REACTIVE SYSTEMS

INTRODUCTION 13.1
snot too long ago that the chemical processes were left almost entirely to the
and the chemical engineer. Then the energy crisis came with the stark
ion that all earthly fuels are finite. Suddenly everybody became involved
nergy regardless of their grasp of the subject matter contained in this
. Although most people will never comprehend combustion, it is expected that
ineers have a working .knowledge of fossil fuels and their rapid oxidation

controlled burning of a fuel in air is an exothermic reaction accompanied by a

tial increase in temperature. Like all working thermodynamic processes, it
.b.e an efficient one. Four factors (among others) must be correct if a
stion process merits any consideration-these follow and spell MATT. M for
... ixing of fuel and oxidizer; A for adequate air to supply the oxygen; T for
ii temperature to start and maintain the combustion process; T for time to
t complete combustion.
haps this chapter should prove interesting since you are so acutely aware of the
at combustion plays with our nation in maintaining its image and status among
her countries of this world.

FUELS 13.2
sil fuels may be classified conveniently as (1) solid, (2) liquid, and (3) gaseous.
in many different grades, is the most common solid fuel. The most widely used
;fuels are hydrocarbon derivatives, of the chemical form Cx H,, where the
ipts x and y have many different values. The alcohols, of the chemical form
Q,, have application where a price disadvantage is outweighed by other
lages. The gaseous fuels are generally the cleanest, and where natural gas is
' pl, probably the cheapest. Manufactured and byproduct gases are also used
ating and power production. The space age has brought about the develop-
of "fuels," particularly reactants that combine rapidly and release large
ts of energy, as needed for rocket propulsion.
341
13.3 ANALYSIS OF FUELS

The ultimate analysis is one that specifies the various percentages by mass
mass fractions fm) of the elements in the fuel, typical for solid and liquid fuels;.
A gaseous fuel may be defined either by a gravimetric or a volumetric (
analysis ( 12.2). The combustible elements are mostly carbon and hydrogen,,
If the reacting fuel is a single molecular type, we may determine a gravl
analysis of the different atoms from the chemical formula. For the hydro
octane CsH1s, which is close to the average molecular form in gasoline (a mix
numerous ilifferent molecules\ we have
(a) 8 x 12 + 18 x 1 ""' 114 lb/pmole of octane
where, in a molecule of fuel, there are 8 atoms of carbon of atomic mass 12'
atoms of hydrogen of approximate atomic mass 1. (In most combustion pi
the whole number nearest the atomic or molecular mass is sufficiently a
Therefore, in 1 mole of octane, there are 8 x 12 = 96 lb C and 18 lb
gravimetric fractions are fmc = 96/114 = 0.842 C, fmH, = 18/114 = 0.15
In thy opposite direction, suppose a hydrocarbon has been found to cont
C and 20% H2 by mass Umc = 0.80, fmH, = 0.20). The corresponding ~)i
atoms is 80/12 = 6.67 and 20/l = 20, which numbers are proportioni\
number of atoms of C and Hz, respectively. Equivalent hydrocarbons wm1(
or or .J,

or any one where the number of H 2 atoms is 20/6.67 = 3 times the num.
atoms; designated (CH 3 )x. Notice that the equivalent molecular mass of (J
100.

13.4 COMPOSITION OF .AIR ,\<//

Atmospheric air has a volumetric composition of 20.99% oxygen, 78;

trogen, somewhat less than 1% argon, with small quantities of several)
such as water vapor, carbon dioxide, helium, hydrogen, and neo,
engineering calculations, it is usually accurate enough to include all in~i;
nitrogen and to use the analysis: 21 % oxygen and 79% "atmospheric" 11.
volume. Thus, in 100 moles of air, there are approximately 21 moles of
moles of Nz, or
79 = . molesN 2 ft'N2
(a) 3 76 or 3 76 3
21 mole0 2 ' ft 02
a useful number for the current study. The approximate gravimetric com
air is 23.1 % Oz, 76.9% Nz, or there are 76.9/23.1 = 3.32 lb N2 /lb 02.

13.5 AIR-FUEL RATIOS

If the proportions of the constituents of the reactants are such

exactly enough molecules of oxidizer to bring about a complete reacti
molecular forms in the products, these are said to be the stoichiometric pr
For these proportions, there is an ideal amount of oxidizer; for fuels
pure 0 2 , we speak of "100% air" (or 100% 0 2 ).
 343

nr<ictice, to assure a complete reaction of the fuel (complete combustion), an

of air or of oxygen is supplied. In this case, for example, we may speak of
~ir, 200% air, and so on; or 20% or 100% excess air, and so on. Any air over
ve the amount practically required for the particular situation results in more
eaving the system as stored (molecular) energy, inasmuch as the temperature
the products are cooled will probably be as low as economically feasible
Experience suggests the following amount of excess air for steam power
naces: pulverized coal, 15-20%, fuel oil, 5-20%; natural gas, 5-12%.
are occasions when there is a deficiency of oxidizer, and for fuels, we speak
ample, "80% air'"(or 80% Oi). In general, if there is not some excess, the
unburned fuel, incomplete combustion, is uneconomically large.
ch as the various principles are familiar, a few examples will serve to
heir application. As you recall, the atomic species are conserved in a
process. If one will therefore methodically write out the atom balance,
t to a mass balance of that element, for each atom involved, one is more
6btain correct chemical equations.
Example-Combustion of Octane 13.6
bus octane CsHrn(g) is burned in ideal air, what volume of air at 140F and 14 psia is
'?Determine the relative volumes and masses of the constituents of the reactants and
'pducts when the H,O is liquid H 2 0(1), and compute the air-fuel ratio. Compute an
;ate value of the equivalent molecular weight for the products when the H 2 0 is
,O(g).
n. For stoichiometric combustion, the products are H 2 0, CO,, and N 2 (the N2 is
d to be inert, passing through the reaction chemically unchanged). Depending on the
'perature, the H,O may be liquid or gas (vapor). If the products return to ap-
ely atmospheric pressure, we assume that all the H 2 0 formed during combustion has
d. In this example, both phases are considered. We recall that the coefficients of the
I, symbols can represent either the number of molecules in the reaction or, preferably,
J each substance. Let 1 mole of fuel be the basis of the equation and write the
].equations with unknown coefficients represented by letters, say, a, b, c.

C,H,,(g) + aO, + 3.76aN2 -> bH2 0 + cC0 2 + 3.76aN,

.6 moles of N, per mole of O, in air, 13.4, the coefficient of atmospheric N2 is 3.76a,

Oles of atmospheric O,. The atom balances give

C: 8 = c or c = 8

H2: 18 = 2b or b =9
o,: 2a = b + 2c or a = 12.5 3.76a = 47

f the final temperature is low enough to have condensed the H 2 0, we get

Reactants Products

C,,H,.(g) + 12.50, + 47N, -> 9H,O(I) + eco, + 47N,

1 + 12.5 + 47 -> 9 +8 + 47
1 + 12.5 + 47 -> 0 +8 + 47
114 + 400 + 1316 = 162 + 352 + 1316
1 + 3.51 + 11.54 = 1.42 + 3.09 + 11.54
 Chapter 13 lllea<>tive
The first line below the equation is simply the number of moles of each compo
complete combustion in stoichiometric air. The "Relative volume" line shows
volumes when reactants and products are at the same temperature and pressure (A
liquid H 2 0 is shown with zero volume (it is so small compared to gas volumes
interpretation: 1 ft' fuel requires 12.5 ft' 0 2 and results in 8 ft' CO, (same p a
volumetric analyses of the reactants and of the products can be obtained by di
volume of one constituent by the total volume: for reactants, suppose 12.5/6
volumetric fraction of o,; for the products, 8/55 is the volumetric fraction of co,. is
The "Relative mass" line is obtained by multiplying the number of moles
component by its molecular mass M lb/mole; for o,, this is (12.5)(32) = 400. The
fuel" line is obtained by dividing ea~h term of the preceding line by the mass of f
Interpretation of the last line: it takes 3.51 lb 0 2 /lb fuel; there results 1.42 lb H
addition to H 2 0 that was already in atmospheric air; f stands for fuel.
One of the required answers is r.11 = 3.51 + 11.54 = 15.05 lb air/lb f, which is)
ratio (r. 11 = 15.1 when the decimal parts of the molecular weights are used); the fu
r11 = 1/15.05 = 0.0664 lb I/lb air. If the relative masses of the reactants are nap
quicker way to compute the air is to use the equivalent molecular weight of air,
the total moles, 12.5 + 47 = 59.5 moles of air. Then

_ lb air/pmole f _ (29)(59.5) _ ir/lb f

(c) ' 1' - lbfuel/pmole - 114 - l 5 .l lba ue1

Small differences in answers by different methods are to be expected when

atomic weights are used.
At this stage, the volume of air may be computed in several different ways.
of air per mole of fuel, equation (6-4) gives

(d) V a = 1545nT
p
= (1545)(59.5)(600) = 27 380 f '/ l f l
(l 4)(l 44 ) , t mo e ue

or 27,380/114 = 240 ft'/lb fuel.

The total mass of products per mole of fuel is 162 + 352 + 1316 = 1830 lb,
moles of gaseous products with H 2 0(g) per mole of fuel is 9 + 8 + 47 = 64. T
mass is then M = 1830/64 = 28.6 lb/mqle of products.

13.7 Example-Volume of Products

For the products of combustion found in 13.6, determine the volume at 240~.
in ft' /lb fuel. \
Solution. There are also several ways in which t*s problem may be solved
Since at the stated temperature, the H 2 0 is gaseous, there are 9 + 8 + 4 7 =
products per mole of fuel. Use the ideal gas equation fbr 114 lb fuel and get

(a) V = 1545nT = (1545)(64)(700) = 301 ft' /lb fuel

114p (114)(14)(144)

Also, the volume can be computed by using any component of the pr<ldt1ct!;
pressure. Since this idea is often useful, let us check the above computation.
partial pressure of the 4 7 moles of nitrogen as

(b) PN = p, = X,pm = (47 /64)14 = 10.3 psia

Use the 11.54 lb N2 /lb fuel obtained from 13.6, and get

(c) V = mRT = (11.54)(1545/28)(700) = 301 ft' /lb fuel

p (10.3)(144)
 e of the mixture. This sort of computation is preferably made with that component
xture that is most nearly an ideal gas and whose volumetric percentage is most
known (if there is a difference).

COMBUSTION IN EXCESS AND DEFICIENT All'! 13.8

air is presumed to pass through the reaction chemically unchanged.
It is desiredto have 100% excess air ("200% air"). First, the combustion
must be balanced for stoichiometric air so that the ideal amount is known;
>amount of air corresponding to a given percentage of excess (or deficiency)
etermined. For fOO% excess air in equation (b), 13.6, there would be 25
.and 94 moles N2 . The balanced equation becomes

C8H 1s(g) + 2502 + 94N2 --> 9H20(l) + 8C02 + 12.502 + 94N2

ficient air, one must make assumptions regarding the composition of the
t this stage. We shall assume that all the H 2 goes into H 2 0 (because there
g affinity between H 2 and 0 2 ) and that the incompleteness of combustion
the appearance of some CO as well as C0 2 For this assumption, there are
any unknowns. As an example, suppose that 80% of stoichiometric air is
'for the octane in equation (b), 13.6; then the 0 2 in the reactants is
.5) = 10 moles, and the corresponding N2 is (3.76)(10) = 37.6 moles. The
equation becomes

C8 H 18(g) + 1002 + 37.6N2 = aCO + bC0 2 + 9H 2 0 + 37.6N 2

carbon and oxygen atom balances,

C: S=a+b or a=S-b

0 2: 20 = a + 2b + 9

aneous solution gives b = 3 moles and a = 5 moles. The balanced equation

be written and other computations made as illustrated in 13.6 and 13.7.

Example-Dew Point of H 2 Cl in Products 13.9

.lchiometric dry air. Let the reaction be for octane, as per equation (b), 13.6. For a
' ure Pm = 14 psia, determine the dew point of the H 2 0.
n. For 9 moles of gaseous H 2 0 and 64 moles of products, the partial pressure of
:by Dalton's law is

Po = X,,Pm = ( : ) 14 = 1.97 psia

4

fresponding saturation temperature is 125.5F, Item B 13, almost the dew point

mid Air, 20% excess. Let there be 20% excess air in the combustion of CsH1s The
'ratio of the air supplied is w = 0.015 lb v/lb da; the total pressure is 14 psia. Find the
of the H 2 0.
The amounts of 0 2 and N2 are obtained by multiplying their coefficients by 1.20
)20% excess); moles of N2 = (1.2)(47) = 56.4. The moles of H 2 0 (= 9) and of C02
 346 Chapter 13
(= 8) are unchanged. But since there are now (1.20)(12.5) = 15 moles of 0 2
needed for the reaction, the products will contain 15 - 12.5 = 2.5 moles of
total number of moles of products as

(b) np =In,= 9 + 8 + 2.5 + 56.4 = 75.9moles

I

The amount of dry air accounted for in the reaction equation is 15 + 56.4 = '
(71.4)(29) lb da/pmole f, where Md, = 29. For w = 0.015 lb v/lb da, the vap
reaction per mole of fuel is m. = (0.015)(71.4)(29) lb, and the moles of erif~

_ m.nd,Md, :__ (0.015)(71.4)(29) _ l

(c) "' - M. - 18 - .72 5 pmoles

Total vapor in products n. = 9 + 1.725 = 10.725 pmoles and

n. 10.725 .
(d) Pv = ~Pm = (14) = 1.934 psia
n, 77. 6 3
from which the saturation temperature (dew point) is 124.S'F. It is coin(lf
answers in parts (a) and (b) are virtually the same. In both cases, there is a sma
the H 20 is not acting ideally at its partial pressure.

