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Solution Manual for Combustion 4th Edition

Irvin Glassman
Department of Mechanical and Aerospace Engineering
Princeton University
Princeton, New Jersey

Richard Yetter
Department of Mechanical and Nuclear Engineering
The Pennsylvania State University
University Park, PA

This solution manual is a revision to the solution manual for "Combustion, 3rd. Ed." that
was written in its final form by Prof. Queiroz and Dr. Black of Brigham Young
University.

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A Solution Manual for:

COMBUSTION. 4th Ed.
by
I. Glassman, and R.A. Yetter
CHAPTER 1
Problem 1
Calculate the heat of reaction when methane and air in stoichiometric proportions are brought
into a calorimeter at 500 K. The product composition is brought to the ambient temperature (298
K) by the cooling water. The pressure in the calorimeter is assumed to remain at 1 atm, but the
water formed has condensed.

Solution: The heat of reaction can be calculated using Eqn. (10) in the text. However, as also
suggested in the textbook, this equation can be simplified for the general case when H0T0 = H0298 .
The modified equation becomes:

−Q= ΔH= ∑ n ⎡⎣( H

i prod
i
0
T2 )
− H0298 + (Δ H0f ) ⎤ −
298 ⎦ i ∑ n ⎡⎣( H
j react
j
0
T1 − H0298 ) 298
+ (Δ H0f )
298
⎤
⎦j
(1)

In this Equation, T2 and T1 are the temperatures of the products and reactants respectively. The
general equation for the complete combustion of one mole of methane in air is:

CH4 + a th ( O2 + 3.76N2 ) → a CO2 + b H2 O + c N2

where ath is a coefficient describing how much air is needed for stoichiometric combustion.
Balancing the above reaction one has:

CH4 + 2 ( O2 + 3.76N2 ) → CO2 + 2 H2 O + 7.52 N2

In order to apply Eqn. (1) to the above reaction, the following properties from Tables in the
textbook are needed (note that for this problem T2 = 298 K and T1 = 500 K):

gases ΔH0f (kJ/mol) H0T1 − H0298 (kJ/mol) H 0T2 − H0298 (kJ/mol)

CH4 −74.90 8.21 0.0
O2 0.0 6.09 0.0
N2 0.0 5.92 0.0
H2O(liq) −286.04 0.0 0.0
CO2 −393.77 0.0 0.0

Equation (1) then becomes:

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− Q = 1 ( −393.77 + 0.0 )CO + 2 (− 286.04 + 0.0 )H O + 7.52 ( 0.0 + 0.0 )N − 1 (− 74.90+ 8.21)CH
2 2 2 4

− 2 ( 0.0 + 6.09 ) O − 7.52 ( 0.0 + 5.92 ) N

2 2

Q=955.85 kJ
or

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Problem 2
Calculate the flame temperature of normal octane (liquid) burning in air at an equivalence ratio
of 0.5. For this problem assume there is no dissociation of the stable products formed. All
reactants are at 298 K and the system operates at 1-atm pressure. Compare your results with
those given in the graphs in the text. Explain any differences.

Solution: We will assume that adiabatic conditions exist and that the water in the products is in
the vapor phase. In this case, Eqn. (10) in the text can be used in an iterative approach to solve
for the adiabatic flame temperature. However, this equation can be simplified for the general
case when H T0 = H 298 . For Q = 0, the modified equation becomes:
0 0

∑ n ⎡⎣( H
i prod
i
0
T2 ) 298 ⎦ i
j react
(
− H 0298 + ( ΔH f0 ) ⎤ = ∑ n j ⎡ H T01 − H 298
⎣
0
)
+ ( ΔH f0 ) ⎤
298 ⎦ j
(1)

In this Equation, T2 and T1 are the temperatures of the products and reactants respectively. Since
the conditions for the reactants are specified, the solution approach is to find T2 such that the
above equality will be satisfied.

The general equation for the complete combustion of one mole of octane with excess air is:

C8 H18( liq ) + ( m)( a th )( O 2 + 3.76N 2 ) → a CO 2 + b H 2O + c O 2 + d N 2

where ath is the coefficient describing how much air is needed for stoichiometric combustion and
m is the coefficient used to represent the amount of excess air, respectively. For the case when c
= 0 and m = 1 (no excess air), a simple mass balance yields ath = 12.5. Therefore, for an excess
air of 100% (m = 2) or an equivalence ratio of 0.5, the chemical reaction becomes:

C8 H18( liq ) + 25 ( O2 + 3.76N2 ) → 8 CO2 + 9 H2 O + 94 N2 + 12.5 O2

Since the conditions of the reactants are specified (T1 = 298 K), Table 2 in the text and Appendix
A provide the following thermodynamic properties:

gases ΔH 0f (kJ/mol) H0T1 − H0298 (kJ/mol)

C8H18(liq) −250.12 0.0
O2 0.0 0.0
N2 0.0 0.0

The enthalpy of the reactants (Hr, given by the right-hand side of Eqn (1)) can be calculated as:
H r = 1( − 250.12 + 0.0 ) C H + 11( 0.0 + 0.0 ) O + 41.36 ( 0.0 + 0.0 ) N = − 250.12kJ
8 18 2 2

