STOICHIOMETRY

Lecture Notes
 Reference Book
Chemical Process Principles
(Part 1)

Second Edition
Material & Energy Balance

Olaf A. Hougen
Kenneth. M. Watson
Roland. A. Ragatz
 Title
Cover
 Chapter 2
Stoichiometric And Composition Relationships
 Conservation of Mass
A system refers to a substance or a group of substances under
consideration
A process refers to the changes taking place within that system.
Within a given isolated system, the mass of the system remains
constant regardless of the changes taking place within the system.
This statement is known as the law of conservation of mass and is the
basis of the so-called material balance of a process.
The state of a system is defined by numerous properties which are
classified as extensive if they are dependent on the mass under
consideration and intensive if they are independent of mass. For
example, volume is an extensive property, whereas density and
temperature are intensive properties.
Stoichiometric Relations
 Mass Relations in Chemical Reactions
In stoichiometric calculations, the mass relations existing between
the reactants and products of a chemical reaction are of primary
interest.
As a typical example of the procedures followed, the reaction
between iron and steam, resulting in the production of hydrogen
and the magnetic oxide of iron, Fe3O4, may be considered.
3Fe 4H 2O Fe3O4 4H 2
Element Atomic Weight Compound Molecular Weight
Fe 55.84 H2O 18.02
H 1.008 Fe3O4 231.5
O 16.00 H2 2.016
Mass Relations in Chemical Reactions
The respective relative weights of the reactants and
products maybe determined by multiplying the respective
atomic or molecular weights by the coefficients that
precede the formulas of the reaction equation.
3Fe 4H 2O Fe3O4 4H 2
3 55.84 4 18.02 231.5 4 2.016
167.52 72.08 231.5 8.064

By the use of these relative weights it is possible to work out

the particular weights desired in a given problem.
Relation Between Mass and Volume for
Gaseous Substances
System Temperature Pressure Volume/Unit
3
SI 273.15 K 101.325 kPa 22.414 m /kg mol
Universal 0 C 760 mm Hg 22.414 L/g mol
Scientific
3
American 491.76 R (32 F) 1 atm 359.05 ft /lb mol
Engineering
3
Natural Gas 59.0 F (15.0 C) 14.696 psia 379.4 ft /lb mol
Industry (101.325 kPa)
Standard Conditions for an Ideal Gas
 ILLUSTRATION 1
A cylinder contains 25 lb of liquid
chlorine. What volume in cubic feet
will the chlorine occupy if it is
released and brought to standard
conditions?
Basis of Calculation: 25 lb of Chlorine
Liquid Chlorine, when vaporized, forms a gas composed of
diatomic molecules, Cl2

lb
M .Wt. of Cl2 gas = 2 35.5 = 71
lb mol
Lb moles of Cl gas = 25 = 0.3521 lb mol

2 71

Volume at standard conditions = 0.3521 359.05
3
= 126.7 ft
 ILLUSTRATION 2
Gaseous propane, C3H8 , is to be
liquefied for storage in steel cylinders.
How many grams of liquid propane will
be formed by the liquefaction of 500
liters of the gas, the volume being
measured at standard conditions?
Basis of Calculation: 500 liters of propane at
standard conditions

g
M .Wt. of C3 H8 = 3 12 + 8 1 = 44
g mol

500
g moles of C3H8 = 22.414 = 22.32 g mol


Weight of C3 H8 = 22.32 44
= 985 grams
 ILLUSTRATION 3
a) Calculate the weight of iron and of
steam required to produce 100 lb
of hydrogen, and the weight of
Fe3O4 formed?
b)What volume will hydrogen occupy
at standard conditions?
Reaction Equation:

3Fe + 4H 2O Fe3O 4 + 4H 2
Basis of Calculation: 100 lb of hydrogen

100
Hydrogen produced = 2.016 = 49.6 lb-moles


3
Iron required = 49.6 = 37.2 lb-atoms
4
= 37.2

ILLUSTRATION 3
55.84 = 2075 lb
 4
Steam required = 49.6 = 49.6 lb-moles

4


= 49.6 18.02 = 894 lb
1
Fe3O 4 formed = 49.6 = 12.4 lb-moles

4


= 12.4 231.5 = 2870 lb
Total Input = 2075 + 894 = 2969 lb
Total Output = 2870 + 100 = 2970 lb
Volume of hydrogen at standard conditions;
= 49.6 359.05 = 17,820 ft 3
 Excess Reactant
In most chemical reactions carried out in industry, the
quantities of reactants supplied usually are not in the
exact proportions demanded by the reaction
equation.
It is generally desirable that some of the reacting
materials be present in excess of the amounts
theoretically required for combination with the
others. Under such conditions the products obtained
will contain some of the uncombined reactants.
 Excess Reactant
The quantities of the desired compounds which are formed
in the reaction will be determined by the quantity of the
limiting reactant, that is, the material which is not present in
excess of that required to combine with any of the other
reacting materials.
The amount by which any reactant is present in excess of
that required to combine with the limiting reactant is usually
expressed as its percentage excess.
The percentage excess of any reactant is defined as the
percentage ratio of the excess to the amount theoretically
required for combination with the limiting reactant.
 Degree of Completion
The degree of completion of a reaction is ordinarily
expressed as the percentage of the limiting reacting
material which is converted or decomposed into other
products. In processes in which two or more
successive reactions of the same materials take place,
the degree of completion of each step may be
separately expressed.
 ILLUSTRATION 4
An aqueous solution contains 40%
Na2CO3 by weight. Express the
composition in mole per cent?
Basis of Calculation: 100 grams of solution
g
M .Wt. of Na 2 CO3 = 44
g mol
Na CO
present = 40 g = 40 = 0.377 g-mol