13.1 ll Example-Finding Air R"q"ir"d and Pmd.,cts from Comb.,stion,

Given the Gravimetric Analysis of F"el
Whenever a gravimetric analysis is given, a common practice with coal
convert to moles of each element; that is, if fm is a percentage number,

(a) (!.. lb/100 lb fuel) = fm, moles/100 lb fuel

(M, lb/mole) M,

Given the ultimate analysis of an Illinois coal' 133l as follows, dry basis:

f.. 67.34% C 4.67% H, 8.47% 0 2 1.25% N 2 4.77% S

fm/M 5.61 C 2.33 H2 0.265 0 2 0.045 N 2 0.149 S

The second line is obtained by dividing each fm by the corresponding M

the numbers may now be taken as moles per 100 lb of dry fuel. Since the
chemical equation are moles, we write

[5.61C + 2.33H2 + 0.2650 2 + 0.045N 2 + 0.149S] + a02 + 3.76a

(b)
bC02 + cH2 0 + dSO, +
where the brackets are used only to keep the elements of the fuel clearly
material balances are

C: 5.61 = b b = 5.61

H,: 2.33 x 2 = 2c c = 2.33

S: 0.149 = d d = 0.149

o,: (0.265 x 2) + 2a = 2b + c + 2d a = 6.66

 equation for stoichiometric air is

fS.61C + 2.33H2 + 0.2650, + 0.045N, + 0.149S] + 6.660 2 + 25.04N2 ->

5.61C0 2 + 2.33H2 0 + 0.149S0 2 + 25.09N,

air are 6.66 + 25.04 = 31.7 moles/100 lb dry fuel. At 29 lb/mole, we get

. 3.17 x 29 = 919.3 lb air/100 lb dry fuel or 9.19 lb air/lb dry fuel

':chemical equation, almost any desired ratio is easily found. Common ratios found
Of dry products (no H,O) per pound of carbon in the fuel; mass of dry products per
ry coal; volumetric percentage of CO, in the products; partial pressure of the H,O
-products; and the volumetric and gravimetric analyses of the products. In furnace
products are called flue gas.
is considerable moisture in the coal, as in many low-grade coals, some of the
Ille of the combustible elements is necessarily used to evaporate the H 2 0 and the
tof evaporation goes out the stack as a loss. Naturally, we shall be interested in the
1
tio for coal as fired. As an example, let the moisture content of the coal be 12%.
fe is JOO - 12 = 88% of~dry coal, or 0.88 lb dry fuel/lb wet fuel (as fired-
d f.a.f.). Thus,

lb air ~ lb dry fuel) .

r.11 = ( 9.19 lb dry fue1 0.88lb fi =8.llbair/lbf.a.f.
\ as red

!fur content is frequently neglected in computations such as these. Moreover, the

i1l the fuel is usually a small quantity, and as such it would be little missed in sliderule
(ms. On the other hand, the practice is to include the oxygen, letting it count toward
ired for combustion, as in this example.

ANALYZING THE PRODUCTS OF COMBUSTION 13.11

'roducts of combustion are analyzed in order to learn about the combustion
, say, the amount of air supplied. The Orsat apparatus, Fig. 13/1, determines
'centages of CO,, CO, and 0 2 in the dry products (although the test sample is
d with H 2 0). Since the products from an internal combustion engine contain
en H 2 and hydrocarbons, principally methane, CH4 , these constituents can
'ignored, (2) determined by more complete test, or (3) estimated. Experience
that the amount of CH4 is about 0.22% of the volume of dry exhaust gas,
!the amount of free H 2 by volume is about half of the volumetric percentage
q,241

the product analysis, we can construct the corresponding theoretical chemi-

ation or obtain part of it, depending on what is known about the fuel. There
vitable sources of error, such as unburned fuel in the ash and smoke. The
s of the fuel and of the products may be complete, in which case several
)balances may be made. However, we can get a good approximation of the
lied (if the free 0 2 , H 2 , and N2 contents are small), from a carbon balance,
g only the amount of carbon burned per unit mass of fuel. Detail is best
by examples.
Fig.13/1 Flue-Gas Analyzer. The bottle C, containing water, is con-
nected to the burette B by a rubber tube. Raising and
lowering the bottle causes the water to flow into and out of
the burette. In operation, the air in the burette and the
adjoining passages is first driven out by displacing it with
the water in C. A sample of the products of combustion is
then drawn into the burette B. During these preliminary
operations, the needle valves N,, N2 , and N3 to the solution
containers D, E, and F have been closed. With valve N 1
open, the sample of flue gas in the burette is forced into
container D by raising bottle C. A solution of potassium
hydroxide in D absorbs the carbon dioxide of the flue gas,
leaving the other constituents unaffected. Remaining gas is
returned to the burette by lowering C, and the loss of
volume is noted. Successively, the gas is then forced into ,
where a solution of pyrogallic acid in a solution of potas-
sium hydroxide absorbs the oxygen, and into F, where a
solution of cuprous chloride in ammonia absorbs the car-
bon monoxide. The remaining gas is assumed to be all
nitrogen, or an estimation of other products is made.
(Courtesy Ellison-Draft Gage Co., Chicago)

13.12 Example-Actual Air-Fuel Ratio

A flue-gas analysis of the dry products of the coal in the example of 13.10 is
found to be 15% CO,, 3.5% O,, and 0.2% CO, with the remainder assumed.to
81.3% N2 ; all by volume of dry gases. What excess or deficiency of air is suppli~
Approximate Solution, Assuming Carbon Only Is Known. For the coal o
know that the carbon is 0.6734 lb C/lb dry fuel or 5.61 moles per 100 lb of dry fil
chemical equation is .

(a) a[5.61C + ] + ..,,. 15C02 + 0.2CO + 3.502 + 81.3N2 +

The dry-product analysis is written as given, the basis of the equation being 1
products. The coefficient a is obtained from a carbon balance;

C: 5.61a = 15 + 0.2 or a = 2.71 5.61a = 15.2

(b) 15.2C + ..,,. 15C02 + 0.2CO + 3.502 + 81.3N2 +

In this approach, we assume that the nitrogen measures the amount of air, a
if no N1 is in the fuel, since it passes through the ideal reaction unaffected. The
that accompanied 81.3 moles N2 in the air are 81.3/3.76 = 21.6 moles O,, from
air are 81.3+21.6= 102.9. The mass of air per pound of carbon, which is
 (102.9)(29) lb air =
16 .J, 61b air
. /lb Cb d
(15.2)(12)lb C urne

wn carbon content (0.6734) and moisture content (0.12 or 0.88 lb dry fuel/lb

r11 = (16.36lbair)(o.6734~)(o.8Slbdryf) = 9.7 lb air

a lb C, lb dry f lb f.a.f. lb f.a.f.

ir for stoichiometric combustion. The excess is (9.7 - 8.1)/8.1 = 19.8%.

m Ultimate Analysis, When more is known of the fuel analysis, a somewhat
computation of the air can be made. Except in extreme cases, the sulfur is
Oz is in the C02 percentage as determined by the Orsat because potassium
rbs it too). Using mole values from 13.10, we have

. a[5.61C + 2.33H2 + 0.26502 + 0.045N,] + bO, + 3.76bN,->

15C02 + 0.2CO + 3.50 2 + (0.045a + 3.76b)N2 + dH,O
'Jiydrogen in the fuel, there is bound to be some H20 in the products. The
(is determined from the carbon balance and was found above; a = 2.71. From
l balances, we have,

(2.71)(2.33)(2) = 2d d = 6.31

(2.71)(0.265)(2) + 2b = 30 + 0.2 + 7 + 6.31 b = 21.03

(0.045a + 3.76b) = 79.19

d equation is (3.76b = 79.07)

[15.2C + 6.31H 2 + 0.7202 + 0.122N,] + 21.0302 + 79.07N,->

15C02 + 0.2CO + 3.50 2 + 79.19N2 + 6.31H,O
pplied is the 0 2 and N 2 on the left-hand side, outside the brackets that enclose the
+ 79.07 = 100.l moles of air. As before,
- (100.1)(29)(0.6734)(0.88) - 9 43 . /l f f
'If - (l 5 .2 )(l 2 ) - . lb air b .a..

>ith the preceding answer. Besides different procedures, an experimental error is no

yed in taking readings. The advantage of the second method is that any desired . ~
kly obtained with the balanced equation. Perhaps you may notice, though it is not
'this example to do so, that the amount of fuel represented within the brackets is
llb/100 moles dry products.

Exampl-Air for Hydrocarbon of Unknown Compo,,;tion 13.13

mmercial petroleum fuels are mixtures of numerous hydrocarbons, it is often
:us to get an estimate of the air-fuel ratio without the expense of an analysis of the
. h no doubt varies from delivery to delivery). In the following approach, the fuel is
 Chapt@r 13 R<1aetiw@

assumed to be composed of carbon and hydrogen only in the form C, H,, and
therefore contain only small amounts of O,, N,, and S in order to avoid significant
The dry exhaust from an automotive engine at 1-atm pressure has a volumetric
follows: 12.5% CO,, 3.1% O,, 0.3% CO, which is the information obtained from
(There should also be about 0.22% CH. and 0.15% H 2. See 13.11. These quantit
included if desired, but we shall omit them to shorten the presentation.) Assull).
remainder of the exhaust is N, = 84.1 %. (a) Set up the theoretical combustion
finding values of x and y in C,H,. (b) Determine the air-fuel ratio.
Solutiou. (a) The products analysis shows no H 20, but do not forget to include it
is sure to be there when the fuel contains hydrogen. Since there is assumed to be no
fuel, the 0 2 on the left-hand side..of the chemical equation is that which accompanies"
the air; 84.1/3.76 = 22.4 moles 0 2.

C,H, + 24.402 + 84.lN,-> 12.5CO, + 3.10 2 + 0.3CO + 84.1N2 +

The material balances:

C: x = 12.5 + 0.3 x = 12.8

o,: (2)(22.4) = (2)(12.5) + (2)(3.1) + 0.3 + a a = 13.3

H,: y = 2a = (2)(13.3) y = 26.6

Thus, provided all the carbon and hydrogen burned, the fuel is a mixture of hydr
which the average molecule is C12.sH2. or for which the ratio y/x = 26.6.
chemical equation tells no more. The balanced equation then is

C12.sH2. + 22.40, + 84.lN,-> 12.5C02 + 3.10, + 0.3CO + 84.lN, + 13,

(b) The "molecular mass" of C 12 .8 H 26.6 is (12)(12.8) + 26.6 = 180.2 lb/mol<>.

moles of air per mole of fuel are 22.4 + 84.1 = 106.5, we have

(106.5)(29) .
ralf = . = 17.llbair/lbfuel
180 2

If other information is desired, such as pounds of H 20 in exhaust per pound o!J

point of the H 2 0 in the products, and the estimated gravimetric analysis of the
procedures previously explained. (If the reader desires to do these as an exercisen
are, respectively, 1.33, 121F, 0.854C, 0.146H.)

13.14 HEATS OF REACTIONS

For fuels, the heat of the chemical reaction is called heating vaf
combustion, enthalpy of reaction h,P, or internal energy of reaction u,p. R
is a general name, without specific meaning unless the way in which it is
defined (or implied) by the context. If the heating value is measured
calorimeter (ideally a rigid constant volume chamber), typical for soli.
fuels, the heating value obtained is that at constant volume qv, the s.,
internal energy of the reaction -u,P. The heating value of gaseous fuels
found in a steady-flow, essentially constant pressure calorimeter, fr?
obtained the constant pressure heating value qp, the same numen
enthalpy of reaction lh,vl In each case for fuels that contain hydrogen;;:
 heating value q"'" qv1., when the HzO in the products has condensed [H 2 0(l)],
fower heating value q"" q"'' when the H 2 0 has not condensed [H 2 0(g)]. The
'heating value q, is equal to the higher heating valne minus the latent heat of
ensed water vapor. In test work the heating value is converted to a standard
mbolized as q;, qi, and so on, and with sufficient data any heating value can
uted from another, as explained later. The enthalpy and the internal energy
action, from the chemistry point of view, are negative when the reaction is
ic. On the other hand, engineers customarily think of heating value as
o _ ho d o _ o
"' hence, qp - - rp an qv - -urp

ENTHALPY OF COMBUSTION 13.15

''deration of equation (4-14) in the form dQ = dH - V dp makes it evident
heat of a p = C process is t:.H, whether the process occurs in an open
ow system or a closed system. For a steady-flow calorimeter, we first
the process to be at standard temperature (77F, 25C in our tables) and
(1 atm), and set up the energy diagram of Fig. 13 /2. The energy of the
's, say fuel and air (saturated with H 2 0), consists of the sensible internal
fall the reactants u; and the chemical energy of the fuel Ech, giving a total
content of E, = U: + Ech Also crossing the boundary of the system is the
'rk energy p v;. Departing the system are the internal energy of the products
. flow work pV;, plus heat Q. This particular heat is the enthalpy of the
h':,,. When the fuel is oxidized by a molecular oxygen, engineers call it the
value; q = -h':,,.

t0 =77F Control Volume for Open-System Calorimeter. The Fig.13/2

energy balance presumes that at the entrance and
exit sections there is internal local thermal equili-
brium, with negligible change of kinetic energy;
p = C, T2 = T,.

total enthalpy HR of the reactants in the standard state is the total energy
fn the reactants u; + Ech plus the flow work pV; (no nuclear); Fig. 13/2. An
.balance for Fig. 13/2 gives

HR.= H; + Ech = H; + (-h;.)

[IN] [our]

)t equation is a definition of enthalpy of reaction, which is to say that the total

y of the reactants at T 0 , p 0 is greater than the enthalpy of the products at T 0 ,
he amount -h':,,.
~he test of Fig. 13/2 was defined (entering air saturated with H20), the
onding heating value is the higher one qi. at constant pressure, because, since
is already saturated, practically all the H 2 0 formed by combustion is
rily condensed when the original temperature is reached; part of the heat
 352 Chapter 13 lfleactlwe

rejected q; is the latent heat of evaporation of this H20. We may compute

heating value from

(13-2) qi' = qJ; - mwh{g = qi. - 1050. l mw Btu/lb fuel

where mw is pounds of H20 formed per pound of fuel, h1 =

77F, and 1050.1 mw is the latent heat of the water formed.

13.16 SOME REMARKS ON HEATING VALUES

The energy derived from combustion in support of a working (and
process is the base for determining the efficiency of that thermodynamic,
The measure is taken as the product of the amount of fuel consumed, cf
process, and its heating value. A choice of which heating value (lower or h
use poses a problem. The solution is somewhat simple. .:
If the thermodynamic system can utilize the ener.gy contained in the wat
derived from burning the hydrogen in the fuel, the higher heating value. is'
case in question is the electric generating plant using fossil fuel. It is qui(
reduce the temperature of the exit products to below their dewpoint (which'
do for maintenance reasons). ,,
On the other hand, it is expected that the exhaust products from an au1:
engine will never approach their dewpoint temperature or utilize the ene(
water vapor-thus, the lower heating value is used here.

13.17 ENTHALPY CHANGE DURING REACTION

Since there is no common datum for measuring the energy of different su
we must have a known "crossover" (a known enthalpy of the reaction) f
change of enthalpy between the reactants in any state 1 and the products in.
2. This known enthalpy of reaction may be at any p, T, but the availa~
usually for the standard state p 0 , T 0 Referring to Fig. 13/3, we see that th/
change from state 1 to 2 is the algebraic sum of the changes 1 to d, d to~.~
2; therefore t:..H = H,. is

(a)

Fig. 13/3 Enthalpy Change, Reactants to Products. Since

curves bc-2 and ad-1 are not parallel, -h,P along 77F
mn at temperature Tis in general not the same as
at T. Process 1-g, where Q = 0 and W = O, is an
adiabatic combustion process, equation (13-5);
s = c. b
"- H':,1 = h;P Btu/lb (or I!;" Btu/pmole)
H;, is !iHp for the products from the crossover de to the actual state 2,
H,i is !iH, for all the reactants from the actual state 1 to the crossover de.

