Page 2
Rev. 0
Fluid Flow
CONTINUITY EQUATION
If a body weighs more than the liquid it displaces, it sinks but will appear to lose an amount of
weight equal to that of the displaced liquid, as our rock. If the body weighs less than that of the
displaced liquid, the body will rise to the surface eventually floating at such a depth that will
displace a volume of liquid whose weight will just equal its own weight. A floating body
displaces its own weight of the fluid in which it floats.
Compressibility
Compressibility is the measure of the change in volume a substance undergoes when a pressure
is exerted on the substance. Liquids are generally considered to be incompressible. For instance,
a pressure of 16,400 psig will cause a given volume of water to decrease by only 5% from its
volume at atmospheric pressure. Gases on the other hand, are very compressible. The volume
of a gas can be readily changed by exerting an external pressure on the gas
Relationship Between Depth and Pressure

Anyone who dives under the surface of the water notices that the pressure on his eardrums at a
depth of even a few feet is noticeably greater than atmospheric pressure. Careful measurements
show that the pressure of a liquid is directly proportional to the depth, and for a given depth the
liquid exerts the same pressure in all directions.
Figure 1
Rev. 0
Pressure Versus Depth
Page 3
HT-03
CONTINUITY EQUATION
Fluid Flow
As shown in Figure 1 the pressure at different levels in the tank varies and this causes the fluid
to leave the tank at varying velocities. Pressure was defined to be force per unit area. In the
case of this tank, the force is due to the weight of the water above the point where the pressure
is being determined.
Example:
Pressure
Force
Area
Weight
Area
m g
A gc
V g
A gc
where:
m = mass in lbm
g
= acceleration due to earths gravity 32.17
gc = 32.17
ft
sec2
lbm ft
lbf sec2
A = area in ft2
V = volume in ft3
= density of fluid in
lbm
ft 3
The volume is equal to the cross-sectional area times the height (h) of liquid. Substituting
this in to the above equation yields:
HT-03
A h g
A gc
h g
gc
Page 4
Rev. 0
Fluid Flow
CONTINUITY EQUATION
This equation tells us that the pressure exerted by a column of water is directly proportional to
the height of the column and the density of the water and is independent of the cross-sectional
area of the column. The pressure thirty feet below the surface of a one inch diameter standpipe
is the same as the pressure thirty feet below the surface of a large lake.
Example 1:
If the tank in Figure 1 is filled with water that has a density of 62.4 lbm/ft3, calculate the
pressures at depths of 10, 20, and 30 feet.
Solution:
P
P10 feet
P20 feet
h g
gc
ft
32.17
sec
lbm
62.4
10 ft
3
ft
32.17 lbm ft
lbf sec2
624
lbf 1 ft 2
ft 2 144 in 2
4.33
lbf
in 2
ft
32.17
sec2
62.4 lbm 20 ft
ft 3
32.17 lbm ft
lbf sec2
lbf 1 ft 2
1248
ft 2 144 in 2
8.67
Rev. 0
lbf
in 2
Page 5
HT-03
CONTINUITY EQUATION
Fluid Flow
ft
32.17
sec2
62.4 lbm 30 ft
ft 3
32.17 lbm ft
lbf sec2
P30 feet
lbf 1 ft 2
1872
ft 2 144 in 2
13.00
lbf
in 2
Example 2:
A cylindrical water tank 40 ft high and 20 ft in diameter is filled with water that has a
density of 61.9 lbm/ft3.
(a)
What is the water pressure on the bottom of the tank?
(b)
What is the average force on the bottom?
Solution:
(a)
h g
gc
ft
32.17
sec2
61.9 lbm 40 ft
ft 3
32.17 lbm ft
lbf sec2
lbf 1 ft 2
2476
ft 2 144 in 2
17.2
HT-03
lbf
in 2
Page 6
Rev. 0
Fluid Flow
(b)
CONTINUITY EQUATION
Pressure
Force
Area
Force
Area
(Pressure) (Area)
r 2
17.2 lbf 10 ft 2 144 in 2
2
in 2
1 ft
7.78 x 105 lbf
Pascals Law
The pressure of the liquids in each of the previously cited cases has been due to the weight of
the liquid. Liquid pressures may also result from application of external forces on the liquid.
Consider the following examples. Figure 2 represents a container completely filled with liquid.
A, B, C, D, and E represent pistons of equal cross-sectional areas fitted into the walls of the
vessel. There will be forces acting on the pistons C, D, and E due to the pressures caused by
the different depths of the liquid. Assume that the forces on the pistons due to the pressure
caused by the weight of the liquid are as follows: A = 0 lbf, B = 0 lbf, C = 10 lbf, D = 30 lbf,
and E = 25 lbf. Now let an external force of 50 lbf be applied to piston A. This external force
will cause the pressure at all points in the container to increase by the same amount. Since the
pistons all have the same cross-sectional area, the increase in pressure will result in the forces
on the pistons all increasing by 50 lbf. So if an external force of 50 lbf is applied to piston A,
the force exerted by the fluid on the other pistons will now be as follows: B = 50 lbf, C = 60
lbf, D = 80 lbf, and E = 75 lbf.
This effect of an external force on a confined fluid was first stated by Pascal in 1653.
Pressure applied to a confined fluid is transmitted undiminished throughout the
confining vessel of the system.
Rev. 0
Page 7
HT-03
CONTINUITY EQUATION
Fluid Flow
Figure 2
Pascals Law
Control Volume
In thermodynamics, a control volume was defined as a fixed region in space where one studies
the masses and energies crossing the boundaries of the region. This concept of a control volume
is also very useful in analyzing fluid flow problems. The boundary of a control volume for fluid
flow is usually taken as the physical boundary of the part through which the flow is occurring.
The control volume concept is used in fluid dynamics applications, utilizing the continuity,
momentum, and energy principles mentioned at the beginning of this chapter. Once the control
volume and its boundary are established, the various forms of energy crossing the boundary with
the fluid can be dealt with in equation form to solve the fluid problem. Since fluid flow
problems usually treat a fluid crossing the boundaries of a control volume, the control volume
approach is referred to as an "open" system analysis, which is similar to the concepts studied in
thermodynamics. There are special cases in the nuclear field where fluid does not cross the
control boundary. Such cases are studied utilizing the "closed" system approach.
Regardless of the nature of the flow, all flow situations are found to be subject to the established
basic laws of nature that engineers have expressed in equation form. Conservation of mass and
conservation of energy are always satisfied in fluid problems, along with Newtons laws of
motion. In addition, each problem will have physical constraints, referred to mathematically as
boundary conditions, that must be satisfied before a solution to the problem will be consistent
with the physical results.
HT-03
Page 8
Rev. 0
Fluid Flow
CONTINUITY EQUATION
Volumetric Flow Rate

) of a system is a measure of the volume of fluid passing a point in
The volumetric flow rate ( V
the system per unit time. The volumetric flow rate can be calculated as the product of the crosssectional area (A) for flow and the average flow velocity (v).
A v
(3-1)
If area is measured in square feet and velocity in feet per second, Equation 3-1 results in
volumetric flow rate measured in cubic feet per second. Other common units for volumetric flow
rate include gallons per minute, cubic centimeters per second, liters per minute, and gallons per
hour.
Example:
A pipe with an inner diameter of 4 inches contains water that flows at an average velocity
of 14 feet per second. Calculate the volumetric flow rate of water in the pipe.
Solution:
Use Equation 3-1 and substitute for the area.
( r 2) v
(3.14) (
1.22
2
ft
ft)2 (14
)
12
sec
ft 3
sec
Mass Flow Rate