2 3
106
H O
present = 60 g = 60 = 3.33 g-mol


18.02
2

Total g-moles = 0.377 + 3.33 = 3.71 g-mol
0.377
Mole % of Na 2 CO3 =

3.71
100 =
ILLUSTRATION 4
10.16%
3.33 100 = 89.9%
Mole % of H 2 O =
3.71

A solution of naphthalene, C10H8 , in
benzene, C6H6 , contains 25 mole per
cent of naphthalene. Express the
composition of the solution in
weight per cent?
Basis of Calculation: 100 g-moles of solution
ILLUSTRATION 5
Molecular Weights:
g g
C10 H 8 = 128.1 , C6 H 6 = 78.1
g mol g mol
C10 H 8 present = 25 g-mol = 25 128.1 = 3200 g
C6 H 6 present = 75 g-mol = 75 78.1 = 5860 g
Total weight = 3200 + 5860 = 9060 g

3200
Weight % of C10 H 8 = 9060 100 = 35.3%


5860
Weighte % of C6 H 6 = 9060 100 = 64.7%

 Important Note
In the case of ideal gases, the composition in mole per cent
is exactly the same as the composition in volumetric per
cent. This deduction follows from a consideration of
Avogadro's law. It should be emphasized that this relation
holds only for gases, and does not apply to liquid or to solid
systems.
 A natural gas has the following composition,
all figures being in volumetric per cent:

Methane, CH4 83.5%

ILLUSTRATION 6
Ethane, C2H6 12.5%
Nitrogen, N2 4.0%
100%
Calculate:
a) The composition in mole per cent
b) Composition in weight per cent
c) Average molecular weight
d) Density at standard conditions, as pounds per cubic foot
a) For the gaseous substances, the composition in the mole
per cent is identical with the composition in the volumetric
per cent. Accordingly, the above figures give the respective
mole per cent directly.
b) For the calculation of composition in the weight per cent,
Basis of Calculation: 100 lb-moles of a gas
Weight, lb
Compound Lb-moles M. Wt. (m = n x Weight %
M.Wt.)
CH4 83.5 16.03 1339 73.3
C2H6 12.5 30.05 376 20.6
N2 4.0 28.02 112 6.1
100 1827 100%
c) Average molecular weight of a natural gas is;
Total mass 1827 = 18.27
M.Wt. =
Total moles = 100
d) ) Density at standard conditions, lb 3 ;
as ft

volume at standard conditions = 100 359.05 = 35,900 ft 3

1827
Density at standard conditions = = 0.0509 lb 3
35, 900 ft
 ILLUSTRATION 7
A solution of sodium chloride in
water contains 230 grams of NaCl
per liter at 20 oC. The density of the
solution at this temperature is 1.148
grams per cubic centimeter.
Calculate the following items:
a) Composition in weight per cent
b)Volumetric per cent of water
c) Composition in the mole per cent
d)Composition in the atomic per cent
e)Molality
f) Pounds NaCl per pounds H2O
Basis of Calculation: 1000 cm3 of solution
Total weight 1000 1.148 = 1148 g
230
NaCl = 230 grams or = 3.93 g-moles
58.5
H 2 O = 1148 230 = 918 grams = 50.9 g-moles
Total moles = 3.93 + 50.9 = 54.8 g-moles
a) Composition in weight per cent :

Weight % of NaCl = 230 100 = 20.0%
1148


Weighte % of H 2 O = 918 100 = 80.0%
1148

b) Volumetric per cent water:
o g
Density of pure water at 20 C = 0.998 3
cm
918 3
Volume of pure water = = 920 cm
0.998
920
Volumetric % of water = 100 = 92.0 %

1000
c) Composition in the mole per cent:
3.93 100 = 7.17 %
Mole % of NaCl = 54.8


50.9
Volumetric % of H 2 O = 54.8 100 = 92.8 %

d) Composition in atomic per cent:
G-atoms of sodium = 3.93
G-atoms of chlorine = 3.93
G-atoms of hydrogen = 2 50.9 = 101.8
G-atoms of oxygen = 50.9
Total = 160.6
3.93
Atomic % of sodium = 100 = 2.45 %


Atomic % of chlorine = 160.6
3.93 100 = 2.45 %


160.6

101.8


Atomic % of hydrogen = 160.6 100 = 63.4 %


Atomic % of oxygen = 50.9 100 = 31.7 %

160.6

 1000
e) Molality = 3.93
918

= 4.28 lb-moles of NaCl per 1000 lb of H 2 O
230
f ) Lb NaCl per lb H 2 O = = 0.251
918
Specific Gravity Scales
Specific gravities are made the basis for the control of
many industrial processes in which solutions are
involved.
To meet the needs of such industries, special means of
numerically designating specific gravities have been
developed. Several scales are in use in which specific
gravities are expressed in terms of degrees which are
related to specific gravities and densities by more or
less complicated and arbitrarily defined functions.
Baume Gravity Scale:
Two so-called Baume gravity scales are in common
use.
One for use with liquids lighter and the other for
liquids heavier than water.
The former is defined by the following expression:

140
Degrees Baume 130
G
 It is apparent from this definition that lighter liquids
will have higher gravities on the Baum6 scale. Thus, a
material having a specific gravity of 0.60 will have a
gravity of 103 Baume.
The Baume scale for liquids heavier than water is
defined as follows:

145
Degrees Baume 145
G
American Petroleum Institute (API)
Scale

Degrees API 141.5 131.5

G
Twaddell Scale
The Twaddell scale is used only for liquids heavier
than water.
Its definition is as follows:
Degrees Twaddell 200(G 1.0)