1 the foregoing equations may be in terms of either moles n or mass m. Since

efficients in the chemical equation give the moles of each constituent, the mole
is usually the more convenient. If the constant pressure specific heats Cm of the
' res are known,

r
H;d - H,, = n, f
T,
CmdT

ver, we commonly compute sensible enthalpy changes of the individual con-

.nts and add them; thus,
. T
Hv2 - H; = I
P
f 'CvidT
ni
T"'
= I
P
[ni(hi2 - hf)].

r
H; - H,, = In; f cri dT = I [n,(hi' - hn)],
r T1 r

subscripts p and r stand for products and reactants; ni> n 1 are the number of
of j, i constituents; and Cvi> C,1 are constant pressure, molal specific heats of
tuents j, i in products and reactants, respectively. For the more common
ons of fuels, one may have at hand tabular values of sensible enthalpies, as in
. as Tables, Items B 2 through B 10. The foregoing discussion presumes that the
's completely oxidized to stable forms. If this is not true, the use of the enthalpy
rmation, 13.29, is a handier procedure in obtaining the /iH of the reaction.

COMBUSTION PROCESS, RANDOM STATES 13.18

.. get an equation for a reaction between any two states 1 and 2 for the case of
plete oxidation, first set up an energy balance. In Fig. 13 / 4, let the reactants
'Jrom a local equilibrium state 1 at the entrance boundary of the control volume
efinable state 2 at the exit. We have

-Q = H,1 - Hv2 + E,h

lhe value of E,h from equation (13-lB) in (a) and get

Open System, Steady Flow ll.K = 0. Fig. 13/4

 354 Chapter 13 Raatiwe

where q; = -h;P may be either the lower or higher value, depending on I

state 2. At times it will be convenient to let Hp2 - H; = H; 2 , which is the e
of the products in state 2 measured from the standard state. Similarly, let
H,, - H; + q;, where HR. 1 is the total enthalpy at state 1 measured .fr
standard state. With these symbols, equation (13-4A) becomes

(13-4B)

Obtain Hv 2 - H; and H,, - H; in accordance with equation (13-3).

For adiabatic combustion,.. Q ~ 0 and equation (13-4) becomes

(13-5) Hp2 - H; = H,, - H; + qr

[ADIABATIC COMBUSTION]

where the units of each term match those of qr = -h;p, Btu/lb fuel or Bt.
fuel. Equation (13-5) can be used to determine the enthalpy of the products
the temperature at state 2. This temperatur.e T2 is called the adiaba(
temperature (with dissociation neglected here-see 13.34 and 13.35). .. .
In most problems related to combustion, the variation of enthalpy with.
can be neglected. Remember to observe the phase of each substance in the.
especially whether the fuel is liquid, gaseous, or solid (heating value q is diff.
each phase) and whether the H 2 0 is liquid or gaseous.
To get the entropy change during a reaction, first compute the absolute
each constituent of the reactants at its temperature and partial pressure;
these values is the entropy of the reactants. The absolute entropy of the
determined similarly. In mathematical shorthand,

(13-6) b.S = S,p = 2: n;sj - 2: n,S:

p

where there are j constituents of products and i constituents of reactants;

are in accordance withs" of equation (6-15).

T Cp dT - p - - -
(6-15) s" S" + -- - R In 0 = S" + </> - </> 0 R In p
=
J
T" T p
-

for p atm. Since ($0 in the gas tables in Appendix B is approximately the
Item B 11, s = (ii - Rln p for this case.

13.19 SENSIBLE ENTHALPY OF LIQUID OCTANE

With respect to a zero datum for octane vapor at 0R, the enthalp~
octane at temperature T 0 R may be taken as [o. 6 J

(13-7) hr = 0.5 T - 287 Btu/lb fuel

Since the amount of energy is relatively small and since the sensible
other hydrocarbons is not too different, equation (13-7) may be used
error for any hydrocarbon fuel.
Ex.eniipff,o~:re1m1se1ratureAtteu Coff'Ovbusti&ll1.,. Ideal Diesel 355
E111ilmple-Temperat11re After Comb11stien, Ma"i Diesel Engine 13.:!ll
constant pressure combustion process be adiabatic from state 2 to state 3, Fig. 13/5;
erature at the end of compression T, = 1510'R; and let there be 200% stoi-
'c air (100% excess air), compression ratio rk = 13.5. (a) Compute the temperature
end of combustion if liquid octane fuel, C8 H 18 , is injected at SO'F. (Octane is not a
l, but we already have the combustion equation for it and the results would not be
fferent for the actual fuel.)

', Co1nbustible C8 H1s (l) in

' at so~F; qi=-h;1,
hfiJJ-li/77+ q; 9(h 3 -h") [H 2 0(g)]
T2 -15!0'R 8(h 3 -h') [C0 2 ]
25(1i2 -h") [02 j
12.5(1i,-h') 10,1
94(h 3 -h') [N 2 ]

(b) Diesel Cycle V

(a) Enthalpy Balance, States 2-3
Enthalpies are measured from t' = 77'F; fuel and air have different entering Fig.13/5
temperatures.

n Using Prodncts Table, Item B9. [The "Products" tables are strictly for a
' ban of the form (CH2 ) The error in using them for the usual hydrocarbons is
to be small.] If there is 200% air, the number of moles of air is doubled and the
equation from equation (b), 13.6, is

C8 H 18(l) + 250 2 + 94N, -> 9H2 0(g) + 8C0 2 + 12.502 + 94N 2

e shall use the standard enthalpy of reaction (at 77F), all sensible enthalpies are
' measured from this temperature. Knowing that Q = t.H for a p = C process, we
:an "enthalpy diagram" to get the energy balance. The enthalpy at state 2, Fig. 13/5,
pfthe air plus that of the fuel. After equation (13-3), for 1 pmole of fuel, the sensible
y of the reactants measured from the 77'F datum is

j,
,, - H; = l:r [n,(h,, - h;)]

= M 1(0.5)(T2 - T') + 119M.(h02 - h~)

= (114.2)(1.5) + (119)(29)(371.82 - 128.34) = 840,420 Btu/pmole fuel

is the molecular mass of octane, used to convert equation (13-7) to a mole basis; M.
1
lecular mass of air to convert the unit mass values of h to a mole basis: 119 = moles
om equation (a); and h0 , , h~ are from Item B 2 for the specified temperatures.
uch as Item B 9 gives the enthalpy of the products for "200% air" directly, we have
'alpy H.,
measured from the 77F datum as

H;, = n.(ii,, - ii;)= 123.5(ii., - 3774.9)Btu

= H, 2 - H; + (-ii;,), for Q = H;, - H)h = 0, and with H;, from (c), we get

- _ 840,420 (114.2)(19,100) _ B I f
h'' - 37 74 9 + 123.5 + 123.5 - 28 ' 242 tu pmo1e
 Chapter 13

where -ii;,, = (114.2)(19,100), from Item B 12, for a pmole of liquid octane. (Note
value of -ii;,, = iii accounts for the heat to vaporize the liquid fuel at 77F; th
difference between the columns headed "Gaseous Fuel" and "Liquid" in Item B
latent heat of evaporation.) With hv, = 28,242, enter Item B 9, interpolate to .t
whole degree, and find T, = 3466R, the adiabatic flame temperature.
Solution Using Individual Products. If the mixture is one that is neither exact
air" nor "400/o air," interpolation can be made as explained in the Keenan and:
Tables for a hydrocarbon fuel. But in the general case, one does not have the prope
product mix of reaction, and it may be necessary to consider each component sepaf
also 13.28). In this event, a plan of tabulation somewhat as follows can be used(
Fig. 13/5. .

CsH1s: ii"o - hn1 - ii~v = 114.2(1.5 + 19,100) = 2,182,390'

Enthalpy at 2 02: 25(11,098.3 - 3725.1) =

N2: 94(10,724.6 - 3729.5)

Total enthalpy (measured from 77F), HR. 2

H20: 9(h, - 4258) 0 2: 12.5(h3 - 3725.1)}

Enthalpy at 3 _ -
Hp3
{ C02: 8(h, - 4030.2) N2: 94(h 3 - 3729.5)

For H;, - HR. 2 = 0, we have

3,024,230 = 9(ii, - 4258) + 8(ii, - 4030.2) + 12.5(ii, - 3725.1) + 94(ii, -j'

[H20] [C02] (0 2]

The procedure from here is: assume some temperature T, and compute the enthal~
of the components of the products, continuing to do so until the equatio~
T, = 3466R as found from the Products table should result in a virtual balance,

13.21 Example-Availability and Irreversibility for Combustion

Let the events of this example be an adiabatic reaction of C8H 18 (1) with air, as.Im
a constant pressure of 254 psia from a temperature of 1510 to 3466R, foU
steady-flow process to the dead state. The combustion is represented by process;
previous example, Fig. 13/5(b). Find (a) the steady-flow availability of the products
Fig. 13/5(b); (b) the change of entropy and the irreversibility of the combustion
(c) the change of availability of the combustion process. Assume a sink at lo = t'
p0 = 14.4 psia. The chemical equation for convenient reference is

(a) C8H 18 (l) + 2502 + 94N2 -> 9H20(g) + 8C0 2 + 12.50, + 94Nz

Solution. (a) Assume that the properties of the products are as given in Item
true. The availability of the 123.5 moles of products at 3466R and 254 psia is, eq

(b) -1!..s!/.f/O = -1!.H + T0 l!.S = nv[(ii, - ii0 ) - To(s, - so)],

= 123.5 [ 28,242 - 3774.9 - 537 ( 61.24 - 46.3 -

?54)J<f
R In ; 4.4 . )

= 2,408,890 Btu/pmole C8H 18 , or 21,094 Btu/lb f

 - - - p,
s3 - So = q,, - <Po - R In -
Po
perties taken from Item B 9; n0 = h 0 because the sink temperature is taken as 77F.
ue from (b) is the work that would be done as the products pass reversibly to the
'.dead state. [NOTE: The reader may be bothered by the fact that the availability from
(b) is greater than the enthalpy of the reaction which, at 1510R, is about
tu/lb. But about 30% of this availability represents an input of availability in getting
from the dead state to 1510R and 254 psia. Also, if the combustion occurred in a
ngine, the "practical" ..idea1 engine would be able to utilize availability only in an
ic expansion to the pressure of the surroundings, leaving in the working substance at
some 25% of the availability in (b). The compression and expansion in a Diesel
re not steady flow, but the order of magnitude of the numbers is the same. More
the Diesel cycle is in Chapter 15.]
get the change of entropy during 2-3, Fig. 13/5(b), we first find the entropy of each
'n state 2 and then of each product in state 3. Let the specific heat of liquid octane be
b.5 Btu/lb-0 R or (0.5)(114.2) = 57.1 Btu/pmole-0 R. The absolute entropy of the fuel
rs the pump that delivers it to the cylinder at 80F (540R) is closely

CdT 540
C 8 H 18 (l) at 1 atm: s" = S + T
f = 85.5 + 57.1 ln 537
85.8 Btu/pmole-0 R; all S values are from Item B 11. Its entropy at the beginning of
.tion is its value after the pump work has been done. Taking f3 = 0.43 x 10-' 0 R- 1 ,
lb/ft' from a convenient handbook,f1 4 71 assuming that the pumping to 254 psia is
al, and following equation (d) in the example of 11.9, we get the change of entropy

s- = -{3v(p, - Pi) = (0.43)(254 - 14.4)(144)(114) - -0 0483 Btu/p ol oR

(10')(45)(778) - m e-

mpared to" above, is seen to be rather negligible. So, we say'/ = 85.8 Btu/pmole-
isentropic pumping, 6.s = 0.
mole values from equation (a), we find the partial pressures of the various gaseous
nts:

;
"i[O,] = ( -25) 17 .28 = 3.63 atm
119
p,[H,O] = (i 2~_ 5 ) 17.28 = 1.26 atm

4 8
p,[N,] = (: ) 17.28 = 13.65 atm p 3 [C02 ] = ( -)17.28 = l.12atm
19 12 3.5

= ( ~:_ ) 17.28 = 13.15 atm

1 5 = (i ;~~5 ) 17.28 = 1.75 atm
1
,[N,] p,[O,]

e are assuming that the N 2 passes through the reaction with its molecular structure
ed, its change of entropy must be computed directly by equation (6-13); from 1510 to
and with partial pressures as just computed,

6.S[N2 ] = n, (6.o/-1 - - p,)

R In -
P2

= 94(59.861 - 53.121 - R In~~:~!) = 640.5 Btu/R

 Chapter 13 Rea@tlv

Next, compute the absolute entropy S" of the other constituents by equation (6-15) or (

(I) S2[0,] = n,(;, - ii. ln p,),

= 25(56.709 - ii. ln 3.63) = 1353.7 Btu/'R
(g) S3[H20] = 9(62.7587 - R ln 1.26) = 560.7 Btu/'R
(h) S3[C02] = 8(73.3219 - ii. ln 1.12) = 585 Btu/'R
(i) S3[02]= li.5(63.8263 - ii. ln 1.75) = 783.9 Btu/'R H[C

If desired, AS for 12.5 moles of 02 could be computed, as is done for N2; then equa
would have been for 12.5 moles, or half the value computed. The difference of the
entropies computed, state 3 minus state 2, is

(j) 560.7 + 585 + 783.9 - 1353.7 - 85.8 = 490.1 Btu/'R

Including the change for the N,, the change of entropy for the reaction is

(k) S,, = 640.5 + 490.1 = 1130.6 Btu/'R-pmole C8H, 8

Since the closed-system combustion process is adiabatic, there is no interaction ...

surroundings except for the work done on the boundary (piston); therefore the irreve
is

(I) I= T,,S,, = (537)(1130.6) = 607, 132 Btu per mole of fuel or 5316 Btu/lb f

(c) The change of availability during the combustion

availability of the products. Since H;3 = HR.z,

(m) Adr = H;3 - HR.2 - T0 (S, 3 - S,2) = -T0 S"' = -607,132 Btu

the negative of the irreversibility (in this case).

13.l!l! Exampl-fuel Cell Reaction .