The mass flow rate (m)
of a system is a measure of the mass of fluid passing a point in the
system per unit time. The mass flow rate is related to the volumetric flow rate as shown in
Equation 3-2 where is the density of the fluid.
m
(3-2)
If the volumetric flow rate is in cubic feet per second and the density is in pounds-mass per cubic
foot, Equation 3-2 results in mass flow rate measured in pounds-mass per second. Other
common units for measurement of mass flow rate include kilograms per second and pounds-mass
per hour.
Rev. 0
Page 9
HT-03
CONTINUITY EQUATION
Fluid Flow
in Equation 3-2 with the appropriate terms from Equation 3-1 allows the direct
Replacing V
calculation of the mass flow rate.
m
A v
(3-3)
Example:
The water in the pipe of the previous example had a density of 62.44 lbm/ft3. Calculate
the mass flow rate.
Solution:
m
(62.44
76.2
lbm
ft 3
) (1.22
)
sec
ft 3
lbm
sec
Conservation of Mass
In thermodynamics, you learned that energy can neither be created nor destroyed, only changed
in form. The same is true for mass. Conservation of mass is a principle of engineering that
states that all mass flow rates into a control volume are equal to all mass flow rates out of the
control volume plus the rate of change of mass within the control volume. This principle is
expressed mathematically by Equation 3-4.
m
in
m
out
m
t
(3-4)
where:
m
=
t
the increase or decrease of the mass within the control volume over a
(specified time period)
Steady-State Flow
Steady-state flow refers to the condition where the fluid properties at any single point in the
system do not change over time. These fluid properties include temperature, pressure, and
velocity. One of the most significant properties that is constant in a steady-state flow system is
the system mass flow rate. This means that there is no accumulation of mass within any
component in the system.
HT-03
Page 10
Rev. 0
Fluid Flow
CONTINUITY EQUATION
Continuity Equation
The continuity equation is simply a mathematical expression of the principle of conservation of
mass. For a control volume that has a single inlet and a single outlet, the principle of
conservation of mass states that, for steady-state flow, the mass flow rate into the volume must
equal the mass flow rate out. The continuity equation for this situation is expressed by Equation
3-5.
m
inlet
m
outlet
(3-5)
(Av)inlet = (Av)outlet
For a control volume with multiple inlets and outlets, the principle of conservation of mass
requires that the sum of the mass flow rates into the control volume equal the sum of the mass
flow rates out of the control volume. The continuity equation for this more general situation is
expressed by Equation 3-6.
m
inlets
m
outlets
(3-6)
One of the simplest applications of the continuity equation is determining the change in fluid
velocity due to an expansion or contraction in the diameter of a pipe.
Example:
Continuity Equation - Piping Expansion
Steady-state flow exists in a pipe that undergoes a gradual expansion from a diameter of
6 in. to a diameter of 8 in. The density of the fluid in the pipe is constant at 60.8 lbm/ft3.
If the flow velocity is 22.4 ft/sec in the 6 in. section, what is the flow velocity in the 8
in. section?
Solution:
From the continuity equation we know that the mass flow rate in the 6 in. section must
equal the mass flow rate in the 8 in. section. Letting the subscript 1 represent the 6 in.
section and 2 represent the 8 in. section we have the following.
Rev. 0
Page 11
HT-03
CONTINUITY EQUATION
Fluid Flow
m
1
1 A1 v1
v2
m
2
2 A2 v2
v1
1 A1
2 A2
r1
v1
r2
ft (3 in)2
22.4
sec (4 in)2
ft
sec
So by using the continuity equation, we find that the increase in pipe diameter from 6 to 8 inches
caused a decrease in flow velocity from 22.4 to 12.6 ft/sec.
v2 12.6
The continuity equation can also be used to show that a decrease in pipe diameter will cause an
increase in flow velocity.
Figure 3
HT-03
Continuity Equation
Page 12
Rev. 0
Fluid Flow
Example:
CONTINUITY EQUATION
Continuity Equation - Centrifugal Pump
The inlet diameter of the reactor coolant pump shown in Figure 3 is 28 in. while the
outlet flow through the pump is 9200 lbm/sec. The density of the water is 49 lbm/ft3.
What is the velocity at the pump inlet?
Solution:
Ainlet
1 ft 2
(3.14) 14 in
12 in
r 2
4.28 ft 2
m
inlet
m
outlet
(Av)inlet
9200
9200
lbm
sec
lbm
sec
lbm
sec
A
9200
vinlet
9200
lbm
sec
lbm
(4.28 ft 2) 49
ft 3
vinlet
43.9
ft
sec
The above example indicates that the flow rate into the system is the same as that out of the
system. The same concept is true even though more than one flow path may enter or leave the
system at the same time. The mass balance is simply adjusted to state that the sum of all flows
entering the system is equal to the sum of all the flows leaving the system if steady-state
conditions exist. An example of this physical case is included in the following example.
Rev. 0
Page 13
HT-03
CONTINUITY EQUATION
Fluid Flow
Figure 4
Example:
"Y" Configuration for Example Problem
Continuity Equation - Multiple Outlets
A piping system has a "Y" configuration for separating the flow as shown in Figure 4.
The diameter of the inlet leg is 12 in., and the diameters of the outlet legs are 8 and 10
in. The velocity in the 10 in. leg is 10 ft/sec. The flow through the main portion is 500
lbm/sec. The density of water is 62.4 lbm/ft3. What is the velocity out of the 8 in. pipe
section?
HT-03
Page 14
Rev. 0
Fluid Flow
CONTINUITY EQUATION
Solution:
A8
1 ft 2
4 in.
12 in.
0.349 ft 2
A10
1 ft 2
5 in.
12 in.
0.545 ft 2
m
inlets
m
outlets
m
12
m
10
m
8
m
8
m
12
m
10
(Av)8
m
12
(Av)10
m
12
(Av)10
v8
(A)8
500
v8
7.3
lbm
sec
62.4 lbm (0.545 ft 2)
ft 3
62.4 lbm (0.349 ft 2)
ft 3
ft
10
sec
ft
sec
Summary
The main points of this chapter are summarized on the next page.
Rev. 0
Page 15
HT-03
CONTINUITY EQUATION
Fluid Flow
Continuity Equation Summary
Density changes in a fluid are inversely proportional to temperature changes.
Buoyancy is the tendency of a body to float or rise when submerged in a

fluid.
The pressure exerted by a column of water is directly proportional to the

height of the column and the density of the water.
h g
P =
gc
Pascals law states that pressure applied to a confined fluid is transmitted

undiminished throughout the confining vessel of a system.
Volumetric flow rate is the volume of fluid per unit time passing a point in
a fluid system.
Mass flow rate is the mass of fluid per unit time passing a point in a fluid
system.
The volumetric flow rate is calculated by the product of the average fluid
velocity and the cross-sectional area for flow.
A v
The mass flow rate is calculated by the product of the volumetric flow rate
and the fluid density.
A v
The principle of conservation of mass states that all mass flow rates into a
control volume are equal to all mass flow rates out of the control volume
plus the rate of change of mass within the control volume.
For a control volume with a single inlet and outlet, the continuity equation
can be expressed as follows:
m
inlet
For a control volume with multiple inlets and outlets, the continuity
equation is:
m
inlets
HT-03
m
outlet
m
outlets
Page 16
Rev. 0
Fluid Flow
LAMINAR AND TURBULENT FLOW

The characteristics of laminar and turbulent flow are very different.
To understand why turbulent or laminar flow is desirable in the
operation of a particular system, it is necessary to understand the
characteristics of laminar and turbulent flow.
EO 1.9
DESCRIBE the characteristics and flow velocity profiles

of laminar flow and turbulent flow.
EO 1.10
DEFINE the property of viscosity.
EO 1.11
DESCRIBE how the viscosity of a fluid varies with

temperature.
EO 1.12
DESCRIBE the characteristics of an ideal fluid.
EO 1.13
DESCRIBE the relationship between the Reynolds

number and the degree of turbulence of the flow.
Flow Regimes
All fluid flow is classified into one of two broad categories or regimes. These two flow regimes
are laminar flow and turbulent flow. The flow regime, whether laminar or turbulent, is important
in the design and operation of any fluid system. The amount of fluid friction, which determines
the amount of energy required to maintain the desired flow, depends upon the mode of flow.
This is also an important consideration in certain applications that involve heat transfer to the
fluid.
Laminar Flow
Laminar flow is also referred to as streamline or viscous flow. These terms are descriptive of
the flow because, in laminar flow, (1) layers of water flowing over one another at different
speeds with virtually no mixing between layers, (2) fluid particles move in definite and
observable paths or streamlines, and (3) the flow is characteristic of viscous (thick) fluid or is
one in which viscosity of the fluid plays a significant part.
Turbulent Flow
Turbulent flow is characterized by the irregular movement of particles of the fluid. There is no
definite frequency as there is in wave motion. The particles travel in irregular paths with no
observable pattern and no definite layers.
Rev. 0
Page 17
HT-03
Fluid Flow
Flow Velocity Profiles

Not all fluid particles travel at the same velocity within a pipe. The shape of the velocity curve
(the velocity profile across any given section of the pipe) depends upon whether the flow is
laminar or turbulent. If the flow in a pipe is laminar, the velocity distribution at a cross section
will be parabolic in shape with the maximum velocity at the center being about twice the average
velocity in the pipe. In turbulent flow, a fairly flat velocity distribution exists across the section
of pipe, with the result that the entire fluid flows at a given single value. Figure 5 helps illustrate
the above ideas. The velocity of the fluid in contact with the pipe wall is essentially zero and
increases the further away from the wall.
Figure 5
Laminar and Turbulent Flow Velocity Profiles
Note from Figure 5 that the velocity profile depends upon the surface condition of the pipe wall.
A smoother wall results in a more uniform velocity profile than a rough pipe wall.
HT-03
Page 18
Rev. 0
Fluid Flow
Average (Bulk) Velocity

In many fluid flow problems, instead of determining exact velocities at different locations in the
same flow cross-section, it is sufficient to allow a single average velocity to represent the
velocity of all fluid at that point in the pipe. This is fairly simple for turbulent flow since the
velocity profile is flat over the majority of the pipe cross-section. It is reasonable to assume that
the average velocity is the same as the velocity at the center of the pipe.
If the flow regime is laminar (the velocity profile is parabolic), the problem still exists of trying
to represent the "average" velocity at any given cross-section since an average value is used in
the fluid flow equations. Technically, this is done by means of integral calculus. Practically, the
student should use an average value that is half of the center line value.
Viscosity
Viscosity is a fluid property that measures the resistance of the fluid to deforming due to a shear
force. Viscosity is the internal friction of a fluid which makes it resist flowing past a solid
surface or other layers of the fluid. Viscosity can also be considered to be a measure of the
resistance of a fluid to flowing. A thick oil has a high viscosity; water has a low viscosity. The
unit of measurement for absolute viscosity is:
= absolute viscosity of fluid (lbf-sec/ft2).
The viscosity of a fluid is usually significantly dependent on the temperature of the fluid and
relatively independent of the pressure. For most fluids, as the temperature of the fluid increases,
the viscosity of the fluid decreases. An example of this can be seen in the lubricating oil of
engines. When the engine and its lubricating oil are cold, the oil is very viscous, or thick. After
the engine is started and the lubricating oil increases in temperature, the viscosity of the oil
decreases significantly and the oil seems much thinner.
Ideal Fluid
An ideal fluid is one that is incompressible and has no viscosity. Ideal fluids do not actually
exist, but sometimes it is useful to consider what would happen to an ideal fluid in a particular
fluid flow problem in order to simplify the problem.
Reynolds Number
The flow regime (either laminar or turbulent) is determined by evaluating the Reynolds number
of the flow (refer to figure 5). The Reynolds number, based on studies of Osborn Reynolds, is
a dimensionless number comprised of the physical characteristics of the flow. Equation 3-7 is
used to calculate the Reynolds number (NR) for fluid flow.
NR = v D / gc
Rev. 0
(3-7)
Page 19
HT-03
Fluid Flow
where:
NR
v
D
gc
=
=
=
=
=
=
Reynolds number (unitless)