This scale has the advantage of a very simple

relationship to specific gravities.
Brix Scale
Numerous other scales have been adopted for special
industrial uses; for example, the Brix scale measures
directly the concentration of sugar solutions.
One degree Brix (1.0 oBx) is 1 gram of sucrose in 100
grams of solution and represents the strength of the
solution as percentage by mass.
 Assignment
Solution of the following problems to be submitted on
1) In the combustion of heptane, CO2 is produced. Assume
that you want to produce 500 kg of dry ice per hour and
that 50% of the CO2 can be converted into dry ice, as
shown in figure. How many kilograms of heptane must be
burned per hour?
Other Products
CO2 Gas
50% CO2 Solid (D ry Ice)
C7H16 Gas 50%
REACTOR
2) A limestone analysis;

CaCO3 92.89%
MgCO3 5.41%
Insoluble 1.70%
a) How many pounds of CaO can be made from 5 tons
of this limestone?
b) How many pounds of CO2 can be recovered per
pound of limestone?
c) How many pounds of limestone are needed to make
1 ton of lime?
 Calculations for the following:
1) Limiting Reactant
2) Excess Reactant
3) Degree of Conversion
4) Degree of Completion
5) Selectivity
6) Yield

Reference: Basic Principles and Calculations in Chemical Engineering, 6th Edition

 Limiting Reactant
Limiting reactant is the reactant that is present in the
smallest stoichiometric amount OR If two or more
reactants are mixed and if the reaction were to proceed
according to the chemical equation to completion,
whether it does or not, the reactant that would first
disappear is termed the limiting reactant
If more that two reactants are present, you have to use one
reactant as the reference substance, calculate the mole
ratios of the other reactants in the feed relative to the
reference, make pairwise comparisons versus the analogous
ratios in the chemical equation, and rank each compound.
 Example;
A 3B 2C products
And; 1.1 moles of A, 3.2 moles of B, and 2.4 moles of
C are fed as reactants in the reactor, we choose A as
the reference substance and calculate
Ratio in Feed Ratio in Chemical Equation
3
B 3.2 2.91 3
:
A 1.1 1
2
C 2.4 2.18 2
:
A 1.1 1
We conclude that B is the limiting reactant
relative to A, and that A is the limiting reactant
relative to C, hence B is the limiting reactant
among the set of three reactants.
B < A < C
 Excess Reactant
Excess reactant is the reactant present in
excess of the limiting reactant
The percent excess of a reactant is based on the
amount of any excess reactant above the
amount required to react with the limiting
reactant according to the chemical equation.
 moles in excess
% Excess = 100
moles required to react with limiting reactant

Where the moles in excess can be calculated

as the total available moles of a reactant
less the moles required to react with the
limiting reactant.
 Conversion And Completion
moles or mass of feed that react
% Conversion = 100
moles or mass of feed introduced

Conversion is related to the degree of

completion of a reaction, which is usually the
percentage or fraction of the limiting reactant
converted into the product.
 Selectivity & Yield
Selectivity is the ratio of the moles of a particular
(usually the desired) product produced to the moles
of another (usually the undesired or by-product)
product produced in a set of reactions.
Yield for a single reactant and product, is the weight
(mass) or moles of final product divided by the weight
(mass) or moles of initial or key reactant (P lb of
product A per R lb of reactant B) either fed or
consumed.
 EXAMPLE
Antimony is obtained by heating pulverized stibnite (Sb2S3) with
scrap iron and drawing off the molten antimony from the bottom of
the reaction vessel.

Sb 2S3 + 3Fe 2Sb + 3FeS

Suppose that 0.60 kg of stibnite and 0.250 kg of iron turnings are
heated together to give 0.20 kg of Sb metal. Determine:
a) The limiting reactant
b) The percentage of excess reactant
c) The degree of completion (fraction)
d) The percent conversion
e) The yield
Components kg Mol. Wt. g-mol
Sb2S3 0.600 339.7 1.77
Fe 0.250 55.85 4.48
Sb 0.200 121.8 1.64
FeS 87.91
Figure;
1.77 g-mol Sb2S3
REACTOR FeS
4.48 g-mol Fe

1.64 g-mol Sb
a) Ratio in Feed Ratio in Chemical Equation
1
Sb2 S3 1.77 0.395 0.334
Fe : 4.48 3
Therefore,
Sb 2S3 is the excess reactant and Fe is the limiting reactant.
4.48
Sb 2S3 required to react with the limiting reactant =
3
= 1.49 g-mol
b) The percentage of the excess reactant is,
1.77 1.4 100 = 18.8% excess
= 9
1.49
c) As we know that Fe is the limiting reactant that reacts,
but not all. Therefore, to produce 1.64 g-mol of Sb, we
have to find out how much Fe actually does react:

3 g mol Fe
1.64 g-mol of Sb 2 mol Sb = 2.46 g-mol Fe
g

moles of feed that reacts
Completion fraction =
moles of feed introduced
2.46 = 0.55
= 4.48
d) ) Let us assume that the percent conversion refers to the
Sb 2S3 since the reference compound is not specified.
Therefore,
1.64 g-mol of Sb 1
g mol Sb 2S3
= 0.82 g-mol Fe
2 g mol Sb

moles of feed that reacts
% Conversion = 100
moles of feed introduced
0.82 100 = 46.3%
= 1.77
0.200 kg Sb kg Sb
e) Yield = = 0.33
0.600 kg Sb 2S3 kg Sb2 S3
Problems
1) Sulfur dioxide may be produced by the reaction:

Cu + 2H 2SO 4 CuSO 4 + 2H 2 O + SO 2
a) How much copper must be used to obtain 32 pounds of sulfur dioxide?
b) How much 94% H2S04 must be used to obtain 32 pounds of sulfur dioxide?
2) In the reactions:
2KMnO 4 + 8H 2SO 4 + 10FeSO 4 5Fe 2 SO 4 3 +K 2SO 4 +2MnSO 4 +8H 2 O
K 2 Cr2O7 + 7H 2SO 4 + 6FeSO 4 3Fe 2 SO 4 3 +K 2SO 4 +Cr2 (SO 4 )3 +7H 2O

How many grams of potassium dichromate are equivalent

to 5.0 grams of potassium permanganate? How many
grams of potassium permanganate are equivalent to 3.0
grams of potassium dichromate?
3) For the operation of a refrigeration plant it is desired to
prepare a solution of sodium chloride containing 20% by
weight of the anhydrous salt.
a) Calculate the weight of sodium chloride which should be added
to one gallon of water at 30C in order to prepare this solution.
b) Calculate the volume of solution formed per gallon of water
used, keeping the temperature at 30 C.
4) A solution has a gravity of 80 Twaddell. Calculate its
specific gravity and its gravity in degrees Baume?
5) An oil has a specific gravity at 60/60F of 0.651. Calculate
its gravity in degrees API and degrees Baume?
Assignment
problem
The species recovered after the reaction takes place for some time are Jisted in
Table

TABLE
gmol
Cl 2 141.0
C3H6 6SI.O
C3H5Cl 4.6
C3H6Cl2 24.5
HCI 4.6

Based on the product distribution assumins that no allyl chlorides were pre-
sent in the feed, calculate the following:
a. How much Cl2 and C3H6 were fed to the reactor in g mol?
b. What was the limiting reactant?
e. What was the excess reactant?
d. What WS:S the fraction conversion of C3H6 to C3H5CI?
e. What was the selectivity of C3H CI relative to C3 Cl1?
f. What was the yield of C3H5Cl expressed in g of C3H5Cl to the g of C3H6
fed to the reactor?
g. What was the extent of reaction of the first and second reactions?
 Chapter 3
Behavior of Ideal Gases
 Energy
Energy is defined as the action of a force moving
under restraint through a distance.
All matter and the properties of matter are
manifestations of energy. Energy is the capacity of
matter to perform work and to affect the senses.
Energy is distributed throughout the universe in a
variety of forms, all of which may be directly or
indirectly converted into one another.
 Classification of Energy
1) Potential Energy
2) Kinetic Energy
3) Heat
4) Work
5) Internal Energy
6) Enthalpy
Potential Energy
Under the classification of -potential energy are
included all forms of energy not associated with
motion but resulting from the position and
arrangement of matter.
The energy possessed by an elevated weight, a
compressed spring, a charged storage battery, a tank
of gasoline, or a lump of coal are examples of
potential energy.
 Similarly, potential energy is stored within an atom as
the result of forces of attraction among its subatomic
parts.
Thus potential energy can be further classified as
external potential energy, which is inherent in matter
as a, result of its position relative to the earth, or as
internal potential energy, which resides within the
structure of matter.
Kinetic Energy
Energy associated with motion is referred to as kinetic
energy.
The energy represented by the flow-of a river, the
flight of a bullet, or the rotation of a flywheel are
examples of kinetic energy. Also individual molecules
possess kinetic energy by virtue of their translational,
rotational, and vibrational motions.
 Similar to the sub-classification of potential energy,
kinetic energy is sub-classified as internal kinetic
energy, such as associated with molecular and atomic
structure, and as external kinetic energy, such as
associated with the external motion of visible objects.
In addition to the forms of energy associated with
composition, position, or motion of matter, energy
exists in the forms of electricity, magnetism, and
radiation, which are associated with electronic
phenomena.
Temperature & Heat
The science pertaining to the transformation of one
form of energy to another is termed thermodynamics.
Energy can be transformed from one form to another
but it can never be destroyed and that the total
energy of the universe is constant. This principle of
the conservation of energy is referred to as the first
law of thermodynamics.
Energy may be transferred not only from one form to
another but also from one aggregation of matter to
another without change of form.
 The transformation of energy from one form to
another or the transfer of energy from one body to
another always requires the influence of some driving
force. As an example, if a hot metal bar is placed in
contact with a cold one, the former will be cooled and
the latter warmed. The sense of " hotness " is an
indication of the internal kinetic energy of matter. The
driving force which, even in the absence of electrical,
magnetic, or mechanical forces, produces a transfer of
energy is termed temperature and that form of energy
which is transferred from one body to another as a
result of a difference in temperature is termed heat.
Calculate the volume occupied by 30
lb of chlorine at a pressure 743 mm
Hg and 70 oF?
Basis of Calculation: 30 lb of chlorine
Lb
moles of ClILLUSTRATION 1
= 30 = 0.423 lb-mol
2 71

Volume at S.C. V = 0.423 359.05 = 152 ft 3
1

Applying Ideal gas law,

V V p1 T2
2 1
p2 T1
o o
T2 70 F 70 460 530 R
530
Volume at 743 mm Hg, 70 F = 152
o
760 = 167 ft 3

743 492
Calculate the weight of 100 ft3 of
water vapor, measured at a pressure
o
15.5 mm Hg and 23 C?
Basis of Calculation: 100 ft3 of water vapors
ILLUSTRATION 2
Volume at S.C. ;
Applying Ideal gas law,
V V p2 T1
1 2
p1 T2
o
T2 23 C 23 273 296 K
Volume at S.C. = 100 15.5 273 = 1.88 ft 3

760 296
1.88
Moles of Water = 0.00523 lb-mole
359.05
Weight of water = 0.00523 18 = 0.0942 lb
It is desired to compress 10 lb of
carbon dioxide to a volume of 20 ft3.
Calculate the pressure in psi that is
required at a temperature of 30 oC,
assuming the applicability of the
ideal gas law?
Basis of Calculation: 30 lb of CO2
ILLUSTRATION