For the products it follows from thermodynamic properties in the text that:

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gases Δ H0f (kJ/mol)

O2 0.0
N2 0.0
H2O(vap) −242.00
CO2 −393.77

Therefore, the expression for the enthalpy of the products (Hp, given by the left-hand side of
Eqn. (1) in terms of the enthalpy of the individual gases in the products becomes
( )
let ΔH = H T2 − H 298 :
0 0

( ) ( ) ( ) (
Hp = 8 −393.77 + ΔHCO 2 + 9 −242.00 + ΔH H 2O + 12.5 0.0 + Δ HO 2 + 94 0.0 + Δ HN 2 )
Simplifying the above equation yields:

8 ΔHCO2 + 9 ΔHH2O + 12.5ΔHO 2 + 94Δ HN 2 = 5,078.04

A first guess for the products temperature can be obtained by assuming that all product gases are
N2. This approach gives the following as an initial guess for T 2 (Note that 123.5 = 8 + 9 + 12.5 +
94):

123.5 ΔH N2 = 5,078.04 so ΔH N2 = 41.12 kJ/mol therefore T2 = 1577

We will then assume that T2 is between 1500 and 1600 K. If that is so, we can develop the
following table (all ΔH’s are in kJ/mol and (Hp - Hr)'s are in kJ):

T2 ΔH CO2 (kJ/mol) ΔH H2 O ΔH O2 ΔHN 2 Hp – Hr (kJ)

1500 61.76 48.13 40.64 38.43 -30.37
1550 64.69 50.51 42.48 40.18 202.00
1506 62.11 48.41 40.86 38.64 -2.55

Interpolate 1500 -30.37

T2 00
1550 202.00
T2 −1500 30.37
 = 
50 232.37
so
T2 = 1506 K

The enthalpy difference for this temperature was also calculated in the above table to show that
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once you have a good idea of the temperature interval where the adiabatic temperature should be
in, linear interpolation does a good job of predicting the temperature.

Comparing the results for the adiabatic flame temperature found above to that found using Fig. 3
on page 22 of the textbook is done as follows:

−250.12 18
Enthalpy per gram C8H18 = = 2.194 kJ/gm H/C = = 2.25
96 + 18 8

With these values Fig. 3 yields T2 ≅ 1505 K, which is very close to the calculated adiabatic
temperature.

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Problem 3

Carbon monoxide is oxidized to carbon dioxide in an excess of air (1 atm) in an afterburner so

that the final temperature is 1300 K. Under the assumption of no dissociation determine the air-
fuel ratio required. Report the results on both a molar and mass basis. For the purposes of this
problem assume that air has the composition of 1 mole of oxygen to 4 moles of nitrogen. The
carbon monoxide and air enter the system at 298 K.

Solution: We will assume that adiabatic conditions exist. In this case, Eqn. (1.10) in the
textbook can be used to calculate the initial composition of the mixture which will give an
adiabatic flame temperature of T2 = 1300 K. This equation can be simplified for the general case
when H 0T0 = H 0298 For Q = 0, the modified equation becomes:

∑ n ⎡⎣( H
i prod
i
0
T2 − H 0298 + ( ΔH f0 ) ⎤ = ∑ n j ⎡ H T01 − H 298
) 298 ⎦ i
j react
(⎣
0
+ ( ΔHf0 ) ⎤
) 298 ⎦ j
(1)

In this Equation, T2 and T1 are the temperatures of the products and reactants, respectively.
Since the temperature for the reactants and products have been given (T1 = 298 K and T2 = 1300
K), the problem simplifies to finding x in the reaction shown below, which will satisfy Eqn. (1)
above.

CO + x ( O2 + 4 N2 ) = CO2 + ( x − 0.5 ) O2 + 4x N2

The following table can be developed from information in the textbook.

Gases ΔH0f (kJ/mol) H0T1300 − H0298 (kJ/mol)

CO2 −393.77 50.19
CO −110.62 Not needed
O2 0.0 33.37
N2 0.0 31.52

Substituting these values in Eqn. (1) one has:

2 x −1
1( −393.77 + 50.19 ) CO2 + ( 0.0 + 33.37 ) O2 + 4 x ( 0.0 + 31.52 ) N2
2
−1 ( −110.62 + 0.0 )CO − x (0.0 + 0.0 )O + 4 x (0.0 + 0.0 )N = 0.0
2 2

−343.58 + 33.37 x −16.69 +126.08 x + 110.62 = 0.0

159.45 x = 249.65
x = 1.566

Therefore the total number of moles of air needed to react with one mole of CO is 1.566 * (1 +
7

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4) = 7.83 moles (which is the A/F ratio on a molar basis). The air/fuel ratio on a mass basis is:

mair 7.83 moles of air × 29 kg / mol

AF = =
m fuel 1 mole of CO × 28 kg / mol

kg of air
so AF = 8.11 
kg of CO

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Problem 4
The exhaust of a carbureted engine, which is operated slightly fuel rich, has an efflux of
unburned hydrocarbons entering the exhaust manifold. One can assume that all the hydrocarbons
are equivalent to ethylene (C2H4) and all the remaining gases are equivalent to inert nitrogen
(N2). On a molar basis there are 40 moles of nitrogen for every mole of ethylene. The
hydrocarbons are to be burned over an oxidative catalyst and converted to carbon dioxide and
water vapor only. In order to accomplish this objective, ambient (298 K) air must be injected
into the manifold before the catalyst. If the catalyst is to be maintained at 1000 K, how many
moles of air per mole of ethylene must be added? Take the temperature of the manifold gases
before air injection as 400 K. Assume the composition of air to be 1 mole of oxygen to 4 moles
of nitrogen.