average velocity (ft/sec)
diameter of pipe (ft)
absolute viscosity of fluid (lbf-sec/ft2)
fluid mass density (lbm/ft3)
gravitational constant (32.2 ft-lbm/lbf-sec2)
For practical purposes, if the Reynolds number is less than 2000, the flow is laminar. If it is
greater than 3500, the flow is turbulent. Flows with Reynolds numbers between 2000 and 3500
are sometimes referred to as transitional flows. Most fluid systems in nuclear facilities operate
with turbulent flow. Reynolds numbers can be conveniently determined using a Moody Chart;
an example of which is shown in Appendix B. Additional detail on the use of the Moody Chart
is provided in subsequent text.
Summary
The main points of this chapter are summarized below.
Laminar and Turbulent Flow Summary

Laminar Flow
Layers of water flow over one another at different speeds with virtually no
mixing between layers.
The flow velocity profile for laminar flow in circular pipes is parabolic in shape,
with a maximum flow in the center of the pipe and a minimum flow at the pipe
walls.
The average flow velocity is approximately one half of the maximum velocity.
Turbulent Flow
The flow is characterized by the irregular movement of particles of the fluid.
The flow velocity profile for turbulent flow is fairly flat across the center section
of a pipe and drops rapidly extremely close to the walls.
The average flow velocity is approximately equal to the velocity at the center of
the pipe.
Viscosity is the fluid property that measures the resistance of the fluid to deforming
due to a shear force. For most fluids, temperature and viscosity are inversely
proportional.
An ideal fluid is one that is incompressible and has no viscosity.
An increasing Reynolds number indicates an increasing turbulence of flow.
HT-03
Page 20
Rev. 0
Fluid Flow
BERNOULLIS EQUATION
BERNOULLIS EQUATION
Bernoullis equation is a special case of the general energy equation
that is probably the most widely-used tool for solving fluid flow
problems. It provides an easy way to relate the elevation head,
velocity head, and pressure head of a fluid. It is possible to modify
Bernoullis equation in a manner that accounts for head losses and
pump work.
EO 1.14
DESCRIBE the relationship between Bernoullis

equation and the First Law of Thermodynamics.
EO 1.15
DEFINE the term head with respect to its use in fluid

flow.
EO 1.16
EXPLAIN the energy conversions that take place in a

fluid system between the velocity, elevation, and
pressure heads as flow continues through a piping
system.
EO 1.17
Given the initial and final conditions of the system,

CALCULATE the unknown fluid properties using the
simplified Bernoulli equation.
EO 1.18
DESCRIBE the restrictions applied to Bernoullis

equation when presented in its simplest form.
EO 1.19
EXPLAIN how to extend the Bernoulli equation to

more general applications.
EO 1.20
RELATE Bernoullis principle to the operation of a

venturi.
General Energy Equation

The conservation of energy principle states that energy can be neither created nor destroyed.
This is equivalent to the First Law of Thermodynamics, which was used to develop the general
energy equation in the module on thermodynamics. Equation 3-8 is a statement of the general
energy equation for an open system.
Q + (U + PE + KE + PV)in =
W + (U + PE + KE + PV)out + (U + PE + KE + PV)stored
Rev. 0
Page 21
(3-8)
HT-03
BERNOULLIS EQUATION
Fluid Flow
where:
Q
U
PE
KE
P
V
W
=
=
=
=
=
=
=
heat (Btu)
internal energy (Btu)
potential energy (ft-lbf)
kinetic energy (ft-lbf)
pressure (lbf/ft2)
volume (ft3)
work (ft-lbf)
Simplified Bernoulli Equation

Bernoullis equation results from the application of the general energy equation and the first law
of thermodynamics to a steady flow system in which no work is done on or by the fluid, no heat
is transferred to or from the fluid, and no change occurs in the internal energy (i.e., no
temperature change) of the fluid. Under these conditions, the general energy equation is
simplified to Equation 3-9.
(PE + KE + PV)1 = (PE + KE + PV)2
(3-9)
Substituting appropriate expressions for the potential energy and kinetic energy, Equation 3-9 can
be rewritten as Equation 3-10.
mgz1
mv1
gc
2gc
P1V1
mgz2
mv2
gc
2gc
P2V2
(3-10)
where:
m
z
v
g
gc
=
=
=
=
=
mass (lbm)
height above reference (ft)
average velocity (ft/sec)
acceleration due to gravity (32.17 ft/sec2)
gravitational constant, (32.17 ft-lbm/lbf-sec2)
Note: The factor gc is only required when the English System of measurement is used and mass
is measured in pound mass. It is essentially a conversion factor needed to allow the units
to come out directly. No factor is necessary if mass is measured in slugs or if the metric
system of measurement is used.
Each term in Equation 3-10 represents a form of energy possessed by a moving fluid (potential,
kinetic, and pressure related energies). In essence, the equation physically represents a balance
of the KE, PE, PV energies so that if one form of energy increases, one or more of the others
will decrease to compensate and vice versa.
HT-03
Page 22
Rev. 0
Fluid Flow
BERNOULLIS EQUATION
Multiplying all terms in Equation 3-10 by the factor gc/mg results in the form of Bernoullis
equation shown by Equation 3-11.
z1
v1
2g
P11
gc
g
z2
v2
2g
P22
gc
g
(3-11)
Head
Since the units for all the different forms of energy in Equation 3-11 are measured in units of
distance, these terms are sometimes referred to as "heads" (pressure head, velocity head, and
elevation head). The term head is used by engineers in reference to pressure. It is a reference
to the height, typically in feet, of a column of water that a given pressure will support. Each of
the energies possessed by a fluid can be expressed in terms of head. The elevation head
represents the potential energy of a fluid due to its elevation above a reference level. The
velocity head represents the kinetic energy of the fluid. It is the height in feet that a flowing
fluid would rise in a column if all of its kinetic energy were converted to potential energy. The
pressure head represents the flow energy of a column of fluid whose weight is equivalent to the
pressure of the fluid.
The sum of the elevation head, velocity head, and pressure head of a fluid is called the total
head. Thus, Bernoullis equation states that the total head of the fluid is constant.
Energy Conversions in Fluid Systems

Bernoullis equation makes it easy to examine how energy transfers take place among elevation
head, velocity head, and pressure head. It is possible to examine individual components of piping
systems and determine what fluid properties are varying and how the energy balance is affected.
If a pipe containing an ideal fluid undergoes a gradual expansion in diameter, the continuity
equation tells us that as the diameter and flow area get bigger, the flow velocity must decrease
to maintain the same mass flow rate. Since the outlet velocity is less than the inlet velocity, the
velocity head of the flow must decrease from the inlet to the outlet. If the pipe lies horizontal,
there is no change in elevation head; therefore, the decrease in velocity head must be
compensated for by an increase in pressure head. Since we are considering an ideal fluid that
is incompressible, the specific volume of the fluid will not change. The only way that the
pressure head for an incompressible fluid can increase is for the pressure to increase. So the
Bernoulli equation indicates that a decrease in flow velocity in a horizontal pipe will result in an
increase in pressure.
If a constant diameter pipe containing an ideal fluid undergoes a decrease in elevation, the same
net effect results, but for different reasons. In this case the flow velocity and the velocity head
must be constant to satisfy the mass continuity equation.
Rev. 0
Page 23
HT-03
BERNOULLIS EQUATION
Fluid Flow
So the decrease in elevation head can only be compensated for by an increase in pressure head.
Again, the fluid is incompressible so the increase in pressure head must result in an increase in
pressure.
Although the Bernoulli equation has several restrictions placed upon it, there are many physical
fluid problems to which it is applied. As in the case of the conservation of mass, the Bernoulli
equation may be applied to problems in which more than one flow may enter or leave the system
at the same time. Of particular note is the fact that series and parallel piping system problems
are solved using the Bernoulli equation.
Example:
Bernoullis Equation
Assume frictionless flow in a long, horizontal, conical pipe. The diameter is 2.0 ft at one
end and 4.0 ft at the other. The pressure head at the smaller end is 16 ft of water. If
water flows through this cone at a rate of 125.6 ft3/sec, find the velocities at the two ends
and the pressure head at the larger end.
Solution:
V
1
v1
A1v1
V
1
V
2
v2
A1
ft 3
sec
(1 ft)2
A2
ft 3
sec
(2 ft)2
125.6
v1
v1
z1
P22
v2
2g
gc
v2
ft
sec
40
v1
125.6
gc
P11
P11
z2
g
gc
g
16 ft
(z1
0 ft
v2
2g
z 2)
ft
sec
10
P22
v1
gc
g
v2
2g
ft 2
ft 2
40
10
sec
sec
ft lbm
2 32.17
lbf sec2
39.3 ft
HT-03
Page 24
Rev. 0
Fluid Flow
BERNOULLIS EQUATION
Restrictions on the Simplified Bernoulli Equation