Lb moles of CO =
10 3
= 0.228 lb-mol
44
2

Volume at S.C. V1 = 0.228 359.05 = 81.7 ft 3

Applying Ideal gas law,

p p V1 T2
2 1
V2 T1
3
Pressure at 20 ft , 30 Co
= 14.7 81.7 303 = 66.6 lb f

20 273 in 2
Assuming the applicability of the
ideal gas law, calculate the maximum
temperature to which 10 lb of
nitrogen, enclosed in a 30 ft3
chamber, may be heated without the
pressure exceeding 150 psi?
Basis of Calculation: 10 lb of nitrogen
ILLUSTRATION 4
Lb moles of N = 10 = 0.357 lb-mol
2
28

Volume at S.C. V1 = 0.357 359.05 = 128.1 ft 3
Applying Ideal gas law,
T T V2 p2
2 1
V1 p1
Temperature at 30 ft , 150 psi = 273
3
30 150

128.1 14.7
o
= 652 K = 379 C
When heated to 100 oC and 720 mm
Hg pressure 17.2 grams of N2O4
occupy a volume of 11,450 cc.
Assuming that the ideal-gas law
applies, calculate the percentage
dissociation of N2O4 to NO2?
SOLUTION:
ILLUSTRATION 5
Applying Ideal gas law,
V V p2 T1
1 2
p1 T2
Volume at S.C. = 11,450 720 273 = 7939.22 cm3 7.94 L

760 373
7.94
Total Moles after dissociation = = 0.354 g-mole (1)
22.414
17.2
G-moles of N 2 O 4 initially present = = 0.187 g-mole
92
Let, x = g-mol of N 2 O 4 dissociated then,
2 x = g-mol of NO 2 formed
Total Moles after dissociation = 0.187 - x + 2x (2)
Equating 1 & 2, we get,
0.187 x = 0.354 x = 0354 - 0.187 = 0.168
0.168
% Dissociation = 100 = 90%
0.187
 Gaseous Mixtures
In a mixture of different gases the molecules of each
component gas are distributed throughout the entire
volume of the containing vessel and the molecules of
each component gas contribute by their impacts to
the total pressure exerted by the entire mixture.
The total pressure is equal to the sum of the
pressures exerted by the molecules of each
component gas. These statements apply to all gases,
whether or not their behavior is ideal.
 In a mixture of ideal gases the molecules of each
component gas behave independently as though they alone
were present in the container. Before considering the actual
behavior of gaseous mixtures it will be necessary to define
two terms commonly employed, namely, partial pressure
and pure-component volume.
Partial pressure of a component gas which is present in a
mixture of gases is the pressure that would be exerted by
that component gas if it alone were present in the same
volume and at the same temperature as the mixture.
Pure-component volume of a component gas which is
present in a mixture of gases is the volume that would be
occupied by that component gas if it alone were present at
the same pressure and temperature as the mixture.
 Laws of Dalton & Amagat
Dalton's law states that the total pressure exerted by a
gaseous mixture is equal to the sum of the partial
pressures of each component gas present in that
gaseous mixture, that is:

p p A pB pC ...... (1)

where p is the total pressure of the mixture and pA, pB,
pC, etc., are the partial pressures of the component
gases as defined above.
 Similarly, the additive nature of pure-component
volumes is given by the law of Amagat, or Leduc's
law, which states that the total volume occupied by a
gaseous mixture is equal to the sum of the pure-
component volumes, that is:
V VA VB VC ...... (2)
where V is the total volume of the mixture and VA, VB,
VC, etc., are the pure-component volumes of the
component gases as defined above.
 Calculations for Partial Pressure
Conditions are such that the ideal gas law is applicable:
nA R T
pA = (3)
Where, V
V = total volume of mixture
n = number of moles of component A in mixture
Similar equations represent the partial pressures of
components B, C, etc. Combining these equations with
Dalton's law, Equation 1 Becomes:
RT
p (nA nB nC ...) (4)
V
 This equation relates the pressure, temperature, volume,
and molal quantity of any gaseous mixture under such
conditions that the mixture and each of the components
follow the ideal gas law and Dalton's law.
By combining Equations 3 and 4 a useful relationship
between total and partial pressure is obtained.
nA p
pA = n n ... (5)
n A B C

nA
(6)
N = n n n ...
A
 A B C
The quantity NA is the mole fraction of component
A. Equation 5 then signifies that, where the ideal gas
law may be applied, the partial pressure of a
component of a mixture is equal to the product of
the total pressure and the mole fraction of that
component. Combining Equation 5 and 6; we may
get,

pA N A p (7)
 Calculations for Pure-component Volume
Similar procedure is for the calculations of pure-
component volume as defined by Amagats Law

VA N A V (8)
Equation 8 signifies that, where the ideal gas law may
be applied, the pure-component volume of a
component of a gaseous mixture is equal to the
product of the total volume and the mole fraction of
that component.
 ILLUSTRATION 6
Calculate the average molecular CO2 13.1 %
weight of a flue gas having the O2 7.7 %
following composition by volume: N2 79.2 %
100%
Basis: 1.0 g-mole of mixture
Components g-mol Mol. Wt. grams
CO2 0.131 44 5.76
O2 0.077 32 2.46
Avg. M. Wt. =
N2 0.792 28 22.18 30.40 g/g-mol
Total 1.00 30.40
Calculate the density in pounds per
cubic foot at 29 in. of Hg and 30C of
a mixture of hydrogen and oxygen
which contains 11.1 % H2 by weight?
Basis of Calculation: 1 lb of mixture
H 0.111 lb 0.111 = 0.0555 lb-mol