Solution: We will assume that adiabatic conditions exist and that no dissociation of the stable
products will take place. In this case, Eqn. (1.10) in the textbook can be used to calculate the
initial composition of the mixture which will give an adiabatic flame temperature of T2 = 1000
K. This equation can be simplified for the general case when H0T0 = H0298 . For Q = 0 , the
modified equation becomes:

∑ n ⎡⎣( H
i prod
i
0
T2 − H 0298 + ( ΔH f0 ) ⎤ = ∑ n j ⎡ H T01 − H 298
) 298 ⎦ i
j react
(
⎣
0
+ ( ΔH f0 ) ⎤
) 298 ⎦ j
(1)

In this Equation, T2 and T1 are the temperatures of the products and reactants, respectively. Since
the temperature for the reactants and products have been given (Tl = 400 K and T2 = 1000 K), the
problem simplifies to finding x in the reaction shown below, which will satisfy equation (1)
above.

C2H4 + 40N2 + x(O2 + 4N2) → 2 CO2 + 2 H2O + (x - 3) O2 + (40 + 4x) N2 (2)

The following table can be developed from information in the text.

Gases ΔH0f (kJ/mol H0T400 − H0298 (kJ/mol) H0T1000 − H0298 (kJ/mol)

C2H4 52.34 4.89 Not needed
N2 0.0 2.97 21.47
O2 0.0 3.03 22.72
CO2 −393.77 Not needed 33.43
H2O(vap) −242.00 Not needed 26.00

Substituting these values in Eqn. (1) with the coefficients from Eqn. (2) one has:

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1( 52.34 + 4.89 ) C H + 40 ( 0.0 + 2.97 ) N + x ( 0.0 + 0.0 ) O + 4 x ( 0.0 + 0.0 ) N −

2 4 2 2 2

2 ( −393.77 + 33.43)CO − 2 ( −242.00 + 26.00 )H O − ( x − 3)( 0.0 + 22.72 )O −

2 2 2

(40 + 4 x )(0.0 + 21.47 )N = 0.0

2

57.22 + 118.91 + 720.68 + 432.00 − 22.72x + 68.17 − 858.96 − 85.90x = 0.0

108.62 x = 538.01 and

x = 4 .953

Therefore, the total number of moles of air needed to react with one mole of C2H4 is

4.953
 x (1 + 4) = 24.75 moles.

10

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Problem 5
A combustion test was performed at 20-atm pressure in a hydrogen-oxygen system. Analysis of
the combustion products, which were considered to be in equilibrium, was as follows:

Compound Mole fraction

H 2O 0.4855
H2 0.4858
O2 0.0
O 0.0
H 0.0216
OH 0.0069

What must the combustion temperature have been in the test?

Solution: Since all the products are in equilibrium, any equilibrium reaction between the
products can be used to solve for the temperature. The simplest reaction to choose (and the only
one that is an equilibrium reaction of formation) is:

1
H2 ⇔ H
2

The expression for the equilibrium constant of formation is then given by

1/ 2
nH ⎛ P ⎞
KP,f( H) = ⎜ ⎟
n H2 1/ 2 ⎜⎝ ∑ n ⎟⎠

Since values are given in mole fraction ∑n = 1 . Therefore,

0.0216
KP,f( H) = ( 20)1/ 2 = 0.138593
0.48581/ 2

log10 K P,f (H ) = − 0.85826

Looking up the temperature in Table 2 in the appendix for H which corresponds to this value
yields
 T ~ 2959 K

If one desires to use the other possible equilibrium reaction given by

1
H 2 + OH ⇔ H 2O
2
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The equilibrium constant is given by

1/ 2
n H2 O ⎛ P ⎞ 0.4855 1
KP = ⎜⎜ ⎟⎟ = = 22.573349
⎝∑n⎠ (0.0069 ) (0.4858 )
1/ 2 1/ 2
nH 2 nOH 20

or

log10 KP = 1.353596

Then, in order to solve for the final temperature of the mixture one would have to calculate the
value for the equilibrium constant for the above reaction and find the corresponding temperature
as shown below.

