Chapter 9 Solutions

Engineering and Chemical Thermodynamics 2e

Milo Koretsky
Wyatt Tenhaeff

School of Chemical, Biological, and Environmental Engineering

Oregon State University

[email protected]
9.1
You need to neglect the solid in the vapor mole fraction

yD
K 2
y A yB P

2
9.2
Some products can form. Since g rxn
o
0 , K < 1. But some products form

3
9.3
g rxn
o
,298 = -500 J/mol and KT = 4

4
9.4
It would not change

5
9.5
The value of the equilibrium constant does not depend on pressure; it would not change

6
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

7
9.7
Yes, but only if it is rate limited (kinetics). Equilibrium conversion decreases for this exothermic
reaction

8
9.8
(d) High pressure increases conversion, high temperature increases rate.

9
9.9
1
K
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
K1 2
x A2 0.252
x 0.25
K2 C 2
xB 0.125

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 2O2 H 2O

Therefore,

g
f ,298 H O
2 2
grxn,298

g f ,298
H 2O

From Appendix A.3.2:

kJ
g
f ,298
H 2O
237.14
mol

kJ kJ
g
f ,298
H 2O2
116.8
mol
237.14
mol
kJ
gf ,298 H2O2 120.34 mol

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:

n I 2 nI 2 1

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

80000
(J)

60000

40000

20000

G
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

-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
K 298 exp 764.76
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,

J
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
NH 3

kJ
g
f ,1000 NH 3
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
K1000 K 298.15 exp rxn

R T2 T1
88.51103 126.110 3 1 1
K1000 exp exp
8.314 298.15 8.314 1000 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
yC 4 H 8 yC 4 H 10
11 11
10
yH 2
11

The gas is assumed ideal; therefore,

K P 1

yC4 H10


yC4 H8 yH 2


11
1 5 bar 1
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
4.49
nC 4 H 8

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 -296.813 -300.1
O2 0 0
SO3 -395.77 -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
K 973 K 298 exp rxn

R T2 T1
70.92 10 3 98.96 10 3 1 1
K 973 exp exp
8.314 298 8.314 973 298

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 3.76
y SO 2 yN2
5.76 / 2 5.76 / 2
1 / 2
yO2 y SO3
5.76 / 2 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
hrxn 0.481 98.96 q
mol
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 SO3

5.76 / 2
y y
1/2 1/2
SO3 O2
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)

The variation of hrxn is described by the following equation

B 2 C 3 1 1
hrxn

hrxn,298

R A T 298
2
T 2982
3
T 2983 D
T 298
The A, B, C, and D parameters are calculated with data from Table A.2.2:

Species v A B 10 3 C 10 6 D 10 5
SO2 -1 5.699 0.801 0 -1.015
O2 -1/2 3.639 0.506 0 -0.227
SO3 1 8.06 1.056 0 -2.028

1
A 1 5.699 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

From Problem 9.21:

3 J
hrxn ,298 98.96 10
mol

Therefore, at 700 C:
2 10 6 2
J J 0.5415 T 298
2
T 2982
hrxn

98.96 10 3 8.314
mol mol 4 1 1
8.99510 T 298

Substituting the above expression, we get

2 106 2
J J
0.5415 T 298
2

T 2982
98.96 103 8.314

mol
mol 1 1
d ln K
8.995 104
T 298


dT RT 2

27
Integrating:

K 973.15
ln 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) 0 0
C6H6 (2) 82.98 129.75
C6H12 (3) -123.22 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
K 538 K 298 exp rxn

R T2 298.15
98.0 10 3 206.2 10 3 1 1
K 538 exp exp
8.314 298.15 8.314 538.15 298.15

K 538 11.44

Take 1 mole of C6H6 as the basis for the calculations. Create expressions for the compositions of
the reaction components as functions of conversion:

10 3 1
y1 y2
11 3 11 3

y3
11 3

The gas is assumed ideal. Therefore,

29
 1 y3
K
y1 y2
3
P3

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 y2 0 y3 0.125

(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:

11 3 3
K P3
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 4
y SiCl 4 y HCl
3 3
2 2
yH 2
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,

yHCl
4

KP
SiCl4 yH 2
y 2

31
 0.8
4
K 0.001 bar
0.0667 0.133
2

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
y1 y3
3 3
2
y2
3

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.

17.2 182.26 10 3 1 1
ln T 298
141.29 10 3 8.314
exp
8.314 298.15

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

3
1 3
KP
1 2
1 3 2 3

We calculate the fugacity coefficients using

a P
i exp b
RT RT

The following table was created with the above equation

Species
C2H4 (1) 1.00
Cl2 (2) 0.996
C2H4Cl2 (3) 0.977

Therefore,

0.977
17.2 30 bar 1 3
1 2
1.00 0.996
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:

hrxn,298

1
ln K C
R T

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) K ln(K)