To complete the picture and emphasize the comparison of a reversible reaction to.t,
calculations, compute the work that would be done if C8 H 18 (1) reacted reversibly wit
fuel cell at 600R and 5 atm pressure.
Solution. Let the reaction be

(a) CsH1s(l) + 12.502 -> 9H,O(g) + 8C02

Concerning entropy computations, we found above that the entropy of the liqll,\'
changed very little for a much larger increase in pressure; hence, we shall ig.
correction, in view of the size of other pertinent entropy values. For 17 moles ?f
products, the partial pressures (assuming Dalton's law is not too much in error) are.!!
(9/17)5 = 2.65 atm and p(C02) = (8/17)5 = 2.35 atm.For C8H 18 (l), use c, = 0.5 B.
or 57.1 Btu/pmole-0 R. At 600R, we have

1- - =
60
CdT 600
(b) .i'"[C8H 18 (l)] = S + 85.5 + 57.1 l n - = 94.61 Btu/'R-pmole u;
s31 T 537

(c) S 0 [0 2 ] = n,(;, - ii. ln p,) = 12.5(49.762 - ii. ln 5) = 582.075 Btu/'R

 S"[H,O(g)] = 9(45.97 - R ln 2.65) = 396.3123 Btu/R
S"[C02] = 8(52.038 - R In 2.35) = 402.7296 Btu/R
S,. = 396.31 + 402.73 - 582.07 - 94.61 = 122.36 Btu/'R

mole of C8 H 18 . Obtain enthalpies, measured from 77F, and use the lower heating

H[CsH1s(l)] = C(T - T') + (-ii':,,)

= 57.1(600 - 537) + (19,100)(114.2) = 2,184,817 Btu/pmole
H[O,] = n(fi - Fi') = 12.5(4168.3 - 3725.1) = 5540 Btu

H[H2 0(g)] = 9(4764.7 - 4258.0) = 4560 Btu

H[C0 2 ] = 8(4600.9 - 4030.2) = 4566 Btu

H = H,,, = 4560 + 4566 - 2,184,817 - 5540 = -2,181,231 Btu/pmole C8H1 8

(he constant T, p process, the reversible work is W = -b.G, or

W = -(b.H - T b.S) = 2,181,231 - (600)(122.36)

= 2,107,815 Btu/pmole C8 H1s or 18,457 Btu/lb

imding to an efficiency based on the standard enthalpy of reaction of W/ ij/ =

/19,100 = 96.6%.

CONSTANT VOLUME COMBUSTION 13.23

e closed, constant volume system (bomb calorimeter), place a small amount
for in order to saturate the reactants with H 2 0. Then, when the products have
back to the standard temperature of 77F, the H 2 0 formed by combustion
ses and the higher heating value is obtained. The total energy stored initially
sensible internal energy of the reactants u:
plus the chemical energy E,h,
. magnitude is unknown and unneeded. After combustion and cooling to the
rd temperature, the energy stored in the system is u;, the internal energy of
!Jducts. There is no work, so that the energy crossing the boundary consists
f heat Q, a particular value represented by the symbol q~ = -u:P. The
se in stored energy is equal to the energy leaving the system, from Q =
W, equation (4-6);

agnitude of q~ is all that is learned from the test. Substitute El1 = U; + E,h
12 = u;, Fig. 13/6, and find

E,h = u; - u: + q~ Btu/lb fuel, or Btu/pmole fuel

f;g.13/6 Closed-System Calorimeter, V = C, 12 = 11 = 77'F.

Now consider a constant volume reaction between any two states 1 and
energy diagram as in Fig. 13 /7. By the first law,

(c)

where E, is the total stored energy. The value of Ech in equation (b) substitut
this one gives

(13-8)

with Q of conventional sign [heat added (+ ), rejected (-)]. When Q = 0,

(13-9) Up2 - u; = Ur1 - u: + q~ = U,1 - u: - u~

(ADIABATIC COMBUSTION-CONSTANT VOLUME]

Fig. 13/7 For Adiabatic Combustion, Q = 0.

If the H 2 0 is condensed after combustion, the higher heating value at c

volume ql:v applies. If the H 2 0 is not condensed, as it would not be for a
combustion, use the lower heating value at constant volume, which is obta"
subtracting the internal energy change during vaporization of the H20 at
temperature. Let mw lb/lb fuel be the mass of H 2 0 formed during combusti
for u{8 = 990.8 Btu/lb at 77F,

(13-10) qi. = q);. - mwUfg = ql:v - 990.8 mw Btu/lb fuel

13.24 RELATION OF CONSTANT PRESSURE AND CONSTANT

VOLUME HEATING VALUES
Since we are assuming that the gaseous constituents are ideal, let H = ..;
U + nRT, for n moles of ideal gaseous constituents. Then by equations (13
(b), 13.21, we have (-h;;, = q;)

(a) q; = H; - H; + Ech = u; + n,RT 0

- (U; + n,,RT0 ) + Ech

(b) ij~ = u; - u; + Ech Btu/pmole fuel

 q~ - ij~ = n,RT0 - n,fl.T0 = RT0 (n, - np) Btu/pmole

Mr is the molecular weight of the fuel; R = 1.986. The moles of gaseous

:els
np may be .greater than, equal to, or less than the moles of gaseous
'ts n,; thus, either q; < q~; or q; >q~, where both are either higher heating
"r lower heating values. Since the moles of inert gases appear on each side of
ical equation, they may be ignored in equations (c) and (13-11).

Example 13.25
lvely compare the heating values q~ and q~, higher and lower, for propane C,H 8
The stoichiometric equation is

lC,Hs + 502 -> 3C02 + 4H20

higher heating value, the water condenses and n, = 3; n, = 6. Thus,

RT'
q~ - q~ = --(n, - n,)
m,
q; - q~ >0

e lower heating value, n, = 7 and n, = 6. Here

q; - q~ <0

Example-Computing Heating Values at Constant Volume 13.26

at are the lower and higher heating values of octane C 8 H 18 at constant volume, liquid

~lion. Although the bomb calorimeter in general gives more accurate results than the
'flow calorimeter, most reports in the literature are for -h~,. From Item B 12, we have
20,591 for C 8 H 18 (l). Ignore the quantity of inert gases in the difference n, - n,. From

C,H 1 ,(l) + 12.502 + -> 9H20 + 8CO, + ...

20(1), n, = 12.5 and nP = 8. Therefore, from (13-11), we get

RT (1.986)(537)
qh, = qh, + -(n, - 1!,) = 20,591 + (-4.5) = 20,549 Btu/lb
M, 114.2
 the higher heating value at V = C. From (13-10),

(b) q/. =qi.. - 990.8 m,. = 20,549 - (990.8)(1.42) = 19,140 Btu/lb

where m,. = (9)(18)/114 = 1.42 lb H,O/lb f is taken from 13.6. The lower heating
constant volume can also be obtained directly from the lower heating value at
pressure, -h;, [CsH 18 (1)] = 19,100 Btu/lb [H,O(g)]. The reaction equation above shows'
for H,O gaseous, n, = 12.5 and n, = 17; thus,

RT' , (1.986)(537)
(c) q/. = qi,,+ M, (n, - .. n,) = 19,100 + _ (+4.5) = 19,142 Btu/lb
114 2

From the test value of the bomb calorimeter, we may similarly compute -h';p.

13.27 HEATING VAU.IE AT OTHER THAN STANDARD TEMPERATURE

1
If it is desired to convert the heating value at standard temperature to thata:'f'
other temperature, imagine the calorimeter test to be run from and back t
desired temperature, say, state 2. Then the heating value at temperature 2 is

(a)

after Fig, 13/2. Equation (13-1) may be written

(13-1)

Subtract corresponding sides of this equation from equation (a) and solve for

(b) qp2 = q; + (H,2 - H;) - (Hp2 - H;)

(PRESSURE CONSTANT]

the heating value qp 2 at any temperature 2, each term in the same units, ~
parenthetic terms are obtained in accordance with equation (13-4), The nit{
the reactants is the same as in the products and may be ignored in the fo
equation with some saving in time. A similar treatment of the constant .
combustion yields (qv 2 at T2):

(c) qv2 = q~ + (U,2 - U;) - (Up2 - u;)

(VOLUME CONSTANT]

COi
The hypothetical heating value at O'R is obtained by letting the sensible
bj
H,2 and Hp 2 be zero; thus,

(d)

If tabulated values of qvo were available, the arithmetic of some solutions

much reduced. For example, substituting the value of q; from the foregoing
 e Hvz and Hd are measured from 0R; thus the gas value tables could be used
out a subtraction involving the standard state (h 0 ).

Example-Enthalpy of Reaction at 01'1 Temperature 13.211

pute the lower heating value of gaseous octane at O'R; all components in the reaction
ous with their enthalpies taken as zero at 0R.
lion. The reaction equatioh is C8 H"(g) + 12.50, -> 8CO, + 9H2 0(g). The enthalpy
'5 of N 2 and other diluting gases are zero and can be ignored. From Item B 12, we find
~h~ = 19,256 Btu/lb C8 H 18 (g), the lower heating value [H20(g)]. In equation (b),
\t, the second state is at O'R, designated as H 0 ; H 2 - H 0 = Ho - H 0 Since the partial
're of the octane is low if the reaction occurs at 1-atm pressure, we could estimate its
lifo enthalpy as cPT, but we recall that this value is usually high if c, is the value at T'R. If
'se' equation (13-7), the results should be somewhat more accurate; from this, we get
10.5T - 287 = -18.5 Btu/lb. From Item B 11, we have h1, = 17,856/114.22 =
Btu/lb for C8 H1s at 77F; from Item B 12, we get h1, = q/(g) - ql(l) =
6 - 19,100 = 156 Btu/lb; take your choice. Then, as measured from an ideal gas state
, the sensible enthalpy of the octane is

h(CsH1sl = -18.5 + 156.3 = 137.8 Btu/lb

inarizing according to equation (b), 13.27, for 537R, we have

C8 H": Ho - H' = 0 - 137 .8 = -137 .8 Btu/lb

0 (12.5)(3725.1)
0 2: H0 - H =0- _ = -407.7 Btu/lb fuel
114 22

Reactants: H, 0 - H: = -137.8 - 407.7 = -545.5 Btu/lb fuel

(8)(4030.2)
CO,: Ho - H' = 0- _ = -282.3 Btu/lb fuel
114 22

0 (9)(4258)
H 2 0: H0 - H = 0- _ = -335.5 Btu/lb fuel
114 22

Products: H,o - H; = -282.3 - 335.5 = -617.8Btu/lbfuel

.n from equation (b), 13.27, we get the heating value at O'R as

-h.,, 0 = q10 = 19,256 - 545.5 - (-617.8) = 19,328.3 Btu/lb fuel

is, of course, a figment of the imagination, but since enthalpy is a point function, it does
. matter by what path the change of enthalpy between two particular states is obtained.

ENTHALPY OF FORMATION 13.29

e heat involved (exothermic or endothermic) when a compound is formed from
~lements at constant temperature and pressure is called the
heat of formation or
the enthalpy of formation A.hr. When the reaction occurs (or is imagined to occur
a standard state, usually 77F and 1 atm for each constituent as before, the hea
the standard enthalpy of formation t:.h{. According to this plan, the enthalpy'
formation is the enthalpy of the compound as measured from a datum at which <
elements (most stable isotope) have zero enthalpy. Let C02 be formed by a reac
of C with 0 2 at 77F;

(a) C(s) + 02 ...,. C02(g)

'
We could measure the heat Q of this reaction and this would be the enthal]'.l ),
formation of C0 2 because this reaction is forming C0 2 from its elements; fi.
-169,293 Btu/pmole of CO,, Item B 11, naturally a negative number for;
reaction because energy leaves the system when T = C. In this case, this heat is
the heating value of 1 mole of carbon, which is 14,097 Btu/lb C, Item B 12,
the C is oxidized by 0 2. The enthalpy of combustion and the enthalpy of form
are the same only when an element is oxidized by an element (0 2). The same
involved, except for sign, if the reaction is performed in the opposite direcf;,
compound (C0 2) converted into its elements (C and 02). From this observat
Hess formulated the law that the net enthalpy change (p = C) in chemical pro
is independent of the sequence of the processes. From this principle, it follows
the change of enthalpy of formation during a constant p, T chemical reactiO
equal to the enthalpy of the reaction; at the standard state,

(13-12) - H':,, = (t:.Hl), - (A.Hl)p

where

the sum for i constituents of reactants

(A.Hf)p = I. n;(Ahlli the sum for j constituents of products

p

In making an enthalpy balance as we did in 13.20, with the enthalpies me

from the defined 77F datum, we use the enthalpies of formation for whi
datum is zero enthalpy for elements at 1 atm and 77F, the standard state. A
temperature other than standard, the total enthalpy h, measured from the b
defined is

(b) h, = /:;hJ + (h - h 0
)

for either unit mass or 1 mole, where h is the sensible enthalpy at a sp(l
temperature. For n; moles of the ith constituent, the enthalpy of a mixture !l
temperature T is then

(13-13) Hm = I. [n;(Ahf); + n;(h; - hi)]

;

applicable to reactants HR or products Hp; see equation (13-4). This appr

 366

!larly advantageous when a reaction is incomplete and when significant dis-

on ( 13 .35) is to be accounted for. The energy balance for a steady-flow
with W = 0 and !:J.P = 0 is
Q + HR + KR = Hp + Kp

HR and Hv are computed according to equation (13-13) and K = mv2 /(2k),

for m lb/pmole of fuel. (Normally during a reaction, no mass crosses the
clary of the control volume except the main streams.) Formalizing, the change
thalpy in terms of enthalpjes of formation from state 1 to state 2 is, for j
;onents of products and ./ components of reactants,

/:J.H = L ni(h2 - h 0 )i + L ni(!:!.ii{)i - L n;(l:!.hf), - L n;(h1 - h 0

);
p p r r

ample will help with the detail.

Exampl-Tamparature After Combustion, Diesel Engine 13.30

the data be the same as in example of 13.20, except that enthalpies of formation of
ompound are to be used.
'lion. Use the results of 13.20 as far as possible: the moles of each component; the
of hrso - hm = 171.3 Btu/pmole for the fuel (all combustible). The standard enthalpy
ation of C8 H 18{1) is !:i.ii; = -107,532Btu/mole, Item B 11. Compute the enthalpies in
ance with equation (13-13), and as set up in Fig. 13/8, letting H, 3 - HRz = 0.
rdingly, we have (Item B 11 for Mil)
.
CsHis(l)J,: 171.3 + (-107,532) = -107,361
Oz],: 25(11,098.3 - 3725.1) = +184,330
Nz],: 94(10,724.6 - 3729.5) = +657,539
HR2 = +734,508 Btu/pmole C8 H 18
H20(g)],: 9(ii, - 4258 - 104,036) = 9h,(H20) - 974,646

C02],: 8(h3 - 4030.2 - 169,293) = 8h3 (C02) - 1,386,584

02],: 12.3(ii, - 3725.1) = 12.5ii,(02) - 46,564

N 2],: 94(h3 - 3729.5) = 94h3 (N2) - 350,573

,, = SUM: 9h 3 (H2 0) + 8h3 (C02) + 12.5h3 (02) + 94h3 (N2) - 2,758,367 = 734,508

State 3:
Combustible in at SO'F
/'J~ -l'J:1 +L>.hj [C,H"(l)] 9(~,-~+l>.~() [H 20(gJ}
8(h 3 -h"+L>.h[) [C0 2 J Hp,
HR2 25(h,-h') [O,J
12.5(h,-h [0,J 0
)

[
94(h 2 -h 0
) [N 2 J 94(h3 -h 0
) [N 2 j

Enthalpv Balance with Enthalpies of Formation. If there are energies involved !Fig. 13/ll
such as Wand K, they should be included.
 Chapter 13 Reeetlve
At this point, the procedure is to assume a temperature T,, look up the co
enthalpies, check in the foregoing equation; repeat this process until a balance is fou
temperature of 3461R (interpolating to the nearest whole degree), the enthalpy e
nearly balances; therefore, T3 = 3461R. This solution is basically the same as the
13.20 because -H:,, = (Iliff), - (llifi)v, equation (13-12). It does .assume air to b~.
posed entirely of oxygen and nitrogen.