KP,f ( H 2O )
KP =
K P,f (OH )

Temp. KP,f (OH ) K P,f( H2 O) KP Log10 KP

2900 K 1.1066 31.2608 28.2494 1.4510
3000 K 1.1614 22.0293 18.9679 1.2780

Interpolating for the temperature between 2900 and 3000 K that would give log10 KP
= 1.353596 yields:

T ~ 2956 K

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Problem 6
Whenever carbon monoxide is present in a reacting system it is possible for it to
disproportionate into carbon dioxide according to the equilibrium 2CO ⇔ Cs + CO2. Assume
that such an equilibrium can exist in some crevice in an automotive cylinder or manifold.
Determine whether raising the temperature decreases or increases the amount of carbon
present. Determine the K P for the reaction equilibrium and the effect of raising the
pressure on the amount of carbon formed.

Solution: One simply considers how the equilibrium is shifted by the temperature and pressure
to solve the problem.

(i) Temperature effect

2 CO ⇔ Cs + CO2 (1)

pCO 2
KP = 2
(2)
pCO

in terms of equilibrium constants of formation for C + O2 ⇔ CO2 one has

p CO2
KP,f( CO 2) = (3)
pO 2

1
and for C + O2 ⇔ CO
2

pCO
KP,f( CO) = (4)
p1O22

For Eqn. (1) it follows that

KP,f (CO 2 )
KP =
K2P,f ( CO)

or log10 KP = log10 KP,f (CO 2 ) − 2 log10 KP,f (CO )

Evaluating this log equation in two different temperatures one has

(a) At 1000 K

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log10 K P,f ( CO2 ) = 20.68 and 2log 10 K P,f ( CO) = 2 (10.46 ) = 20.92 so
log Kp = −0.24

or KP = 0.58

(b) At 2000 K

log10 K P,f ( CO2 ) = 10.35 and 2log 10 K P,f ( CO) = 2 (7.47) = 14.94 so

log KP = −4.59

or KP = 2.57 × 10−5

Therefore, KP drops as temperature increases.

Equation (1) and (2) show that as KP decreases, the reaction given by Eqn. (1) is shifting to the
left, thus less carbon forms as the temperature increases.

(ii) Pressure effect

−1
pCO2 nCO2 ⎛ P ⎞
KP = = ⎜ ⎟
p2CO n CO2 ⎜⎝ ∑ n ⎟⎠

Thus, as the pressure increases more CO2 forms, shifting the reaction from left to right and thus
more carbon forms as the pressure is increased.

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Problem 7
Determine the equilibrium constant KP at 1000 K for the following reaction

2 CH4 ⇔ 2 H2 + C2H4

Solution: As explained on page 14 of the text, the equilibrium constant (given in terms of the
equilibrium constant of formation) is:

K2P,f (H 2 )K P,f (C 2H 4 )
KP = 2
KP,f (CH 4 )

At 1000 K it follows from Table 2 in the appendix that (note Table 2 provides the logl0 of K):

KP,f( H2 ) = 100 = 1
KP,f( C 2H 4) = 10−6.213 = 6.1235× 10−7
KP,f( CH 4) = 10−1.011 = 0.0975

so evaluating Eqn. (1) for KP one has

1× ( 6.1235× 10−7 )
KP = = 6.442 × 10− 5
(0.0975 ) 2

so K P = 6.442 × 10-5

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Problem 8
The atmosphere of Venus is said to contain 5% carbon dioxide and 95% nitrogen by volume. It
is possible to simulate this atmosphere for Venus reentry studies by burning gaseous cyanogen
(C2N2) and oxygen and diluting with nitrogen in the stagnation chamber of a continuously
operating wind tunnel. If the stagnation pressure is 20 atm, what is the maximum stagnation
temperature that could be reached and still have Venus atmosphere conditions? If the stagnation
pressure were 1 atm, what would be the maximum temperature? Assume all gases enter the
chamber at 298 K. Take the heat of formation of cyanogen as ( ΔH 0f ) = 381.84 k/mol.
298

Solution: In order to maintain Venus atmosphere, the composition of 100 moles of products
would have to be 5 CO2 + 95 N2. Eqn. (10) in the textbook can be used to calculate the
stagnation temperature of this system. This equation can be simplified for the general case when
H 0T0 = H0298 . For Q = 0, the modified equation becomes:

∑ n ⎡⎣( H
i prod
i
0
T2 )
− H 0298 + (Δ H 0f ) ⎤ =
⎦
298 i ∑ n ⎡⎣( H
j react
j
0
T1 )
− H 0298 + (Δ H f0 )
298
⎤
⎦j (1)

In this Equation, T2 and T1 are the temperatures of the products and reactants respectively. Since
the conditions for the reactants are specified the solution approach is to find T2 such that the
above equality will be satisfied.