Practical applications of the simplified Bernoulli Equation to real piping systems is not possible
due to two restrictions. One serious restriction of the Bernoulli equation in its present form is
that no fluid friction is allowed in solving piping problems. Therefore, Equation 3-10 only
applies to ideal fluids. However, in reality, the total head possessed by the fluid cannot be
transferred completely from one point to another because of friction. Taking these losses of head
into account would provide a much more accurate description of what takes place physically.
This is especially true because one purpose of a pump in a fluid system is to overcome the losses
in pressure due to pipe friction.
The second restriction on Bernoullis equation is that no work is allowed to be done on or by the
fluid. This restriction prevents two points in a fluid stream from being analyzed if a pump exists
between the two points. Since most flow systems include pumps, this is a significant limitation.
Fortunately, the simplified Bernoulli equation can be modified in a manner that satisfactorily
deals with both head losses and pump work.
Extended Bernoulli
The Bernoulli equation can be modified to take into account gains and losses of head. The
resulting equation, referred to as the Extended Bernoulli equation, is very useful in solving most
fluid flow problems. In fact, the Extended Bernoulli equation is probably used more than any
other fluid flow equation. Equation 3-12 is one form of the Extended Bernoulli equation.
z1
v1
2g
P11
gc
g
Hp
z2
v2
2g
P22
gc
g
Hf
(3-12)
where:
z
v
P
Hp
Hf
g
=
=
=
=
=
=
=
height above reference level (ft)

average velocity of fluid (ft/sec)
pressure of fluid (lbf/ft2)
specific volume of fluid (ft3/lbm)
head added by pump (ft)
head loss due to fluid friction (ft)
acceleration due to gravity (ft/sec2)
The head loss due to fluid friction (Hf) represents the energy used in overcoming friction caused
by the walls of the pipe. Although it represents a loss of energy from the standpoint of fluid
flow, it does not normally represent a significant loss of total energy of the fluid. It also does
not violate the law of conservation of energy since the head loss due to friction results in an
equivalent increase in the internal energy (u) of the fluid. These losses are greatest as the fluid
flows through entrances, exits, pumps, valves, fittings, and any other piping with rough inner
surfaces.
Rev. 0
Page 25
HT-03
BERNOULLIS EQUATION
Fluid Flow
Most techniques for evaluating head loss due to friction are empirical (based almost exclusively
on experimental evidence) and are based on a proportionality constant called the friction factor
(f), which will be discussed in the next section.
Example:
Extended Bernoulli
Water is pumped from a large reservoir to a point 65 feet higher than the reservoir. How
many feet of head must be added by the pump if 8000 lbm/hr flows through a 6-inch pipe
and the frictional head loss is 2 feet? The density of the fluid is 62.4 lbm/ft3, and the
cross-sectional area of a 6-inch pipe is 0.2006 ft2.
Solution:
To use the modified form of Bernoullis equation, reference points are chosen at the
surface of the reservoir (point 1) and at the outlet of the pipe (point 2). The pressure at
the surface of the reservoir is the same as the pressure at the exit of the pipe, i.e.,
atmospheric pressure. The velocity at point 1 will be essentially zero.
Using the equation for the mass flow rate to determine the velocity at point 2:
m
2
v2
A2v2
m
2
A2
8000
v2
HT-03
lbm
hr
62.4 lbm (0.2006 ft 2)
ft 3
ft 1 hr
hr 3600 sec
v2
639
v2
0.178
ft
sec
Page 26
Rev. 0
Fluid Flow
BERNOULLIS EQUATION
Now we can use the Extended Bernoulli equation to determine the required pump head.
z1
Hp
v1
2g
(z2
65 ft
Hp
P11
z1)
gc
g
Hp
z2
2
2
v1
v2
2g
v2
P22
2g
(P2
P1)
ft 2 ft 2
0.178
sec
sec
ft lbm
2 32.17
lbf sec2
gc
g
gc
g
0 ft
Hf
Hf
2 ft
67 ft
The student should note that the solution of this example problem has a numerical value that
"makes sense" from the data given in the problem. The total head increase of 67 ft. is due
primarily to the 65 ft. evaluation increase and the 2 ft. of friction head.
Application of Bernoullis Equation to a Venturi

Many plant components, such as a venturi, may be analyzed using Bernoullis equation and the
continuity equation. A venturi is a flow measuring device that consists of a gradual contraction
followed by a gradual expansion. An example of a venturi is shown in Figure 6. By measuring
the differential pressure between the inlet of the venturi (point 1) and the throat of the venturi
(point 2), the flow velocity and mass flow rate can be determined based on Bernoullis equation.
Figure 6
Rev. 0
Venturi Meter
Page 27
HT-03
BERNOULLIS EQUATION
Fluid Flow
Bernoullis equation states that the total head of the flow must be constant. Since the elevation
does not change significantly, if at all, between points 1 and 2, the elevation head at the two
points will be essentially the same and will cancel out of the equation. So Bernoullis equation
simplifies to Equation 3-13 for a venturi.
v1
P11
2g
gc
v2
2g
P22
gc
(3-13)
Applying the continuity equation to points 1 and 2 allows us to express the flow velocity at point
1 as a function of the flow velocity at point 2 and the ratio of the two flow areas.
1A1v1
2A2v2
2A2v2
v1
1A1
v1
v2
A2
A1
Using algebra to rearrange Equation 3-13 and substituting the above result for v1 allows us to
solve for v2.
v2
v1
2g
v2
v2
HT-03
A 2
2
v
2 A
1
A 2
2
A
1
gc
(P1
P2)
(P1
P2) 2gc
(P1
P2) 2gc
Page 28
Rev. 0
Fluid Flow
BERNOULLIS EQUATION
Therefore the flow velocity at the throat of the venturi and the volumetric flow rate are directly
proportional to the square root of the differential pressure.
The pressures at the upstream section and throat are actual pressures, and velocities from
Bernoullis equation without a loss term are theoretical velocities. When losses are considered
in the energy equation, the velocities are actual velocities. First, with the Bernoulli equation (that
is, without a head-loss term), the theoretical velocity at the throat is obtained. Then by
multiplying this by the venturi factor (Cv), which accounts for friction losses and equals 0.98 for
most venturis, the actual velocity is obtained. The actual velocity times the actual area of the
throat determines the actual discharge volumetric flow rate.
The pressure drop, P1-P2, across the venturi can be used to measure the flow rate using a U-tube
manometer as shown in Figure 6. The reading, R, of the manometer is proportional to the
pressure drop and thus the velocity of the fluid.
Rev. 0
Page 29
HT-03
BERNOULLIS EQUATION
Fluid Flow
Summary
Bernoullis Equation Summary

Bernoullis equation is an application of the First Law of Thermodynamics.
Bernoullis equation is an application of the general energy equation to a steady
flow system in which no work is done on or by the fluid, no heat is transferred
to or from the fluid, and no change occurs in the internal energy of the fluid.
Head is the term used to describe pressure exerted on or by a fluid.
As fluid flows in a piping system, changes in elevation, velocity, and pressure
heads must be consistent so that Bernoullis equation is satisfied.
Bernoullis equation can be modified to take into account friction losses and
pump work.
A venturi can be used to determine mass flow rates due to changes in pressure
and fluid velocity.
The volumetric flow rate through a venturi is directly proportional to the square
root of the differential pressure between the venturis inlet and its throat.
HT-03
Page 30
Rev. 0
Fluid Flow
HEAD LOSS
HEAD LOSS
The head loss that occurs in pipes is dependent on the flow velocity,
pipe length and diameter, and a friction factor based on the roughness
of the pipe and the Reynolds number of the flow. The head loss that
occurs in the components of a flow path can be correlated to a piping
length that would cause an equivalent head loss.
EO 1.21
DEFINE the terms head loss, frictional loss, and minor

losses.
EO 1.22
DETERMINE friction factors for various flow situations

using the Moody chart.
EO 1.23
CALCULATE the head loss in a fluid system due to

frictional losses using Darcys equation.
EO 1.24
CALCULATE the equivalent length of pipe that would

cause the same head loss as the minor losses that occur
in individual components.
Head Loss
Head loss is a measure of the reduction in the total head (sum of elevation head, velocity head
and pressure head) of the fluid as it moves through a fluid system. Head loss is unavoidable in
real fluids. It is present because of: the friction between the fluid and the walls of the pipe; the
friction between adjacent fluid particles as they move relative to one another; and the turbulence
caused whenever the flow is redirected or affected in any way by such components as piping
entrances and exits, pumps, valves, flow reducers, and fittings.
Frictional loss is that part of the total head loss that occurs as the fluid flows through straight
pipes. The head loss for fluid flow is directly proportional to the length of pipe, the square of
the fluid velocity, and a term accounting for fluid friction called the friction factor. The head
loss is inversely proportional to the diameter of the pipe.
Head Loss f
Lv 2
D
Friction Factor
The friction factor has been determined to depend on the Reynolds number for the flow and the
degree of roughness of the pipes inner surface.
Rev. 0
Page 31
HT-03
HEAD LOSS
Fluid Flow
The quantity used to measure the roughness of the pipe is called the relative roughness, which
equals the average height of surface irregularities () divided by the pipe diameter (D).
Relative Roughness
The value of the friction factor is usually obtained from the Moody Chart (Figure B-1 of
Appendix B). The Moody Chart can be used to determine the friction factor based on the
Reynolds number and the relative roughness.
Example:
Determine the friction factor (f) for fluid flow in a pipe that has a Reynolds number of
40,000 and a relative roughness of 0.01.
Solution:
Using the Moody Chart, a Reynolds number of 40,000 intersects the curve corresponding
to a relative roughness of 0.01 at a friction factor of 0.04.
Darcys Equation
The frictional head loss can be calculated using a mathematical relationship that is known as
Darcys equation for head loss. The equation takes two distinct forms. The first form of Darcys
equation determines the losses in the system associated with the length of the pipe.
Hf
L v2
D 2 g
(3-14)
where:
f
L
D
v
g
Example:
=
=
=
=
=
friction factor (unitless)