13.31 ENTHALPY OF FORMATION FROM HEATING VALUE

When appropriate heats gf r~action are known, these can be used to detl
1

enthalpies of formation. For example, assume that the enthalpy of formatr

C 8H 18 is unknown. Heating values -ii; for the following reactions are takel1.
Item B 12:

(a) C8 H1s(g) + 12.502 _,. 9H20(I) + 8C02 ii;= -(20,747)(114.224)

(b) 9H2 + 4.502 _,. 9H20(I) H;v = -(9)(60,998)(2.016)

(e) SC + 802 _,. 8C02 H':,, = -(8)(14,097)(12.01)

in which -H';,, is now the value for the number of moles involved. These equ
can be manipulated by the rules of algebra. If corresponding sides of equatr
are subtracted from the sum of (b) and (e), we get

(d) 9H2 + 8C :;:::: CsHrn(g)

which is the equation for the formation of C8 H 18 (g) from its elements-L!.iiJr
elements is zero. See Fig. 13/9. The enthalpy change of this process is thee~
of formation by definition (and is the enthalpy of the reaction shown) but nof
combustion reaction, and is obtained by subtracting the H':,,'s of (b) and (c) fro
of (a); thus,

(e) -L!.iif[CaH1a(g)) = ii; - [H';,,(H2) + H';,,(C))

= -2,369,805 + 2,461,188 = 91,383 Btu/pmole Cs

The difference between this value and LI.ii{ = -89,676 from Item B 11
tributable to the inconsistency in the basic data behind certain values in Ite
and B 12. If C8 H 18(1) liquid is formed from its elements, the additional heat
is the enthalpy of evaporation h18 At 77F, ii{8 = 17,856 Btu/pmole frg
B 11; hence LI.fit [CaH 18(1)) is -89,676 - 17 ,856 = -107,532 Btu/pmole, W
used the Item B 11 value for LI.ii{. In general,

(f) L!.h{(Iiq) = L!.h{(vap) - hr.11

f
Ele1nents Have SC
Zero Enthalpy gH
2
Fig. 13/9 Enthalpy of Formation. For ideal
Each at 1 atm _ /
gases, enthalpy is not a function of p.
 HEATING VAUJE Fi'IOl\1 ENTHALPY OF FORMATION 13.32
similar procedure may be used to find heating values when enthalpies of
ation are available. Illustrating with CO, we have

CO + 0.502 ..,. C02(g)

tying equation (13-12), we get

;;, = (b.Hl)v - (b.Hl), = -169,293 - (-47,548) = -121,745 Btu/pmoleCO

... -121,745 I
H,v = .0l = 434 6 Btu lb CO
28
(COMPARE WITH ITEM B 12]

me heating values cannot be measured directly, for example, the reaction of C

, O, because some C0 2 is inevitably formed when C is oxidized. By experiment,
.can find heating values of C to C0 2 and CO to C0 2.

C + 02 ..,. C0 2(g) h~p = -(14,097)(12.01)

CO + 0.502 ..,. C02(g) ii; = -(4346)(28.01)

'tracting corresponding sides of (d) and (c) and combining the 0 2 terms, we get

c + 0.502..,. co ii~v = -47,574 Btu/pmole C

'?h is the negative of the heating value of C burned to CO and also the enthalpy
ormation of CO; b.hJ = -47,574 Btu/pmole CO.

GIBBS FUNCTION OF FORMATION 13.33

he values of the Gibbs functions b.GJ in Item B 11 are the respective changes of
>Gibbs function during the formation of the compound from its elements with
h. element and the compound in the standard state of 1 atm and 77F. This
nition is analogous to that for the enthalpy of formation b.hJ; however, the Gibbs
lion is a function of pressure (entropy is also involved), whereas enthalpy of an
!l,I gas is not. Since G = h - Ts, we find

dGr = dh - Tds at T =C
integration of which for the formation of the compound at the standard state is ~~
kg, moles, and so on, as convenient)

b.G = b.GJ = b.hJ - 0

T S~.

re, for the mole basis, the entropy change for the reaction is
 ~ is the absolute entropy of the product (compound) whose Gibbs functio
formation is desired, and the sum covers all i elements of the reactants; si for
reactant is the standard value, 1 atm and 77F.
Considering the Gibbs function further, we note that, for an ideal gas, the cf{
of G with pressure but at constant temperature is AG = -T As because Ah
and by equation (6-13), As= -R lnp 2 /p 1 If 0 in the standard state is krt
then at any other pressure, we have

(13-14) (Ji (at Pi) = Gi + RT0 In Pi

for Pi atm. Note that if (13-14) is applied to an element with Gi measured fro
base defined for the Gibbs function of formation, (AGf), = 0. From (13"1
follows that for a mixture of i ideal gas components ( 12.4) the Gibbs functi
the mixture is

(c) G~n = L niGi = L ni(Gi + RT 0

In Pi)

at standard temperature, each component at its partial pressure Pi; Pm = "'i p1

same reasoning, if a; at any temperature T' and 1 arm pressure is known, the
at any other pressure is

(13-15) Gi = G! + RT' In Pi

(13-16) a;,.= L:n (G! + RT'lnpi)

1

where Pi atm is the pressure of the ith component and the temperature is T'

13.34 REVERSIBLE REACTIONS

Imagine 1 mole of H 2 and a half mole of 0 2 in a reaction chamber at some ty
atmospheric pressure and temperature. Any reaction that occurs will be accord!'

(a)

However, as far as any normal measurement shows, nothing happens. Ap

given time, some H 2 and 0 2 will get together so that a few molecules of fl
formed; the number can be calculated for a mixture in equilibrium, even if it
be measured. Let the temperature be raised a few hundred degrees. More
formed, and the amount soon becomes detectable as the temperature increa
any particular temperature, the equilibrium mixture consists of a certain am().
each of the reactants and products. (By the judicious use of a catalyst, the r
can be promoted, as in a fuel cell.) Notice that even if the reactants are ,
stoichiometric proportions, say, the amount of H 2 is doubled, any reaction\,
* Common practice in the literature is to use the symbol G0 (or F) as the Gibbs function
temperature and 1 atm pressure; the standard state is for 1 atm and any tern
Considering our limited application, we shall let the superscript 0 imply also the
temperature, 25C. In the case. of extended work in this area, many tabulated values of a
entropy, enthalpy, and Gibbs functions of formation against temperature are available.
rs is always according to equation (a)-two molecules of H 2 and one of 0 2
pear for every two molecules of H10 formed. When the mixture arrives at a
foal equilibrium condition, I:Iz and 02 may still react to give H 2 0, but for the
nt of H 2 0 formed, an equal amount dissociates into H 2 and 0 2; the reaction
then proceeding in both directions and is a reversible reaction, written as

Hz + ! 02 :;::'! HzO(g)

. 1 substances in the gaseous phase. If the proportion of reactants is changed and

t gases are included, ~he extent of the reaction will be different at a particular
rature and total pressure, but the equilibrium reaction remains as given in
7). Other equilibrium equations that we shall find useful are

) CO+ !02 :;::'! C02

C02 + Hz :;::'! CO + H10 [WATER GAS REACTION]

Jso Item B 32. Equilibrium reactions are often written with the equals sign, as
2N, Hz = 2H, and so on.
get an aspect about which we are concerned, consider the octane reaction in
epresented as follows:

CsHlB + a02 + bD, -? cC02 + dCO + eH20 + fH2 + g02 + hDp

e.D, represents all diluting components of the reactants (principally N2) and DP
esents all other components in the products (again principally N2), but there are
to be many others, say C, N, 0, H, CH., NO, 0 3 , NO,, NH,, C2N2, OH, and
. Most of these will be in small enough quantities that they are negligible for
engineering calculations (but not necessarily so as related to smog problems).
me that the temperature and available 0 2 are such that no C8 H 18 remains and
. of the products as shown in an isolated system in equilibrium at constant p, T.
is condition, all the equilibrium reactions of equations (13-17) through (13-19)
ccurring, plus many more. When a molecule of C0 2 combines with a molecule
. 2 to form CO and H 20, equation (13-19), the opposite reaction is occurring or
soon do so. Typical of the numerous other reversible reactions that are going on:
:"' 20, H10 = !H2 +OH, N1 + 02 = 2NO, and so on .
. hen we assumed a simple stoichiometric reaction, 13.6, atom balances for the
ent atomic species supplied sufficient conditions to obtain all unknowns.
ever, there are more unknowns in equation (b) above than can be found by
balances; therefore, additional conditions must be obtained, as explained next.

CONDITION FOR CHEMICAL EQUILIBRIUM, IDEAL GASES 13.35

ppose we place any quantity of reactants A and B into a reaction chamber to be
tained at constant p, T (think of A and B being H 2 and O,, if desired). Before
.hing happens, Gibbs function Gm of this mixture is computed and plotted at r,
13/10. Different proportions of the components of reactants and products may
be assumed, and the corresponding value of Gm computed. At p, the value of
is its value for the mixture being products only, say X and Y. The significant
 370 Chapter 13 Reactiv

observation is that the curve shows a minimum, defined by dGm = 0. A sponta

reaction may take place along rdc, but no further, because the second law says
spontaneous reaction with increasing G cannot occur, 5.26. This observati
significant when l:iG is used as a criterion concerning the probability of a reacti
specified amounts of products.

Fig. 13/1 il Variation of Gibbs Function with Change of Composition of dG=O

Mixture. Observe that t>.Gd,o = 0 but that this reaction is not
an equilibrium reaction; it can only go to c. For the specified
p, T, point c also represents the state of maximum entropy, Reactants
in accordance with the second law. Only

Suppose we represent all equilibrium equations (T, p constant) by

(a) vaA + v,,B + ... = l'xX + v,Y +

where the number of reactants A, B and of products X, Y may be more orle

two. Now let a small amount dna moles of A react; the corresponding amoun
X, Y, and so on, are dnb, dn,, dn,. Note that these reacting quantiti
proportional to the stoichiometric coefficients in equation (a), as explained
that is, dnb/ dna = vb/va, dn,/ dna = vx/va, dn,/ dna = v,/ Va. For convenien
sume that there are two each of reactants and of products, write the express!
the change of G for the dn reaction, and manipulate as follows;

(b)

dG,. - dnx - dn, - - dnb

-- = Gx-+ G , - - Ga - Gb--
dna dno dno dna
(c)

Multiply through equation (c) by Va dna and equate to zero, since

equilibrium, dG,. = 0.

(d)

Inasmuch as dna # 0, the parenthetical part must equal zero. Let the temp
during the reaction be any value T' and substitute for each of the G's
parentheses its value from equation (13-15);
-
vxG~
- In Px + v,G,
+ v,RT' -, + v,RT'
-
In p,
(e)
-vaG~ - vaRT' In Pa - vbG - v.RT' In
 the overall change in G with each constituent at the standard 1 atm and
perature T' be represented by a;r;

Ill equation (e), we then have

or G;r = -T'R In Kr

e Kr is called the pressure equilibrium constant, and where the pressures p,, p,.
nd Pb are the actual pressures of the particular constituents in the actual mixture
; es, say in the products of equation (b), 13.34, and v; is the number of moles
nstituent i in the equilibrium equation, say (13-17) through (13-19). The
rium constant Kr is defined by

e the second form generalizes the definition for any number of constituents, j
esenting "products," i representing "reactants"; all the i's and J's are ideal gases.
"products" and "reactants" are defined by the equilibrium equation; the equili-
m constant is not the same for

C0 2 = CO + 0.502 as for CO + 0.502 = C02

[Kril [Kr2J

'a).lse reactants and products have exchanged places. Evidently, Kr 2 = 1/K. 1 ; it

'ows that log Kr 2 = log(l/ Kr 1) = -log Kri The logarithm of the equilibrium
'stant, logKri. for ~0 2 = 0 is half logKr 2 for the equilibrium equation 0 2 = 20;
tis, 2 log K. 1 = log Krz. or Kr2 = K; 1
, e definition of the equilibrium constant gives additional conditions that may be
.d to determine unknown coefficients in the chemical equation, say (b), 13.34.
t example, two independent equilibrium equations make possible the deter-
ation of two more coefficients than can be found from the atom balances alone, a
.ement that becomes more evident if the partial pressures are expressed in terms
,the total pressure Pm
y equations (12-2) and (6-10), we have the volumetric fraction of the jth
ponent in a mixture of gases as

P; P; n; _ ni _ ni
X;=-=-=-- or P; - ~Pm - ~Pm
L. P;
j
Pm Lj n; ;_, ni Ln

ere the final form is written simply for convenience in handling. Let the reaction
ation be represented by
 372

Then I. ni = na + n& + .. for all coefficients on the product side. Using the value
Pi from (h) in equation (13-21), we get

K = [ (nx/I. n )Pm J"" [(n,/I. n )Pm]"

(j)
P [(na/I. n)pmJ"[(n&/:E n)pmJ"'

In terms of the volumetric fraction X in equation (h), equation (j) reduces to

(k)

In general, the exponent of Pm for any number of reactants and products is t

algebraic sum of the v's with the v's for the reactants of the equilibrium equatl
being negative, symbolized by I. v.
The amount of dissociation of the products of a combustion equation depends
the temperature, which means that, in an engineering analysis, a decision must
made as to the composition of the mixture. This decision is based on experience, !(
making it is practicing the art of engineering. For example, the temperature mus~
rather high for the reaction ~ 0 2 = 0 to be significant. With respect to ene '
balances, the dissociation of C0 2 begins to be important above about 3500F;:
H20, above about 4500F.