900 1173.15 0.000852 0.00533 8.07E-10 -20.9376
960 1233.15 0.000811 0.0253 4.10E-07 -14.7078
1000 1273.15 0.000785 0.0547 8.95E-06 -11.6236
1040 1313.15 0.000762 0.11 1.46E-04 -8.8291
1080 1353.15 0.000739 0.206 1.80E-03 -6.31952
1120 1393.15 0.000718 0.317 1.01E-02 -4.59541

ln K vs. 1/T

0
0.0007 0.00075 0.0008 0.00085 0.0009
-5

-10
y = -121600x + 83.40
ln K

R2 = 0.991
-15

-20

-25
1/T (K-1)

35
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 1
K exp rxn,298
exp
R 298 K R T 298

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

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
K exp 1.29 109
8.314 298

(b)
From data in Appendix A.3:

3 J
hrxn , 298 74.81 10
mol

Calculate K with Equation 9.21:

74.8110 3 1 1
K 1.29 10 exp
9
2.04
8.314 1000 298

(c)
Create expressions for gas compositions in terms of conversion:

2 1
yH 2 yCH 4
1 1
Note: The moles of carbon are not considered when developing these expressions
because it is in the solid phase.

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

K 4 2

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 1i

Find the mole fractions of A and B by equating liquid and vapor fugacities.

yA P x A PAsat yB P xB PBsat

xA
1 / 3 0.1 atm 1 xB
2 / 3 0.1atm 2
0.1 atm 3 0.5 atm 15

Therefore,

8
x A2
15

Now calculate the equilibrium constant

K
8 /15 4.8
1 / 3
2

(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,

B
yB P

2 / 3 0.1 atm 1.53
xB PBsat 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:

J
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 v A B 10 3 C 10 6 D 10 5
CH4 -1 1.702 9.081 -2.164 0
H2O -2 3.470 1.45 0 0.121
CO2 1 5.457 1.045 0 -1.157
H2 4 3.249 0.422 0 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
K 2 K1 exp rxn

R T2 T1
113.5103 164.94 103 1 1
K 773 exp exp
8.314 298.15 8.314 773.15 298.15

K 773 0.00739

Take 1 mole of CH4 as the basis for the calculations. Create expressions for the compositions of
the reaction components as functions of conversion:

1
yCH 4 yCO 2
6 2 6 2

41
 5 2 4
yH 2O yH 2
6 2 6 2

Since the temperature is 500 C and the pressure is 1 bar, the gas can be assumed ideal.
Therefore,

y 4

K P2
CO 2
y H 2

CH 4 yH 2O
y 2

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

i v dP RT ln
Plow
Plow

For the EOS given in the problem statement

1
vi RT Bi'
P

Therefore,

fv P 1
dP ln P B ' P P
ln i Bi
'
Plow P i low
Plow P low

Let Plow go to zero and simplify:

'
iv e B P
i

For H2S and SO2

BH' 2 S P '
BSO P
Hv S e
2
SO
v
2
e 2

(b)
The equilibrium constant can be calculated at 500 C (773.15 K) with the following equation

K 773.15 K hrxn,298

ln 773.15 2
1 C T 298 dT
K 298.15 298.15 K RT

grxn,298
773.15 K hrxn,298

K 773.15 exp exp 2
1 C T 298 dT
RT 298.15 K RT

From data in Appendix A.3

J
g rxn , 298 90,440
mol

43
 J
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 3 2
y SO2 y SO2
4 4
2
yH 2O
4

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

y P y
2 2 2

H 2O H 2O H 2O H 2O
K P 1
y SO P yH S H S P y y
2 2 2
SO2 2 2 2 SO2 H 2S SO2 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 kJ
h 3373.6 s 6.5965 (500 C, 10 MPa)
kg kg K
kJ J
g 1726.5 g 31102.6
kg mol

kJ kJ
h 3489.0 s 9.8977 (500 C, 10 kPa)
kg kg K
kJ J
g 4163.4 g 75002.8
kg mol

We can calculate the fugacity from the following equation

44
 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

0.925
2
4
100 bar
1
0.824


2 2
1 3 2 exp 4.4 109 10 10 6 exp 2.2 10 9 10 10 6

4 4

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
4 0.95 P
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:

0.40 mol/s H2O

1 mol/s H2 P = 1.5 bar H2
2 mol/s CO


CO
1 mol/s CO2 T=?K 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 0 0
CO2 -393.51 -394.36
H2O -241.82 -228.57
CO -110.53 -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
 Number of moles/s
Initial number of Moles/s of species
Species being produced
moles/s (n) as a function of
()
nH2 1 -1 1-
nCO2 1 -1 1-
nH2O 0 1
nCO 2 1 2+
nT 4 0 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 Mole fraction

yH2 0.15
yCO2 0.15
yH2O 0.1
yCO 0.6
yi 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 1
yA
1
nC nC 2 2
2
, nT 1 yC
1

Now apply Equation 9.27 (we are told to assume an ideal gas phase):
2
2 2
( yC P) 2 1 P 2 P
2
12 2
K 4 yi i
v
P
v

i ( y A P)1 1
P
1 1 1 2
1

4 1 2 12 2

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

g rxn
Recall that we can also write the equilibrium constant as K e 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 = 62.76 228.57 163.08

K= . 3

(b)