(a) for Venus atmosphere the general combustion reaction would be

a C2N2 + b O2 + c N2 → 5 CO2 + 95 N2

which can be balanced for one mole of C2N2 as follows:

C2N2 + 2 O2 + 36 N2 → 2 CO2 + 38 N2,

In preparation to apply Eqn. (1) the following tables can be generated.

gases ΔH 0f (kJ mol ) H 0T1 − H0298 ( kJ mol )

C2N2 381.84 0.0
O2 0.0 0.0
N2 0.0 0.0

An expression for the enthalpy of the reactants (Hr, given by the right-hand side of Eqn. (1)) in
terms of the enthalpy of the individual gases in the reactants becomes:

Hr = 1( 381.84 + 0.0)C N + 2 ( 0.0 + 0.0 )O + 36 (0.0 + 0.0 )N = − 381.84 kJ

2 2 2 2

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For the products it follows that:

gases ΔH 0f (kJ mol )

N2 0.0
CO2 −393.77

Thus, an expression for the enthalpy of the products (Hp, given by the left-hand side of Eqn. (1))
(
in terms of the enthalpy of the individual gases in the products becomes let ΔH = H 0T2 − H 0298 :)
( ) (
Hp = 2 −393.77 + ΔH CO2 + 38 0.0 + ΔH N 2 )
Equating Hr and Hp yields:

2 ΔH CO2 + 38 ΔH N2 = 1,169.37

A first guess for the products temperature can be obtained by assuming that all product gases are
N2. This approach gives the following as an initial guess for T2 (Note that 40 = 2 + 38):

40 ΔH N2 = 1,169.37 so
ΔH N2 = 29.23kJ mol , therefore, T2 ≈ 1232 K

We will then assume that T2 is between 1200 and 1300 K. If that is so, we can develop the
following table (all ΔH’s are in kJ/mol and (Hp - Hr)'s are in kJ):

T2 ΔH CO2 ( kJ mol ) ΔH N2 Hp − Hr (kJ)

1200 44.51 28.13 −11.51
1300 50.19 31.52 128.87

Interpolate 1200 −11.51

T2 00
1300 128.31

T2 − 1200 11.51
=
100 139.88

so T 2 = 1208 K

Since K P,f( CO2 ) = 1.75 ×1017 at 1200 K, no significant dissociation of the products occurs.
Therefore, pressure has no effect and T2 would remain the same at all pressures.
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Problem 9
A mixture of 1 mole of N2 and 0.5 mole O2 is heated to 4000 K at 0.5 atm pressure and results in
an equilibrium mixture of N2, O2, and NO only. If the O2 and N2 were initially at 298 K and the
process is one of steady heating, how much heat was required to bring the final mixture to 4000
K on the basis of one initial mole of N2?

Solution: The first step is to find the equilibrium concentration of products. Once this is done,
one can use Eqn. (1.10) to calculate the amount of heat necessary to bring the final mixture to
4000 K. Consider the following reaction at equilibrium.

1
1 N 2 + O 2 → a N 2 + b O 2 + c NO (1)
2

balancing this reaction yields the following relationship between a, b and c.

N: 2 = 2 a + c
0: 1 = 2 b + c

Solving these two equations for b and c in terms of a it follows that

2a −1
b= and c = 2 − 2a
2

Therefore, Eqn. ( 1) becomes:

2a − 1
1N 2 + 0.5O 2 → a N 2 + O 2 + ( 2 − 2a ) NO
2

1 1
For the equilibrium reaction given by N2 + O2 ⇔ NO , the expression for the equilibrium
2 2
constant of formation is given by:

1−1 2−1 2
n ⎛ P ⎞
K P,f (NO ) = 1/ 2NO 1/ 2 ⎜ ⎟
n N 2 nO 2 ⎜⎝ ∑ n ⎟⎠

2a −1
The total number of moles is given by ∑n= a+
2
+ 2 − 2a = 3 . At 4000 K, 1og10 KP,f(NO) =
- 0.524 or KP,f(NO) = 0.29923. Squaring Eqn. (3) would give the following equation for the
variable a:

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( 2 − 2a ) 2
− K 2P,f( NO) = 0,
2a − 1
a
2

Solving for a in the above equation and then using the mass balance equations to solve for b and
c yields: a = 0.909, b = 0.409 and c = 0.182. Equation (2) now becomes

1 N2 + 0.5 O2 → 0.909 N2 + 0.409 O2 + 0.182NO

The amount of heat required to bring the above mixture to 4000 K is calculated using Eqn. (1.10)
in the text by taking T2 = 298 K and T1 = 4000 K:

−Q = ∑ n ⎡⎣( H
i prod
i
0
T2 )
− H 0298 + (Δ H 0f )
298 i
⎤ −
⎦ ∑ n ⎡⎣( H
j react
j
0
T1 )
− H 0298 + ( Δ H 0f )
298
⎤
⎦j
(4)

from tables in the text one has:

gases ΔH 0f (kJ mol ) H 0T1 − H 0298 (kJ mol ) H 0T 2 − H0298 (kJ mol)
O2 0.0 139.01 0.0
N2 0.0 130.16 0.0
NO 90.43 132.76 0.0

so the equation for Q becomes

− Q = 0.182( 90.43 + 132.76) NO + 0.409( 0.0 + 139.01) O + 0.909 ( 0.0 + 130.16)N −

2 2

1 (0.0 + 0.0 )N2 − 1/ 2 (0.0 + 0.0 )O2

so Q = - 215.79 kJ

if no dissociation occurred the value of Q would be

− Q = 1/ 2 ( 0.0 + 139.01)O + 1( 0.0 + 130.16 )N −

2 2

1 (0.0 + 0.0 )N2 − 1/ 2 (0.0 + 0.0 )O2

so Q
 = - 199.67 kJ

Therefore, more energy is required to raise the temperature of the mixture to 4000 K due to
dissociation.