length of pipe (ft)
diameter of pipe (ft)
fluid velocity (ft/sec)
gravitational acceleration (ft/sec2)
Darcys Head Loss Equation
A pipe 100 feet long and 20 inches in diameter contains water at 200F flowing at a mass
flow rate of 700 lbm/sec. The water has a density of 60 lbm/ft3 and a viscosity of 1.978
x 10-7 lbf-sec/ft2. The relative roughness of the pipe is 0.00008. Calculate the head loss
for the pipe.
HT-03
Page 32
Rev. 0
Fluid Flow
HEAD LOSS
Solution:
The sequence of steps necessary to solve this problem is first to determine the flow
velocity. Second, using the flow velocity and the fluid properties given, calculate the
Reynolds number. Third, determine the friction factor from the Reynolds number and the
relative roughness. Finally, use Darcys equation to determine the head loss.
m
Av
A
700
lbm
sec
60 lbm (10 in) 2 1 ft 2
ft 3
144 in 2
ft
sec
5.35
NR
vD
gc
NR
60 lbm 5.35 ft

sec
ft 3
lbf sec
1.978 x 10 7
ft 2
1 ft
20 in
12 in
ft lbm
32.17
lbf sec2
8.4 x 107
Use the Moody Chart for a Reynolds number of 8.4 x 107 and a relative roughness of
0.00008.
f
Hf
0.012
f
L v2
D 2g
(0.012)
Hf
Rev. 0
100 ft
1 ft
20 in
12 in
ft 2
5.35
sec
ft
2 32.17
sec2
0.32 ft
Page 33
HT-03
HEAD LOSS
Fluid Flow
Minor Losses
The losses that occur in pipelines due to bends, elbows, joints, valves, etc. are sometimes called
minor losses. This is a misnomer because in many cases these losses are more important than
the losses due to pipe friction, considered in the preceding section. For all minor losses in
turbulent flow, the head loss varies as the square of the velocity. Thus a convenient method of
expressing the minor losses in flow is by means of a loss coefficient (k). Values of the loss
coefficient (k) for typical situations and fittings is found in standard handbooks. The form of
Darcys equation used to calculate minor losses of individual fluid system components is
expressed by Equation 3-15.
Hf
v2
2g
(3-15)
Equivalent Piping Length

Minor losses may be expressed in terms of the equivalent length (Leq) of pipe that would have
the same head loss for the same discharge flow rate. This relationship can be found by setting
the two forms of Darcys equation equal to each other.
f
L v2
D 2 g
v2
2 g
This yields two relationships that are useful.

Leq
D
f
(3-16)
Leq
D
(3-17)
Typical values of Leq/D for common piping system components are listed in Table 1. The
equivalent length of piping that will cause the same head loss as a particular component can be
determined by multiplying the value of Leq/D for that component by the diameter of the pipe.
The higher the value of Leq/D, the longer the equivalent length of pipe.
HT-03
Page 34
Rev. 0
Fluid Flow
HEAD LOSS
TABLE 1
Typical Values of
Leq
D
Leq
Item
Globe Valve
Conventional
Y-Pattern
400
160
Gate Valve
Fully Open
75% Open
50% Open
25% Open
10
35
150
900
Standard Tee
Flow through Run
Flow through Branch
90 Standard Elbow
45 Standard Elbow
Return Bend
10
60
30
16
50
Example:
A fully-open gate valve is in a pipe with a diameter of 10 inches. What equivalent length
of pipe would cause the same head loss as the gate valve?
Solution:
From Table 1, we find that the value of Leq/D for a fully-open gate valve is 10.
Leq
= (L/D) D
= 10 (10 inches)
= 100 inches
By adding the equivalent lengths of all components to the actual length of pipe in a system we
can obtain the Leq value for the entire piping system.
Rev. 0
Page 35
HT-03
HEAD LOSS
Fluid Flow
Summary
Head Loss Summary
Head loss is the reduction in the total head (sum of potential head, velocity head,
and pressure head) of a fluid caused by the friction present in the fluids motion.
Frictional loss is that part of the total head loss that occurs as the fluid flows
through straight pipes.
Minor losses are the head losses that occur due to bends, elbows, joints, valves,
and other components. Any time the flow experiences a change in direction or
a change in cross-sectional area, it will experience a head loss.
The friction factor for fluid flow can be determined using a Moody Chart if the
relative roughness of the pipe and the Reynolds number of the flow can be
determined.
Darcys equation can be used to calculate frictional losses.
A special form of Darcys equation can be used to calculate minor losses.
The length of pipe that would cause the same head loss as a valve or fitting can
be determined by multiplying the value of L/D for the component found in
handbooks or vendor manuals by the diameter of the pipe.
HT-03
Page 36
Rev. 0
Fluid Flow
NATURAL CIRCULATION
NATURAL CIRCULATION
Natural circulation is the circulation of fluid within piping systems or
open pools that is due to the density changes caused by temperature
differences. Natural circulation does not require any mechanical
devices to maintain flow.
EO 1.25
DEFINE natural circulation and forced circulation.
EO 1.26
DEFINE thermal driving head.
EO 1.27
DESCRIBE the conditions necessary for natural

circulation to exist.
EO 1.28
EXPLAIN the relationship between flow rate and

temperature difference in natural circulation flow.
EO 1.29
DESCRIBE how the operator can determine whether

natural circulation exists in the reactor coolant system
and other heat removal systems.
EO 1.30
DESCRIBE how to enhance natural circulation flow.
Forced and Natural Circulation

In the previous chapters on fluid flow, it was explained that any time that fluid flows there is
some friction associated with the movement, which will cause head loss. It was pointed out that
this head loss is commonly compensated for in piping systems by pumps that do work on the
fluid, compensating for the head loss due to friction. Circulation of fluid in systems by pumps
is referred to as forced circulation.
It is possible to design some fluid systems in a manner that does not require the presence of
pumps to provide circulation. The head required to compensate for the head losses is created by
density gradients and elevation changes. Flow that occurs under these circumstances is called
natural circulation.
Thermal Driving Head

Thermal driving head is the force that causes natural circulation to take place. It is caused by
the difference in density between two bodies or areas of fluid.
Rev. 0
Page 37
HT-03
NATURAL CIRCULATION
Fluid Flow
Consider two equal volumes of the same type of fluid. If the two volumes are not at the same
temperature, then the volume with the higher temperature will also have a lower density and,
therefore, less mass. Since the volume at the higher temperature will have a lower mass, it will
also have less force exerted on it by gravity. This difference in the force of gravity exerted on
the fluid will tend to cause the hotter fluid to rise and the colder fluid to sink.
This effect is seen in many places. One example of this is a hot air balloon. The force causing
a hot air balloon to rise is a result of a difference in density between the hot air inside the
balloon and the cooler air surrounding it.
Heat added to the air in the balloon adds energy to the molecules of air. The movement of the
air molecules increases and the air molecules take up more space. The air molecules inside the
balloon take up more space than the same amount of air molecules outside the balloon. This
means the hot air is less dense and lighter than the surrounding air. Since the air in the balloon
is less dense, gravity has less effect on it. The result is that the balloon weighs less than the
surrounding air. Gravity pulls cooler air down into the space occupied by the balloon. The
downward movement of the cooler air forces the balloon out of the space previously occupied,
and the balloon rises.
Conditions Required for Natural Circulation

Natural circulation will only occur if the correct conditions exist. Even after natural circulation
has begun, removal of any one of these conditions will cause the natural circulation to stop. The
conditions for natural circulation are as follows.
1.
A temperature difference exists (heat source and heat sink exists).
2.
The heat source is at a lower elevation than the heat sink.
3.
The fluids must be in contact with each other.
There must be two bodies of fluid at different temperatures. This could also be one body of fluid
with areas of different temperatures. The difference in temperature is necessary to cause a
density difference in the fluid. The density difference is the driving force for natural circulation
flow.
The difference in temperature must be maintained for the natural circulation to continue.
Addition of heat by a heat source must exist at the high temperature area. Continuous removal
of heat by a heat sink must exist at the low temperature area. Otherwise the temperatures would
eventually equalize, and no further circulation would occur.
The heat source must be at a lower elevation than the heat sink. As shown by the example of
the balloon, a warmer fluid is less dense and will tend to rise, and a cooler fluid is more dense
and will tend to sink. To take advantage of the natural movement of warm and cool fluids, the
heat source and heat sink must be at the proper elevations.
HT-03
Page 38
Rev. 0
Fluid Flow
NATURAL CIRCULATION
The two areas must be in contact so that flow between the areas is possible. If the flow path is
obstructed or blocked, then natural circulation cannot occur.
Example of Natural Circulation Cooling