13.311 Example-Dissociation of CCl2

Carbon monoxide is burned in 200% ideal air during a steady-flow process at Pm = 5 a
If the temperature of the products is maintained at 5400R (3000 K), what is the
transferred (a) when the reactants enter the process at 77F and (b) when the reactants e
at 2540F?
olulion. (a) Before the heat can be computed, the composition of the products mu .
determined. In Item B 32, we find log K, = 0.485 for the following equilibrium reacti
3000K;

(a) CO + 0.502 = C02

From this equation, we see that the stoichiometric amount of 02 i.s 0.5 mole; therefore
200% air, there will be 1 mole of 0 2 per mole of CO. The reaction for all gas
components may then be assumed to be

(b) CO + 02 + 3.76N2-> n,C02 + n2CO + n,02 + 3.76N2

The total moles of products are 2 n1 = n 1 + n 2 + n, + 3.76. Using the carbon and
balances,

(c) C: 1 = n, + n1 0 2: 1 +2 = 2n 1 + n 2 + 2n 3

we find

1 + n2
(d) n3=-- also I n1 = 5.26 + 0.5n2
2

where the coefficients n 1 and n 3 are expressed in terms of n,, which is the moles of CO in
products and in this context is called the degree of dissociatio11 (n 1 would be called th~ d
 1fg,ampic1-J'/11is1so"i<lti<m off C02

of l'eaclion ). The various partial pressures, with n 1 and n 3 from (d), are:

n1 n1Pm (1 - 1!2)5
p(C02) = ~Pm
..c.. n,
= 5 .26 + 0 .5 n2 = 5.26 + 0.5n2

n2Pm n2S
p(CO) = 5.26 + 0.5n 2 = 5.26 + 0.5n 2

p(0 2 ) = n,pm (1 + n2)5

.5.26 + 0.5n2 2(5.26 + 0.5n,)

log K, = 0.485, we have K, = 10.485 = 3.055. Notice that tabulating log K, instead of
i:luces the range of numbers considerably, yet leaves it easy to find K,. Substituting the
oing values into equation (13-21) for K,, taking the exponents v from (a), we get

p(C0 2 )
K, = 3.055 = [p(CO)][p(0 2)]'12
12
=[ (1 - n2)5 ][5.26 + 0.5n2][2(5.26 + 0.5n 2)]'
5.26 + 0.5n2 5n2 (1 + n 2 )5
)he occasional problem, simplify this equation and solve for n2 by trial; say, from

3.055 = 1 - "'[10.52 +
1!2 5(1 + nz)
"']1/l
yseveral trials, we find that n, = 0.297 nearly satisfies (i). From equations (d), n 1 =
3 and n 3 = 0.6485. The reaction equation (b) now becomes

CO+ 02 + 3.76N2 ~ 0.703C02 + 0.297CO + 0.648502 + 3.76N2

enthalpy balance for the process is shown, Fig. 13/11, where ii, = ii" because the
!ants enter at 77"F; moles of air = 1 + 3.76 = 4.76. The enthalpies of formation, as
. n, are probably safer and more convenient than heating values when stoichiometric
~tities are not involved; ii2 values at 5400R are by extrapolation from the gas tables; !lii{
s from Item B 11. Substituting into the expressions on the diagram of Fig. 13/11, we
'ethe enthalpies departing as:

C02 : 0.703(-169,293 + 69,975.9 - 4030.2) = -72,653

CO: 0.297(-47,560 + 43,951.8 - 3729.5) -2,179

0 2: 0.6485(45,872.2 - 3725.1) +27,332

N,: 3.76(43,612.9 - 3729.5) = +149,962

Total enthalpy leaving = + 102,462 Btu/pmole CO

T2 - 5400R - 3000 K
0.703(<'.liii+ h ,-h'Jco,
0.297(<'.llij+ ii 2 -iiJco
0.6485(h2 -h') 0 , Energy Diagram Using
0 Enthalpies of For- Fig. 1;01/11
3. 76(h,-h ) N,
mation.
 Chspt:liw 113
From the enthalpy balances of Fig. 13/11 and for l!i.h[ = -47,560 for

or 150,022/28 = 5358 Btu/lb CO. The positive sign indicates that the
this system in order to m!'lintain a T2 = 5400R. It also follows that if we
the adiabatic flame temperature, Q should be zero and the next gue
substantially lower than 5400R.
(b) The fact that the reactants are heated to 2540F = 3000R = 1666.
the partial pressures of th~. prollucts, the equilibrium constant, and the
component in the products. Thus, the only effect is that the reactants en
more enthalpy than before. As measured from the 77F datum of the ele
enthalpy HR at 3000R is found by equation (13-13):

CO: -47,560 + 22,97:3.4 - 3725.1 = -28,312

Air: (4.76)(29)(790.68 - 128.34) = +91,429
for which HR = +63,117 Btu/pmole CO. In this case, Q for the system of

Q = 102,462 - 63,117 = +39,345 Btu/pmole CO

13.37 Example-Effect of Pressure on Dissociation of C02

Find the composition of the products of combustion of the reaction
example when Pm = 1 atm (instead of 5 atm).
Solutiou. The equilibrium constant, being a function of temperature m
before; K 0 = 3.055. The partial pressures are given by the same equatid
Substitution of these pressures in equation (13-21) yields
112
(a) 3 .055 =1- n 2 [10.52 + n 2]
n1 1 + ni

n 2 = 0.472 closely satisfies this equation. The products are therefore

0.7360,, 3.76N2. Observe that the extent of the reaction for CO to CO,'.
higher pressure in the preceding example, 0.703C0 2 versus 0.528CO,. If th
in 100% ideal air, the extent of the reaction will not be so large as with ex
Also, for more engineering experience, check 13.36 with no N 2

13.38 Example-Dissocietion of H2 0
If pure H 20(g) is heated to 5000R (2778 K) and maintained there at 1 atm
is the equilibrium composition if there are only H 20, H,, and 0 2? .
Solution. If dissociation occurs (and it does), the composition of the produ

(a) H 20(g) -> n 1H 20(g) + n 2 H 2 + n 3 0 2

if the dissociation of 0 2 is negligible. Taking atom balances and solving for

terms, bf, say, n. 2 , we find

(b) H2: 2 = 2111 + 2112

(c) 1 = n 1 + 2n 3
 the total number of moles and Pm = 1, we get

n1 2 -1~ n2
I n1 = n1 + nz + n, = 1 + 2 = --2-

_ n1p,. _ 2(1 - ni)

p (Hi 0 ) - - - - -'---"-'
In1 2+n2

p (0) -~-
2n2 n2
p(H,) = 2 + n2 2- ----
2 + n2 2 + n,

lie equilibrium reaction of equation (13-17), we find in Item B 32 that logK, = 1.697
,7) at 2778 K; K, = lOi.7 = 50. Then

K
'
= 50 = p(H 20)
p(H2)[p(0 2 )]' 12
= [2(12 +-n 2)][2 2n2
n + n 2][2 +
n2
n2 ]
112
2

the exponents of the partial pressures are given by the equilibrium reaction, equation
). Simplified for a trial solution, we could use

50 1- n2 (2-+-n-2)
= ---
112

n1 n2

ii, = 0.0885, this equation is closely satisfied; and the composition is 0.9115H20,
SSH,, and 0.04430,. Notice that even at this temperature, the dissociation of H 2 0 is not
iJarge.

VAN'T HOFF EQUILIBRIUM BOX 13.39

will be helpful to set up a physical picture of ideal processes back of the
lusions of 13.35. Figure 13/12 represents an equilibrium reaction box. It is
tained at constant pressure Pm, and the reaction proceeds from, at, and to a
perature T'. The components A and B are delivered to the box through

L_

Van't Hoff Equilibrium Box. Equilibrium reactian: v.A + vbB vxX + vyY. Fig.13/12
A and 8 enter the box in strictly stoichiometrip proportions vb molecules of 8
for 110 molecules of A; also X and Y depart in stoichiometric proportions; the
mass of each element in the box remains constant; steady flow, AK = 0.
x passes only" gas X; and so on.
 376
semipermeable membranes, membranes that permit the passage of only one co
ponent. The semipermeable membranes on the right-hand side permit passage of
Y only, as seen.*
Suppose the properties of the components are known at some standard pressur
say p = 1 atm. The isothermal engines, Fig. 13/12, which may be compressors()
0

expanders, provide the work needed to change the original pressure of the coijl
ponents p to the partial pressure of the same component in the box, an increase d
0

decrease as required. The work of an isothermal process for an ideal gas, fro
7.12, is W = nRT In (p,jp 2 ) for n moles. Thus, the net work of the system in F'
13/12 (C,,K = 0, M' =.. 0, but they can be included if significant) is the sum of t
works; with RT' factored,

(a)

If all the pressures p 0 are unity (1 atm) as previously suggested, the second "ln''L
zero and equation (a) is the same as (13-20) because the maximum (or minim
negative) work on the overall reversible process is -a;.( 13.33). Either derivatf
indicates that a particular equilibrium reaction is unconcerned about the presence
other substances, including catalysts (which affect rate).

13.40 EQUILIBRIUM CONSTANT

As previously mentioned, the pressure equilibrium constant for ideal gases
function of temperature only. This is seen from equation (13-20), which is, with;
primes dropped for convenience,

(13-20) lnK =

-~
a,.
TR
or K. =exp -TR( a,.)
where G,. is the change in Gibbs function for a stoichiometric reaction with
pure component involved being at 1 atm and temperature T; in the literature t~
called the standard Gibbs (free energy) function at temperature T. Equation (13
may be used to determine K. from a known G,., or G,. from a known K .
Let h,.. represent the enthalpy of the reaction per mole of a reactant (at T
and similarly, s,. for entropy. Then since the change of Gibbs function a
perature T is C,,Gr = C,,H - T f}.S, we have G,. = ii,. - Ts,. This value of
(13-20) gives

(a) In K = - ~,. + 8'!

RT R
* These are, of cpurse, ideal semipermeable membranes, but many actual membrane$/<
varying degrees of effectiveness, exist. There are many in living matter, including
Membranes permeable to positive ions and others permeable to negative ions are ,,
parts of one method of desalting water. The fact that hot palladium foil is permeable (vi
only to hydrogen provides a means of producing high purity H2 , for example, from r
off-gases. The details of the mass exchanges are not known with certainty.
fferentiate this equation with respect to T and find

d In Kp ii,p ii,p ds,p

dT = RT 2 - RTdT + _R_d_T

equation (4-15), TdS = dH - Vdp, we have TdS = dH for p = C; or for

reaction Ts,P = ii,P. If this value of ii,,, is substituted into equation (b), the last
;terms cancel, being numerically equal but of opposite sign; thus,

d In Kp ii,P
or
d(l/T) = - R

e ii,,, does not vary rapidly with temperature, (13-22) can be integrated for small
perature differences with ii,. held constant. The second form of (13-22) shows
if ii,P is constant, a plot of In Kp against 1/ T is a straight line with a negative
for exothermic reactions; KP values are often given graphically on this basis in
iterature. Integrating (13-22) from state 1 to state 2, we get

In Kp2 - In Kp1 = In -Kp2 = ii,p(

-~ -
1 - -1 )
Kp1 R T 2 T,

for example, Kp 2 at T 2 can be determined if ii"' and Kp 1 are known.

observed, the foregoing applications require an equilibrium constant for each
'on at the temperature of the reaction. Since the number of possible reactions
relatively common elements and compounds is quite large and since the number
~actions in general is indefinitely large, we find in the literature[0 221 tabulations
e equilibrium constant of compounds and of other substances. The equilibrium
'tan! of a compound, for instance, is at chemical equilibrium between the
;pound and the elements from which it is formed. Take, for example, the
'librium equation (13-17); the equilibrium constant for this reaction at tem-
ture T is the equilibrium constant for the compound H 2 0 at temperature T. If
'reaction involves compounds in reactants i and products j at a particular

log (Kp),eaction = L log (Kp)j - L log (Kp);

p

ere the stable elements have zero equilibrium constants.

Example-Equilibrium Constant from D.Gr 13.4.1

) Determine the log K; at 77F ( = 298 K) for the reaction

H2 + ! 02 ""' H20(g)

) Using the value found in (a), compute log K, at 1080R = 600 K, assuming constant 11,,,.
Intion. (a) For the given reaction, the Gibbs function of the reaction G~ is the same as
ibbs function of formation t!.G7, since the reactants are elements, each in the standard
Therefore, from Item B 11, we find t!.G7 = G~0 = -98,344 Btu/mole; then at 537R,
 378
approximately 77F, we get from (13-20)

(a)
lnK
log K = - - ' - =
0
0
a;;, 98,344
4
p 2.3026 2.3026T 0 R = (2.3026)(537)(1.986) = 0

(b) Divide each term of equation (c), 13.40, by 2.3026 to convert natural logarithms
base of 10 and get

-ii,, ( 1 1)
log K,2 =. logK; + 2.3026R T2 - T,
(b)
104,036 ( 1 1 )
40
= + (2.3026)(1.986) 1080 - 537 = 18 ' 7

The temperatures must be T 0 R for R = 1.986 Btu/pmole-0 R; the enthalpy of the reaction
is for 1 pmole of H 2[= -(2.016)(51,605), Item B 12], the same as l:i.h{ for H 20, Item B 11.
order of this approximation is revealed by comparing the answers above with values give!J
Item B 32; to wit, 40.048 at 298 K (=77F), 18.633 at 600 K (1080R).

13.42 Exampl-Adiabatic Flame Temperature with Dissociation

If C8 H 18 (g) is burned in steady flow from a state 2 at 1510R and 25-atm pressure in 20.
ideal air, what is the adiabatic flame temperature T 3 ?
Solution. This problem will not be solved completely, but additional light can be th
on the subject by setting it up and discussing a few more points. First, one decides
products are significant. If there is an appreciable amount of dissociation for hydroc.~
fuels, it should be assumed that there are CO, H,, and probably OH, as well as the .
products of complete combustion. At higher temperatures than can be obtained adiab.ad
in 200% air, the reactions !02 = 0, !H2 = H, and !N2 + &0 2 =NO may be significa
well as several others. To keep the detail at a minimum, we shall assume that the reacti
(all gases)

(a) C8 H" + 250 2 + 94N2-> aC02 + bCO + cH20 + dH2 + e02 + 94N2

Since there are three appropriate atom balances, the first step is to obtain three Q
unknown coefficients in terms of the other two. For best accuracy in the inevitable triai
error solutions, one should keep the symbols for what will be the smallest numbers; and,!.
are likely to be the amounts dissociated b and d. Thus

C: 8=a+b a=8-b 18 = 2c + 2d c = 9 - d
b+d
02: 50 = 2a + b + c + 2e or e = 12.5 + --
2

b+d
(b) ~ n1 = a + b + c + d + e + 94 = 123.5 + - -
2
Since the temperature is unknown, there are now three unknowns, b, d, and T,. Co~,
for two of these can be found from the equilibrium constants of two independent equ1h
reactions; say,

Reaction A: CO + 0.50 2 ;;=: C02 [EQUATION (1

Reaction B: C02 + H2 ;;=: CO + H20

 were decided, for example, that the NO content were significant, an additional
llbrium equation would be needed.) One of the three conditions needed must be the
gy balance for adiabatic combustion because this balance for Q = 0 tells whether or not
bas found the right temperature. The procedure is to assume a temperature, look up the
nding values of log KP for the equilibrium reactions involved, and solve for b and d
case). Then, knowing the composition of the products for the assumed temperature,
rms of the energy equation can be evaluated as in 13.36; if HP - Hn "" 0, assume
~r temperature and repeat. See the enthalpy balance of Fig. 13/13. Following this plan,
e T, = 3400R; from Item B 32 (KpA refers to reaction A above),

logKpA = 3.314. K,A = 2061 log Kp 8 = 0.582 KpB = 3.819

p(COi)

!
KpA = p(CO)[p(02)]';2

~
12
( _ b)pm
8
123.5 + -b+2 -dj 123.5 + -b+2 -d )'
[123.5 + -b +2 -d [ bpm [ 12.5 + -b+d]
- Pm
2

2061 = 8 - b J 123.5 + (b + d)/2 }'"

b 1[12.5 + (b + d)/2]Pm

K _ p(CO)p(H20) _ b(9 - d) _
pB - p(C02)p(H2) - (8 - b)d - 3 819

the exponents are all unity for equation (e), kn and Pm cancel. Solve these equations
ltaneously for b and d; then determine a, c, and e. Now we know the moles of each of the
ucts in Fig. 13/13; compute Hn at T2 = 1510R and HP at the assumed T, = 3400R; if
Hn is not zero, assume another T,, and repeat. For the C8 H 18 in Fig. 13/13, Cp
0
R-pmole is the mean value between T 0 and T 2 ; for estimation purposes, the value in
B 1 may be used. (See also Table I, p. 53.) Try to straddle the expected answer. A
ful technique may be to solve for b, say, from the energy equation after setting Hn = Hp.
f .the values of b against the temperature, obtaining one curve from the equilibrium
.gitions and another from the energy equation; a satisfactory value of T, would probably
,where these intersect.