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Problem 6
Whenever carbon monoxide is present in a reacting system it is possible for it to
disproportionate into carbon dioxide according to the equilibrium 2CO ⇔ Cs + CO2. Assume
that such an equilibrium can exist in some crevice in an automotive cylinder or manifold.
Determine whether raising the temperature decreases or increases the amount of carbon
present. Determine the K P for the reaction equilibrium and the effect of raising the
pressure on the amount of carbon formed.

Solution: One simply considers how the equilibrium is shifted by the temperature and pressure
to solve the problem.

(i) Temperature effect

2 CO ⇔ Cs + CO2 (1)

pCO 2
KP = 2
(2)
pCO

in terms of equilibrium constants of formation for C + O2 ⇔ CO2 one has

17 0
p CO2
KP,f( CO 2) = (3)
pO 2
 1
and for C + O2 ⇔ CO
2

pCO
KP,f( CO) = (4)
p1O22

For Eqn. (1) it follows that

KP,f (CO 2 )
KP =
K2P,f ( CO)

or log10 KP = log10 KP,f (CO 2 ) − 2 log10 KP,f (CO )

Evaluating this log equation in two different temperatures one has

(a) At 1000 K

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log10 K P,f ( CO2 ) = 20.68 and 2log 10 K P,f ( CO) = 2 (10.46 ) = 20.92 so
log Kp = −0.24

or KP = 0.58

(b) At 2000 K

log10 K P,f ( CO2 ) = 10.35 and 2log 10 K P,f ( CO) = 2 (7.47) = 14.94 so

log KP = −4.59

or KP = 2.57 × 10−5

Therefore, KP drops as temperature increases.

Equation (1) and (2) show that as KP decreases, the reaction given by Eqn. (1) is shifting to the
left, thus less carbon forms as the temperature increases.

(ii) Pressure effect

−1
pCO2 nCO2 ⎛ P ⎞
KP = = ⎜ ⎟
p2CO n CO2 ⎜⎝ ∑ n ⎟⎠

Thus, as the pressure increases more CO2 forms, shifting the reaction from left to right and thus
more carbon forms as the pressure is increased.

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
Problem 7
Determine the equilibrium constant KP at 1000 K for the following reaction

2 CH4 ⇔ 2 H2 + C2H4

Solution: As explained on page 14 of the text, the equilibrium constant (given in terms of the
equilibrium constant of formation) is:

K2P,f (H 2 )K P,f (C 2H 4 )
KP = 2
KP,f (CH 4 )

At 1000 K it follows from Table 2 in the appendix that (note Table 2 provides the logl0 of K):

KP,f( H2 ) = 100 = 1
KP,f( C 2H 4) = 10−6.213 = 6.1235× 10−7
KP,f( CH 4) = 10−1.011 = 0.0975

so evaluating Eqn. (1) for KP one has

1× ( 6.1235× 10−7 )
KP = = 6.442 × 10− 5
(0.0975 ) 2

so K P = 6.442 × 10-5

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Problem 8
The atmosphere of Venus is said to contain 5% carbon dioxide and 95% nitrogen by volume. It
is possible to simulate this atmosphere for Venus reentry studies by burning gaseous cyanogen
(C2N2) and oxygen and diluting with nitrogen in the stagnation chamber of a continuously
operating wind tunnel. If the stagnation pressure is 20 atm, what is the maximum stagnation
temperature that could be reached and still have Venus atmosphere conditions? If the stagnation
pressure were 1 atm, what would be the maximum temperature? Assume all gases enter the
chamber at 298 K. Take the heat of formation of cyanogen as ( ΔH 0f ) = 381.84 k/mol.
298

Solution: In order to maintain Venus atmosphere, the composition of 100 moles of products
would have to be 5 CO2 + 95 N2. Eqn. (10) in the textbook can be used to calculate the
stagnation temperature of this system. This equation can be simplified for the general case when
H 0T0 = H0298 . For Q = 0, the modified equation becomes:
17 0

∑ n ⎡⎣( H
i
0
T2 )
− H 0298 + (Δ H 0f ) ⎤ =
⎦
298 i ∑ n ⎡⎣( H
j
0
T1 )
− H 0298 + (Δ H f0 )
298
⎤
⎦j (1)
 i prod i j react j

In this Equation, T2 and T1 are the temperatures of the products and reactants respectively. Since
the conditions for the reactants are specified the solution approach is to find T2 such that the
above equality will be satisfied.

