Thermodynamics CH

Chapter 9 Solutions
Engineering and Chemical Thermodynamics 2e
Milo Koretsky
Wyatt Tenhaeff
School of Chemical, Biological, and Environmental Engineering
Oregon State University
milo.koretsky@oregonstate.edu
9.1
You need to neglect the solid in the vapor mole fraction
yD
2
y A yB P
9.2
o
Some products can form. Since g rxn
0 , K < 1. But some products form
9.3
o
g rxn
,298 = -500 J/mol and KT = 4
9.4
It would not change
9.5
The value of the equilibrium constant does not depend on pressure; it would not change
9.6
(a)
Yes since there are more moles of reactant see Example 9.5
(b)
No - inspection of Appendix A3 shows that this reaction is exothermic, equilibrium conversion
decreases with increasing temperature
(c)
No since there are more reactants - see Example 9.5
9.7
Yes, but only if it is rate limited (kinetics). Equilibrium conversion decreases for this exothermic
reaction
9.8
(d) High pressure increases conversion, high temperature increases rate.
9.9
1
AP
10
9.10
To find the equilibrium constants we look at the concentrations at long time. Assuming ideal
solutions, we get
xB 0.125
2
x A2 0.252
x
0.25
K2 C
2
xB 0.125
K1
11
9.11
It does not change
12
9.12
No
13
9.13
Largest
0.1 m CaCl2
0.1 m NaCl
0.1 m scrose
smallest
14
9.15
C on the Ga site
C on the As site
15
9.16
(a) Both are approximately the same
(b) Ge
16
9.16 (second one)

(a) Ge
(b) Ge
17
9.17
The reaction is
H2O (l) + O2 (g) H2O2 (l)

The Gibbs energy of reaction is calculated as follows
grxn,298
g f ,298
g f ,298
H 2O
grxn,298
g f ,298
H 2O
H 2O2
Therefore,
f ,298 H O
2 2
From Appendix A.3.2:
f ,298
kJ
237.14
H 2O
mol
kJ
kJ
237.14
116.8
H 2O2
mol
mol
kJ
gf ,298 H2O2 120.34 mol
f ,298
18
9.18
We will simplify the problem by assuming the gaseous reaction mixture behaves ideally. This
assumption is valid since the temperature is 1300 K and the pressure is 1 bar. We first need to
obtain expressions for H , TS , and G :
H H H 0 n I hI n I 2 hI 2 n I0 h I 2
2
Assuming we start with 1 mole of I2 and no I, we have:
nI 2 1
n I 2
Therefore,
1
H 2 hI 1 hI 2 hI 2 2 hI hI 2
2
Applying the definition of the heat of formation gives:

H 2h f , I
For entropy, we must also include the entropy of mixing term after the reaction has commenced:
S n I s I n I 2 s I 2 s mix n I0 s I 2
2
So
1
S 2 sI sI 2 R nI ln yI nI 2 ln yI2
2

or
S 2s f , I R nI ln yI nI2 ln yI2
:
We can find the change in Gibbs energy from its definition:
G H TS
Now we can create a spreadsheet that computes the desired quantities for various extents of
reaction. Plotting the data in the table, we obtain
19
Thermodynamic Quantities as a Function of Extent of Reaction

160000
H
140000
S
120000
100000
(J)
80000
60000
40000
20000
G
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
-20000
Extent of Reaction ()
To find the equilibrium conversion, we must locate the minimum on the plot of G. This occurs
when
0.23
At this extent of reaction
yI 0.37
yI 2 0.63
20
9.19
The Gibbs energy of formation of NH3 can be calculated by considering the following reaction:
1
3
N 2 H 2 NH 3
2
2
At 298 K,
3 J
g rxn
,298 16.45 10
mol
3 J
hrxn
,298 46.11 10
mol
Therefore,
16.4510 3 J/mol
764.76
K 298 exp
8.314 J/mol K 298 K
We will use Equation 9.24 to calculate the equilibrium constant at 1000 K, but to do so, we need
heat capacity data from Appendices A.2 and A.3:
A 2.9357 , B 0.00209 , C 0, D 33050

Substituting numerical values into Equation 9.24 and evaluating, we obtain
K1000 5.6 10 4
Therefore,
grxn,1000
8.314 1000 ln 5.6 10 4 62250
mol
Since the Gibbs energies of formation of N2 and H2 are zero at 1000 K,
grxn,1000
g f ,1000
f ,1000
NH 3
NH 3
kJ
62.25
mol
21
9.20
First, calculate the equilibrium constant. From data in Appendix A.3
3 J
g rxn
, 298 88.51 10
mol
3 J
hrxn
,298 126.1 10
mol
Use Equation 9.20:
h 1 1
rxn
K1000 K 298.15 exp

R
T2 T1
88.51103 126.110 3 1
1
K1000 exp
exp
1000 298.15
8.314
8.314 298.15
K1000 1
Take 1 mole of C4H8 as the basis for the calculations. Create expressions for the compositions of
the reaction components as functions of conversion:
1
11
10
yH 2
11
yC 4 H 8
yC 4 H 10
11
The gas is assumed ideal; therefore,
yC4 H10
K P 1
yC4 H8 yH 2
11
1
1 5 bar
1 10

11 11
Solving:
0.818
Therefore,
22
nC 4 H 10 10.818 0.818 mol

nC 4 H 8 1 0.818 0.182 mol
nC 4 H 10
nC 4 H 8
4.49
23
9.21
(a)
The reaction is
SO2 (g) + O2 (g) SO3 (g)

From Table A.3.2.
Species
h f ,298 kJ/mol
g f ,298 kJ/mol
SO2
O2
SO3
-296.813
0
-395.77
-300.1
0
-371.02
From these data:
3 J
g rxn
, 298 70.92 10
mol
3 J
hrxn
, 298 98.96 10
mol
Use Equation 9.21:
h 1 1
rxn
K 973 K 298 exp

R
T2 T1
70.92 10 3 98.96 10 3 1
1
K 973 exp
exp
973 298
8.314
8.314 298
K 973 2.5
(b)
Take 1 mole of SO2 as the basis for the calculations. Create expressions for the compositions of
the reactor components as functions of conversion:
1
5.76 / 2
1 / 2
yO2
5.76 / 2
y SO 2
yN2
3.76
5.76 / 2
y SO3
5.76 / 2
Since the temperature is 700 C and the pressure is 1 bar, the gas can be assumed ideal.
Therefore,
24
1 ySO3
K 1/2
P ySO yO 1/2
3
2
1
5.76 / 2
2.5
1/2
1/2
1 bar 1 1 / 2
5.76 / 2 5.76 / 2
Solving, we get
0.481
The compositions are calculated using the extent of reaction
y SO 2 0.094
yO2 0.138
y N 2 0.681
y SO3 0.087
(c)
The energy balance around the reactor is
hout hin q
Since the reaction is isothermal, the change in enthalpy comes from the enthalpy of reaction.
Therefore,
kJ
q
mol
hrxn 0.481 98.96
kJ
q 47.6
mol
(d)
The equilibrium constant does not change with pressure; however, the term
KP1 / 2
increases, which is equal to
25
y
y y
SO3
1/2
SO3
O2
5.76 / 2
1/2
1 1 / 2
5.76 / 2 5.76 / 2
Therefore, the extent of reaction increases.

(e)
The equilibrium constant is a function of temperature only, so increasing pressure does not
change the equilibrium constant.
(f)
An increase in pressure is justified because the extent of reaction will increase.
26
9.22
The reaction is
SO2 (g) + O2 (g) SO3 (g)
is described by the following equation

The variation of hrxn
1
B 2
C 3
1
hrxn
hrxn,298
R A T 298
T 2982
T 2983 D
T 298
2
3
The A, B, C, and D parameters are calculated with data from Table A.2.2:
Species
SO2
O2
SO3
v
-1
-1/2
1
B 10 3
0.801
0.506
1.056
A
5.699
3.639
8.06
C 10 6
0
0
0
D 10 5
-1.015
-0.227
-2.028
1
3.639 18.06 0.5415
2
1
B 1 0.801103 0.506 10 3 11.056 10 3 2 10 6
2
C 0
1
D 1 1.015 10 5 0.227 10 5 1 2.02810 5 8.99510 4
2
A 1 5.699
From Problem 9.21:
3 J
hrxn
,298 98.96 10
mol
Therefore, at 700 C:
2 10 6 2
0.5415
T
298
T 2982
J
J
2
8.314
hrxn
98.96 10 3
mol
mol
1
4 1
8.99510 T 298
Substituting the above expression, we get
2 106 2
T 2982
0.5415 T 298
2
J
J
98.96 103
8.314
1
1
mol
mol
8.995 104
d ln K
T 298
dT
RT 2
27
Integrating:
ln
K 973.15
27.67
K 298
At 298 K
K 298 2.66 1012
Therefore,
K 973.15 2.56
28
9.23
(a)
The reaction is
3 H2 (g) + C6H6 (g) C6H12 (g)

From Table A.3.2:
Species
h f ,298 kJ/mol
g f ,298 kJ/mol
H2 (1)
C6H6 (2)
C6H12 (3)
0
82.98
-123.22
0
129.75
31.78
From these data:
3 J
g rxn
, 298 98.0 10
mol
3 J
hrxn
,298 206.2 10
mol
We do not need to calculate the composition at the exit of the first reactor to determine the
equilibrium composition at the exit of the second reactor. For the second reactor, Equation 9.21
gives:
h 1
1
rxn
K 538 K 298 exp

R T2 298.15
98.0 10 3 206.2 10 3 1
1
K 538 exp
exp
538.15 298.15
8.314
8.314 298.15
K 538 11.44
y1
y3
10 3
11 3
y2
11 3
The gas is assumed ideal. Therefore,
29
1
11 3
1
P3
y3
3
y1 y2
1
11 3
11.44
3
3
5 bar 1 10 3
11 3 11 3
Solving, we get
0.999
Therefore, the final compositions are
y1 0.875
y3 0.125
y2 0
(b)
The purpose of the first reactor is to increase the speed the reaction process. At higher
temperatures, more collisions occur with sufficient energy to overcome the activation energy of
the reaction. However, as the temperature increases, the conversion decreases. The second
reactor increases the conversion.
(c)
Less product will be obtained if the pressure decreases. This becomes clear be rearranging the
expression for equilibrium:
K P3
11 3 3
1 10 3 3
Therefore, as the left-hand side decreases due to lower pressures, the right hand-side decreases
correspondingly resulting in a lower extent of reaction.
(d)
Addition of inert will cause the yield to decrease. The inert molecules interfere with collisions
between reactant molecules. In other words, the reactant molecules collide less frequently.
Dilution is not recommended.
30
9.24
(a)
First, obtain an expression for the equilibrium constant. From data in Appendix A.3:
3 J
g rxn
,298 241.6 10
mol
3 J
hrxn
,298 293.5 10
mol
Use Equation 9.20 (assume the heat of reaction is constant):
hrxn
1
1
KT K 298.15 exp