From the Antoine equation

Pasat 0.027 bar Pbsat 0.031 bar

3 4
3.62
3 4
1.14

From the equilibrium constant expression:

3
3 0.67

50
 3 2.11

(c)
0.009

0.013

0.977

51
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
v
T P 0.5 bar

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
 i Species g f ,298 K kJ/mol hf ,298 K kJ/mol
-1 C5H12 - 8.37 -146.54
+5 CO - 137.17 -110.53
-5 H2O - 228.57 -241.82
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 gas-
phase composition above):

g rxn ,298 K g f ,298 K 465.37 kJ/mol , and

h
rxn ,298 K hf ,298 K 802.99 kJ/mol
i

g rxn

82
K 298 exp ,298
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:

KT hrxn

,298 1 1
ln .
K 298 R T 298

Substituting the values of KT and K298 provides an equation with only one unknown: T.

802,990 J/mol 1 1
180.4
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 A B C D E
C5H12 2.464 45.351x10-3 -14.111 x10-6 0 0
H2O 3.470 1.45 x10-3 0 0.121 x105 0
CO 3.376 0.557 x10-3 0 -0.031 x105 0

53
(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 Cool to
T<36C
effluent

CO
H2O (liq) (b.p. -191.5C)

Liquid-Liquid Cryogenic
Separation 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

Initial number of Number of moles/s Moles/s of species as a

Species
moles/s (n) being produced (v) function of
nSiClH3 1 -1 1-
nHCl 0 1
nH 2 0 1
v
n T 1 1 1+

1
ySiClH3
1

yHCl yH 2
1
So the equilibrium constant can be written:

yHCl PyH 2 P 2P
K
ySiClH3 P 1 2

Using the thermochemical data:

grxn,298 = 24 10

hrxn,298 = 49.6 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

, ,

,
H2O -241.82 -228.57
131.29
H2 0 0
CO -110.53 -137.17
91.4
131.29 91.4
kJ/mol kJ/mol

91,400
9.5 10
8.314298

1 1 131,290 1 1
ln 37.2
298 8.314 1000 298

1.36

.
2.72 2.72
.

2.72
0.86
3.72

0.86

56
(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?

5
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

24.3 2 mol Mg 0.4 mol 47.9

.
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.

56000
0.0012
8.314 1000

2 298 642 56

0.4
0.0012
0.6

0.4
374
0.6 0.0012

58
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
R T2 298.15

Take 1 mole of C2H4 as the basis for the calculations. Create expressions for the compositions of
the reaction components as functions of conversion:

1 1
y1 y2
2 2

y3
2

The gas is assumed ideal. Therefore,

y3
K
Py1 y2

59
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
RT x2 A
K
Ax 1 x2
2
exp
RT
1 2x2

x1 exp 2
RT

From Appendix A.3:

3 J
g rxn , 298 128.75 10
mol

Therefore,

K 3.7 10 22

A
3.7 1022
x2
exp 1 2 x2
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) (Equation 1)

1 - butene 1 trans butene (3) (Equation 2)

From Table A.3.1:

Species g f ,298 kJ/mol

1-butene (1) 71.34
cis-butene (2) 65.90
trans-butene (3) 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 y 2 1 y3 2

Assuming ideal gas behavior, we obtain two equations for two unknowns:

y y
K1 2 K2 3
y1 y1
1 2
8.99 28.85
1 1 2 1 1 2

Solving, we get

1 0.231
2 0.743

62
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
R T 298
hrxn,298

1 1
K 2,1000 K 2,298 exp
R T 298

From Table A.3.1:

Species h f ,298 kJ/mol

1-butene (1) -0.13
cis-butene (2) -6.99
trans-butene (3) -11.18

Using these data, calculate the equilibrium constants

6.99 0.13 1 1
K1,1000 8.99 exp 1.29
0.008314 1000 298
11.18 0.13 1 1
K 2,1000 28.85 exp 1.26
0.008314 1000 298

Using 1 mole of species 1 as the basis results in the following expressions

y1 1 1 2 y 2 1 y3 2

Assuming ideal gas behavior, we obtain two equations for two unknowns:

y y
K1 2 K2 3
y1 y1
1 2
1.29 1.26
1 1 2 1 1 2

63
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) (Equation 1)
C 3 H 8 O 1 C 3 H 8 O (3) (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 y 2 1 y3 2

Assuming ideal gas behavior, we obtain two equations for two unknowns:

y y
K1 2 K2 3
y1 y1
1 2
1.06 10 6 6.92 10 6
1 1 2 1 1 2

Solving, we get

1 0.133
2 0.867

65
Therefore,

y1 0
y 2 0.133
y3 0.867

(b)
First, write down the and b matrices.