IN at T2 =1510R OUT at Ta

C,(T2-T'') + t!.hj [CsH 18 (g)] -!-!>-a(h 3 -ii'+l!.h{) [C0 2 ]

b(h3 -h'+l!.hj) [CO]
25(h2 -h') [Oz]
-!-!>-c(ii,-h'+l!.iij) [H 2 0]
p -25 atm
"' -!-!>-d(!i 3 -h') [H 2 ]
94(h2 -h') [N 2 [
-1-!>-e(ii3 -/i') [0 2 ]
94(7i 3 -h') [N 2 ]

Adiabatic Combustion Chamber. Fig. 13/13

he data of this example were purposely chosen to highlight the statement previously made
t the dissociation for a considerable excess air is insignificant. Make an order of magnitude
tion for b from (d) with Pm = 25 atm, and find that b is about 0.0026 (and d is smaller).
 Chapter 13 Roactive S
In short, the temperature is practically the same as previously computed without consider!
dissociation.

13.43 FllJGACITY AND ACTIVITY

In dealing with mixtures of other than ideal gases that might undergo a chemi
process, there are several concepts that are particularly helpful. While it is beyq
the intended scope of this text to investigate these situations in detail, it is fitting'
make the reader aware of ideas.that he may find elaborated elsewhere, principa]]
chemical engineering thermodynamics.
Recall in 10.15 we introduced the property fugacity f, as defined by G.;
Lewis, 11.1sJ and the generalized fugacity coefficient f/p-chart, Item B 37. For ,;,
perfect gases we note that

dG = RTd(lnf)

and

G= RTlnf + C(T)

during a T = C change of state.

For known fugacities, the Gibbs function at temperature T' then becomes

(a) G = G' +RT' lnf!r

where r = p0 , a reference state at sufficiently low pressure such that the

and the pressure are equal as for an ideal gas. Now introducing the activity a
equation (a) becomes

(b) a= G' + RT'lna

where the units of (RT') are the same as those for G. By analogy with the;
obtained in equations (13-20) and (13-21), we write expressions for equill
constants as

(c) and
\/

for the case of products X and Y, reactants A and B, 13.35. If the referencf
for the gases is at 1 atm, then r
= p 0 = 1 atm, and Ka = Kt> and the ac!i.
equal to the fugacity.

13.44 CHEMICAL POTENTIAL

Consider a mixture of phases, a solution of liquids and vapors, of soli
mixture of gases, and so on, consisting of n0 , nb, ... moles of A, B, .... If the
of one or more of the constituents changes while independent proper!
unchanged, the change of any extensive property, say the Gibbs function,
tten for total quantities as [after equation (11-1)]

00
=I (a
0
dG = ( 00 ) dna + ( ) dnb + ... ) dn,
ana p,T,n ()nb p.T,ti J ()ni p,T,n

re G (na, nb, ... ) and where the subscript n is to say that all mole values are held
tant except n1 In this context, the partials of equation (a) are called partial molal
functions G; G, = (aG/an,)p,T,n This partial is called the chemical potential, a
e first used by Gibbs. This molal property is evaluated at the p, T of the
ure, but at its actual c0 pdition in the mixture. We shall explain further by an
()gy. Any extensive property may be expressed as shown for G in equation (a).
e property is volume, a familiar one, then the partial molal volume, by analogy,
; == (aV/an,)v,T,n From prior experience, the reader knows that a gallon each of
''liquids (say, alcohol and water) mixed together do not always add to 2 gal of
re. That is, the molal partial volume of i is now always the same volume as a
f~ of the pure i. This observation applies to all other partial molal properties.
'happens that from the differentials of the Holmholz function A and of the
'alpy, written analogously to equation (a), we can say that the chemical potential
he ith constituent is

; = (!;,) T,p,n = (!:,) T, V,n = (!!;;t,p,n

aps 1 from the Gibbs function is most used. Let the partial molal Gibbs
lion be represented by G, for the ith constituent, 1 = G,, and write the function
,p, n1), total quantities;

dG = (aaG)
-
T p,n1
dT + - (a;)
ap T,ft1
dp + I
j
(aG)
-
an; T,p,n
dn,

= -SdT + Vdp + I,dn,

i

ere equivalent values of the partials from Table V, 11.3, are used. Equation (c)
evidently a more complete definition of dG than we have previously used.
erve that if T and p are constant, dG = "'i, 1 dn 1 ; but dG = 0 at equilibrium
.clitions. From the foregoing, we can conceive of 1 = G, (an intensive property
being limited to a mole) as a driving potential for mass transfer, in the sense of T
'i:tg a potential for the transfer of heat, ff; for electricity, and so on. For
ilibrium, all potentials, pressure (force), temperature, Gibbs , and others, must
'n balance.
onsider a two-phase mixture, as liquid-vapor or solid-vapor, for which p, T are
!ant. Then equation (a) or (c) holds, or

dG = I (-aG) dn, =I -
G, dn, = I, dn,
i fJn; p,T,n i i

!primed symbols represent the different phases, as dn' and dn" being infinitesimal
anti ties of each of the two phases. Suppose dn' moles of one phase pass to the
 Chapter 13 /Reactive Sl'te~.

other phase, increasing its quantity by dn" moles; that is, dn" = -dn'.
equation (d) we now get

(e) dG = G" dn" + G' dn' = G" dn" - G' dn" = dn"(G" - G')

If the two phases are in equilibrium at this p, T, then dG = 0, and we conclude fro
(e) that G" = G', which is to say that the molal (or specific) Gibbs function of ea~
phase (at a particular p, T) is the same, a conclusion reached in a different context(
3.7. From (d), we see also that,' = ,"by the same logic (or, = G). If,'> Jh.
there is a potential for mass to move from phase ' to phase ". Even in an equilibriu
state, some of the liquid molecules at the interface of a liquid-vapor mixture w
have enough energy to escape to the vapor phase; but simultaneously, on
macroscopic scale, a balancing number of vapor molecules will be "captured" by tli.
liquid phase, maintaining dG = 0.
It is beyond the intended scope of this text to proceed to the detailed developmtj
of these concepts, but we should point out a certain characteristic. For illustratitj
consider liquefied air to be a mixture of 0 2 and N2 If this liquid is in equilibrhi
with its vapor, there are two components, each in two phases. The proportions of;
and N2 in the liquid are different from the proportions in the vapor; hence(
mixture is not only not a pure substance, but it cannot be treated as a pu
substance, as ordinary air is handled. (See 18.9.)

13.45 CLOSURE
Perhaps the most important idea for the reader to carry away from all chap
having to do with applications of theory is that the aim here is to highlight the u .
the most basic thermodynamic principles, and that in the case of all applicat(
mentioned in this book there is much more to be learned. Since chemical proce .
occur in so many contexts, several books would be needed to cover all. /
Notice that thermodynamics gives no help concerning the rate of a reaction,
this is one of the most important factors in any commercial reaction. The thrust CJ
rocket is directly dependent on the rate at which the reaction can be made to oc
perhaps helped along by use of a catalytic agent.

PROBLEMS
SI UNITS
13.1 (a) The volumetric analysis of air is
21 % O,, 79% N,. Find the moles of N2 per
mole O,. What is the ratio kg N2/kg 0 2? (b)
Air is mixed with propane in the ratio 15 kg
air /kg C 3 H 8 In 1 kg of this mixture, find the
grams of C, H,, O,, N,.
13.2 Gaseous fuel flowing in a pipeline
is composed volumetrically of 75% CH.,,
15% C,Hs, 6% O,, and 4% CO. (a) Con-
vert this to a percentage mass basis. (b) In
1 kg of this fuel mixture, find the grams of
C, H,, 0,.
13.3 A gravimetric analysis of a t.
automotive gasoline gives 86% C and
H,. What average chemical formula }
form C,H, approximates this fuel?
13.4 An ultimate analysis of a bitum.
coal as received is 77 .5% C, 3:7
1.5% N,, 4.3% O,, 0.5% S, 6.5% ash;
H 20. (a) Convert this analysis to a dry
(b) Find the analysis on a dry-and
basis. (c) If this fuel as received is bur
the rate of 100 metric tons/hr and the
is analyzed as being 10% combustible
bon in the ash), how many kilograil) .
refuse must be handled each hour?
 (s) 82.45% C, (b) 88.57% C, (c) 7222
5 Set up the simple combustion equa-
or each of the basic combustibles C, H,,
oichiometric air and note the amount of
uired to burn each element.
. Air required: C/11.5, H 2/34.3, S/4.3
/kg element.
6 Assume 2 mo! of CO are burned in
, mo! air. Write and balance the
J'etical combustion equat\on and find (a)
ass of C02 formed, (b) the percentage
air, (c) the air/fuel ratio.
.7 Pure carbon reacts with all the 02 in
of ideal air. Balance the resulting
etical combustion equation, and find the
s of CO and C02 formed per 100 kg of
pplied.
Ans. 10.21 kg CO, 24.05 kg CO,.
;8 Set up the necessary combustion
ations and determine the amount of air
'retically required to burn 1 kg of pure
n (a) to equal masses of CO and CO,,
where the mass of C0 2 is double that
CO. Ans. (a) 7.98 kg air.
.9 If 1000 e of a gaseous mixture has
.following gravimetric analysis: 30% O,,
CO, is there sufficient oxygen present to
'ort complete combustion of the CO?
:10 A hydrocarbon fuel (CHx)n
uires equal masses of oxygen for a com-
e reaction of each of its components car-
.and hydrogen, respectively. Determine x
n on the basis of 1 mo! of (CHx).
Ans. 4, 1.
3.11 Consider the process wherein oc-
is burned with 80% stoichiometric air,
'd assume that CO is the only combustible
'pearing in the products. Find the products
alysis by volume and by mass.
Ans. C02: 5.49% vol., 8.86% grav.
13.12 Assume 5 mol/hr of propane C,H,
completely burned in the stoichiometric
ount of air. Determine (a) the volume
'/min) of air required measured at 1 atm,
9C, (b) the partial pressure of the C0 2 in
products, measured at 1 atm, 149'C, (c)
volume (m3 /min) of the products
sured at 1 atm and 149'C, and (d) the
w point of the H 20 in the products.
Ans. (a) 48.50 m3 /min, (b) 11.8 kPaa, (c)
.43 m3 /min, (d) 55'C.
13.13 The same as 13.18 except that the
is nonane CoH20 , a rocket fuel.
13.14 Hydrogen peroxide H 2 0 2 (g),
sometimes used as an oxidizer for rocket
fuels, reacts with nonane C9 H 20 (g) to produce
only CO, and H 2 0(g) products at 1 atm
presssure. Balance the equation for a stoi-
chiometric reaction and determine (a) the
mass of H,0 2 used per kg fuel, (b) the mass
of HiO formed per kg fuel, (c) the partial
pressure of the H 20 in the products, (d) the
dew point of the water in the products, (e)
the volume of the products at 226. 7'C, (f)
the gravimetric percentage of carbon in the
nonane.
Ans. (a) 7.43, (b) 5.34 kg, (c) 81.91 kPaa,
(d) 94.2'C, (e) 1930m', (f) 84.4%.
13.15 There are burned 141.6 m' /min of
coke oven gas (measured at 1 atm, 65.6'C) in
the stoichiometric amount of air. The gas has
the following volumetric composition: 36.9%
CH., 52% H,, 5% CO, 0.5% O,, 4.2% N,,
1.4% CO,. What volume of air measured at
1 atm, 65.6'C is required?
Ans. 625.6 m' /min.
13.16 Two hundred metric tons per hour
of coal are burned in 125% (25% excess)
stoichiometric air; the as-fired ultimate
analysis is 75% C, 4% H,, 0.5% S, 6% O,,
1.5% N,, 8% H 20, 5% ash. Find (a) the
mass of air required, kg/hr, (b) the mass of
refuse collected if all ash shows in the refuse
which tests 25% combustible. (c) What is the
carbon content of the coal on a dry basis?
Ans. (a) 2.442 x 106 kg/hr, (b)
13,340 kg/hr, (c) 81.5%.
13.17 An average Texas lignite coal, as-
received, has the following ultimate analysis:
40% C, 3.0% H,, 1.0% S, 11 % O,, 1.5%
N,, 32% H 2 0, 11.5% ash. Balance the
combustion equation for this coal burned as
received in 85% stoichiometric air. Find (a)
the air/fuel ratios as received and for dry
coal, (b) the mass of dry gaseous products
per kilogram of the as received fuel burned.
13.18 An anthracite coal has the follow-
ing dry-basis ultimate analysis: 81.63% C,
2.23% H,, 0.48% S, 2.92% O,, 0.80% N,,
11.94% ash. (a) Balance the combustion
equation for stoichiometric air, and find the
air/fuel ratio on the dry basis; also on the
as-received basis if the moisture content is
3.43%. (b) The same as (a) except that the
air supplied is 90% of the stoichiometric
amount. (c) Assume that CO is the only
combustible element in the products and find