R T 298.15
241.6 103 293.510 3 1
1
KT exp
exp

8.314 298.15 8.314 T 298.15
Take 1 mole of SiCl4 and 2 moles of H2 as the basis for the calculations. Create expressions for
the gas-phase components as functions of conversion:
1
3
2 2
yH 2
3
y SiCl 4
y HCl
4
3
Now calculate the required equilibrium constant needed to obtain the given conversion. For the
specified conversion,
0.75
Therefore,
y SiCl 4 0.0667
y HCl 0.8
y H 2 0.133
If the gas is assumed ideal,
4
yHCl
KP
2
y
SiCl4 yH 2
31
0.8
K 0.001 bar
2
0.0667 0.133
K 0.347
Now we can solve for the required temperature:
241.6 10 3 293.510 3 1
1
0.347 exp
exp

8.314 298.15 8.314 T 298.15

T 1605 K
(b)
i. Decreasing the pressure will reduce the minimum temperature because the pressure appears in
the numerator. As the pressure is decreased, the required equilibrium constant decreases.
ii. Diluting the feed stream will decrease the required minimum temperature. For this proposed
ratio, the mole fraction of hydrogen essentially remains constant at one despite the reaction.
Therefore, the equilibrium constant becomes equal in magnitude to the pressure, which is less
than the equilibrium constant in Part (a). Therefore, the temperature can be lower.
32
9.25
(a)
The reaction is
C 2 H 4 g Cl 2 g C 2 H 4 Cl 2 g
Let C2H4 be species 1, Cl2 be species 2, and C2H4Cl2 be species 3. Create expressions for the
compositions of the reaction components as functions of conversion:
1
3
2
y2
3
y1
y3
For 90% conversion, 0.9 . Therefore,

y1 0.0476
y 2 0.524
y3 0.429
Now calculate the equilibrium constant:
0.429
K 1 bar 1
0.5240.0476
K 17.2
From Appendix A.3:
3 J
g rxn
, 298 141.29 10
mol
3 J
hrxn
, 298 182.26 10
mol
To calculate the minimum temperature we can use Equation 9.21.

ln
17.2
141.29 10 3
exp
8.314 298.15
182.26 10 3
8.314
1
1
T 298
T 1131 K
33
(b)
The equilibrium constant remains the same, but the fugacity terms in the expression for the
equilibrium constant are different. The expression is
1
KP
1 2
1 3 2 3

We calculate the fugacity coefficients using
i exp b
a P
RT RT
The following table was created with the above equation

Species
C2H4 (1)
Cl2 (2)
C2H4Cl2 (3)
1.00
0.996
0.977
Therefore,
0.977
17.2 30 bar 1
1
2
0.996

1.00
3
3
0.996
34
9.26
The equilibrium constant can be expressed as follows
4
y P f
SO2 SO2 CaO
fSO2 fCaO
K
3
f
f
CaSO4
Ca
f
CaSO4 fCa
We can assume that the solids form distinct phases and are immiscible with each other.
Furthermore, the gas is assumed ideal. Therefore,
4
K p SO
2
We also have another relationship involving K assuming the heat of reaction is independent of
temperature:
ln K
1
hrxn,298
C
T
R
Below, we have plotted ln K vs. 1/T with data given in the problem statement.
T (C)
T (K)
1/T (K)
pSO2 (bar)
ln(K)
900
960
1000
1040
1080
1120
1173.15
1233.15
1273.15
1313.15
1353.15
1393.15
0.000852
0.000811
0.000785
0.000762
0.000739
0.000718
0.00533
0.0253
0.0547
0.11
0.206
0.317
8.07E-10
4.10E-07
8.95E-06
1.46E-04
1.80E-03
1.01E-02
-20.9376
-14.7078
-11.6236
-8.8291
-6.31952
-4.59541
ln K vs. 1/T
0
0.0007
0.00075
0.0008
0.00085
ln K
-5
-10
y = -121600x + 83.40
R2 = 0.991
-15
-20
-25
1/T (K-1)
35
0.0009
We can see there is a systematic deviation from the linear fit, indicating the enthalpy of reaction
is not constant. From the slope, we obtain
kJ
hrxn
,298 1011
mol
Now we can use the following expression to obtain g rxn

, 298 at each temperature.
g
h
1
rxn,298
rxn,298 1
K exp
exp

T 298
R
R 298 K
T (K)
1173.15
1233.15
1273.15
1313.15
1353.15
1393.15
grxn,298
(kJ mol-1)
805.6
802.6
802.6
802.9
803.5
805.6
Calculate the average

kJ
g rxn
, 298 803.8
mol
36
9.27
(a)
From data in Appendix A.3:
3 J
g rxn
,298 50.72 10
mol
Therefore,
50.72 10 3
1.29 109
K exp
8.314 298
(b)
3 J
hrxn
, 298 74.81 10
mol
Calculate K with Equation 9.21:
74.8110 3 1
1
K 1.29 10 exp
2.04
8.314 1000 298
9
(c)
Create expressions for gas compositions in terms of conversion:
2
1
yCH 4
1
1
Note: The moles of carbon are not considered when developing these expressions
because it is in the solid phase.
yH 2
The expression for the equilibrium constant:
4 2
K P
1 1
4 2
2.04 0.01 bar
1 1
Solve for :
37
0.99
The amount of H2:
n H 2 2 1.98 mol
(d)
We run at 1000 K because it increases the reaction rate and equilibrium conversion.
(e)
Pressure appears in the numerator of the expression for the equilibrium constant. Decreasing the
pressure makes
4 2
K
P 1 1
larger. Correspondingly, the equilibrium conversion must be larger.
38
9.28
(a)
Use the following equation
v
xi i fi i
K o
fi
which for ideal solutions reduces to
K xi
vi
To find the mole fractions of A and A2, we apply the following constraint:
x 1
i
Find the mole fractions of A and B by equating liquid and vapor fugacities.
yA P x A PAsat
yB P xB PBsat
1 / 3 0.1 atm 1
2 / 3 0.1atm 2
xA
xB
3
15
0.1 atm
0.5 atm
Therefore,
x A2
8
15
Now calculate the equilibrium constant
8 /15 4.8
2
1 / 3
(b)
Multiply the total number of moles by the liquid mole fractions:
n A 166.7 moles
n A2 266.7 moles
n B 66.7 moles
39
(c)
If the dimerization reaction does not occur, then for every mole of A2 calculated in Part (b), two
moles of A actually exist. Therefore,
n A total n A 2n A2 700 moles
(d)
Equate the liquid and vapor fugacities of species B.
y B P x B B PBsat
Hence,
yB P
2 / 3 0.1 atm
1.53
sat
xB PB
66.7 mol
0.5 atm
700 mol 66.7 mol
(e)
Both the model containing the dimerization reaction and the colleagues model represent the
data. There is no reason to exclude one or the other; they are different ways of viewing reality.
Since the colleagues model will always predict more moles of A in the liquid phase than the
total number of moles, the model can only predict positive deviations from ideality. However,
solvation reactions can be used to predict negative deviations.
40
9.29
(a)
First, calculate the equilibrium constant. From data in Appendix A.3:
grxn,298
113.5 10 3
mol
J
hrxn,298
164.94 103
mol
The A, B, C, and D parameters are calculated with data from Table A.2.2:
Species
CH4
H2O
CO2
H2
v
-1
-2
1
4
B 10 3
9.081
1.45
1.045
0.422
A
1.702
3.470
5.457
3.249
C 10 6
-2.164
0
0
0
D 10 5
0
0.121
-1.157
0.083
A 9.811
B 9.248 103
C 2.164 106
D 1.067 105
Using Equation 9.24, we get

K 773 0.0503
(Alternatively if we assume hrxn

= const, we can use Equation 9.20:
h 1 1
rxn
K 2 K1 exp

R
T2 T1
113.5103 164.94 103 1

1
K 773 exp
exp
773.15 298.15
8.314
8.314 298.15
K 773 0.00739
Take 1 mole of CH4 as the basis for the calculations. Create expressions for the compositions of
yCH 4
1
6 2
yCO 2
41
6 2
yH 2O
5 2
6 2
yH 2
4
6 2
Since the temperature is 500 C and the pressure is 1 bar, the gas can be assumed ideal.
Therefore,
4
y
y
CO
H
2
2
K P2
2
y
CH 4 yH 2O
4 4

2 6 2 6 2
0.00739 1 bar
1 5 2 2

6 2 6 2
Solving:
0.576
Therefore,
nH 2 4 0.576 2.30 mol
(Alternatively, solving if we assume hrxn

= const):
0.423
Therefore,
nH 2 4 0.423 1.69 mol

These values are significantly different)
(b)
At the process conditions, a higher conversion can never be achieved. Equilibrium is the upper
limit. However, low conversions may be achieved. Equilibrium does not say anything about the
kinetics. Kinetic considerations may result in lower conversions.
(c)
Increasing the pressure does not make sense. In order to increase conversion, you should
decrease the pressure since the pressure term appears in the numerator of the expression for the
equilibrium constant.
42
9.30
(a)
The fugacity can be found as follows
P
f iv
v
dP
RT
ln
i
Plow
Plow
For the EOS given in the problem statement
1
vi RT Bi'
P
Therefore,
fv P 1
'
ln i Bi
Plow
Plow P
dP ln P B ' P P
i
low
P
low
Let Plow go to zero and simplify:

'
i
iv e B P
For H2S and SO2
Hv S e
BH' 2 S P
v
SO
e
'
BSO
P
2
(b)
The equilibrium constant can be calculated at 500 C (773.15 K) with the following equation
K
773.15 K hrxn,298
1 C T 298 dT
ln 773.15
2
K 298.15 298.15 K RT
773.15 K hrxn,298
grxn,298
1 C T 298 dT
exp
K 773.15 exp

2
RT
298.15 K RT
From data in Appendix A.3

J
g rxn
, 298 90,440
mol
43
hrxn
, 298 145,830
mol
Substituting these and other values from the problem statement into the expression for the
equilibrium constant provides
K 773.15 0.824
(c)
Consider a basis of 3 moles of H2S and 1 mole of SO2. Create expressions for the mole fractions
of the gaseous species as functions of extent of reaction:
1
4
2
yH 2O
4
y SO2
y SO2
3 2
4
The equation for the equilibrium constant can be written as follows:
SO2
H 2O H 2O
SO P yH S H S
2
P y y
H 2O
H 2O
SO2
H 2S
SO2
P 1
H2S
(We are approximating the fugacity coefficients by the pure species fugacity
coefficients.)
We have expressions or values for all of the variables in the above expression except H 2 O .
From the steam tables:
kJ
h 3373.6
kg
kJ
g 1726.5
kg
kJ
s 6.5965
kg K
J
g 31102.6
mol
kJ
h 3489.0
kg
kJ
g 4163.4
kg
kJ
s 9.8977
kg K
J
g 75002.8
mol
We can calculate the fugacity from the following equation
44
(500 C, 10 MPa)
(500 C, 10 kPa)
fv
g g RT ln
Plow
Substituting values, we obtain

f Hv O 9.25 MPa
2
Therefore,
H O 0.925
2
Now solve the following equation for the extent of reaction.