3 8 1 3
3 8 1 b 8
3 8 1 1

Equation 9.45 gives:

3 8 1 3
n1 n2 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
47.3 0.008314 500 ln 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
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 2
yA yC
3 3
2 2
yB
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
K 473.15 R 573.15 473.15

Determine the enthalpy of reaction:

J
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
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
First, calculate the equilibrium constant. From data in Appendix A.3:

J
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
the reaction components as functions of conversion:

6 1
yH 2O yH 2
8 8
1
yCO yCO2
8 8

The gas is assumed ideal; therefore

y y
K P0 2
H CO2

yH 2O yCO
1
1.46 1 bar
0

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

y12
KP
y2

Calculate the equilibrium constant required for 10% O:

0.10
2

K 1 bar
0.90
K 0.011

From Table A.3.2:

Species h f ,298 kJ/mol g f ,298 kJ/mol

1 249.17 231.74
2 0 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
R T 298
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

From data in Appendix A.3:

J
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
KT K 298.15 exp rxn

R T2 298.15
173.2 10 3 180.58 10 3 1 1
KT exp exp
8.314 298.15 8.314 T 298.15

The following table has been created using the above equation.

T (K) K
1100 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
compositions of the reaction components as functions of conversion:

0.79 2
yN2 y NO
1 1

72
 0.21
yO 2
1

The gas is assumed ideal; therefore

y
KP NO
0

yN 2 yO2

As an example, the conversion is calculated below at 1100 K:

2
2
5.22 10 1 bar
0
8

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

5.00E-02
yNO (mole fraction)

4.00E-02

3.00E-02

2.00E-02

1.00E-02

0.00E+00
1000 1500 2000 2500 3000
Temperature (K)

73
9.46
The reaction is

N 2 2O2 2 NO2

From Appendix A.3:

J
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
compositions of the reaction components as functions of conversion:

0.79 2
yN2 y NO
1 1
0.21 2
yO 2
1

The gas is assumed ideal; therefore

y
K P 1
NO2

yN2 yO2

For 1 bar:

2
2

1 1
3.0510 1 bar
8
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
2

1 1
3.05 10 500 bar
8
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 J
g
rxn,298
1
173.2 10 3
mol
g
rxn,298 51.26 10 3
2 mol
J J
hrxn,298

1 180.58 103 mol hrxn ,298 2 33.1103 mol

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
the reaction components as functions of conversion:

0.79 1 0.5 2 21
yN2 y NO
1 0.5 2 1 0.5 2
0.21 1 2 2
yO 2 y NO 2
1 0.5 2 1 0.5 2

Assuming ideal gas behavior, we obtain the following expressions for the equilibrium constants:
21
2

1 0.5
0.0154 P 0 2

0.79 1 0.5 2 0.21 1 2
1 0.5 2 1 0.5 2
2

1 0.5
0.000142 P 0.5 2

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
constant. From Appendix A.3:

J J
g

rxn,298 1 173.2 10 3
mol
g

rxn,298 2 35.34 10 3
mol
J J
hrxn,298

1 180.58 103 mol hrxn,298

2 57.19 103 mol
From Appendix A.2:

A1 1.45 , B1 0.000159 , C1 0 , D1 21500

A2 0.2245 , B2 0.000313 , C1 0 , D1 69250

Using Equation 9.24, we find

K1 0.0154
K 2 0.00114

Take 1 mole of air as the basis for the calculations. Create expressions for the compositions of
the reaction components as functions of conversion:

0.79 1 21 2
yN 2 yNO
1 0.5 2 1 0.5 2
0.21 1 0.5 2 2
yO2 yNO2
1 0.5 2 1 0.5 2

77
Assuming ideal gas behavior, we obtain the following expressions for the equilibrium constants:

21 2
2

0 1 0.5 2
0.0154 P
0.79 1 0.21 1 0.5 2

1 0.5 2 1 0.5 2

2

0.5 1 0.5 2
0.00114 P

0.5

0.21 1 0.5 2 21 2
1 0.5 2 1 0.5 2

Solving simultaneously:

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) 9.079 97.79
NO2 (2) 33.1 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,

1 2
y1 y2
1 1

Assuming ideal gas behavior:

y 22
KP
y1
2
2

1
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,

1 2
y1 y2
2 2

Assuming ideal gas behavior:

y2
KP 2
y1
2
2

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:

d ln K


d g rxn
/ RT (I)
dT dT

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,

d g rxn / RT


1 757000

7 .5
dT R T2 T ln 10

hrxn 1 757000 7 .5

RT 2 R T 2 T ln 10

7.5
hrxn 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
constant. From Appendix A.3:

J J
g
rxn,298
1
142.12 10 3
mol
g
rxn,298
28.62 10 3
2 mol
J J
hrxn,298

1 206.1103 mol
hrxn,298

2 41.16 103 mol

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

Using Equation 9.24, we find

K1,800 0.03
K 2,800 4.29

Create expressions for the compositions of the reaction components as functions of conversion:

1 1 31 2
yCH 4 yH 2
5 21 5 21
4 1 2
yH 2O yCO 1 2
5 21 5 21
2
yCO 2
5 21

Assuming ideal gas behavior, we obtain the following expressions for the equilibrium constants:

31 2
3
3

1 2
2 1 2
2 5 21 5 21 5 21 5 21
0.03 P 4.29 P 0
4
1 1 4 1 2 1 2 1 2

5 21 5 21 5 2 1 5 2 1

Solving simultaneously:

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
First, calculate the equilibrium constant. From data in Appendix A.3:

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
yC 2 H 2 y HCN
2 2
1
yN2
2

The gas mixture is assumed ideal; therefore

y
K P0 HCN

yC2 H 2 yN 2
2
2

2
0.021 1 bar
0

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 1
K pO 2
pO 2 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

grxn
3.40 10 5 14.24T lnT 248T
K exp exp
RT RT

The following table has been created

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

We can also plot the data.