2
ILLUSTRATION 7
2
0.889
O2 0.889 lb 32 = 0.0278 lb-mol

Total Molal quantity = 0.0833 lb-mol
Volume at S.C. V1 = 0.0833 359.05 = 29.9 ft 3
Applying Ideal gas law,
T2
V V p1 = 29.9 29.921 303 = 34.2 ft 3
2 1
p2 T1 29 273
Density at 29 in. Hg, 30 oC 1 lb 0.0292 lb
3 3
34.2 ft ft
Air is assumed to contain 79.0 %
nitrogen and 21.0 % oxygen by
volume. Calculate its density in
grams per liter at a temperature of
70 F and a pressure of 741 mm of
Hg?
Basis of Calculation: 1 g-mole of Air
O2 0.21 g - mol 0.21 32 = 6.72 g
ILLUSTRATION 8
N 2 0.79 g - mol 0.79 28 = 22.10 g
Total Weight = 28.82 g
Volume at S.C. V1 = 1.0 22.414 = 22.414 L
Applying Ideal gas law,
T2 530
V V p1 = 22.414 760 = 24.8 L
2 1
p2 T1 741 492
28.82 g 1.162 g
Density at 741 mm Hg, 70 C
o

24.8 L L
VOLUME CHANGES WITH CHANGE IN
COMPOSITION
1) Melting
2) Freezing
3) Condensation
4) Vaporization
5) Deposition
6) Sublimation
Some other operations are as;
Absorption
Drying
Evaporation
Adsorption
 ILLUSTRATION 9
Combustion gases having the following molal
composition are passed into an evaporator at
a temperature of 200 C and a pressure of
743 mm of Hg.
CO2 13.6 %
O2 7.2 %
N2 79.2 %
Water is evaporated, the gases leaving at a
temperature of 85 C and a pressure of 740 mm
of Hg with the following molal composition:
CO2 8.3 %
O2 4.4 %
N2 48.3 %
H2O 39.0 %
1) Calculate the volume of gases leaving
the evaporator per 100 ft3 entering.
2) Calculate the weight of water evaporated per
100 ft3 of gas entering.
Figure: E
V
CO2 13.6 % A
P
O2 7.2 %
O 85 C
N2 79.2 % R
200 C A 740 mm of Hg
T
743 mm of Hg O
R CO2 8.3 %
61.0 % O2 4.4 %
H2O N2 48.3 %
H2O 39.0 %
Basis of Calculation: 1.0 g-mole of entering gas

1) N 2 = 0.792 g - mole
O 2 = 0.072 g - mole
CO 2 = 0.136 g - mole
RT
V n n n
( N2 O2 CO2 )
P
1 g-mol 473 K 82.06 cm3 . atm 760 mm Hg 1 ft3
= 743 mm Hg g-mol . K 1 atm 30.483 cm3
 3
= 1.40 ft
This 1.0 g - mole of gas entering
forms 61% by volume of the gases
leaving the evaporator.
 100
Gases leaving 1.0 1.64 g - mole
61
Water leaving 1.64 - 1.0 1.64 0.38 0.64 g - mole
RT
Volume of gas leaving n n n n
(
N2 O2 CO2 CO2 )
P
V at 85 oC & 740 mm Hg,
1.64 g-mol 358 K 82.06 cm3 . atm 760 mm Hg 1 ft3
= 740 mm Hg g-mol . K 1 atm 30.483 cm3
1.75 ft 3

3
Volume of gas leaving per 100 ft entering,
3
1.75 ft leaving 100 ft 3 125 ft 3
3
1.40 ft entering
2) Weight of water leaving evaporator,
0.64 18 11.5 g 0.0254 lb

Weight of water evaporated

3 ,
100 ft of gas entering
3
100 ft
0.0254 lb 1.81 lb
3
1.40 ft
 ILLUSTRATION 10
In the manufacture of hydrochloric acid a gas is
obtained which contains 25.0% HCl and 75.0%
air by volume. This gas is passed through an
absorption system in which 98.0% of the HCl is
removed. The gas enters the system at a
temperature of 120F and a pressure of 743 mm
of Hg and leaves at a temperature of 80F and a
pressure of 738 mm of Hg.
1)Calculate the volume of gas leaving per 100 ft3
entering the absorption apparatus.
2)Calculate the percentage composition by
volume of the gases leaving the absorption
apparatus.
3)Calculate the weight of HCl removed per 100
ft3 of gas entering the absorption apparatus.
Basis of Calculation: 100 ft3 of entering gas (743 mm Hg, 120 F)

1) Pure - component vol. of HCl 25 ft 3

Pure - component vol. of HCl absorbed 24.5 ft 3

Pure - component vol. of HCl remaining 0.50 ft 3
Vol. of gas remaining 75 0.50 75.5 ft 3
o
(743 mm Hg, 120 F )
Vol. of gas leaving 75.5 743 540 70.8 ft 3
738 580
(738 mm Hg, 80 o F )
2) Composition of gases leaving :
0.5
HCl 100 0.61%
75.5
75
Air 100 100 0.61 99.34%
75.5
3) Volume of HCl absorbed at S.C. 24.5 743 492