2
2
2
0.925
4
0.824
2
1 3 2 exp 4.4 109 10 10 6 exp 2.2 10 9 10 10 6
4 4
100 bar
0.915
(d)
By Le Chateliers principle, you would want to increase the pressure.
(e)
Assume that the fugacity coefficients are equal to unity and solve the following equation.
2
2 0.95
1
P
4 0.95
0.824
2
5
1 0.95 3 2 0.95 110
4 0.95 4 0.95
P 221 bar
(f)
Since the reaction is exothermic, you would want to lower the temperature as low as possible in
order to maximize conversion. However, in a real reactor it is better to change pressure because
you want to keep the temperature high for kinetic reasons.
45
(g)
The addition of inerts would lower the conversion. This becomes apparent mathematically by
examining the expressions for the mole fractions in the equilibrium constant equation. However,
it can also be explained physically. The inert molecules block the collisions between gaseous
reactant molecules (more gaseous reactant molecules than gaseous product molecules), so fewer
reactions occur, and the overall conversion is less.
46
9.31
A sketch of the process follows:
P = 1.5 bar
1 mol/s H2
2 mol/s CO
1 mol/s CO2
T=?K
0.40 mol/s H2O

H2
CO
CO2
We first have to determine the chemical reaction occurring. No other species are involved in the
reaction, so lets look at the possibilities. To make H2O we need to react H2 with one or both of
the oxygen containing components. Reacting CO with H2 to produce H2O would also produce
C, which is not an option. Therefore, the reaction for our system must be:
H2(g) + CO2(g) H2O(g) + CO(g)
Next, from table A.3.2
Species (all gas)
hf,298[kJ/mol]
gf,298[kJ/mol]
H2
CO2
H2O
CO
0
-393.51
-241.82
-110.53
0
-394.36
-228.57
-137.17
From these data:

grxn,298 = 28.62
10
hrxn,298 = 41.16
10
Use Equation 9.21:
KT =K298 exp
KT =exp
.
.

exp
.
.
Next, lets examine the number of moles of each species as a function of the extent of a reaction:
47
Species
Initial number of
moles/s (n)
nH2
nCO2
nH2O
nCO
nT
1
1
0
2
4
Number of moles/s
being produced
()
-1
-1
1
1
0
Moles/s of species
as a function of
1-
1-
2+
4
We know what nH2O at the outlet (at equilibrium) is, so we know .

0.4
Now we can look at our mole fractions:

Species
yH2
yCO2
yH2O
yCO
yi
Mole fraction
0.15
0.15
0.1
0.6
1
Next, setting up the equilibrium constant given our known information

.
K=
2.67
Now set sides of our equilibrium constant equation equal to each other and solve for T.
2.67 = exp
.
.
exp
.
.
T = 1213 K
48
9.32
(a)
First, write out the expressions for the moles of each species as a function of the extent of
reaction, . From these, we calculate the gas-phase mole fractions:
nA nA 1
nC nC 2 2
, nT 1
1
1
2
yC
1
yA
Now apply Equation 9.27 (we are told to assume an ideal gas phase):
2
K 4 yi i
v
4 1 2 12 2
2 2
2
1 P
2
2 P
( yC P)
12 2
P
( y A P)1
1
1 1 1 2
P
1
12 mole A reacted .
Since mole of A reacted, and 2 moles of C are formed per mole of A consumed,
nC 1 mole
(b)
Looking at the expression for K given above, we can write:
K
4 2
P 1 2
Recall that we can also write the equilibrium constant as K e
g rxn
RT
(a constant at any T).
Since K is constant at any given temperature, and the expression in the right hand side is greater
than one for all physically valid conversions (what is the domain of ?), a lower P will generate
a higher conversion (or ).
49
9.33
(a)
C3H8O (g) C3H6 (g) + H2O (g)
K298 =
grxn =
K=
62.76
(b)

From the Antoine equation
Pbsat 0.031 bar
Pasat 0.027 bar

3
3.62
1.14
From the equilibrium constant expression:

3
0.67
50
228.57
163.08
3
(c)
0.009
0.013
0.977
51
2.11
9.34
You wish to generate H2 through a gas-phase reaction of pentane with steam. The feed is 1 mole
C5H12 per 10 moles of water, at 0.5 bar. You need 98% conversion.
(a) Calculate the minimum temperature to achieve 98% conversion (assuming hrxn
is constant).
The reaction scheme is given by:

5 CO + 11 H 2
C5 H12 + 5 H 2 O
(1)
(2)
(3)
(4)
The feed has molar compositions n1 1 mole and n2 10 mole . Writing the mole balances for
the four individual species lets us find the overall molar change as a function of :
n1 1
n2 10 5
n3 5
n4 11
nTv 11 10
Since we know that 0.98 (from the problem statement), we can compute the gas-phase mole
fractions for each component:
n1 0.02
y1 0.000962
n2 5.1
y2 0.245
n3 4.9
y3 0.236
n4 10.78
y4 0.518
n 20.8 moles
P 0.5 bar
v
T
Write an expression for the equilibrium constant, KT, of the mixture at the unknown temperature:
( y3 P)5 ( y4 P)11 ( y3 )5 ( y4 )11 P10

KT
0.00060
( y1 P)( y2 P)5
( y1 )( y2 )5
The K value above doesnt have any temperature dependence. This will come from the enthalpy
of formation in the next steps. From Appendix A.3, we can tabulate the standard Gibbs energy
and enthalpy of formation for each species in the gas phase:
52
g f ,298 K kJ/mol
hf ,298 K kJ/mol
Species
i
-1
C5H12
- 8.37
-146.54
+5
CO
- 137.17
-110.53
- 228.57
-241.82
-5
H2O
Next, calculate the Gibbs energy and heat of reaction of the overall reaction, and the equilibrium
constant K for the reaction (note that this K is different from the K we computed from the gasphase composition above):
g rxn
,298 K g f ,298 K 465.37 kJ/mol , and
i
rxn ,298 K
hf ,298 K 802.99 kJ/mol

i
g rxn
,298
82
K 298 exp
2.66 10 .
RT
Note that the K value is for equilibrium the reference temperature, 298K, but unless were really
lucky (hint: dont bet on it), the reaction is probably not occurring at exactly that temperature.
What does the magnitude of K298 tell you about how much pentane will react at room
temperature?
We can introduce the temperature dependency by correcting the K value using Equation 9.21:
ln
hrxn
1
KT
,298 1
K 298
R
T 298
Substituting the values of KT and K298 provides an equation with only one unknown: T.
180.4
802,990 J/mol 1
1
8.314 J/mol K T 298
Solving for the unknown T, we find that the reaction temperature must be
T 672 K 400C
(b) In Part (a), we made the implicit assumption that the enthalpy of reaction is not a function of
temperature. While this may be justifiable for a small deviation from the reference temperature,
we are operating 375C higher than the reference. We could achieve much better accuracy by
taking into account the change in the enthalpy of reaction as the temperature changes. To do this,
we would need to use the (admittedly unwieldly) Equation 9.24 from the text. We would need
the heat capacity constants for each species, from Appendix A.2:
Species
C5H12
H2O
CO
A
2.464
3.470
3.376
B
45.351x10-3
1.45 x10-3
0.557 x10-3
C
-14.111 x10-6
0
0
53
D
0
0.121 x105
-0.031 x105
E
0
0
0
(c) The reaction stoichiometry shows that every mole of pentane gas reacted produces a net
increase of 10 moles of gas in the reactor.
5 CO + 11 H 2
C5 H12 + 5 H 2 O
n = 6 moles
n = 16 moles
Assuming the reactor has a fixed volume and temperature, this would cause a net increase in
pressure as the reaction proceeds (P = nRT/V).
Using LeChateliers Principle, a decrease in the system pressure will drive the reaction to the
right, producing more H2 and CO than at higher pressures.
While it may be preferable from an equilibrium standpoint to operate at low pressures, keep in
mind that the reaction rates will increase dramatically with pressure (why?), so that it may be
more economical to operate at different temperatures or pressures. Again, equilibrium does not
determine the reaction kinetics (or process economics).
(d) Separation could be achieved in many ways. The following process is one possibility. We
will use liquid-liquid separation (settling) of the cooled vapor effluent to remove pentane and
water from the gas stream. The remaining hydrogen and carbon monoxide can be separated by
cryogenic distillation (note the large difference in boiling points between the two gases).
C5H12 (liq)
H2
(b.p. -252.5C)
Reactor
effluent
Cool to
T<36C
CO
H2O (liq)
(b.p. -191.5C)
Liquid-Liquid
Separation
Cryogenic
Distillation
One possible scheme to separate a mixed reactor effluent containing pentane, water, hydrogen
and carbon monoxide vapors.
54
9.35
SiClH 3 g Si s HCl g H 2 g
Species
Initial number of
moles/s (n)
Number of moles/s
being produced (v)
Moles/s of species as a
function of
nSiClH3
-1
1-
nHCl
nH 2
1+
v
T
ySiClH3
1
1
yHCl yH 2
So the equilibrium constant can be written:
yHCl PyH 2 P
ySiClH3 P
2P
1 2
Using the thermochemical data:

grxn,298 = 24
hrxn,298 = 49.6
10
10
We find K
KT =K298 exp
13.43
K/P
1
1 K / P
55
9.36
(a)
At equilibrium, how much H2 is produced per mole of steam fed?

(1)
(2)
(3)
1
1
1
__________
1
-241.82
-228.57
H2
CO
-110.53
131.29
kJ/mol
-137.17
91.4
kJ/mol
91,400
8.314298
1
1
298
2.72
2.72

3.72
9.5
131,290 1
8.314 1000
1.36
.
H2O
ln
2.72
0.86
0.86
56
10
1
298
37.2
131.29
91.4
(b)
If the flow rate of steam into the reactor is 5 mol/s, how much heat needs to be added or removed
to keep the system at 727 C?