Partial Pressure of O2 as a Function of

Temperature
1.00E-02
1.00E-09
1.00E-16
PO2 (bar)

1.00E-23
1.00E-30
1.00E-37
1.00E-44
1.00E-51
100 300 500 700 900 1100 1300 1500
Temperature (K)

86
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:

K2 h o 1 1
ln rxn
K1 R T2 T1

Substitute numerical values to solve the enthalpy of reaction:

1.12 10 3
8.314 J/mol K ln 5
1.98 10 J
hrxn
o
1.88 10 5
1 1 mol

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

1 bar y2
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
 1 2
yH 2 y HCl
1 1

Substitute these expressions into the expression for the equilibrium constant and solve for :

2
2

1 4 2
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

K n2 4 2
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 ) Reaction 1

C2 H 4 ( g ) 4 H 2O( g ) 2CO2 ( g ) 6 H 2 ( g ) 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) 0 0

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 T2 298.15

And for Reaction 2:

hrxn

1 1 7
K 355 K 298 exp 3.5 10
R T2 298.15

Take 1 mole of C2H4 as the basis for the calculations. Create expressions for the compositions of
the reaction components as functions of conversion:

89
 1 1 2 1 1 4 2
y1 y2
2 1 3 2 2 1 3 2
1 2 2
y3 y4
2 1 3 2 2 1 3 2

The gas is assumed ideal. Therefore,

y3
K1
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 g f (kcal/mol) Expected Rank

4-methyloctane
161.90 Highest
(B)
nonane
162.15 :
(A)
4-ethylheptane
164.22 :
(C)
2,2,3-trimethylhexane
168.13 :
(D)
3,3-diethylpentane
171.79 :
(E)
2,2,3,4-tetramethylpentane
175.62 Lowest
(F)

(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 nonane

(A)

4-methyloctane (B) and 4-ethyl-heptane (C). Each isomer K1 K2

will be in equilibrium with nonane, as shown at right. The
isomers can interchange with one other by first going through 4-methyloctane 4-ethylheptane
nonane, then isomerizing to the other species. (B) (C)

We can write the following equilibrium expressions for the system:

B yB P yB
A K1
K1 yA P yA

91
 C yC P yC
A K2
K2 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,

nA 1 1 2 y A 1 1 2

nB 1 nT 1 (constant) , yB 1
nC 2 yC 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?

161,900 162,150 mol

cal
K1 exp 1.13
1.987 cal 1000 K
molK
164, 220 162,150 mol
cal
K 2 exp 0.35
1.987 cal 1000 K
molK

Now write the two equilibrium expressions together:

1
K1 K
1 1 2 1 1

2 K2 2
K2
1 1 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
1 yB 0.402
1 K1 K 2
y A 1 y A yB 0.456
K2
2 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-2-
butene formed per mole of pentane fed. You may assume that for each reaction does not
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 -146.54 -8.37

C3H6 20.43 62.76
C2H6 -84.68 -32.84
trans C4H8 -11.18 63.01
CH4 -74.81 -50.72

From these data:

, 38.29 10

, 20.66 10

, 82.29 10

, 60.55 10

Use Equation 9.21:

, ,

94
 . .
, 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.

Number of Moles of
Moles of Initial number
moles being species as a
species of moles (n)
produced (v) function of
nC5H12 1 -11 - 12 1 - 1 - 2
nC3H6 0 11 1
nC2H6 0 11 1
ntrans C4H8 0 12 2
nCH4 0 12 2
nT 1 11 + 12 1 + 1 + 2

Next we look at the mole fractions

Species Mole fraction

1
yC5H12
1

yC3H6
1

yC2H6
1

ytrans C4H8
1

yCH4
1
yi 1

95
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
. .

, 0.5
. .

, 1.14 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.

moles
0.76
mol C H fed

96
9.57

C2H2 + N2 2HCN
(1) (2) (3)

C H O 2CO 5H O
(4) (5) (6)

1 mole C2H2

5 25
5 moles O moles O
2 2
0.72 25
moles N 47 moles N
0.21 2

n1 = 1
. . .
n2 = 47
n3 = 2
K
n4 = 12.5
nT = 60.5

(kJ/mol) (kJ/mol)
C2H2 226.88 209.24
HCN 130.63 120.2

kJ
, 2 130.63 226.88 34.38 mol

kJ
, 2 120.2 209.24 31.16 mol

/ / .
K , 3.45 10

ln 10.6

.
K 3.46 10 0.14

97
 4
0.14
48 47

1.77 1.77 4 1.73

0.7
2

2
0.0231
60.5

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 -146.54 -8.37 -1
H2O -241.82 -228.57 -10
CO2 -393.51 -394.36 5
H2O 0 0 16
rxn 597.19 322.27