Natural circulation is frequently the primary means of cooling for pool-type reactors and for
irradiated fuel assemblies stored in pools of water after removal from the reactor. The heat
source is the fuel assembly. The heat sink is the bulk of the water in the pool.
Water at the bottom of a fuel assembly absorbs energy generated by the assembly. The water
increases in temperature and decreases in density. Gravity pulls cooler (more dense) water into
the bottom of the assembly displacing the warmer water. The warmer (lighter) water is forced
to give up its position to the cooler (heavier) water. The warmer (lighter) water rises higher in
the assembly. As water travels up the length of the assembly, it absorbs more energy. The water
becomes lighter and lighter being continuously forced upward by more dense water moving in
below it. In turn, the cooler water absorbs energy from the assembly and is also forced to rise
as natural circulation flow continues. Water exiting the top of the fuel assembly gives up its
energy as it mixes with the bulk of the water in the pool. The bulk of the water in the pool is
commonly cooled by circulation through heat exchangers in a separate process.
Flow Rate and Temperature Difference

The thermal driving head that causes natural circulation is due to the density change caused by
a temperature difference. In general, the greater the temperature difference between the hot and
cold areas of fluid, the greater the thermal driving head and the resulting flow rate. However,
it is good practice to keep the hot fluid subcooled to prevent a change of phase from occurring.
It is possible to have natural circulation take place in two-phase flow, but it is usually more
difficult to maintain flow.
Various parameters can be used to indicate or verify natural circulation is occurring. This is
dependent on plant type. For instance for a pressurized water reactor (PWR) selected Reactor
Coolant System (RCS) parameters that would be used are as follows.
1.
RCS T (THot - TCold) should be 25-80% of the full power value and either steady or
slowly decreasing. This indicates that the decay heat is being removed from the system
at an adequate rate to maintain or reduce core temperatures.
2.
RCS Hot and Cold leg temperatures should be steady or slowly decreasing. Again, this
indicates that heat is being removed and the decay heat load is decreasing as expected.
3.
Steam generator steam pressure (secondary side pressure) should be following RCS
temperature. This verifies that the steam generator is removing heat from the RCS
coolant.
If natural circulation for a PWR is in progress or is imminent, several actions can be performed
to ensure or enhance core cooling capabilities. First, pressurizer level can be maintained greater
than 50%. Secondly, maintain the RCS subcooled by 15oF or greater.
Rev. 0
Page 39
HT-03
NATURAL CIRCULATION
Fluid Flow
Both of these actions will help ensure steam/vapor pockets are not formed in the RCS where they
would restrict RCS flow. Thirdly, maintain steam generator water level normal range. This
provides an adequate heat sink to ensure heat removal is sufficient to prevent boiling of the RCS.
Summary
The main points of this chapter are listed below.
Natural Circulation Flow Summary

Natural circulation flow is circulation of a fluid without the use of
mechanical devices.
Forced circulation flow is circulation of a fluid through a system by pumps.
Thermal driving head is the driving force for natural circulation caused
by the difference in density between two areas of fluid.
Three items are necessary to support natural circulation:
There must be a heat sink and a heat source.
The heat source must be located below the heat sink.
Flowpaths must exist between the warm fluid and the cold fluid.
Generally, the greater the temperature difference, the higher the natural
circulation flow rate.
Natural circulation in a PWR can be verified by monitoring:
RCS T 25%-80% full power value
THot / TCold steady or slowly decreasing
S/G steam pressure - tracking RCS temperature
Natural circulation in a PWR can be enhanced by:
maintain pressurizer level >50%
maintain RCS 15oF subcooling
maintain adequate heat sink, S/G level normal range
HT-03
Page 40
Rev. 0
Fluid Flow
TWO-PHASE FLUID FLOW

Water at saturation conditions may exist as both a fluid and a vapor.
This mixture of steam and water can cause unusual flow
characteristics within fluid systems.
EO 1.31
DEFINE two-phase flow.
EO 1.32
DESCRIBE two-phase flow including such phenomena

as bubbly, slug, and annular flow.
EO 1.33
DESCRIBE the problems associated with core flow

oscillations and flow instability.
EO 1.34
DESCRIBE the conditions that could lead to core flow

oscillation and instability.
EO 1.35
DESCRIBE the phenomenon of pipe whip.
EO 1.36
DESCRIBE the phenomenon of water hammer.
Two-Phase Fluid Flow

All of the fluid flow relationships discussed previously are for the flow of a single phase of fluid
whether liquid or vapor. At certain important locations in fluid flow systems the simultaneous
flow of liquid water and steam occurs, known as two-phase flow. These simple relationships
used for analyzing single-phase flow are insufficient for analyzing two-phase flow.
There are several techniques used to predict the head loss due to fluid friction for two-phase
flow. Two-phase flow friction is greater than single-phase friction for the same conduit
dimensions and mass flow rate. The difference appears to be a function of the type of flow and
results from increased flow speeds. Two-phase friction losses are experimentally determined by
measuring pressure drops across different piping elements. The two-phase losses are generally
related to single-phase losses through the same elements.
One accepted technique for determining the two-phase friction loss based on the single-phase loss
involves the two-phase friction multiplier (R), which is defined as the ratio of the two-phase head
loss divided by the head loss evaluated using saturated liquid properties.
R
Rev. 0
Hf , two phase
(3-18)
Hf , saturated liquid
Page 41
HT-03
Fluid Flow
where:
R
= two-phase friction multiplier (no units)
Hf , two-phase
= two-phase head loss due to friction (ft)
Hf , saturated liquid = single-phase head loss due to friction (ft)

The friction multiplier (R) has been found to be much higher at lower pressures than at higher
pressures. The two-phase head loss can be many times greater than the single-phase head loss.
Although a wide range of names has been used for two-phase flow patterns, we shall define only
three types of flow. The flow patterns to be used are defined as follows:
1.
Bubbly flow: there is dispersion of vapor bubbles in a continuum of liquid.
2.
Slug flow: in bubbly flow, the bubbles grow by coalescence and ultimately
become of the same order of diameter as the tube. This generates the typical
bullet-shaped bubbles that are characteristic of the slug-flow regime.
3.
Annular flow: the liquid is now distributed between a liquid film flowing up the
wall and a dispersion of droplets flowing in the vapor core of the flow.
Flow Instability
Unstable flow can occur in the form of flow oscillations or flow reversals. Flow oscillations are
variations in flow due to void formations or mechanical obstructions from design and
manufacturing. A flow oscillation in one reactor coolant channel sometimes causes flow
oscillations in the surrounding coolant channels due to flow redistribution. Flow oscillations are
undesirable for several reasons. First, sustained flow oscillations can cause undesirable forced
mechanical vibration of components. This can lead to failure of those components due to fatigue.
Second, flow oscillations can cause system control problems of particular importance in liquidcooled nuclear reactors because the coolant is also used as the moderator. Third, flow
oscillations affect the local heat transfer characteristics and boiling. It has been found through
testing that the critical heat flux (CHF) required for departure from nucleate boiling (DNB) can
be lowered by as much as 40% when flow is oscillating. This severely reduces the thermal limit
and the power density along the length of the reactor core. Again, it has been found through
testing that flow oscillations are not a significant problem for some pressurized water reactors
unless power is above 150% for the normal flow conditions. Flow oscillations can be a problem
during natural circulation operations because of the low flow rates present.
During natural circulation, the steam bubbles formed during a flow oscillation may have enough
of an effect to actually cause complete flow reversal in the affected channel.
HT-03
Page 42
Rev. 0
Fluid Flow
Both the flow oscillations and flow reversals lead to a very unstable condition since the steam
blankets formed on heated surfaces directly affect the ability to transfer heat away from those
surfaces.
Pipe Whip
If a pipe were to rupture, the reaction force created by the high velocity fluid jet could cause the
piping to displace and cause extensive damage to components, instrumentation, and equipment
in the area of the rupture. This characteristic is similar to an unattended garden hose or fire hose
"whipping" about unpredictably. This type of failure is analyzed to minimize damage if pipe
whip were to occur in the vicinity of safety-related equipment.
Water Hammer
Water hammer is a liquid shock wave resulting from the sudden starting or stopping of flow.
It is affected by the initial system pressure, the density of the fluid, the speed of sound in the
fluid, the elasticity of the fluid and pipe, the change in velocity of the fluid, the diameter and
thickness of the pipe, and the valve operating time.
During the closing of a valve, kinetic energy of the moving fluid is converted into potential
energy. Elasticity of the fluid and pipe wall produces a wave of positive pressure back toward
the fluids source. When this wave reaches the source, the mass of fluid will be at rest, but
under tremendous pressure. The compressed liquid and stretched pipe walls will now start to
release the liquid in the pipe back to the source and return to the static pressure of the source.
This release of energy will form another pressure wave back to the valve. When this shockwave
reaches the valve, due to the momentum of the fluid, the pipe wall will begin to contract. This
contraction is transmitted back to the source, which places the pressure in the piping below that
of the static pressure of the source. These pressure waves will travel back and forth several times
until the fluid friction dampens the alternating pressure waves to the static pressure of the source.
Normally, the entire hammer process takes place in under one second.
The initial shock of suddenly stopped flow can induce transient pressure changes that exceed the
static pressure. If the valve is closed slowly, the loss of kinetic energy is gradual. If it is closed
quickly, the loss of kinetic energy is very rapid. A shock wave results because of this rapid loss
of kinetic energy. The shock wave caused by water hammer can be of sufficient magnitude to
cause physical damage to piping, equipment, and personnel. Water hammer in pipes has been
known to pull pipe supports from their mounts, rupture piping, and cause pipe whip.
Pressure Spike
A pressure spike is the resulting rapid rise in pressure above static pressure caused by water
hammer. The highest pressure spike attained will be at the instant the flow changed and is
governed by the following equation.
c v
P
gc
Rev. 0
Page 43
HT-03
Fluid Flow
where:
lbf
P = Pressure spike
2
ft
lbm
= Density of the fluid
3
ft
c
ft
sec
= Velocity of the pressure wave