760 580
20.3 ft 3
20.3
HCl absorbed 0.0565 lb mole
359.05
Weight of HCl absorbed 2.07 lb
 ILLUSTRATION 11
Calcium hypochlorite is produced by absorbing
chlorine in milk of lime. A gas produced by the
Deacon chlorine process enters the absorption
apparatus at a pressure of 740 mm of Hg and a
temperature of 76F. The partial pressure of the
chlorine is 59 mm of Hg, the remainder being
inert gases. The gas leaves the absorption
apparatus at a temperature of 80F and a
pressure of 743 mm of Hg with a partial pressure
of chlorine of 0.5 mm of Hg.
1)Calculate the volume of gases leaving the
3
apparatus per 100 ft entering.
2)Calculate the weight of chlorine absorbed,
per 100 ft3 of gas entering.
 Basis of Calculation: 100 ft3 of entering gas (740 mm Hg, 75 F)
pCl2 = 59 mm Hg 75 F 80 F
Absorption V2 = ?92ft.53 ft3
pInert gas = 681 mm Hg
Apparatus
V1 = 100 ft3 740 mm of Hg 743 mm of Hg

Volume at S.C. of Cl entepring 100T 59 4p9C2l2 7.=140.f5t 3mm Hg

V2 V1 2 1inert gas 2760 5p
3I5nert gas = 742.5 mm Hg
p T
inert gas inert gas 2inert gas
10.5 492 3

Volume at S.C. of Cl2 leaving 92.5 0.055 ft

This is also the total volume of gases leaving7(7 6403 m5m
40Hg, 80F). The actual
enter6 g 1an 5
in8 le4a0
ving are also 100 a3nd 92.5 ft3
volumes of chlorine C
VoluV of0 0 l 2 absorbed 7.14 0.055 7.08 ft
me at S .C. 1
respectiv2einleyrt. gas 742.5 535
Cl2 absorbed 7.08 0.0197 lbmole 1.40 lb
359
 ILLUSTRATION 12
Nitric acid is produced in the Ostwald
process by the oxidation of ammonia with
air. In the first step of the process ammonia
and air are mixed together and passed over a
catalyst at a temperature of 700 C. Theo

following reaction takes place:

4NH 3 5O2 6H 2O 4NO
The gases from this process are passed
into tower where they are cooled, and
the oxidation is completed according to
the following theoretical reactions:

2NO O2 2NO2
3NO2 H 2O 2HNO3 NO
The NO liberated is in part reoxidized and forms more
nitric acid in successive repetitions of the above
reactions. The ammonia and air enter the process at a
temperature of 20 oC and a pressure of 755 mm Hg.
The air is present in such proportion that the oxygen
will be 20% in excess of that required for complete
oxidation of ammonia to nitric acid and water. The
gases leave the catalyzer at a temperature of 700 oC
and a pressure of 743 mm Hg.
a) Calculate the volume of air to be used per 100 ft3
of ammonia entering the process
b) Calculate the percentage composition by volume of the gases
entering the catalyzer
c) Calculate the percentage composition by volume of the gases
leaving the catalyzer, assuming that the degree of completion
of the reaction is 85% and that no other decomposition takes
place.
d) Calculate the volume of the gases leaving the catalyzer per
100 ft3 of ammonia entering the process
e) Calculate the weight of nitric acid produced per 100 ft3 of
ammonia entering the process, assuming that 90% of the
nitric oxide entering the tower is oxidized to nitric acid.
Figure:
Ostwald Process for producing Nitric Acid
Basis of Calculation: 1.0 lb-mole of NH3
NH 3 2O2 HNO3 H 2O

a) For 1 lb - mole of NH 3 , O2 required 2.0 lb - mole

O2 in excess 2.0 0.20 0.4 lb - mole
Total O2 sup plied 2.0 0.4 2.4 lb - mole
Total Air sup plied 2.4 100 11.42 lb - mole
21

Therefore,
Volume of Air 11.42 Volume of ammonia at same conditions

Volume of NH 3 entering 359.05 760 293 388 ft 3

755 273
 Volume of Air 11.42 388 4440 ft 3
Volume of Air per 100 ft 3 of ammonia entering,
100
4440 1142 ft 3
388
b) Gases entering process, N 2 , O2 , NH 3
N 2 present in air 0.79 11.42 9.02 lb - moles
Total moles of gases entering 9.02 1.0 2.4 12.42 lb - moles
Composition by Volume :

NH 3 1.0 100 8.0%

12.42
O2 2.4 100 19.3%
12.42

N2 9.02 100 72.7%

12.42
c) Gases leaving catalyzer; N 2 , NH 3 , O2 , NO, H 2O
N 2 leaving 9.02 lb - moles
NH 3 oxidized in catalyzer 0.85 lb - moles
NH 3 leaving 1.0 - 0.85 0.15 lb - moles
5
O2 consumed in catalyzer 0.85 1.06 lb - moles
4
O2 leaving 2.4 - 1.06 1.34 lb - moles
NO formed in catalyzer 0.85 lb - moles
6
H 2O formed in catalyzer 0.85 1.275 lb - moles
4
Total moles of gases leaving 9.02 0.15 1.34 0.85 1.275
12.64 lb - moles
Composition by Volume :

NO 0.85 100 6.7%

12.64

H 2O 1.275 100 10.1%

12.64

NH 3 0.15 100 1.2%

12.64
O2 1.34 100 10.6%
12.64
9.02
N2 100 71.4%
12.64
Basis of Calculation: 100 ft3 of NH3 entering process
100
d) ) Moles 1.0 0.258 lb - mole
of NH 3 388
0.258
Moles of gas leaving catalyzer 12.64 3.26 lb - mole
1.0
Volume of gas leaving at S.C. 3.26 359 1170 ft 3