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

Using Equation 9.21 and data from Appendix A.2, we obtain

K 600 ho 1 1 597,190 1 1
ln rxn 121.35
K 298 R T 298 8.314 600 298

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 5
yC5 H12 yCO2
11 10 11 10
10 1 16
y H 2O yH 2
11 10 11 10

The gas mixture is assumed ideal; therefore

y y
5 16
5 16
5 16
10 CO2 H2
P10
K 600 P

y
y 1 10 1 11 10 10
10 10

C5 H12 H 2O

Solving:

0.56

Now calculate the compositions

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

Using Equation 9.21 and data from Appendix A.2, we obtain

100
 K2 hrxn
o
1 1 41,160 1 1
ln 8.36
K 298,2 R T 298 8.314 600 298

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 51 2 2
yC5 H12 yCO2 yCO
11 101 11 101 11 101
10 101 2 161 2
y H 2O yH 2
11 101 11 101

The gas mixture is assumed ideal; therefore

y y
5 16

10 CO2 H2

K1 P
y
y
10

C5 H12 H 2O
And

yH O yCO
K2 2
yCO2 yH 2

Solving:

1 0.584 and 2 0.230

Now calculate the compositions

yC5 H12 0.0247 yCO2 0.160 yCO 0.014
yH 2O 0.260 yH 2 0.542

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;

yD
K1 5
Py A yB

1
K2 9
y P2
2
B

yF2 4
K3
y A yD 15
(b)
Increase the pressure

102
9.61
(a)
C s H O g H CO g

= 1 mol 1
K 1
= 1
= 1
=
= 1
K

kJ kJ
, , , 137.17 228.57 mol 91.4 mol

,
K 96.52 10
R 298

, , , , 110.53 241.82 131.28

K 1 1 131280 1 1
53
K R T 298 8.314 1000 298

K 1.36 K P 2.72

2.72
0.86
3.72

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 2H O g 2H 2CO g

i. K 1.86

ii. same

(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 H O g H CO g Rxn 1 1.36

CO H O CO H Rxn 2 0.89

n1 = 1
1
y1 = 1
n2 =

n3 = y2 = 1

n4 = y3 = 1

nT = 1
y4 = 1

Find KT for rxn 2

394.36 228.57 137.17 28.62

104

K exp 104000

393.51 241.82 110.53 41.16

K
ln 11.66
K

K , 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:

RT i RT cZn2
ln pi i ci im orxn

orxn ln (1)
zF vapors liquids
zF
cCu
2
or
8.314 298 0.5
1.104 ln 1.12 V
2 96, 485 0.1

Since 0, the reaction is spontaneous. To see how far this reaction goes

o
cZn 2 c (2)
Zn 2
cCu 2 c o 2 (3)
Cu

At equilibrium, 0. Substituting Equations (2) and (3) into (1) and solving gives:

1
cZn 2 0.6m
38
cCu 2 10 m

Thus, approximately all the copper in the solution is consumed.

106
9.63
(a)
Anode e- e- Cathode

Pt Pb

cations anions

(b)
The following half reactions can be written, with the corresponding half-cell potentials are
obtained from Table 9.1:

O 0.126 V (reduction reaction)

O 0.000 V (oxidation reaction)
(c)
The overall reaction is

orxn 0.126 V

Applying Equation 9.34 to this system and using the fact that Pb2+ is 1 m:

RT i RT
ln pi i ci im orxn
2
orxn 2.3log10 aH (1)
zF vapors liquids zF

Solving Equation (1) for pH:

F
pH log10 a H orxn
2.3RT

Thus,
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
The following half reactions can be written, with the corresponding half-cell potentials are
obtained from Table 9.1:

o 0.401 V (reduction reaction)

o 0.447 V (oxidation reaction)

The overall reaction is

o
rxn 0.848 V

Applying Equation 9.34 to this system and using the fact that Pb2+ is 1 m:

RT i
ln pi i ci im

orxn
zF vapors liquids
(1)
RT cFe2 RT 2
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

8.314 298 0.1 8.314 298

0.848 ln 2 2.3 0.99 V
2 96, 485 0.21 96, 485

Since 0, the reaction is spontaneous.

108
9.65
(a)
The overall reaction is

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
o
mol
3o 2
0.34 V
zF mol e- C
2 2+
96, 485
mole Cu mole e-

This value is consistent with that reported in Table 9.1.