(a) for Venus atmosphere the general combustion reaction would be

a C2N2 + b O2 + c N2 → 5 CO2 + 95 N2

which can be balanced for one mole of C2N2 as follows:

C2N2 + 2 O2 + 36 N2 → 2 CO2 + 38 N2,

In preparation to apply Eqn. (1) the following tables can be generated.

gases ΔH 0f (kJ mol ) H 0T1 − H0298 ( kJ mol )

C2N2 381.84 0.0
O2 0.0 0.0
N2 0.0 0.0

An expression for the enthalpy of the reactants (Hr, given by the right-hand side of Eqn. (1)) in
terms of the enthalpy of the individual gases in the reactants becomes:

Hr = 1( 381.84 + 0.0)C N + 2 ( 0.0 + 0.0 )O + 36 (0.0 + 0.0 )N = − 381.84 kJ

2 2 2 2

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For the products it follows that:

gases ΔH 0f (kJ mol )

N2 0.0
CO2 −393.77

Thus, an expression for the enthalpy of the products (Hp, given by the left-hand side of Eqn. (1))
( )
in terms of the enthalpy of the individual gases in the products becomes let ΔH = H 0T2 − H 0298 :

( ) (
Hp = 2 −393.77 + ΔH CO2 + 38 0.0 + ΔH N 2 )
Equating Hr and Hp yields:

2 ΔH CO2 + 38 ΔH N2 = 1,169.37

A first guess for the products temperature can be obtained by assuming that all product gases are
N2. This approach gives the following as an initial guess for T2 (Note that 40 = 2 + 38):

40 ΔH N2 = 1,169.37 so
ΔH N2 = 29.23kJ mol , therefore, T2 ≈ 1232 K

We will then assume that T2 is between 1200 and 1300 K. If that is so, we can develop the
following table (all ΔH’s are in kJ/mol and (Hp - Hr)'s are in kJ):

T2 ΔH CO2 ( kJ mol ) ΔH N2 Hp − Hr (kJ)

1200 44.51 28.13 −11.51
1300 50.19 31.52 17 0
128.87

Interpolate 1200 −11.51

 T2 00
1300 128.31

T2 − 1200 11.51
=
100 139.88

so T 2 = 1208 K

Since K P,f( CO2 ) = 1.75 ×1017 at 1200 K, no significant dissociation of the products occurs.
Therefore, pressure has no effect and T2 would remain the same at all pressures.
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18


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Problem 9
A mixture of 1 mole of N2 and 0.5 mole O2 is heated to 4000 K at 0.5 atm pressure and results in
an equilibrium mixture of N2, O2, and NO only. If the O2 and N2 were initially at 298 K and the
process is one of steady heating, how much heat was required to bring the final mixture to 4000
K on the basis of one initial mole of N2?

Solution: The first step is to find the equilibrium concentration of products. Once this is done,
one can use Eqn. (1.10) to calculate the17 amount
0 of heat necessary to bring the final mixture to
4000 K. Consider the following reaction at equilibrium.
 1
1 N 2 + O 2 → a N 2 + b O 2 + c NO (1)
2

balancing this reaction yields the following relationship between a, b and c.

N: 2 = 2 a + c
0: 1 = 2 b + c

Solving these two equations for b and c in terms of a it follows that

2a −1
b= and c = 2 − 2a
2

Therefore, Eqn. ( 1) becomes:

2a − 1
1N 2 + 0.5O 2 → a N 2 + O 2 + ( 2 − 2a ) NO
2

1 1
For the equilibrium reaction given by N2 + O2 ⇔ NO , the expression for the equilibrium
2 2
constant of formation is given by:

1−1 2−1 2
n ⎛ P ⎞
K P,f (NO ) = 1/ 2NO 1/ 2 ⎜ ⎟
n N 2 nO 2 ⎜⎝ ∑ n ⎟⎠

2a −1
The total number of moles is given by ∑n= a+
2
+ 2 − 2a = 3 . At 4000 K, 1og10 KP,f(NO) =
- 0.524 or KP,f(NO) = 0.29923. Squaring Eqn. (3) would give the following equation for the
variable a:

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( 2 − 2a ) 2
− K 2P,f( NO) = 0,
2a − 1
a
2

Solving for a in the above equation and then using the mass balance equations to solve for b and
c yields: a = 0.909, b = 0.409 and c = 0.182. Equation (2) now becomes

1 N2 + 0.5 O2 → 0.909 N2 + 0.409 O2 + 0.182NO

The amount of heat required to bring the above mixture to 4000 K is calculated using Eqn. (1.10)
in the text by taking T2 = 298 K and T1 = 4000 K:

−Q = ∑ n ⎡⎣( H
i prod
i
0
T2 )
− H 0298 + (Δ H 0f ) ⎤ −
298 ⎦i
∑ n ⎡⎣( H
j react
j
0
T1 )
− H 0298 + ( Δ H 0f )
298
⎤
⎦j
(4)

from tables in the text one has:

gases ΔH 0f (kJ mol ) H 0T1 − H 0298 (kJ mol ) H 0T 2 − H0298 (kJ mol)
O2 0.0 139.01 0.0
N2 0.0 130.16 0.0
NO 90.43 132.76 0.0
17 0
so the equation for Q becomes
− Q = 0.182( 90.43 + 132.76) NO + 0.409( 0.0 + 139.01) O + 0.909 ( 0.0 + 130.16)N −
2 2

1 (0.0 + 0.0 )N2 − 1/ 2 (0.0 + 0.0 )O2

so Q = - 215.79 kJ

if no dissociation occurred the value of Q would be

− Q = 1/ 2 ( 0.0 + 139.01)O + 1( 0.0 + 130.16 )N −

2 2

1 (0.0 + 0.0 )N2 − 1/ 2 (0.0 + 0.0 )O2

so Q
 = - 199.67 kJ

Therefore, more energy is required to raise the temperature of the mixture to 4000 K due to
dissociation.