Volume of NH 3 entering 1170 760 973 4270 ft 3

743 273
e) NO produced in catalyzer 0.258 0.85 0.219 lb - moles
NO oxidized in tower 0.219 0.90 0.197 lb - moles
HNO3 formed 0.197 63 12.4 lb
For Solution in Excel
Click here Assignment
Solution of the following problem to be submitted
A gas containing 45% CS2, 20% H2, 15% CO and 20% N2
is charged to a furnace where it is combusted to
produce energy. Air is supplied in such a way that
oxygen in air is 40% in excess of that theoretically
required for complete combustion in feed gas. 90% of
CS2 fed is combusted to sulphur dioxide and carbon
dioxide, the rest remained unconverted. All the H2 and
CO are completely converted to H2O and CO2
respectively.
a) The total number of moles of the feed gas
b) Average Molecular Weight of the feed gas
c) Volume of the feed gas at 150oF and 800 mm Hg
d) Volume of air at the conditions of the feed gas
e) The composition by moles of the leaving gases
f) The volume of leaving gases at 1000oF and 750 mm Hg

You must take 1.0 lbmole of H2 in the

feed gas as the basis of calculation
Problems
 11. A furnace is to be designed to burn coke at &he rate of 200 lb per hour. The
coke has the following compoaition:
Carbon...... .. ... . . . . ... ..... .. 89.1%
Ash. . .. ... .... .. . .... .. .... . .. . .. 10.9%
The grate eflieiency of the furaaee is such thd 90% of the earbon present in the eoke
chaqed is burned. Air is supplied in 30% excelS of that required for the comple&e
eombuation of &II the ea.rbon eh&rged. It may be a88Uined Ulat 97% of the carbon
burned is oxidized to t.be dioxide, the remainder forming monoxide.
(a Cal ula&e the composition, by volume, of the flue gases leaving the fumaee.
(b) If the flue gases leave the furnace at a temperature of M0F and a pleasure
of 743 mm Hg. the ra of flow of gaMe, in cubic feet per minute,
for which the stack must be designed.
Basis of Calculation: 200 lbs of coke entering
Stack gases
mole %
CO2 =15.87%
Coke F P CO
O2
=0.5%
=4.83%

Weight %
FURNACE N2 =78.80%
Carbon = 89.1%
Ash = 10.9% A Excess Air
30% in
mole %
R
Refus
e
weight
%

O2 = 21.0% C = 44.97%
N2 = 79.0% Ash = 55.03%
Basis: 200 lbs of coke entering C O CO
2 2
Stream F; 1
Carbon = 178.2 lbs C O2 CO
2
Ash = 21.8 lbs
Stream P;
Stream R;
Carbon = 0.10 178.2 = 17.82 lbs CO 2 produced = 12.965 lb moles
Ash = 21.8 lbs CO produced = 0.40 lb moles
O 2 produced = 3.95 lb moles
Carbon reacted in F = 160.38 lbs N 2 produced = 64.38 lb moles
= 13.365 lb moles P = 81.695 lb moles
Volume at STP; P V P V
1 1 = 2 2
V1 = 29332.59 ft 3 T1 T2
P1 = 760 mm Hg 3
V2 = 61593.01 ft
hr
T1 = 32 F 3
V = 1026.55 ft
V2 = ? at 550 F & 743 mm Hg 2 min
 18. Coke containing 87.2% carbon and 12.8% ash is burned on a grate. I& is
found that 6% of the carbon in the coke charged is lost with the refuse. The com-
position by volume of the staek gases from the ruru is as follows:
OOt ................... - ..--. . ... .. 12.0%
. ..
00.. or or II or II .. II 0.2%
.. " Ill " " e I+

I 'I
Ot. It It It I It I I It 8.8%
II e It II II a II It t IIt t

Nt. .. .. . ... . . . . ...... . ... .. .... . .. 79.0%

(a) Calculate the volume of lueB, at MOT and 29.3 in. of H1 pre88UI'e; formed
per pound of coke aha.rged.
(b) Calculate t.he per eent of exeeas &ir supplied above that required for com-
plete oxidation of the carbon charged.
(c) Calculate the degree of compleUon of the oxidation, to the dio:lide, of the
carbon burned.
(d) Calculate the volume of air, at -roF and 29.3 in. H1, supplied per pound o1
oob charged.
Basis of Calculation: 100 lbs of coke entering
Stack gases
mole %
CO2 = 12.0%
Coke F P CO
O2
= 0.2%
= 8.8%

Weight %
FURNACE N2 = 79.0%
Carbon = 87.2%
Ash = 12.8% A Air R Refuse
mole % weight %
O2 = 21.0% C = 29.01%
N2 = 79.0% Ash = 70.99%
Basis: 100 lbs of coke entering C O2 CO2
Stream F; Stoichiometric relation;
Carbon = 87.2 lbs 1 lb mole of reacts with O 2 = 1 lb mole
Ash = 12.8 lbs For 6.83 lbmoles of C = 6.83 lb mole of O 2
Stream R; Stream P;
Carbon = 0.06 87.2 = 5.232 lbs CO 2 produced = 6.83 lb moles
Ash = 12.8 lbs CO produced = 0.1138 lb moles
O 2 produced = 5.008 lb moles
Carbon reacted in F = 81.968 lbs
N 2 produced = 44.964 lb moles
= 6.83 lb moles
P = 56.91 lb moles
P = 56.91 lb moles for 100 lb of coke Air = 73.32% in Excess
P = 0.5691 lb moles per lb of coke
Volume at STP; P V P V
1 1 2 2
=
V1 = 0.5691 359.05 = 204.33 ft
3
T1 T2
P1 = 29.921 in. Hg V2 = 424.107 ft 3
T1 = 32 F
V2 = ? at 540 F & 29.3 in. Hg
 Volume of Air at STP;
3
V1 = 203.94 ft
P1 = 29.921 in. Hg

Degree of Completion; T1 = 32 F

Fraction = 0.94 V2 = ? at 70 F & 29.3 in. Hg
% completion = 94% P V P V
1 1 2 2
T1 =
T2
3
V2 = 224.34 ft
 THANKS

Questions

132