110
9.67
(a)
The following half reactions can be written, with the corresponding half-cell potentials are
obtained from Table 9.1:

o 1.229 V
o 0.000 V
The overall reaction is

o
rxn 1.229 V

Applying Equation 9.34 to this system and assuming Zn2 , Cu2 1 gives:

RT i RT 1/2
ln pi i ci im orxn

orxn ln pO2 pH 2 (1)
zF vapors liquids zF

8.314 298
1.229
2 96,485

ln 0.21 0.4 1.25 V

The work can be obtained from as follows. Assuming complete conversion:

kJ
W * zF 241
mol H 2
(b)
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

8.314 923
0.700 ln 0.21 0.4 0.767 V
2 96, 485

The work can be obtained from integrating Equation 9.67. Assuming complete conversion:

kJ
W * zF 148
mol H 2

112
9.68
The following half reactions can be written, with the corresponding half-cell potentials are
obtained from Table 9.1:

o 0.341 V
o 0.342 V

The overall reaction is

o
rxn 0 V

Applying Equation 9.34 to this system:

m
RT RT Cu2 cCu2 0.01m
ln pi ci i
m i
i
o
rxn ln m (1)
zF vapors liquids zF Cu 2 c
Cu 2

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
I
2
zi2ci 4c 2 4c 2 8c 2
2 Cu SO4 Cu

Using the modified Debye-Huckel theory, Equation 9.38, which is valid up to about 1m, we
have:

A z z I 4 1.17 8cCu 2
ln
1 B I 1 0.33 8cCu 2
For 0.01m Cu , ln 1.21
2+

For 0.1m Cu2+, ln 3.23

m
RT RT Cu2 cCu2 0.01m
ln pi ci i
m i
i
rxn
o
ln m
zF vapors zF Cu2 cCu2
0..1m
liquids

m
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
The following half reactions can be written, with the corresponding half-cell potentials are
obtained from Table 9.1:

o 0.000 V

o 0.222 V

The overall reaction is

o
rxn 0.222 V

Applying Equation 9.34 to this system and taking the activities of the solids to be 1 gives:

RT RT H cH Cl cCl
m m

ln pi ci i rxn
m i
i
o
rxn o
ln (1)
zF vapors liquids
zF pH 2

or in terms of the mean activity coefficient

orxn
RT
zF
ln 2cHCl
2

solving gives

zF o
exp
rxn

RT
0.818
cHCl

115
9.70
The following set of equations and equilibrium constant expressions can be written:

Cl a 2
K1 (1)
pCl2 g

K2
ClO n (2)
Cl aVO

K3 pn (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
n
ClO

Using Equation (1), we have:

Cl a K1 pCl g
2

So
K 2 VO K1 pCl2 g
n
ClO

At high ClO
concentrations, electroneutrality gives: ClO
n
So

n K 2 VO K11/4 pCl
1/4
2

and from Equation (3):

K3 K3
p pCl1/4
n K 2 VO K1
1/4 2

116
9.71
For the set of equations given in the problem, the following equilibrium constant expressions can
be written:

K1 VA VB (1)

V A p 2
2

K2 (2)
pB2

K3 VB 2 2
n pB2 (3)
K4 np (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 (5)

Region 1: low pB2

We take V A n and VB p , so electroneutrality gives:

n VB

From Equation (1):

V A VKB1
and from Equation (4)

K4
p
n

Thus, Equation (2) gives

2
VA p 2 K1K 4
2

K2 2
pB2 VB n 2 pB
2

From Electroneutrality:

117

VB n K1K 4 pB1/4
K 2
2

VA K1 K1 K 2 p1/4
K B2
VB 4

And from Equation (4):

K4 K K
p 4 2
p1/4
B2
n K1

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

We take V A n and VB p , so electroneutrality gives:
n p
So from Equation (2):

n p K4

From Equation (2):

K 2 pB2
VA
K4

and from Equation (1),

VB K1 K1 K 4

VA K 2 pB2

Region 3: high pB2 .

We take V A n and VB p , so electroneutrality gives:

V A p
So from Equation (2):

118
 VA p K 2 pB
1/ 4
2

From Equation (1):

VB VKA1 K1 K 2 pB
1/ 4
2

And from Equation (4):

K 1/ 4

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

2
Region 1: Low pB Region 2: Intermediate Region 3: High pB
2 pB 2
2

n VB n p
V A p

1/4
K K 2 1/ 4 p K4 p K2 pB2
p 4 p
K1 B2
1/ 4
K K
n 1 4 pB1 / 4 n K4
n K4 K2 p B2
K 2 2

1/ 4
K K 4 K2 pB2 V A K 2 pB2

V A 1 2 p1/
K4 B2

V A
K4

1/ 4

VB
K K / 4
1 4 p1
VB K1
K4
K2 p B2

VB K1 K2 pB2
K2 B2

119
 low intermediate high
pB2 pB2 pB2

VB n p
V A

Concentration
n p
p n

V A VB

pB2

120
9.72
As in Example 9.24:
K1 Bi VB (1)

K2
V n

B (2)
VB
K3
Bi p
(3)
Bi
Bi 2 (4)
K4
pB2
K5 pn (5)

Inserting Equation 3 into Equation 4 and rearranging

K3 K4 p B2

Bi
p
(6)

Equations 1, 2, and 4 give

VB n KK1K4 p2B (7)

2

And Equation 5 Gives

K (8)
p 5
n

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
2


n VB . Setting Equation (7) becomes:

VB n K1K 2 pB1/4 (10)

K4 2

Equation (8) becomes:

121
 K 4 1/4
p K5 pB (11)
K1K 2 2

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
n pB2
K3K 4

From Equation 8, we have

K 3 K 4 K 5 1/2
p 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
K 5 K 41/4 2