its mass per kilogram of dry fuel and per
kilogram of fuel as received.
Ans. (a) 10.06 (dry), (b) 9.05 kg a/kg f
(dry), (c) 0.408 kg CO/kg f.
13.19 The following is a gravimetric (ul-
timate) analysis of a coal: 70.85% C, 4.48%
H,, 2.11 % S, 6.36% O,, 1.38% N,, 12.3%
ash, 2.52% H 20. During actual combustion,
the following volumetric analysis of the stack
gases was obtained: 12.1 % CO,, 0% CO,
7.2% O,, 80.7% N,. Determine (a) the per-
centage excess or deficiency of air and (b) the
mass of dry products per kilogram of coal
fired. Ans. (a) 49.8% excess, (b) 14.78 kg.
13.20 The burning of a hydrocarbon fuel
(CH,). in an automotive engine results in a
dry exhaust gas analysis, percentage by
volume, of: 11 % CO,, 0.5% CO, 2% CH.,
1.5% H,, 6% O,, and 79% N,. Find (a) the
actual air/fuel ratio, (b) the percentage
excess air, and (c) the mass of water vapor
formed per kilogram of fuel.
Ans. (a) 15.35, (b) 4.71 %, (c) 0.719 kg.
13.21 The dry products of combustion
from a hydrocarbon fuel burned in air, per-
centages by volume, are: 13.6% CO,, 0.8%
CO, 0.4% CH 4 , 0.4% O,, 84.8% N,. Write
the theoretical chemical equation, and find
(a) the values of x and n in (CH,)., (b) the
mass of air supplied per kilogram of fuel, (c)
the percentage of excess or deficiency of air,
and (d) the mass of dry products per kilo-
gram of fuel burned.
Ans. (a) [CH2.31h. (b) 14.75 kg, (c) amount of condensation when the ccf
2.7% def., (d) 14.25 kg.
13.22 Start with the two equalities
-h;;, = q~ and -u;;, = q~, and show that the
difference between the two heating values is
given by the expression q~ - q~ =
(RT'/M,)(n, - n.) where n, and n. are the
moles of reactants and products, respectively,
and Mr is the molecular weight of the fuel.
13.23 Develop the relation between
fugacity f and the compressibility factor Z as
follows: In fl p = J~ (Z - 1) dp/ p. Start with
the change of Gibbs function for an isother-
mal process considering ideal and real gas
conditions.
13.24 Show that for a reversible iso-
thermal steady-flow, steady-state process, the
work is given by W = G1 - G2 =
- RT In (/2 / /1 ) where AK = 0, AP = 0, G
is the Gibbs function, and f is the fugacity.
Chaptar 13 /Rea<:tive S
13.25 There are compressed 4.54 kg
of propane from 1282 kPaa, 60'C
12,790 kPaa in a reversible isother
steady-state, steady-flow manner with A
0, AK = 0. Find the work W by mean
fugacities; see 13.58 and Item B 37.
Ans. -206.6 kJ/' (a
13.26 Prove that the Orsat analyzer"
nores the water vapor and reports the e
analysis of the gaseous mixture as if for
gas. Hint: Assume a mixture of C0 2 , N2:
water vapor-then follow one of the ~
ponents (say the C02) through the o"
absorption process.
ENGLISH UNITS
13.27 One pound of carbon is burne
that 1/2 lb of C goes into CO, and 1
into CO. Set up the combustion equatio
find (a) the pounds of air used per pou
carbon, (b) the volume of this air at 65
14.7 psia, (c) the volumetric and gravi
composition of the products, (d) the vo.
of the products at 65'F and 14.7 psia, an
the partial pressure of each of the prod
Ans. (a) 8.63, (b) 114 ft', (c) 13%,>:
for CO,, (e) 1. 91 psi a for C02
13.28 In a rigid vessel at 1 atm p
and 1OO'F, there are l lb of H 2 and 2
O,. The H 2 reacts completely toe;
Determine (a) the volume of the vesse
the temperature at which the H20 is 9
point of condensing (use steam tables)i!(
are cooled to 80'F, (d) the partial press
the 02 at the final state. ''.
Ans. (a) 562 ft', (b) 170'F, (c) 8.li'J.
0.511 atm.
13.29 A gaseous mixture of 4 mof
and 9 moles 0 2 is ignited. Wri
theoretical combustion equation and
the volumetric analysis of the produ
the equivalent amount of air represe
the O,, (c) the percentage excess of 0
mixture and, if excess, how much mo
could have been burned to complef
the dew point of the products if the'.:.
pressure is 20 psia.
Ans. (a) Xco = 30.76%, (b) 42.84-"
equivalent air, (c) 12.5% excess, O.S
CH 4 , (d) 203.2'F.
13.30 In the combustion of a h:f~
bon fuel at 1 atm, 19 lb da/lb f are so
 bumidity ratio of the air supply is w =
y /lb da. The combustion process
uces 1.4 lb H,O/lb f. For the products
dry air, M = 28.9. What is the dew
of the products?
Ans. 123'F.
1 (a) Set up the chemical equation
combustion of propane C,H, in stoi-
tric air. Show the relative masses and
' , and compute the air/fuel ratio. (b)
~me as (a) except that combustion oc-
15% excess air. (c) Tlie same as (a)
that combustion occurs in 90% of the
metric air and the H 2 reacts com-
to H 2 0. (Ii) Determine the gravi-
.. percentages of carbon and hydrogen
fuel. (e) For the reaction in (a),
ine the gravimetric and volumetric
s of the products with H,O(g).
(a) 15.61, (b) 17.95, (c)
lb a/lb f, (Ii) 81.8% C, (e) CO,:
vol, 18.07% grav.
T32 The same as 13.31 except that the
~:nonane, C9H20, a rocket fuel.
3 A Signal Hill, California, gas sam-
as the following volumetric analysis:
.. CH4 , 32.9% C 2 H 6 , 3.6% H,, 1.0%
alance the chemical equation for this
tned in the stoichiometric amount of
d find (a) the air/fuel ratio, by mass
olume, and (b) the volumetric and
etric analyses of the products.
. (a) 16.4 lb a/lb f, 11.52 ft 3 /ft 3 f, (b)
10.21 % vol, 16.12% grav.
;34 The ultimate gravimetric analysis
oal as received is: 74% C, 1.5% H,, 1%
o/o 0 2 , 2.5% N2 , 5.5% H,O, 9.5% ash.
hat is the percentage carbon on a dry,
ss basis? (b) Find the air/fuel ratio
Yo ideal air) required to burn the fuel
eived. (c) If 100 ton/hr of the as re-
coal are burned and the refuse shows
combustible, find the pounds per hour
se collected.
. 35 Assume 100 ton/hr of pulverized
are burned. Coal analysis by mass
.ed: 76% C, 6% H,, 7% O,, 2% N,, 4%
,; 5% ash. Stack gas analysis by volume
'ed: 13% CO,, 1.5% CO, 5.5% O,,
N,. Refuse pit analysis by mass showed:
C, 77% ash. Find (a) the volume of
al air measured at 14.7 psia and 90'F, (b)
refuse collected each hour, and (c) the
volume of dry products at p,,, = 14. 7 psia
and 310F.
Ans. (a) 605,000 elm, (b) 6.49 tons/hr, (c)
880,000 cfm.
13.36 (a) If propane C3 H 8 (g) is mixed
with the stoichiometric air, what are the
higher and lower heating values (p = C) per
pound of the mixture and per cu ft of mixture
at Pm = 14.7 psia and 77'F? (b) Find q,, and
q1 (p = C) per lb fuel, at 200F and at O'R.
(c) Find q,, and q1 per lb fuel, at 77'F when
v = c.
Ans. (a) q,,: 1294 Btu/lb, 97 .8 Btu/ft', (b)
q,, = 21,624 Btu/lb at 200'F, (c) q1,. =
21,417, q,, = 19,798 Btu/lb .
13.37 The same as 13.36 except that the
fuel is nonane c.H20(g).
13.38 The volumetric analysis of a na-
tural gas fuel is 22.6% C2 H 6 and 77.4% CH4
Find (a) the mass of stoichiometric air per
pound of fuel, (b) the mass of CO, and H 2 0
formed per pound of fuel, (c) the gravimetric
percentage of C and H 2 in the fuel and in the
stoichiometric air-fuel mixture, and (Ii) the
higher and lower heating values at 77F, per
pound of fuel and per pound of stoi-
chiometric air-fuel mixture.
Ans. (a) 16.8 lb, (b) 2.81 lb CO,, (c)
4.31 % C, 1.30% H,, (Ii) q,, = 25,050
Btu/lb f, q,, = 1406 Btu/lb mix.
13.39 Compare the maximum adiabatic
flame temperature of H 2 versus CO when
each fuel is burnfd to completion (no dis-
sociation) in a steady flow system with 200%
air; the reactants enter at 1 atm, 77'F.
Ans. 2967'R (H2 ), 3185'R (CO).
13.40 Gaseous n-butane (C4 H 10 ) is bur-
ned at constant pressure with 400% ideal air
in a steady flow system. The reactants enter
at 77F. Determine the adiabatic flame tem-
perature using Item B 38.
13.41 Gaseous octane and 200% air
react in a steady flow manner; the reactants
cross the boundary at 1OO'F and the products
leave at 2000F. For the process, AK = 0,
W = 0. Determine the heat for a fuel flow of
1 mol/sec. Do not neglect the sensible en-
thalpy of the fuel; use Item B 9.
13.42 A Diesel engine burns dodecane
C 12H 26 in 200% stoichiometric air (100%
excess). At the end of the compression
process (initial point of fuel injection-fuel at
77'F) the air temperature is 1080F. Using
381!
Item B 9, compute the temperature of the
products after constant-pressure combustion
if the combustion efficiency is 94 % . Sketch
energy diagrams.
13.43 Consider a stoichiometric reaction
of nonane C9 H 20 (1) and hydrogen peroxide
H202(g) to C02(g) and H20(1). If the process
begins and ends at 77'F and 1 atm, determine
(a) the enthalpy of reaction, (b) the change
of entropy. (c) If the nonane reacts instead
with pure O,, is more "Or less energy
released? Compare this -h,, with that given
in Item B 12.
Ans. (a) -34,800 Btu/lb f, (b) -504
Btu/'R for 1 mole nonane.
13.44 A torpedo propulsion system in-
volves a reaction of methyl alcohol CH.O(l)
and hydrogen peroxide H 20 2(g). Using t:.h/
and/ or t:.G{, determine the maximum work
that can be done for constant p, T, at Pm =
1 atm and 77'F. What are the entropy change
and heat? Compare the heat of this reaction
with the heating value from Item B 12.
13.45 Let octane C8 H 18 (1) be burned
adiabatically in 400% air with the reactants
initially at 77F; steady flow obtains. Deter-
mine the theoretical flame temperature (a)
using Item B 8, (b) using the enthalpies of
formation of each compound.
13.46 (a) Using the enthalpies of for-
mation, determine the standard enthalpy of
combustion, -h~, of ethane C2H6 (g) with
liquid H 20 in the products. Compare with
Item B 12. (b) Using enthalpies of reaction,
compute the enthalpy of formation. Compare
with Item B 11.
Ans. (a) -22,320 Btu/lb, (b) -36,400
Btu/mole.
13.47 Into a 0.5-ft' bomb calorimeter,
filled with air at 1 atm and 77'F, is placed
0.0001 pmoles of methanol (methyl alcohol,
CH4 0). Complete adiabatic combustion oc-
curs. For no dissociation, compute the final
pressure.
13.41! Using Item B 11, calculate the en-
thalpy of combustion and the internal energy
of combustion for CO at 1 atm, 77'F.
Ans. -121,745, -121,203 Btu/lb-mo!.
13.49 Compute the Gibbs function of
formation of C0 2 at 1 aim and 77'F, using
G = H - TS and the enthalpies of for-
mation and compare with the values given in
Item B 11.
Chapter 13 Reactive S
13.50 Determine the Gibbs function
methane CH.(g) at 5 aim, 140'F measu
from the same datum as the Gibbs fun
of formation given in Item B 11. Assume
specific heat to be constant as given in It
B 1. Ans. -22,786 Btu/
13.51 Benzene C.H.(g) is burned
300% air in a steady flow manner. The re
tants are at 1 atm, 77'F. Determine ;{
maximum work possible if the reaction
curs isothermally.
13.52 (a) Using t:.h{, compute t:.O{
hydroxyl OH(g) and check with value in I
B 11. (b) Using the value from (a), com
the Gibbs function of formation at 400 K.
Using enthalpy of formation, Gibbs func
of formation, and the absolute entropi
the elements, compute the absolute en
of OH(g) in the standard state; compare W.
table value.
13.53 If a way were found to m
gaseous ethane C2H react with 02 in}
ideal fuel cell at 140'F and 1 atm, com
t:.S for the reaction and determine the i
work for H 20(1).
Ans. -69.5 Btu/'R-mole f, 20, 860 Btu/
13.54 Determine the equilibrium .
stant KP for the reaction at 77'F: (a) C.
H20 = C02 + H2; (b) CO, + H
CO+ H20. See Item B 11 for !:i.G'f.
Ans. (a) 98,
13.55 Calculate the equilibrium cons!
for the following reactions occurring at 7.
(a) H2 + 0.5 02 = H20; (b) CO
co+ 0.5 o,.
13.56 When an object enters the ea
atmosphere at high speed, the temper
behind the shock wave in the vicinity of
object may be quite high. Suppose that.!
temperature is 7200R, the total press1;1
0.034 psia, and it is desired to estimat .
extent of dissociation of the oxygen. For.
reversible reaction 02 :;o:!: 2 0 at 7200'R;c
equilibrium constant is K. = 2.4094.
Let the reaction equation be
3.76 N 2 + 0 2 ... 11 10 + n202 + 3.~6N
which assumes that the dissociation of
is negligible. Define K. in terms of llz.
Ans. mols 02 = O.
13.57 Methane CH.(g) is burned
"90% air" in a steady flow adiabatic pro
 ants enter at 77F. Consider dis-
of C0 2 and HzO, except assume
re is no 0 2 in the products (a sim-
ion involving small error in this case).
the adiabatic flame temperature.
se only the water gas reaction for the
An object falls to earth creating a
ave and resulting high temperatures
th. At one point of this path in the
atmosphere, the temperature is
; the pressure is 1 aiin. Estimate the
tion of oxygen at this point. For the
1e reaction 0 2 o= 2 0 at 5400R,
.01441. See 13.56.
Ans. 0.248 mols 0.
Compute the adiabatic flame tem-
l'e for the combustion of CO in stoi-
tric oxygen at a constant pressure of
. starting from 77F and allowing dis-
n. Suggestion. Try 5400R first.
O During the recent energy crisis it
'1'.oposed to utilize cattle manure from
f~ed-lots by hydrogasifying it and burn-
e resulting gaseous mixture in power
'. The following compositions are
: raw cattle manure before gasification,
. ss: 35.4 C, 4.6 Hi. 0.2 S, 30. l Oi.
. 0, 0.7 Ni. 25.6 ash; product gas resul-
;from gasification of raw manure, %
volume: 78.76 CH4, 19.02 C2H6, 1.07 H,,
1.15 C0 2 Find the heating value of each
composition and determine the stoi-
chiometric air required for each.
13.61 In industry, the C0 2 content of the
products of combustion is conveniently used
as an index of the combustion efficiency
and/ or the percentage excess air for a given
fuel. Plot the curve "percentage C02 (by
volume) versus percentage air (theoretical)"
for methane CH4 , allowing the amount of air
to vary from 50% ideal to 150% ideal. For
deficient air, assume that by volume the CO
content is twice that of the H 2 Note that the
resulting curve may be used to indicate the
percentage air supplied when the C0 2 con-
tent only is known.
13.62 It is desired to determine the effect
of excess air on the dewpoint temperature of
the products resulting from burning a selec-
ted hydrocarbon in air at constant pressure
(p = 14.7 psia). Select a fuel from Item B 12
and burn it theoretically in air varying from
that of stoichiometric to 400% excess. Plot a
curve depicting dewpoint temperature vs
percentage excess air. Write the computer
program for this problem.
13.63 Find the fugacity f (see Item B 37)
for each of the following fluids at 2940 psia,
44F; (a) water, (b) propane, (c) hydrogen.