4.

CHEMICAL EQUILIBRIUM

n Equilibrium Constants

4.1. 2A →
← Y + 2Z

Initial amounts: 4 0 0 mol

Amounts at equilibrium: 1 1.5 3.0 mol

Concentrations at equilibrium: 1 1.5 3.0

5 5 5 mol dm–3

(1.5/5) (3.0/5)2 (1.5) (3)2

Kc = mol dm–3 = mol dm–3
(1/5)2 (5)

= 2.7 mol dm–3

4.2. A + B →
← Y + Z

Initial amounts: x 3 0 0 mol

Amounts at equilibrium: x–2 1 2 2 mol
2×2
= 0.1; x – 2 = 40
( x − 2) × 1
x = 42
Thus, initially there must be 42 mol of A.

4.3. A + 2B →
← Z

Initial amounts: x 4 0 mol

Amounts at equilibrium: x–1 2 1 mol

Concentrations at equilibrium: x –1 2 1
5 5 5 mol dm–3
 CHEMICAL EQUILIBRIUM n 73

1/5 25
= 0.25 = 4(x – 1)
[(x – 1)/5] (2/5)2
25 = x – 1 x = 26
Thus, initially there must be 26 mol of A.

4.4. Two moles of SO3(g) produce 3 mol of product; thus Σν = +1 mol. Then, from Eq. 4.26,

KP = Kc(RT)+1

= (0.0271 mol dm–3) (8.3145 J K–1 mol–1 × 1100 K)

= 247.8 J dm–3 = 2.478 × 105 J m–3
= 2.478 × 105 Pa = 2.48 bar

4.5 I2 →
← 2I

Initial amounts: 0.0061 0 mol

Equilibrium amounts: 0.0061(1 – 0.0274) 0.0061 × 2 × 0.0274 mol
= 5.93 × 10–3 = 3.3428 × 10– 4 mol
(3.3428 × 10 4 / 0.5)2
Kc = mol dm–3 = 3.77 × 10–5 mol dm–3
5.93 × 10 3 / 0.5
KP = 3.77 × 10–5 mol dm–3 (8.3145 J K–1 mol–1 × 900 K)

= 0.282 Pa = 2.82 × 10–6 bar

4.6. Addition of N2 at constant volume and temperature necessarily requires the equilibrium to shift to
the right.

[NH3]2 n2NH V2
3
Kc = =
[N2][H2]3 nN nH3
2 2

If nN is increased at constant V, the equilibrium must shift so as to produce more ammonia. If the
2
pressure (as well as the temperature) is held constant, however, addition of N2 requires that V is
increased. If the proportional increase in V 2 is greater than the increase in nN the equilibrium will
2
shift to the left when N2 is added.

The volume V is proportional to nN + nH + nNH , and V 2 is proportional to

2 2 3
(nN + nH + nNH )2
2 2 3
If nN is very much larger than nH + nNH , V 2 will increase approximately with n2N and therefore
2 2 3 2
increases more strongly than nN . If nN is not much larger than nH + nNH , an increase in nN will
2 2 2 3 2
have a relatively smaller effect on V 2 . The increase in ammonia dissociation when N2 is added is
therefore expected when N2 is in excess, but not otherwise.
74 n CHAPTER 4

On the other hand, n3H appears in the equilibrium expression; this varies more strongly than V 2,
2
and added H2 therefore cannot lead to the dissociation of ammonia.

4.7. Suppose that in 1 dm3 there are

x mol of N2O4
y mol of NO2
Pressure = 0.597 bar = (x + y)RT/V
( x + y)mol × 0.0831 bar dm 3 K −1mol −1 × 298.15K
=
1 dm 3
Therefore, x + y = 0.024 08 (1)
(92.02x + 46.01y) g (2x + y) × 46.01 g
Density = 1.477 g dm–3 = =
1 dm3 1 dm3
Therefore, 2x + y = 0.032 10 (2)
From Eqs. (1) and (2), we get x = 0.00802; y = 0.0161

N2O4(g) š 2NO2 (g)

P(1– α) 2 Pα
Since partial pressures are proportional to the number of moles of each species present,
x ∝ P(1 – α) and y ∝ 2Pα, which means that
y 2Pα
x = P(1 – α) ,
from which we get
y
α = (2x + y) = 0.500.

(0.012 86)2
Kc = 0.009 62 mol dm–3 = 0.0322 mol dm–3

KP = KcRT (from Eq. 4.26, with Σν = 1)

= 0.0322 mol dm–3 × 0.083145 × 298.15 dm3 bar mol–1

= 0.798 bar
Kx = KPP–1 (from Eq. 4.32)

= KP (1 bar)–1 = 0.798
Addition of He produces no effect, since concentrations, partial pressures, and mole fractions
remain unchanged.