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Problem 10
Calculate the adiabatic decomposition temperature of benzene under the constant pressure
condition of 20 atm. Assume that benzene enters the decomposition chamber in the liquid state at
298 K and decomposes into the following products: carbon (graphite), hydrogen, and methane.

Solution: The solution for this problem is an iterative one. In order to calculate the final
temperature of the mixture, one needs the composition of the mixture at equilibrium. But the
composition of the mixture can only be found if the final temperature is known. Therefore, one
will guess the final temperature and calculate the mixture composition using the equilibrium
concept. Once the composition is know at the guessed temperature, the adiabatic flame
temperature is calculated and checked against the guessed value. This process is repeated until
the guessed and calculated temperatures are obtained. Consider the following reaction at
equilibrium:

C6H 6 (1) → a C (s) + b H 2 + c CH 4 (1)

balancing this reaction yields the following relationship between a, b and c.

C: 6 = a + c
H: 6 = 2 b + 4 c

solving these two equations for a and b in terms of c it follows that

6 − 4c
b= = 3 − 2c and a = 6 − c
2

Therefore, Eqn. (1) becomes:

6 − 4c
C6 H6 (1 ) → ( 6− c) C(s ) + H2 + cCH4 (2)
2

Now consider the equilibrium reaction given by

C(s) + 2 H2 ⇔ CH4

For this equilibrium reaction, the expression for the equilibrium constant of formation of CH4 is

1 −2
n CH ⎛ P ⎞
KP,f (CH 4 ) = KP = 2 4 ⎜⎜ ⎟ (3)
n H2 ⎝ ∑ n ⎟⎠ 17 0
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17 60 − 4c
The total number of moles is given by ∑n = 2
+ c = 3 − c (note that the number of moles of
graphite are not included in the calculation for the total number of moles at equilibrium).
Equation (3) then becomes:

c b+ c
− KP = 0
b2 20

expressing b in terms of c gives:

c 3+c
− KP = 0 (4)
(3 − 2c ) 20
2

In order to calculate the adiabatic flame temperature one has to apply Eqn. (1.11) in the text
taking T1 = 298 K.

−Q = 0 = ∑ n ⎡⎣( H
i prod
i
0
T2 )
− H 0298 + ( ΔH f0 )
298
⎤ −
⎦i ∑ n ⎡⎣( H
j react
j
0
T1 )
− H0298 + ( ΔHf0 ) ⎤
298 ⎦ j
(5)

With Eqns. (4) and (5) the iterative process may now start. Since the conditions for the reactants
are specified (T1 = 298 K), Table 1 in the text provides the following thermodynamic properties:

gases ΔH 0f (kJ mol ) H 0T1 − H0298 ( kJ mol)

C6H6 (1) 49.03 0.0

And the enthalpy of the reactants (Hr, given by the right-hand side of Eqn. (5)) can be calculated
as:

Hr = 1 (49.03)C6H6 (1) = 49.03 kJ

Let us first guess that T2 = 1000 K; therefore, logl0 KP = - 1.011 or KP = 0.097499. Solving Eqn.
(4) for c using this value of KP and then solving the mass balance equations for a and b results
in:

c = 0.9943, b = 1.0114, and a = 5.0057

For a product temperature of 1000 K, application of Eqn. (5) using the values of a, b, and c found
above yields:

T2 ΔHC( s) ( kJ mol ) ΔHH 2 ΔHCH4 Hp Hp − H r (kJ)

1000 8.47 20.70 38.20 26.87 −22.16

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If T2 = 1100 K, logl0 Kp. = - 1.44 or KP = 0.03631. Solving Eqn. (4) for c using this value of KP
and then solving the mass balance equations for a and b gives:

c = 0.7409, b = 1.5182, and a = 5.2591

Following the same procedure as previously outlined yields:

T2 ΔHC( s) ( kJ mol ) ΔHH 2 ΔHCH4 Hp Hp − H r (kJ)

1100 14.01 23.74 45.58 88.01 38.98

Interpolation for the value of temperature where Hp − Hr = 0 yields T2 ~ 1036 K.

At T2 = 1036K, logl0 Kp = -1.1654 or Kp = 0.06832, c = 0.9101, b = 1.1798, a = 5.0899 and

T2 ΔHC( s) ( kJ mol ) ΔHH 2 ΔHCH4 Hp Hp − H r (kJ)

1036 10.47 21.79 40.86 48.02 −1.01
17 0
Since Hp − Hr ~0 T 2 ~ 1036 K
 23

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