0.86
131.29
561
57
9.37
(a)
For every kg of magnesium placed in the reactor, how many kg of Ti will be produced?
2 mol Mg 0.4 mol Ti

2 mol Mg 0.4 mol 47.9
24.3
1000 Mg
394
0.39
48.6 g Mg = 19.2 g Ti
mTi = 0.39 kg
(b)
Calculate the approximate pressure needed. You can assume ideal gas and ideal liquid behavior.
0.0012
298
642
56000
8.314 1000
56
0.4
0.6
0.4
0.6
0.0012
374
58
0.0012
9.38
(a)
The reaction is
C2 H 4 ( g ) H 2O( g ) C2 H 5OH ( g )
From Table A.3.2:
Species
h f ,298 kJ/mol
g f ,298 kJ/mol
C2 H 4 ( g ) (1)
52.26
68.15
H 2O( g ) (2)
-241.82
-228.57
C2 H 5OH ( g ) (3)
-234.96
-168.39
From these data:
3 J
g rxn
,298 8.0 10
mol
3 J
hrxn
,298 45.4 10
mol
First we calculate the equilibrium constant
hrxn
1
1
K 355 K 298 exp

1.3
298.15
R
T
y1
y3
1
2
y2

K
y3
Py1 y2
59
1
2
Solving, we get
0.34
(b)
The conversion would increase
(c)
At 10 bar, some of the water in the feed would condense
60
9.39
The reaction is
C3 H 6 O propylene oxide C3 H 6 O acetone
Let the subscript 1 represent propylene oxide and 2 represent acetone. Since the pressure is
1 bar, the expression for the equilibrium constant is
x
K 2 2
x1 1
Using the two-suffix Margules equation we obtain the following expression
Ax 2
x2 exp 1
A
x2
RT
K
exp
1 2x2
2
Ax 1 x2
RT
x1 exp 2
RT
From Appendix A.3:
3 J
g rxn
, 298 128.75 10
mol
Therefore,
K 3.7 10 22
3.7 1022
x2
A
1 2 x2
exp
1 x2 RT
Solving:
x2 1
x2 0
61
9.40
(a)
First, calculate the number of independent chemical reactions using Equation 9.44:
R m 2 s 3 2 2 1 0 2
The two independent reactions:

1 - butene 1 cis butene (2)
1 - butene 1 trans butene (3)
(Equation 1)
(Equation 2)
From Table A.3.1:

Species
g f ,298 kJ/mol
1-butene (1)
cis-butene (2)
trans-butene (3)
71.34
65.90
63.01
Using the data in the above table, calculate the equilibrium constants
65.90 71.34
K1 exp
8.99
0.008314 298
63.01 71.34
K 2 exp
28.85
0.008314 298
Using 1 mole of species 1 as the basis results in the following expressions:
y1 1 1 2
y3 2
y 2 1
Assuming ideal gas behavior, we obtain two equations for two unknowns:
y
K1 2
y1
y
K2 3
y1
8.99
28.85
1
1 1 2
Solving, we get
1 0.231
2 0.743
62
2
1 1 2
Therefore,
y1 0.026
y 2 0.231
y3 0.743
(b)
For 1000 K, we need to scale the equilibrium constants appropriately.
hrxn,298
1
1
K1,1000 K1,298 exp
T 298
R
hrxn,298
1
1
K 2,1000 K 2,298 exp

T 298
R
From Table A.3.1:

Species
h f ,298 kJ/mol
1-butene (1)
cis-butene (2)
trans-butene (3)
-0.13
-6.99
-11.18
Using these data, calculate the equilibrium constants
6.99 0.13 1
1
K1,1000 8.99 exp
1.29
1000 298
0.008314
11.18 0.13 1
1
K 2,1000 28.85 exp
1.26
1000 298
0.008314
Using 1 mole of species 1 as the basis results in the following expressions

y1 1 1 2
y3 2
y 2 1
y
K1 2
y1
y
K2 3
y1
1.29
1.26
1
1 1 2
63
2
1 1 2
Solving, we get
1 0.363
2 0.355
Therefore,
y1 0.282
y 2 0.363
y3 0.355
64
9.41
(a)
First, calculate the number of independent chemical reactions using Equation 9.44:
R m 2 s 3 2 2 1 0 2
The two independent reactions:

C 3 H 8 O 1 C 3 H 8 O (2)
C 3 H 8 O 1 C 3 H 8 O (3)
(Equation 1)
(Equation 2)
Calculate the change in Gibbs energy for the reactions:

kJ
g rxn
1,500 48.1
mol
kJ
g rxn
2,500 55.9
mol
Now find the equilibrium constants:
48.1
K1 exp
1.06 10 6
0.008314 500
55.9
K 2 exp
6.92 10 6
0.008314 500
Using 1 mole of species 1 as the basis results in the following expressions:
y1 1 1 2
y3 2
y 2 1
y
K1 2
y1
1.06 10 6
1
1 1 2
y
K2 3
y1
6.92 10 6
Solving, we get
1 0.133
2 0.867
65
2
1 1 2
Therefore,
y1 0
y 2 0.133
y3 0.867
(b)
First, write down the and b matrices.
3 8 1
3 8 1
3 8 1
3
b 8
1
Equation 9.45 gives:
n1
n2
3 8 1 3
n3 3 8 1 8
3 8 1 1
Therefore,
3n1 3n2 3n3 3
8n1 8n2 8n3 8
1n1 1n2 1n3 1
Now, use Equation 9.47 to obtain three more equations:
n1
3C 8H 1O 0
n1 n2 n3
n2
95.4 0.008314 500 ln
3C 8H 1O 0
n1 n2 n3
n3
103.2 0.008314 500 ln
3C 8H 1O 0
n1 n2 n3
47.3 0.008314 500 ln
Simultaneously solving the six equations, we get

n1 0
n2 0.133
n3 0.867
66
Therefore,
y1 0
y 2 0.133
y3 0.867
67
9.42
(a)
First, create expressions for the reaction components in terms of conversion:
1
3
2 2
yB
3
yA
yC
2
3
Assuming ideal gas behavior, the expression for the equilibrium constant is
y2
K P 1 C
y A y B2
At 473.15 K and 1 bar:

yC 0.25
1 / 3 and K 473.15 1
At 573.15 K and 1 bar:
yC 0.539
0.637 and K 573.15 20.05
To find the equilibrium constant at 250 C (523.15 K) we can use Equation 9.20 if we assume the
enthalpy of reaction is constant:
K
hrxn
1
1
ln 573.15
R 573.15 473.15
K 473.15
Determine the enthalpy of reaction:
hrxn
67.6 10 3
mol
Now calculate the equilibrium constant at 250 C:
hrxn
1
1
K 523.15 K 473.15 exp
5.16
R 523.15 473.15
68
The conversion can be calculated using the following expression

2
1
3
5.16 2 bar
1 2 2 2

3 3
0.574
Substituting this value into the expressions for the compositions, we obtain:
y A 0.176
y B 0.351
yC 0.473
(b)
i. Increasing the temperature increases the equilibrium constant because the reaction is
endothermic. Thus, the conversion will increase, as well as the reaction rate.
ii. Increasing the pressure will also increase the conversion because the pressure appears
in the denominator of the expression for the equilibrium constant.
iii. Adding an inert will decrease the conversion because the inert molecules hinder
collisions between reactant molecules. There are more reactant molecules than
product molecules.
69
9.43
grxn,298
28.62 10 3
mol
J
hrxn,298
41.16 10 3
mol
Since we are calculating the compositions at 1000 K, we wont assume that the heat of reaction
is independent of temperature. At 298.15 K
K 298.15 1.0310 5
Using Equation 9.24 and data from Appendix A.2, we get
K1000 1.46
Take 1 mole of CO as the basis for the calculations. Create expressions for the compositions of
6
8
1
yCO
8
yH 2O
yH 2
1
8
yCO2
The gas is assumed ideal; therefore
y y
H
CO2
K P0 2
yH 2O yCO
1
0
1.46 1 bar
6 1
Solving:
0.807
Therefore,
yCO 0.024
yH 2 0.226
yH 2O 0.649
yCO2 0.101
70
9.44
Let
Species 1 = O
Species 2 = O2
Assuming the gas is ideal. Therefore, the equilibrium expression is
KP
y12
y2
Calculate the equilibrium constant required for 10% O:
0.10
K 1 bar
0.90
K 0.011
From Table A.3.2:

Species
h f ,298 kJ/mol
g f ,298 kJ/mol
1
2
249.17
0
231.74
0
Equation 9.15:
2 231.74
K 298 exp
5.711082
0.008314 298
Assuming the heat of reaction is constant, we obtain the following expression:
hrxn,298
1
1
K K 298 exp

T 298
R
498.34 1
1
0.011 5.7110 82 exp

0.008314 T 298
Solve for T:
T 3211 K
To lower the minimum temperature, decrease pressure.
71
9.45
The reaction is
N 2 O2 2 NO
grxn,298
173.2 10 3
mol
J
hrxn,298
180.58 10 3
mol
Since we are assuming the enthalpy of reaction is constant, we can use Equation 9.20 to find the
temperature dependence of K:
h 1
1
rxn
KT K 298.15 exp

R T2 298.15
173.2 10 3 180.58 10 3 1
1
KT exp
exp

T 298.15
8.314
8.314 298.15
The following table has been created using the above equation.
T (K)
1100
K
5.22 10 8
1250
5.58 10 7
1500
1.01 10 5
1750
7.99 10 5
2000
3.77 10 4
2250
1.26 10 3
2500
3.31 10 3
2750
7.29 10 3
3000
1.41 10 2
Take 1 mole of air (79% N2, 21% O2) as the basis for the calculations. Create expressions for the
yN2
0.79
1
y NO
2
1
72
0.21
1
yO 2
y
NO
KP
yN 2 yO2
0
As an example, the conversion is calculated below at 1100 K:

2
2
0
5.22 10 1 bar
0.21 0.79
Solving:
4.65 10 5
Therefore,
y NO 9.3 10 5
This has been repeated for 1100 to 3000 K. The following plot is obtained.
Composition of NO From Air as a Function of Temperature
yNO (mole fraction)
5.00E-02
4.00E-02
3.00E-02
2.00E-02
1.00E-02
0.00E+00
1000
1500
2000
Temperature (K)
73
2500
3000
9.46
The reaction is
N 2 2O2 2 NO2
From Appendix A.3:
grxn,298
102.52 10 3
mol
J
hrxn,298
66.2 10 3
mol
Assuming the enthalpy of reaction is constant, we can use Equation 9.21 to find K:
hrxn
1
1
K3000 K 298.15 exp
R 3000 298.15
102.52 10 3 66.2 10 3 1
1
K3000 exp
exp
8.314 298.15 8.314 3000 298.15
K3000 3.0510 8
Take 1 mole of air (79% N2, 21% O2) as the basis for the calculations. Create expressions for the
0.79
1
0.21 2
yO 2
1
yN2
y NO
2
1
y
NO2
K P 1
yN2 yO2
For 1 bar:
2
1
1
8
3.0510 1 bar
0.21 2 2 0.79
1 1
74
1.63 10 5
Assume ideal gas behavior at 500 bar since the temperature is 3000 K:
2
1
1
8
3.05 10 500 bar
0.21 2 2 0.79
1 1
3.64 10 4
Therefore,
y NO 2 3.266 10 5
(1 bar)
y NO 2 7.283 10 4
(500 bar)
75
9.47
(a)
The subscript 1 refers to the first reaction and 2 refers to second. We will calculate the
equilibrium constants for both reactions at 3000 K without assuming the heats of reaction are
constant. From Appendix A.3:
J
173.2 10 3
mol
J
hrxn,298
1 180.58 103 mol
rxn,298
J
51.26 10 3
mol
J
hrxn ,298 2 33.1103 mol
rxn,298
From Appendix A.2:
A1 1.45 , B1 0.000159 , C1 0 , D1 21500

A2 0.297 , B2 0.0003925 , C1 0 , D1 58500
Using Equation 9.24, we find
K1 0.0154
K 2 0.000142
Take 1 mole of air as the basis for the calculations. Create expressions for the compositions of
0.79 1 0.5 2
1 0.5 2
0.21 1 2
yO 2
1 0.5 2
yN2
y NO
21
1 0.5 2
y NO 2
1 0.5 2
Assuming ideal gas behavior, we obtain the following expressions for the equilibrium constants:
2
21
1
0.5
2
0.0154 P 0
0.79 1 0.5 2 0.21 1 2

1 0.5 2

1 0.5 2
1
0.5
2
0.000142 P 0.5
0.5
0.79 1 0.5 2 0.21 1 2

1 0.5 2
1 0.5 2
76
Solving simultaneously:
1 0.0234
2 0.000517
Therefore,
y NO 0.0468
y NO 2 0.000517
yO2 0.186
y N 2 0.766
(b)
The subscript 1 refers to the first reaction and 2 refers to second. We will calculate the
equilibrium constants for both reactions at 3000 K without assuming the heat of reactions are
J
173.2 10 3
mol
J
hrxn,298
1 180.58 103 mol
J
35.34 10 3
mol
J
hrxn,298
2 57.19 103 mol
rxn,298 1
rxn,298 2
From Appendix A.2:
A1 1.45 , B1 0.000159 , C1 0 , D1 21500

A2 0.2245 , B2 0.000313 , C1 0 , D1 69250
K1 0.0154
K 2 0.00114
Take 1 mole of air as the basis for the calculations. Create expressions for the compositions of
0.79 1
1 0.5 2
0.21 1 0.5 2
yO2
1 0.5 2
yN 2
yNO
yNO2
21 2
1 0.5 2
1 0.5 2
77
2
21 2
1 0.5 2
0
0.0154 P
0.79 1 0.21 1 0.5 2
1 0.5 2
1 0.5 2

1 0.5 2
0.5
0.00114 P
0.5
0.21 1 0.5 2 21 2

1 0.5 2
1 0.5 2
1 0.0237
2 0.00515
Therefore,
y NO 0.047
y NO 2 0.000518
yO2 0.186
y N 2 0.766
(c)
The conversions and compositions in parts A and B are equal.
78
9.48
(a)
First, calculate the equilibrium constant for the reaction. Data from Table A.3.2:
Species
h f ,298 kJ/mol
g f ,298 kJ/mol
N2O4 (1)
NO2 (2)
9.079
33.1
97.79
51.26
At 298 K:
kJ
g rxn
,298 4.73
mol
Calculate the equilibrium constant with Equation 9.15:
4.73
K 298 exp
0.148
0.008314298
Express the moles of reaction components as functions of :
n1 1
n2 2
Therefore,
y1
1
1
y2
2
1
Assuming ideal gas behavior:

y 22
KP
y1
2
0.148 1 bar
1
1
Solving, we get
0.189
79
Use to obtain the compositions

y1 0.682
y 2 0.318
(b)
The equilibrium constant is the same as in Part (a). Express the moles of reaction components as
functions of :
n1 1
n2 2
nI 1
(moles of inert)
Therefore,
y1
1
2
y2
2
2
Assuming ideal gas behavior:

y2
KP 2
y1
2
0.148 1 bar
1
2
Solving, we get
0.25
Use to obtain the compositions
y1 0.333
y 2 0.222
y I 0.444
80
9.49
First we have:
/ RT
d ln K
d g rxn
dT
dT
(I)
From Equation 9.18:
(II)
d ln K hrxn
dT
RT 2
Combine Equation (I) and (II) to yield
d g rxn
/ RT
h
rxn
dT
RT 2
From the problem statement,
g rxn
1 757000

7.5 log T 145
RT
R
T
Now differentiate the expression above,
/ RT
1 757000
7 .5
d g rxn

dT
R T2
T ln 10
hrxn
RT
hrxn
1 757000
7 .5
2
R T
T ln 10
7.5
T 757000
ln10
At 298 K:
5 J
hrxn
, 298 7.56 10
mol
81
9.50
The subscript 1 refers to reaction 1 and 2 refers to reaction 2. We will calculate the
equilibrium constants for both reactions at 800 K without assuming the heat of reactions are
J
142.12 10 3
mol
J
hrxn,298
1 206.1103 mol
rxn,298
J
28.62 10 3
mol
J
hrxn,298
2 41.16 103 mol
rxn,298
From Appendix A.2:

A1 7.951 , B1 0.008708 , C1 2.164 10 6 , D1 9700
A2 1.86 , B2 0.00054 , C1 0 , D1 116400

K1,800 0.03
K 2,800 4.29
Create expressions for the compositions of the reaction components as functions of conversion:
1 1
5 21
4 1 2
yH 2O
5 21
yCH 4
31 2
5 21

yCO 1 2
5 21
yH 2
yCO 2
5 21
3
31 2
1
2

2 5 21 5 21
0.03 P
1 1 4 1 2
5 21 5 21
3
2 1 2
5 21 5 21
4.29 P 0
4
1
2
1 2
1
1
1 0.614
82
2 0.515
Therefore,
yCH 4 0.062
y H 2 O 0.461
y H 2 0.378
yCO 0.016
yCO2 0.083
These compositions are equal to those in Example 9.19.
83
9.51
3 J
g rxn
,298 31.16 10
mol
3 J
hrxn
, 298 34.38 10
mol
We wont assume the heat of reaction is independent of temperature. At 298.15 K

31.16 10 3
6
K 298.15 exp
3.47 10
298.158.314
Using Equation 9.24 and data from Appendix A.2, we obtain
K 800 0.021
Take 1 mole of C2H2 and 1 mole of N2 as the basis for the calculations. Create expressions for
the compositions of the reaction components as functions of conversion:
1
2
1
yN2
2
yC 2 H 2
y HCN
2
2
The gas mixture is assumed ideal; therefore
y
HCN
K P0
yC2 H 2 yN 2
2

0
2
0.021 1 bar
1 1
2 2
Solving:
0.0676
Now calculate the compositions
yC 2 H 2 0.466
84
y N 2 0.466
y HCN 0.0676
85
9.52
We can assume ideal behavior, and since Cu and Cu2O are stable in given the temperature range,
we obtain the following relationship
1
pO 2
pO 2
1
K
To calculate K over the temperature range, we can use the expression for Gibbs energy of
formation given in the problem statement.
grxn
2 g f ,Cu2O 3.40 10 5 14.24T lnT 248T
3.40 10 5 14.24T lnT 248T

grxn
K exp
exp
RT
RT
The following table has been created

T
300
400
500
600
700
800
900
1000
1100
1200
1300
K
3.09E+50
8.00E+35
1.54E+27
2.54E+21
1.95E+17
1.65E+14
6.90E+11
8.79E+09
2.51E+08
1.32E+07
1.10E+06
P (bar)
3.24E-51
1.25E-36
6.47E-28
3.94E-22
5.12E-18
6.05E-15
1.45E-12
1.14E-10
3.98E-09
7.59E-08
9.11E-07
We can also plot the data.
PO2 (bar)
Partial Pressure of O2 as a Function of

Temperature
1.00E-02
1.00E-09
1.00E-16
1.00E-23
1.00E-30
1.00E-37
1.00E-44
1.00E-51
100
300
500
700
900
Temperature (K)
86
1100
1300
1500
9.53
(a)
Assume that the data given in the problem statement is for a pressure of 1 bar. If we also assume
the enthalpy of reaction is independent of temperature, we can use Equation 9.20:
ln
h o
K2
rxn
K1
R
1
1

T2 T1
Substitute numerical values to solve the enthalpy of reaction:
1.12 10 3
8.314 J/mol K ln
5
J
1.98 10
o
hrxn
1.88 10 5
mol
1
1
1079.15 K 905.15 K
(b)
First, calculate the equilibrium constant at 1000 C using Equation 9.20:
1.88 10 5 1
1
K1273.15 1.98 10 5 exp
8.314 1273.15 905.15

K1273.15 0.0271
Since the pressure is 1 bar, we can assume the vapor phase is ideal. Also assume the fugacities
of the solids in the mixture equal their respective pure solid fugacities. The expression for the
equilibrium constant reduces to
2
yHCl P
y2
1 bar
K
HCl P
yH 2 P
yH 2
1 bar
Now, we need to create expressions for the mole fractions containing the extent of reaction. If
we take one mole of H2 and one mole of CrCl2 as the basis, the equations for the number of
moles of each species are
nCrCl 2 1
nCr
nH 2 1
n HCl 2
The expressions for the vapor mole fractions are
87
yH 2
1
1
y HCl
2
1
Substitute these expressions into the expression for the equilibrium constant and solve for :
2
4 2
1
0.0271
1 bar
1 bar
1
1 1
1
0.0820 mol
For every mole of hydrogen fed, 0.082 moles of Cr(s) are produced.
(c)
We can rewrite the expression for the extent of reaction as
n2
4 2
K
vap HCl
P ntotal nH 2 1 1
Since pressure is in the denominator of the left-hand side, we want to reduce pressure to increase
extent of reaction. The reduction in pressure can also be reasoned by employing Le Chteliers
principle. There are more product gas molecules, so as you reduce pressure, the product side
will be favored.
88
9.54
We need a second reaction. The two reactions can be written
C2 H 4 ( g ) H 2O( g ) C2 H 5OH ( g )
C2 H 4 ( g ) 4 H 2O( g ) 2CO2 ( g ) 6 H 2 ( g )
Reaction 1
Reaction 2
From Table A.3.2:

Species
h f ,298 kJ/mol
g f ,298 kJ/mol
C2 H 4 ( g ) (1)
52.26
68.15
H 2O( g ) (2)
-241.82
-228.57
C2 H 5OH ( g ) (3)
-234.96
-168.39
CO2 ( g ) (4)
-393.51
-394.36
H 2 ( g ) (5)
From these data, for Reaction 1, we ger:
3 J
g rxn
,298 8.0 10
mol
3 J
hrxn
,298 45.4 10
mol
From these data, for Reaction 2, we ger:
3 J
g rxn
,298 57.4 10
mol
3 J
hrxn
,298 128 10
mol
First we calculate the equilibrium constant for Reaction 1
hrxn
1
1
K 355 K 298 exp

1.3
R
T
298.15
2
And for Reaction 2:
hrxn
1
1
7
K 355 K 298 exp

3.5 10
R T2 298.15
89
y1
y3
1 1 2
2 1 3 2
1 1 4 2
2 1 3 2
2 2
y4
2 1 3 2
y2
1
2 1 3 2

K1
y3
Py1 y2
y42 y56 3
K2
P
y1 y2
Solving, we get
1 0.290
2 0.031
90
9.55
We are given the Gibbs energies of formation for several isomers of nonane. Rank the isomers in
order of highest- to lowest-expected concentration. Determine the equilibrium composition of a
mixture of the three most important isomers at 1000K.
(a)
I 2 , we can write:
For isomerization reactions of the form I1
g rxn g formation, I 2 g formation, I1

Therefore, the most stable isomers will be those that have the lowest Gibbs energy of formation
(can you explain why?)
Ranking the species in order from lowest to highest Gibbs energy of formation,
Isomer Species
4-methyloctane
(B)
nonane
(A)
4-ethylheptane
(C)
2,2,3-trimethylhexane
(D)
3,3-diethylpentane
(E)
2,2,3,4-tetramethylpentane
(F)
g f (kcal/mol)
Expected Rank
161.90
Highest
162.15
164.22
168.13
171.79
175.62
Lowest
(b)
Determine the equilibrium composition mole fractions of a mixture of the three top species
(highlighted in gray above).
Consider the parallel isomerization reactions of nonane (A) to

4-methyloctane (B) and 4-ethyl-heptane (C). Each isomer
will be in equilibrium with nonane, as shown at right. The
isomers can interchange with one other by first going through
nonane, then isomerizing to the other species.
nonane
(A)
K1
4-methyloctane
4-ethylheptane
(B)
(C)
We can write the following equilibrium expressions for the system:
B
A
K1
K1
yB P yB
yA P yA
91
K2

C
A
K2
K2
yC P yC
yA P yA
Set a basis of starting with one mole of pure A, so that nA 1 mole, and nB nC 0 mole . Then,
y A 1 1 2
nA 1 1 2
yB 1
nB 1
nT 1 (constant) ,
yC 2
nC 2
Now we need to calculate the values of K1 and K2. Can you guess at this point which isomer will
have the highest mole fraction?
cal
161,900 162,150 mol
K1 exp
1.13
1.987 cal 1000 K
molK
cal
164, 220 162,150 mol
K 2 exp
0.35
1.987 cal 1000 K
molK
Now write the two equilibrium expressions together:
1
1 1 2
2
K2
1 1 2
K1
K
1 1
K2 2
Usie the above equations to solve for the unknowns i ,
K
K1 1 1 2 1 1
K1
K
K1 1 1 2 1 1
K1
K1
yB 0.402
1 K1 K 2
y A 1 y A yB 0.456
K2
yC 0.142
1 K1 K 2
So, the equilibrium gas composition is:
92
y A 0.456
yB 0.402
yC 0.142
93
9.56
The following two cracking reactions for n-pentane occur in parallel:
C5H12(g) C3H6(g)
C2H6(g)
(I)
and
C5H12(g)
C4H8(g)
CH4(g)
(II)
At 183 C and 0.5 bar, both these reactions contribute to the equilibrium composition of species
in the system. For every 1.0 mole of n-pentane gas initially fed, 0.10 mol of polypropylene
(C3H6) is formed at equilibrium from Reaction I. Calculate the equilibrium amount of trans-2for each reaction does not
butene formed per mole of pentane fed. You may assume that
change with temperature.
First we take a molar basis of 1 mole of pentane in the feed. Next we can find thermochemical
data for our reactions.
Next, from table A.3.1
Species (all gas)

C5H12
C3H6
C2H6
trans C4H8
CH4
-146.54
20.43
-84.68
-11.18
-74.81
From these data:
38.29
10
20.66
10
82.29
10
60.55
10
Use Equation 9.21:

,
94
-8.37
62.76
-32.84
63.01
-50.72
,
.
0.0193
1.14
Next if we look at the moles of each species as a function of the extent of reactions. Because we
have two reactions we have two extent of reactions, 1 for Reaction I and 2 for Reaction II.
Moles of
species
Initial number
of moles (n)
nC5H12
nC3H6
nC2H6
1
0
0
0
0
1
ntrans C4H8
nCH4
nT
Number of
moles being
produced (v)
-11 - 12
11
11
12
12
11 + 12
Next we look at the mole fractions
Species
yC5H12
yC3H6
yC2H6
ytrans C4H8
yCH4
Mole fraction
1
1
1
1
1
1
yi
95
Moles of
species as a
function of
1 - 1 - 2
1
1
2
2
1 + 1 + 2
Now, reading the problem statement carefully reveals that for every 1.0 mole of n-pentane fed,
0.10 moles of propylene are produced from Reaction I. The number of moles of propylene
produced at equilibrium is equal to the extent of Reaction I.
0.1
Next lets fine the equilibrium constants in terms of the extent of reactions.
.
0.5
0.0193
0.5
1.14
0.5
0.5
Solving either K equation results in the same extent of reaction for Reaction II.
0.76
Now we can find the amount of trans-2-butene formed per mole of pentane fed. Since we took a
molar basis of 1 mole of pentane fed, the amount of trans-2-butene formed is simply equal to the
extent of reaction for Reaction II.
0.76
96
moles
mol C H fed
9.57
C2H2 + N2 2HCN
(1) (2)
(3)
C H
O 2CO
5H O
(4)
(5)
(6)
1 mole C2H2
5
2
5 moles O
25
moles O
2
0.72
25
moles N 47 moles N
0.21
2
n1
= 1
n2
= 47
n3
n4
12.5
nT
60.5
(kJ/mol)
226.88
130.63
2 130.63
226.88
2 120.2
C2H2
HCN
3.46
(kJ/mol)
209.24
120.2
209.24
34.38
31.16
/ .
ln
kJ
mol
mol
3.45
10.6
10
kJ
0.14
97
10
4
48
0.14
1.77
2
60.5
47
1.77
2
4 1.73
0.7
0.0231
98
9.58
The solution assuming hrxn

hrxn
T is presented
hrxn
= const
(a)
First write the chemical reaction:
C5 H12 10 H 2O 5CO2 16 H 2
Calculate the equilibrium constant. From data in Appendix A.3:
C5H12
H2O
CO2
H2O
rxn
-146.54
-241.82
-393.51
0
597.19
-8.37
-228.57
-394.36
0
322.27
-1
-10
5
16
3 J
g rxn
,298 322.27 10
mol
3 J
hrxn
,298 597.19 10
mol
We assume the heat of reaction is independent of temperature. At 298.15 K

322 103
57
K 298.15 exp
3.23 10
298.15 8.314
ln
K 600
ho 1
1
597,190 1
1
rxn
121.35
8.314 600 298
K 298
R T 298
K 600 1.58 104

Take 1 mole of C5H12 and 10 mole of H2O as the basis for the calculations. Create expressions
for the compositions of the reaction components as functions of extent of reaction:
99
1
11 10
10 1
11 10
5
11 10
16
11 10
yC5 H12
yCO2
y H 2O
yH 2
K 600
y
y
y
CO2
10
P
y
C5 H12
5
16
5 16
P10
10
10
1 10 1 11 10 10
16
H2
H 2O
Solving:
0.56
yC5 H12 0.0265
yCO2 0.169
yH 2O 0.265
yH 2 0.540
(b)
We need to write 2 equations:
Equation 1: C5 H12 10 H 2O 5CO2 16 H 2
Equation 2: CO2 H 2 CO H 2O (note there are alternatives to this equation that can
be used)
From above: K1 1.58 104

Similarly:
3 J
g rxn
,298,2 28.62 10
mol
3 J
hrxn
,298,2 41.16 10
mol
We assume the heat of reaction is independent of temperature. At 298.15 K

28.62 103
6
K 298.15,2 exp
9.62 10
298.15 8.314
100
o
hrxn
1
41,160 1
1
K2
1
ln
8.36
8.314 600 298
K 298,2
R T 298
K 2 0.0412
Take 1 mole of C5H12 and 10 mole of H2O as the basis for the calculations. Create expressions
for the compositions of the reaction components as functions of extent of reaction:
1 1
11 101
10 101 2
11 101
51 2
11 101
161 2
11 101
yC5 H12
yCO2
y H 2O
yH 2
y
y
y
CO2
10
K1 P
y
C5 H12
10
16
H2
H 2O
And
yH O yCO
K2 2
yCO2 yH 2
Solving:
1 0.584
and
2 0.230

yC5 H12 0.0247
yCO2 0.160
yH 2O 0.260
yCO 0.014
yH 2 0.542
101
yCO
11 101
9.60
(a)
nA 1 1 3 0.3 mol
nB 3 1 2 2 2 mol
nD 1 3 0.5 mol
nF 23 0.2 mol
nTv 3 mol
yA = 0.1; yB = 2/3; yD = 1/6; yF = 1/15;
K1
yD
5
Py A yB
K2
1
9
y P2
K3
yF2
4
y A yD 15
2
B
(b)
Increase the pressure
102
9.61
(a)
H O g H
C s
1 mol
CO g
1
=
1
K
K
K
137.17
,
R 298
96.52
1
T
1.36 K P
2.72
3.72
kJ
mol
91.4
kJ
mol
10
110.53
1
298
228.57
131280 1
8.314 1000
241.82
1
298
131.28
53
2.72
0.86
0.86 mol H
mol H
(b)
Explain why you think that this reaction runs at 50 kPa instead of at atmospheric
pressure?
Smaller P, larger y2, more H2
103
(c)
In solving part A, you assumed that
constant. What do you think is the single most
important reason that this assumption might not be valid?
Large T difference. cp reactants does not equal cp products.