(Speed of sound in the fluid)
ft
v = Change in velocity of the fluid
sec
gc
Example:
lbm ft
= Gravitational constant 32.17
2
lbf sec
Pressure spike
Water at a density of 62.4 lbm/ft3 and a pressure of 120 psi is flowing through a pipe
at 10 ft/sec. The speed of sound in the water is 4780 ft/sec. A check valve suddenly
closed. What is the maximum pressure of the fluid in psi?
Solution:
HT-03
PMax
= PStatic + PSpike
PMax
= 120
lbf
in 2
lbf
in 2
PMax
= 120
PMax
lbf
= 120
in 2
PMax
= 120
PMax
= 763.3 psi
lbf
in 2
c V
gc
62.4
lbm
ft 3
ft
ft
10
sec
sec
lbm ft
32.17
lbf sec2
4780
lbf ft 2
92,631
ft 2 144 in 2
643.3
lbf
in 2
Page 44
Rev. 0
Fluid Flow
Steam Hammer
Steam hammer is similar to water hammer except it is for a steam system. Steam hammer is a
gaseous shock wave resulting from the sudden starting or stopping of flow. Steam hammer is
not as severe as water hammer for three reasons:
1.
The compressibility of the steam dampens the shock wave
2.
The speed of sound in steam is approximately one third the speed of sound in
water.
3.
The density of steam is approximately 1600 times less than that of water.
The items of concern that deal with steam piping are thermal shock and water slugs (i.e.,
condensation in the steam system) as a result of improper warm up.
Operational Considerations
Water and steam hammer are not uncommon occurrences in industrial plants. Flow changes in
piping systems should be done slowly as part of good operator practice. To prevent water and
steam hammer, operators should ensure liquid systems are properly vented and ensure gaseous
or steam systems are properly drained during start-up. When possible, initiate pump starts
against a closed discharge valve, and open the discharge valve slowly to initiate system flow.
If possible, start-up smaller capacity pumps before larger capacity pumps. Use warm-up valves
around main stream stop valves whenever possible. If possible, close pump discharge valves
before stopping pumps. Periodically verify proper function of moisture traps and air traps during
operation.
Rev. 0
Page 45
HT-03
Fluid Flow
Summary
The main points from this chapter are summarized below.
Two-Phase Fluid Flow Summary

The combination of liquid and vapor flowing through a pipe is called two-phase
flow.
Types of two-phase flow include:
Bubbly flow: there is a dispersion of vapor bubbles in a continuum of liquid.

Slug flow:
the bubbles grow by coalescence and ultimately become of the
same order of diameter as the tube, generating bullet shaped
bubbles.
Annular flow: the liquid is distributed between a liquid film flowing up the wall
and a dispersion of droplets flowing in the vapor core of the
flow.
Core flow oscillations and instabilities can cause:
undesirable mechanical vibration of components.

a reduction in the heat flux required to cause DNB.
interruptions to actual circulation flow.
Flow oscillations and instabilities can occur during the following conditions:
core is outside design conditions, power > 150%

mechanical failure, causing flow blockage
inadequate core cooling during natural circulation, such that boiling is occurring
Pipe whip is the displacement of piping created by the reaction forces of a high
velocity fluid jet following a pipe rupture.
Water hammer is a liquid shock wave resulting from a sudden starting or stopping
of flow.
HT-03
Page 46
Rev. 0
Fluid Flow
CENTRIFUGAL PUMPS
CENTRIFUGAL PUMPS
Centrifugal pumps are one of the most common components found in
fluid systems. In order to understand how a fluid system containing
a centrifugal pump operates, it is necessary to understand the head
and flow relationships for a centrifugal pump.
EO 1.37
DEFINE the terms net positive suction head and

cavitation.
EO 1.38
CALCULATE the new volumetric flow rate, head, or

power for a variable speed centrifugal pump using the
pump laws.
EO 1.39
DESCRIBE the effect on system flow and pump head

for the following changes:
a.
Changing pump speeds
b.
Adding pumps in parallel
c.
Adding pumps in series
Energy Conversion in a Centrifugal Pump

Fluid entering a centrifugal pump is immediately directed to the low pressure area at the center
or eye of the impeller. As the impeller and blading rotate, they transfer momentum to incoming
fluid. A transfer of momentum to the moving fluid increases the fluids velocity. As the fluids
velocity increases its kinetic energy increases. Fluid of high kinetic energy is forced out of the
impeller area and enters the volute.
The volute is a region of continuously increasing cross-sectional area designed to convert the
kinetic energy of the fluid into fluid pressure. The mechanism of this energy conversion is the
same as that for subsonic flow through the diverging section of a nozzle. The mathematical
analysis of flow through the volute is based on the general energy equation, the continuity
equation, and the equation relating the internal properties of a system. The key parameters
influencing the energy conversion are the expanding cross-sectional area of the volute, the higher
system back pressure at the discharge of the volute, and the incompressible, subsonic flow of the
fluid. As a result of the interdependence of these parameters, the fluid flow in the volute, similar
to subsonic flow in a diverging nozzle, experiences a velocity decrease and a pressure increase.
Rev. 0
Page 47
HT-03
CENTRIFUGAL PUMPS
Fluid Flow
Operating Characteristics of a Centrifugal Pump

Normally, a centrifugal pump produces a relatively low pressure increase in the fluid. This
pressure increase can be anywhere from several dozen to several hundred psid across a
centrifugal pump with a single stage impeller. The term PSID (Pounds Force Per Square Inch
Differential) is equivalent to P. In this context, it is the pressure difference between the suction
and discharge of a pump. PSID can also be used to describe a pressure drop across a system
component (strainers, filters, heat exchangers, valves, demineralizers, etc.). When a centrifugal
pump is operating at a constant speed, an increase in the system back pressure on the flowing
stream causes a reduction in the magnitude of volumetric flow rate that the centrifugal pump can
maintain.
Analysis of the relationship between the
) that a centrifugal
volumetric flow rate ( V
pump can maintain and the pressure
differential across the pump (Ppump) is
based on various physical characteristics of
the pump and the system fluid. Variables
evaluated by design engineers to determine
this relationship include the pump efficiency,
the power supplied to the pump, the
rotational speed, the diameter of the impeller
and blading, the fluid density, and the fluid
viscosity. The result of this complicated
analysis for a typical centrifugal pump
operating at one particular speed is
illustrated by the graph in Figure 7.
Figure 7
Typical Centrifugal Pump

Characteristic Curve
Pump head, on the vertical axis, is the

difference between system back pressure and the inlet pressure of the pump (Ppump). Volumetric
), on the horizontal axis, is the rate at which fluid is flowing through the pump. The
flow rate ( V
graph assumes one particular speed (N) for the pump impeller.
Cavitation
When the liquid being pumped enters the eye of a centrifugal pump, the pressure is significantly
reduced. The greater the flow velocity through the pump the greater this pressure drop. If the
pressure drop is great enough, or if the temperature of the liquid is high enough, the pressure
drop may be sufficient to cause the liquid to flash to steam when the local pressure falls below
the saturation pressure for the fluid that is being pumped. These vapor bubbles are swept along
the pump impeller with the fluid. As the flow velocity decreases the fluid pressure increases.
This causes the vapor bubbles to suddenly collapse on the outer portions of the impeller. The
formation of these vapor bubbles and their subsequent collapse is cavitation.
HT-03
Page 48
Rev. 0
Fluid Flow
CENTRIFUGAL PUMPS
Cavitation can be a very serious problem for centrifugal pumps. Some pumps can be designed
to operate with limited amounts of cavitation. Most centrifugal pumps cannot withstand
cavitation for significant periods of time; they are damaged by erosion of the impeller, vibration,
or some other cavitation-induced problem.
Net Positive Suction Head

It is possible to ensure that cavitation is avoided during pump operation by monitoring the net
positive suction head of the pump. Net positive suction head (NPSH) for a pump is the
difference between the suction pressure and the saturation pressure of the fluid being pumped.
NPSH is used to measure how close a fluid is to saturated conditions. Equation 3-19 can be used
to calculate the net positive suction head available for a pump. The units of NPSH are feet of
water.
NPSH = Psuction - Psaturation
(3-19)
where:
Psuction
Psaturation
=
=
suction pressure of the pump

saturation pressure for the fluid
By maintaining the available NPSH at a level greater than the NPSH required by the pump
manufacturer, cavitation can be avoided.
Pump Laws
Centrifugal pumps generally obey what are known as the pump laws. These laws state that the
flow rate or capacity is directly proportional to the pump speed; the discharge head is directly
proportional to the square of the pump speed; and the power required by the pump motor is
directly proportional to the cube of the pump speed. These laws are summarized in the following
equations.
Rev. 0
n
V
(3-20)
Hp n 2
(3-21)
p n3
(3-22)
Page 49
HT-03
CENTRIFUGAL PUMPS
Fluid Flow
where:
n
V
Hp
p
= speed of pump impeller (rpm)