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 pB
2 2 2
n
VB

Bi

VB p
Bi

VB KK11/4K22 p1B2 / 4 Bi K1 KK25K3 VB K1 5K2 41 / 4 3 pB12 / 4

K K K

Bi
K1 K2 K3 K1/
4
4
p1B/ 4 p
K3 K4 K5 1/ 2
p
K1 K2 B2
Bi K3 K1/4 4 p1/B24
K5 2
K5 K1/ 4 K1K 2 K5 1/ 2 K5 1/ 4
p 4
p1B/ 4 n p n 1/4
pB
K1K2 2 K3 K4 B2 K3 K 4 2

From this table, the following Brouwer diagram can be constructed:

low intermediate high

pB2 pB2 pB2

VB n Bi
Bi VB p
Concentration

Bi VB
n p

p n

pB2

123
9.73
From Example 9.23:
Oi 2
K1 (1)
pO
2

K2
p
Oi
(2)
Oi

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
n p1 /4
K2 K11/ 4 O2

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):

O(a)2
K1 (1)
pO
2

and incorporation of the absorbed oxygen into a lattice site, creating two copper vacancies:

VCu 2
K2 (2)
O(a)
Solving Equations (1) and (2) for oxygen partial pressure in terms of copper vacancies gives:

VCu 4
pO 2
2
K1 K2

Hence the ratio of vacancies at 3 torr to that at 760 torr (1 atm) is given by:

VCu 3 torr 3
1/4
0.25
VCu 760 torr 760

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

K ni2 1020 cm-6

hence
K 5 -3
n 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

K400 ni2 1.2 10 25 cm-6

Hence

which gives

Using

gives

K373 9.6 1023 cm-6

Thus

126
 K 8 -3
n 9.6 10 cm
p
(c)
Electroneutrality now becomes:

p PSi BSi n

but PSi p . Hence

n 9 1015 cm-3
and

K
p 1.110 4 cm-3
n

127
9.76

K1 n Cui (1)

K2
CuSi p
3 3
(2)
VSi

K3
PSi n
(3)
VSi

K4 pn (4)

From Table 9.2 K4 = 1020 cm-6

Since Cui =106 cm-3, K1=1016 cm-6

3

Since CuSi =102 cm-3, K2 VSi =1032 cm-12

To get the total copper, we sum together the two defects

1016 1032

Cui CuSi
3

n
3
p

Using Relation (4)

10 20
p
n

so

1016

Cui CuSi
3
n
1028 n 3

The minimum occurs when the derivative with respect to n is zero

d Cui CuSi
3
1016 3 1028 n 2 0
dn 2
n

or
n = 7.6 x 1010 cm-3

128
So you want a P concentration around 7.6 x 1010 cm-3. At this concentration,

1016

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

Thus the defect concentration is reduced by 8.25 x 105 cm-3.

129
9.77
(a)

B(a)
2
pH3 2
K1 (1)
pB2 H 6
BSi p
K2 (2)
B(a) VSi
K3 pn (3)
(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
K3 K3 p3/2
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

K3 p3/4
n 1/4H 2
K 2 VSi K1 pB2 H 6

This we can make the following plot:

 low pB2H 6 high pB2H 6

log Concentration
BSi
p
p n slope = 1/4
n slope = -1/4

BSi
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
0.79 6.5
nN 2 = 24.5 mol
0.21
For 2000K and 50 bar:

Formula n (Initial) y (Initial) n (Equilibrium) y (Equilibrium) Phi*

C4H10 1.000 3.12e-2 2.97e-60 8.85e-62 1.021
O2 6.500 0.203 1.53e-2 4.56e-4 1.006
N2 24.500 0.766 24.494 0.731 1.007
H2O 0.000 0.000 4.991 0.149 1.004
NO 0.000 0.000 1.23e-2 3.68e-4 0.996
NO2 0.000 0.000 6.41e-6 1.91e-7 1.003
H2 0.000 0.000 8.9e-3 2.66e-4 1.005
CO 0.000 0.000 3.4e-2 1.01e-3 1.007
CO2 0.000 0.000 3.966 0.118 1.008

C H O N
Lambda/RT 18.2589 2.15857 1.88732 -1.80261

For 2500K and 50 bar:

Formula n (Initial) y (Initial) n (Equilibrium) y (Equilibrium) Phi*

C4H10 1.000 3.12e-2 1.91e-52 5.66e-54 1.018
O2 6.500 0.203 0.129 3.84e-3 1.005
N2 24.500 0.766 24.446 0.726 1.005
H2O 0.000 0.000 4.938 0.147 1.004
NO 0.000 0.000 0.107 3.18e-3 0.995
NO2 0.000 0.000 8.25e-5 2.45e-6 0.998
H2 0.000 0.000 6.24e-2 1.85e-3 1.004
CO 0.000 0.000 0.304 9.01e-3 1.006
CO2 0.000 0.000 3.696 0.110 1.006

C H O N
Lambda/RT 15.6957 1.18748 0.822376 -1.79841

132