(d)
Without redoing all the calculations that you did in Part A, determine how the values of the
following quantities change if you write the reaction as
2C s
i.
2H O g 2H
2CO g
1.86
K
same
ii.
(e)
You believe that CO2 might also form when water vapor is passed through the bed of
activated carbonwrite the set of equations that you would need to solve to see how much
CO2 forms (as well as CO and H2). You do not need to solve this set of equationsjust set
them up.
One way:
C s
CO
n1
H O g H
H O CO
CO g
H
Rxn 1
Rxn 2
y1 =
n2
n3
y2 =
n4
y3 =
nT
y4 =
Find KT for rxn 2
394.36
228.57
104
137.17
28.62
1.36
0.89
exp
ln
K
K
393.51
104000
241.82
110.53
41.16
11.66
0.89
105
9.62
The following half reactions can be written, with the corresponding half-cell potentials are
obtained from Table 9.1:
o 0.762 V
o 0.342 V
The overall reaction is
o
rxn 1.104 V
Applying Equation 9.34 to this system and assuming Zn2 , Cu2 1 gives:
orxn
i
RT
RT cZn2
ln pi i ci im orxn
ln
zF vapors
zF
c
liquids
Cu
or
1.104
(1)
8.314 298 0.5

ln 1.12 V
2 96, 485 0.1
Since 0, the reaction is spontaneous. To see how far this reaction goes
o
Zn 2
c o 2
Cu
cZn 2 c
(2)
cCu 2
(3)
At equilibrium, 0. Substituting Equations (2) and (3) into (1) and solving gives:
cZn 2 0.6m
cCu 2 10
38
Thus, approximately all the copper in the solution is consumed.
106
9.63
(a)
e-
Anode
e-
Cathode
Pt
Pb
anions
cations
(b)
O 0.126 V
O 0.000 V
(reduction reaction)
(oxidation reaction)
(c)
orxn 0.126 V
Applying Equation 9.34 to this system and using the fact that Pb2+ is 1 m:
orxn
i
2
RT
RT
ln pi i ci im orxn
2.3log10 aH (1)
zF vapors
zF
liquids
Solving Equation (1) for pH:

pH log10 a H orxn
Thus,
F
2.3RT
0.008 V pH=2.0
0.465 V pH=10.0
(d)
We can measure across an equilibrium electrochemical cell to determine pH. The values
above are well within a reasonable experimental range.
107
9.64
o 0.401 V
(reduction reaction)
o 0.447 V
(oxidation reaction)

o
rxn 0.848 V
Applying Equation 9.34 to this system and using the fact that Pb2+ is 1 m:
orxn
i
RT
ln pi i ci im
zF vapors
liquids
2
RT cFe2 RT
orxn
ln 1/2
2.3log10 aOH
zF
pO2 zF
By definition:
log10 aOH 14 pH 2
Taking the oxygen partial pressure to be 0.21 bar gives
0.848
8.314 298 0.1 8.314 298

ln
2 2.3 0.99 V
2 96, 485 0.21

96, 485
Since 0, the reaction is spontaneous.
108
(1)
9.65
(a)
with half reactions
o 1.358 V
o 0.828 V
(b)
Neither the anode nor the cathode directly participate in the half-cell reactions
Anode(s)Cl 2 (g)Cl l OH l H2 (g) Cathode(s)

(c)
Adding together the half-cell potentials from part a gives:
o
rxn 2.186 V
Hence this reaction needs input of electrical energy to proceed.
109
9.66
Only two of these reactions are independent. Therefore, to be consistent, the half-cell potential
of the third reaction can be obtained from the other two. We label reaction 1:
o
1 0.153 V
and reaction 2,
o
2 0.521 V
Applying Equation 9.35 gives:
To get the Gibbs energy for reaction 3, we add reaction 1 and 2:
The half-cell potential is given by:
kJ
65.1
g
mol
3o
0.34 V
mol e-
zF
C
2
96, 485
2+
mole e-
mole Cu
o
2
This value is consistent with that reported in Table 9.1.
110
9.67
(a)
o 1.229 V
o 0.000 V
o
rxn 1.229 V
Applying Equation 9.34 to this system and assuming Zn2 , Cu2 1 gives:
orxn
i
RT
RT 1/2
ln pi i ci im orxn
ln pO2 pH 2
zF vapors
zF
liquids
1.229
(1)
8.314 298
ln 0.21 0.4 1.25 V
2 96,485
The work can be obtained from as follows. Assuming complete conversion:
W * zF 241
(b)
kJ
mol H 2
From the Gibbs-Helmholtz relation:
If the enthalpy of reaction is constant, we can integrate to give:
At 298 K, we can calculate
from orxn 1.229 V
To get the enthalpy of reaction we use values from Appendix A.3:
111
Integration gives:
so
From Equation 1 we have
0.700
8.314 923
ln 0.21 0.4 0.767 V
2 96, 485
The work can be obtained from integrating Equation 9.67. Assuming complete conversion:
W * zF 148
kJ
mol H 2
112
9.68
o 0.341 V
o 0.342 V
o
rxn 0 V
Applying Equation 9.34 to this system:
o
rxn
RT
RT Cu2 cCu2 0.01m
i
m i
ln pi ci i
ln m
zF vapors
zF Cu
2 c
liquids
Cu 2
(1)
0..1m
(a)
Assuming Zn2 , Cu2 1 gives
8.314 298 0.01

ln
0.030 V
2 96,485 0.1
(b)
We first determine the ionic strength. Accounting for cupric and sulfate ions, the ionic strength
is given by:
1
1
zi2ci 4c 2 4c 2 8c 2
Cu
SO4
2
2 Cu
Using the modified Debye-Huckel theory, Equation 9.38, which is valid up to about 1m, we
have:
4 1.17 8cCu 2
A z z I
1 B I
1 0.33 8cCu 2
2+
For 0.01m Cu , ln 1.21
For 0.1m Cu2+, ln 3.23
m
RT Cu2 cCu2 0.01m

RT
i
o
m i
rxn
ln pi ci i
ln m
zF Cu2 cCu2
zF vapors
liquids
0..1m
ln
If we assume the activities of cupric and sulfate are the same, 2

Cu
113
8.314 298 exp1.21 0.01

ln
0.0036 V
2 96,485 exp3.23 0.1
114
9.69
o 0.000 V
o 0.222 V
o
rxn 0.222 V
Applying Equation 9.34 to this system and taking the activities of the solids to be 1 gives:
o
rxn
m
m
i
RT
RT H cH Cl cCl
m i
o
ln pi ci i rxn
ln
zF vapors
zF
pH 2
liquids
or in terms of the mean activity coefficient
orxn
RT
2
ln 2cHCl
zF
solving gives
zF o
rxn
exp
RT

0.818
cHCl
115
(1)
9.70
The following set of equations and equilibrium constant expressions can be written:
K1
K2
Cl a 2
pCl2 g
ClO n
Cl aVO
K3 pn
(1)
(2)
(3)
Note from these expressions we can determine how the hole and electron densities depend on Cl2
pressure as follows: Electroneutrality gives
ClO p n
We can solve for n from Equation (2):
K 2 Cl a VO
ClO
Using Equation (1), we have:
Cl a K1 pCl g
2
So
K 2 VO K1 pCl2 g
ClO
concentrations, electroneutrality gives: ClO

At high ClO
n
So
1/4
n K 2 VO K11/4 pCl
2
and from Equation (3):
K3
K3
pCl1/4
2
1/4
n
K 2 VO K1
116
9.71
For the set of equations given in the problem, the following equilibrium constant expressions can
be written:

2
V A p 2
K1 VA VB
(1)
K2
(2)
pB2
2 2
K3 VB
n pB2
K4 np
(3)
(4)
Note that Equations (2), (3) and (4) are not independent and we only need two of these to
constrain the system. In the solution presented here, we use (2) and (4), but any other 2 could be
chosen. Electroneutrality gives:
VA n VB p
Region 1: low pB2
(5)
We take V A n and VB p , so electroneutrality gives:
n VB
From Equation (1):
V A VKB1
and from Equation (4)
K4
n
Thus, Equation (2) gives

2
2
VA p 2
K1K 4
K2
2
pB2
VB n 2 pB
2
From Electroneutrality:
117
VB n K1K 4 pB1/4
K 2
VA K1 K1 K 2 p1/4

K B2
4
VB
And from Equation (4):
K K
K4
2
4
n
K
p1/4
B2
Region 2: intermediate pB2 In the region of intermediate pB2 , we assume that the
concentration of electronic defects is greater than the vacancy concentration, so
n p
So from Equation (2):
n p K4
From Equation (2):
VA
K 2 pB2
K4
and from Equation (1),
VB K1 K1 K 4

K 2 pB2
VA
Region 3: high pB2 .
V A p
So from Equation (2):
118
VA p K 2 pB
1/ 4
From Equation (1):
VB VKA1 K1 K 2 pB
1/ 4
And from Equation (4):

1/ 4
K
n 4 K4 K 2 pB2
p
From the Brouwer diagram, we see that the material is intrinsic at intermediate pB2 . It is n- type
at low pB2 and it is p-type at high pB2 .
Summary Table: Defect concentrations for three regions of pB
Region 1: Low
pB
Region 2:
pB
Intermediate
Region 3: High
pB
n VB
n p
V A p
K K 2 1/ 4
p
p 4
K1 B2
p K4
p K2 pB2
K K
n 1 4 pB1 / 4
K 2 2
n K4
n K4 K2 p B2
V A
K K 4
1 2 p1/
K4 B2
K K / 4
1 4 p1
K2 B2
VB
V A
K2 pB2
VB K1
K4
K4
K2 p B2
119
1/4
V A K 2 pB2
1/ 4
1/ 4
VB K1 K2 pB2
1/ 4
Concentration
low
pB2
VB n
intermediate
pB2
n p
high
pB2
V A
n
V A
VB
pB2
120
9.72
As in Example 9.24:
K1 Bi VB
K2
V n
(1)
(2)
Bi p
(3)
K3
K4
VB
Bi
Bi 2
(4)
pB2
(5)
K5 pn
Inserting Equation 3 into Equation 4 and rearranging
Bi
K3 K4 p B2
(6)
Equations 1, 2, and 4 give
VB n KK1K4 p2B
(7)
And Equation 5 Gives
K
p 5
n
(8)
Electroneutrality yields
n Bi VB p
(9)
In region 1, we have low pB so we take VB p and n Bi , and Equation (9) reduces to
n VB . Setting Equation (7) becomes:
VB n K1K 2 pB1/4
K4 2
(10)
Equation (8) becomes:
121
p K5
K 4 1/4
pB
K1K 2 2
(11)
and Equation (6) becomes:
Bi K 3 K1K 2 K 4 p1/4
B2
K5
In region 2, we have intermediate pB . We now assume the atomic defect concentration is
2
larger than the electronic defect concentration. Thus we have n Bi and p VB , and
Equation E22.9 reduces to Bi VB .