= volumetric flow rate of pump (gpm or ft3/hr)
= head developed by pump (psid or feet)
= pump power (kW)
Using these proportionalities, it is possible to develop equations relating the condition at one
speed to those at a different speed.
n
2
V
1
n1
V
2
(3-23)
n 2
Hp 2
n1
Hp
(3-24)
n 3
p1 2
n1
p2
(3-25)
Example:
Pump Laws
A cooling water pump is operating at a speed of 1800 rpm. Its flow rate is 400 gpm at
a head of 48 ft. The power of the pump is 45 kW. Determine the pump flow rate, head,
and power requirements if the pump speed is increased to 3600 rpm.
Solution:
Flow rate
V
2
n
2
V
1
n1
3600 rpm
(400 gpm)
1800 rpm
800 gpm
HT-03
Page 50
Rev. 0
Fluid Flow
CENTRIFUGAL PUMPS
Head
Hp
n 2
HP 2
n1
1
3600 rpm 2
48 ft
1800 rpm
192 ft
Power
P2
n 3
P1 2
n1
3600 rpm 3
45 kW
1800 rpm
360 kW
It is possible to develop the characteristic curve for the new speed of a pump based on the curve
for its original speed. The technique is to take several points on the original curve and apply the
pump laws to determine the new head and flow at the new speed. The pump head versus flow
rate curve that results from a change in pump speed is graphically illustrated in Figure 8.
Figure 8
Rev. 0
Changing Speeds for Centrifugal Pump
Page 51
HT-03
CENTRIFUGAL PUMPS
Fluid Flow
System Characteristic Curve

In the chapter on head loss, it was determined
that both frictional losses and minor losses in
piping systems were proportional to the
square of the flow velocity. Since flow
velocity is directly proportional to the
volumetric flow rate, the system head loss
must be directly proportional to the square of
the volumetric flow rate.
From this
relationship, it is possible to develop a curve
of system head loss versus volumetric flow
rate. The head loss curve for a typical piping
system is in the shape of a parabola as shown
in Figure 9.
Figure 9
Typical System Head Loss Curve
System Operating Point

The point at which a pump
operates in a given piping system
depends on the flow rate and head
loss of that system. For a given
system, volumetric flow rate is
compared to system head loss on a
system characteristic curve. By
graphing a system characteristic
curve and the pump characteristic
curve on the same coordinate
system, the point at which the
pump must operate is identified.
For example, in Figure 10, the
operating point for the centrifugal
pump in the original system is
designated by the intersection of
the pump curve and the system
curve (hLo).
Figure 10
HT-03
Page 52
Operating Point for a Centrifugal Pump
Rev. 0
Fluid Flow
CENTRIFUGAL PUMPS
and a total system head loss equal to Po. In order to

The system has a flow rate equal to V
o
) , the pump head must be equal to Po. In the system described by
maintain the flow rate (V
o
the system curve (hL1), a valve has been opened in the system to reduce the systems resistance
) at a smaller pump head
to flow. For this system, the pump maintains a large flow rate (V
1
(P1).
System Use of Multiple Centrifugal Pumps

A typical centrifugal pump has a relatively low number of moving parts and can be easily
adapted to a variety of prime movers. These prime movers include AC and DC electric motors,
diesel engines, steam turbines, and air motors. Centrifugal pumps are typically small in size and
can usually be built for a relatively low cost. In addition, centrifugal pumps provide a high
volumetric flow rate with a relatively low pressure.
In order to increase the volumetric flow rate in a system or to compensate for large flow
resistances, centrifugal pumps are often used in parallel or in series. Figure 11 depicts two
identical centrifugal pumps operating at the same speed in parallel.
Figure 11
Pump Characteristic Curve for Two Identical Centrifugal Pumps Used in Parallel
Centrifugal Pumps in Parallel

Since the inlet and the outlet of each pump shown in Figure 11 are at identical points in the
system, each pump must produce the same pump head. The total flow rate in the system,
however, is the sum of the individual flow rates for each pump.
Rev. 0
Page 53
HT-03
CENTRIFUGAL PUMPS
Fluid Flow
When the system characteristic curve is considered with the curve for pumps in parallel, the
operating point at the intersection of the two curves represents a higher volumetric flow rate than
for a single pump and a greater system head loss. As shown in Figure 12, a greater system head
loss occurs with the increased fluid velocity resulting from the increased volumetric flow rate.
Because of the greater system head, the volumetric flow rate is actually less than twice the flow
rate achieved by using a single pump.
Figure 12
Operating Point for Two Parallel Centrifugal Pumps
Centrifugal Pumps in Series

Centrifugal pumps are used in
series to overcome a larger system
head loss than one pump can
compensate for individually. As
illustrated in Figure 13, two
identical centrifugal pumps
operating at the same speed with
the same volumetric flow rate
contribute the same pump head.
Since the inlet to the second pump
is the outlet of the first pump, the
head produced by both pumps is
the sum of the individual heads.
The volumetric flow rate from the
inlet of the first pump to the outlet
of the second remains the same.
Figure 13 Pump Characteristic Curve for Two Identical Centrifugal

Pumps Used in Series
HT-03
Page 54
Rev. 0
Fluid Flow
CENTRIFUGAL PUMPS
As shown in Figure 14, using two pumps in series does not actually double the resistance to flow
in the system. The two pumps provide adequate pump head for the new system and also
maintain a slightly higher volumetric flow rate.
Figure 14
Rev. 0
Operating Point for Two Centrifugal Pumps in Series
Page 55
HT-03
CENTRIFUGAL PUMPS
Fluid Flow
Summary
The main points from this chapter are summarized below.
Centrifugal Pumps Summary
Net positive suction head is the difference between the pump suction
pressure and the saturation pressure for the fluid.
Cavitation is the formation and subsequent collapse of vapor bubbles on the

impeller of a pump as the local pressure falls below and then rises above
the saturation pressure of the fluid being pumped.
The pump laws can be used to determine the effect of varying the speed of
a centrifugal pump on the flow, head, and power.
n
V1 2
n1
V
2
n 2
Hp 2
n1
Hp
n 3
p1 2
n1
p2
The combined pump curve for two centrifugal pumps in parallel can be
determined by adding the individual flows for any given head.
The combined pump curve for two centrifugal pumps in series can be
determined by adding the individual heads for any given flow.
The operating point (head and flow) of a system can be determined by

plotting the pump curve and the system head loss curve on the same axes.
The system will operate at the intersection of the two curves.
HT-03
Page 56
Rev. 0
Appendix B
Fluid Flow
APPENDIX B
Fluid Flow
end of text.
CONCLUDING MATERIAL
Review activities:
Preparing activity:

DOE - NE-73
Project Number 6910-0018/3
HT-03
Page B-2
Rev. 0

ThermoFluid Chemistry Nuclear Physics

Загружено:

Сведения о документе

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

ThermoFluid Chemistry Nuclear Physics

Загружено:

Авторское право:

Доступные форматы

DOE-HDBK-1015/2-93

DOE FUNDAMENTALS HANDBOOK

U.S. Department of Energy

Washington, D.C. 20585

Reactor Water Chemistry

Reactor Water Chemistry

Reactor Water Chemistry

Reactor Water Chemistry

Reactor Water Chemistry

DESCRIBE the process of radiolytic decomposition and recombination of water.

STATE the advantage of maintaining excess hydrogen in reactor water.

STATE the following for reactor water chemistry.

Nine parameters controlled

STATE the possible effects of abnormal chemistry on core conditions.

Reactor Water Chemistry

Intentionally Left Blank

Reactor Water Chemistry

DESCRIBE the process of radiolytic decomposition and

DESCRIBE the process of radiolytic decomposition and

STATE the advantage of maintaining excess hydrogen in

STATE the three sources of radioactivity in reactor water

Reactor Water Chemistry

Reaction (3-4) usually predominates.

Reactor Water Chemistry

H2O2 (hydrogen peroxide)

Reactor Water Chemistry

Reactor Water Chemistry

Reactor Water Chemistry

Reactor Water Chemistry

Reactor Water Chemistry

Figure 1 Change in pH, Gas Concentration, and Nitrogen Compounds

Reactor Water Chemistry

O (n, p) 167N (t1/2 = 7.13 seconds)

Oxygen-17 undergoes a similar reaction.

O (n, p) 177N (t1/2 = 4.1 seconds)

N decays by emission of a beta particle, a neutron, and a gamma ray.

Reactor Water Chemistry

O (p, n) 189F (t1/2 = 112 minutes)

O (p, ) 137N (t1/2 = 10 minutes)

H (n, ) 31H (t1/2 = 12.3 years)

Reactor Water Chemistry

Effects of Radiation on Water Chemistry (Synthesis) Summary

Excess hydrogen is added to suppress the decomposition of reactor water. It also

Reactor Water Chemistry

STATE the following for reactor water chemistry.

Nine parameters controlled

STATE the possible effects of abnormal chemistry on core

Ion exchange in the primary system demineralizer(s) or by supplemental

Oxygen scavenging by hydrogen or hydrazine addition

Reactor Water Chemistry

Total Gas Content

To indicate air in leakage

Deaeration of makeup water

To minimize scale formation

To indicate increased corrosion

Feed and Bleed

To preclude chloride stress

Feed and Bleed

Boric acid addition

To indicate increased corrosion

Feed and bleed

To indicate a crud burst

To indicate a core fuel defect

Feed and bleed