Setting Equation (6) equal to Equation (7) and using Equation (8) gives
K1K 2 K 5 1/2
pB2
K3K 4
From Equation 8, we have
K 3 K 4 K 5 1/2
pB2
K1K 2
Using Equation (6), we have
Bi VB K1K 2 K 3
K5
In region 3, we have high pB so we take Bi n and p VB , and Equation (9) reduces

2
to p Bi . Thus Equation (6) becomes:
Bi p K 3 K 4 p1/4
B2
and Equation (8) gives:
K5
n
pB1/ 4
2
K3 K 4
And Equation (7) gives
122
VB K1K 2 K 3 pB1/4
2
K 5 K 41/4
A summary of the defect concentrations for three regions of pB is shown below
2
Region 1: Low pB
Region 2: Intermediate pB Region 3: High

VB KK11/4K22 p1B2 / 4
n
VB

Bi K1 KK25K3
Bi
4
K1 K2 K3 K1/
4
p1B/ 4
K5
2
Bi
4
K5 K1/
4
p1B/ 4
K1K2
2
VB
K3 K4 K5 1/ 2
p
K1 K2 B2
K1K 2 K5 1/ 2
p
K3 K4 B2
From this table, the following Brouwer diagram can be constructed:
Concentration
low
pB2
VB n
Bi
intermediate
pB2
Bi VB
n
high
pB2
Bi
VB
p
n
pB2
123

K K K
VB K1 5K2 41 / 4 3 pB12 / 4
Bi K3 K1/4 4 p1/B24
p
pB
Bi
K5
1/4
K3 K 4
1/ 4
pB
9.73
From Example 9.23:
K1
Oi 2
pO
(1)
K2
p
Oi
Oi
(2)
K3 Zn i n
(3)
K4 pn
(4)
Electroneutrality gives:
p Zni n Oi
At high oxygen partial pressures:
p Oi
Combining Equations (1) and (2)
p K2 K11/ 4 p1O/ 4
2
Therefore,
K4
K2 K11/ 4
/4
p1
O
2
The conductivity decreases as the oxygen partial pressure increases. An increase in the oxygen
partial pressure by 10 causes a decrease in n by 0.56.
124
9.74
Possible reactions include dissociative adsorption of oxygen to form an adsorbed oxygen atom,
O(a):
K1
O(a)2
pO
(1)
and incorporation of the absorbed oxygen into a lattice site, creating two copper vacancies:
K2
VCu 2
O(a)
(2)
Solving Equations (1) and (2) for oxygen partial pressure in terms of copper vacancies gives:
pO
2
VCu 4
2
K1 K2
Hence the ratio of vacancies at 3 torr to that at 760 torr (1 atm) is given by:
VCu 3 torr
VCu 760 torr
1/4
760
0.25
125
9.75
Electroneutrality gives
p BSi n
Since the boron concentration, BSi , is much larger than the intrinsic carrier concentration, we
have approximately:
p BSi 10
15
-3
cm
We can calculate the electron concentrations using the following expression:
K pn
(a)
At 25 0C, Table 9.2 gives
hence
K ni2 1020 cm-6

n
K
5
-3
10 cm
p
(b)
At 100 oC, we again use Table 9.2. Now we must interpolate; however, we know the
Tdependence of K as given by Equation 9.21. At 400 K
Hence
K400 ni2 1.2 10 25 cm-6
which gives
Using
gives
Thus
K373 9.6 1023 cm-6
126
K
8
-3
9.6 10 cm
p
(c)
Electroneutrality now becomes:
p PSi BSi n
but PSi p . Hence
and
n 9 1015 cm-3
K
1.110 4 cm-3
n
127
9.76
K1 n Cui
K2
3 3
CuSi
(2)
K3
PSi n
(3)
VSi
VSi
K4 pn
From Table 9.2 K4 = 1020 cm-6
Since Cui =106 cm-3, K1=1016 cm-6
Since CuSi =102 cm-3, K2 VSi =1032 cm-12

To get the total copper, we sum together the two defects
1016 1032
3
Cui CuSi
3
n
p
Using Relation (4)
10 20
p
n
so
3
Cui CuSi
1016
1028 n 3
n
The minimum occurs when the derivative with respect to n is zero
3
d Cui CuSi
dn
or
1016 3 1028 n 2 0
n
(1)
n = 7.6 x 1010 cm-3
128
(4)
So you want a P concentration around 7.6 x 1010 cm-3. At this concentration,

Cui
3
CuSi
1016
1028 n 3 1.75 10 5 cm-3

n
Thus the defect concentration is reduced by 8.25 x 105 cm-3.
129
9.77
(a)
K1
B(a)
pH3 2
pB2 H 6
BSi p
K2
B(a) VSi
(1)
(2)
K3 pn
(b)
p n BSi
(c)
At low pB2H 6 , p n
p n K3
p1/2
BSi K 2 B(a) VSi K 2 VSi K1 B2 H 6
p3/2
K3
K3
H2
At high pB2H 6 , p BSi
p1/4
BSi p K 2 B(a) VSi K 2 VSi K1 B2 H 6
p3/4
H2
n
K3
K 2 VSi
p3/4
1/4H 2
K1 pB2 H 6
This we can make the following plot:
(3)
pB2H 6
log Concentration
low
pB2H 6
high
BSi
slope = 1/4
BSi
slope = -1/4
slope = 1/2
log pB2H 6
131
9.78
Consider the combustion reaction of butane:
Choose a basis of 1 mol butane. For a stoichiometric amount of air, we have,
nC 4 H10 1 mol
nO2 6.5 mol
nN 2
0.79 6.5
= 24.5 mol
0.21
For 2000K and 50 bar:
Formula
n (Initial)
y (Initial)
n (Equilibrium)
y (Equilibrium)
C4H10
O2
N2
H2O
NO
NO2
H2
CO
CO2
1.000
6.500
24.500
0.000
0.000
0.000
0.000
0.000
0.000
3.12e-2
0.203
0.766
0.000
0.000
0.000
0.000
0.000
0.000
2.97e-60
1.53e-2
24.494
4.991
1.23e-2
6.41e-6
8.9e-3
3.4e-2
3.966
8.85e-62
4.56e-4
0.731
0.149
3.68e-4
1.91e-7
2.66e-4
1.01e-3
0.118
Lambda/RT
C
18.2589
H
2.15857
O
1.88732
Phi*
1.021
1.006
1.007
1.004
0.996
1.003
1.005
1.007
1.008
N
-1.80261
For 2500K and 50 bar:
Formula
n (Initial)
y (Initial)
n (Equilibrium)
y (Equilibrium) Phi*
C4H10
O2
N2
H2O
NO
NO2
H2
CO
CO2
1.000
6.500
24.500
0.000
0.000
0.000
0.000
0.000
0.000
3.12e-2
0.203
0.766
0.000
0.000
0.000
0.000
0.000
0.000
1.91e-52
0.129
24.446
4.938
0.107
8.25e-5
6.24e-2
0.304
3.696
5.66e-54
3.84e-3
0.726
0.147
3.18e-3
2.45e-6
1.85e-3
9.01e-3
0.110
Lambda/RT
C
15.6957
H
1.18748
O
0.822376
132
N
-1.79841
1.018
1.005
1.005
1.004
0.995
0.998
1.004
1.006
1.006

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Chapter 9 Solutions

Engineering and Chemical Thermodynamics 2e

9.16 (second one)

H2O (l) + O2 (g) H2O2 (l)

From Appendix A.3.2:

Assuming we start with 1 mole of I2 and no I, we have:

Applying the definition of the heat of formation gives:

Thermodynamic Quantities as a Function of Extent of Reaction

A 2.9357 , B 0.00209 , C 0, D 33050

Use Equation 9.20:

The gas is assumed ideal; therefore,

nC 4 H 10 10.818 0.818 mol

SO2 (g) + O2 (g) SO3 (g)

From these data:

Use Equation 9.21:

hrxn 0.481 98.96

Therefore, the extent of reaction increases.

SO2 (g) + O2 (g) SO3 (g)

is described by the following equation

From Problem 9.21:

Substituting the above expression, we get

3 H2 (g) + C6H6 (g) C6H12 (g)

From these data:

The gas is assumed ideal. Therefore,

Use Equation 9.20 (assume the heat of reaction is constant):

Now we can solve for the required temperature:

8.314 298.15 8.314 T 298.15

For 90% conversion, 0.9 . Therefore,

Now calculate the equilibrium constant:

To calculate the minimum temperature we can use Equation 9.21.

We calculate the fugacity coefficients using

The following table was created with the above equation

Now we can use the following expression to obtain g rxn

Calculate the average

Calculate K with Equation 9.21:

The expression for the equilibrium constant:

Now calculate the equilibrium constant

Using Equation 9.24, we get

(Alternatively if we assume hrxn

113.5103 164.94 103 1

(Alternatively, solving if we assume hrxn

nH 2 4 0.423 1.69 mol

Let Plow go to zero and simplify:

From data in Appendix A.3

The equation for the equilibrium constant can be written as follows:

We can calculate the fugacity from the following equation

Substituting values, we obtain

Now solve the following equation for the extent of reaction.

0.40 mol/s H2O

From these data:

Use Equation 9.21:

We know what nH2O at the outlet (at equilibrium) is, so we know .

Now we can look at our mole fractions:

Next, setting up the equilibrium constant given our known information

Recall that we can also write the equilibrium constant as K e

(a constant at any T).

C3H8O (g) C3H6 (g) + H2O (g)

From the Antoine equation

Pbsat 0.031 bar

Pasat 0.027 bar

From the equilibrium constant expression:

The reaction scheme is given by:

( y3 P)5 ( y4 P)11 ( y3 )5 ( y4 )11 P10