1.10 g NOBr
4.8. 1.10 g NOBr = = 0.010 mol NOBr
14.01 g mol–1 N + 16.00 g mol–1 O + 79.91 g mol–1 Br
If α is the degree of dissociation,
 CHEMICAL EQUILIBRIUM n 75

nNOBr = 0.01 (1 – α) mol; nNO = 0.01 α mol

nBr = 0.005 α mol

2

Total amount, n = 0.01 + 0.005 α mol

PV 0.355 bar × 1 dm 3
= RT =
0.0831 × 298.15 bar dm 3 mol −1
= 0.0143 mol
α = 0.861; n = 0.0143
nNOBr = 1.39 × 10–3 mol; nNO = 8.61 × 10–3 mol

nBr = 4.305 × 10–3 mol

2

(8.61 × 10–3 mol dm–3)2 (4.305 × 10–3 mol dm–3)

Kc =
(1.39 × 10–3 mol dm–3)2
= 0.165 mol dm–3
KP = KcRT (from Eq. 4.26)

= 0.165 mol dm–3 × 0.0831 × 298.15 dm3 atm mol–1

= 4.09 bar
Kx = KP (0.355 bar)–1 (from Eq. 4.32) = 11.5

4.9. Suppose that, if there were no dissociation, the partial pressure of COCl2 was P; then the actual
partial pressures are

COCl2(g) →
← CO(g) + Cl2(g)

P(1 – α) Pα Pα
P + Pα = 2 bar
With α = 6.30 × 10–5
2 bar
P =
1 + (6.3 × 10–5)
≈ 2 bar

(2 × 6.3 × 10–5)2
KP =
2[1 – (6.3 × 10–5)]
≈ 2 × (6.3 × 10–5)2 bar

= 7.94 × 10–9 bar

Kc = KP(RT)–1 (from Eq. 4.26)

= 7.94 × 10–9 bar × (0.0831 × 373.15 dm3 bar mol–1)–1

= 2.56 × 10–10 mol dm–3
Kx = KPP–1 (from Eq. 4.32) = 7.94 × 10–9 bar (2 bar)–1 = 3.97 × 10–9
76 n CHAPTER 4

4.10. H2 + I2 →
← 2HI

Initially: 1 3 0 mol

At equilibrium: x x x mol
1–2 3–2

After addition of 2 mol H2: 3–x 3–x 2x mol

x2 4x2
K = =
1 – x 3 – x (3 – x)2
 2  2
x = 3/2
4(3/2)2
K = =4
(3/2)2

4.11. 12.7 g iodine = 0.05 mol I2

When all of the solid iodine has just gone, the iodine pressure is 0.10 atm. The consumption of 0.05
mol I2 leads to the formation of 0.10 mol HI, which exerts a pressure of

0.1 mol × 0.0831 dm3 bar K–1 mol–1 × 313.15 K

PHI =
10 dm3
= 0.260 bar
Then, if PH is the partial pressure of H2 after equilibrium is established,
2

(0.260 bar)2
= 20
PH 2 × 0.10 bar

PH = 0.0338 bar
2

0.0338 bar × 10 dm3

nH =
2 0.0831 × 313.15 bar dm3 mol–1
= 0.0130 mol
Thus, 0.0130 mol of H2 is produced in the equilibrium mixture, and 0.05 mol of H2 is required to
remove the 0.05 mol of I2. Therefore, 0.065 mol of H2 must be added.

4.12. Assuming that we start with one mole of N2O4(g),

N2O4(g) š 2NO2 (g)

1– α 2α
We obtain (1+α) moles of gas at equilibrium. Therefore, equilibrium partial pressures are
1−α 2α
PN 2O4 = P; PNO2 = P,
1+α 1+α
and
 CHEMICAL EQUILIBRIUM n 77

4α 2
KP = P; K c = K P ( RT ) −1 ; K x = K P / P.
1−α 2

Therefore, at 0.597 bar,

KP = 1.08 bar, Kc = 4.35 × 10–2 mol dm–3, Kx = 1.81,

and at 6.18 bar,

KP = 1.45 bar, Kc = 5.84 × 10–2 mol dm–3, Kx = 0.234.

4.13. Rewriting the reaction in terms of one mole of HCl, we get

1 →
←
1 1
HCl(g) + 4O 2(g) 2Cl2(g) + 2H2O(g)

(1 – y) PO y/2 y/2
2

From examining the equation above, it is possible to establish the following relationships:

x Cl 2 y x H 2O
= ; = 1.
x HCl 2(1 − y ) x Cl 2

It is important to remember that the same ratios hold for partial pressures also. Now,

PCl1 /22 × PH1 /22O PCl 2 y 1

KP = = = × 1/ 4 .
PHCl × PO12/ 4 PHCl × PO12/ 4 2(1 − y ) PO
2

4.14. Assuming ideal behavior, the partial pressure of oxygen is 0.51 bar. Therefore,

0.76 1
KP = × = 1.87 bar −1 / 4 .
2(1 − 0.76) 0.510.25

4.15. Since no reactants are initially present, we write

H2(g) + I2(g) →
←
HI(g)

x x n – 2x

where n is the initial amount of HI: n = 10.0 g/(127.912 g mol–1) = 7.8179 × 10–2 mol.
(n − 2 x )2 n − 2x
Since K P = 65.0 = , or 65 = , we can solve for x. The solution is x = 7.7695 ×
x2 x
10–3 mol. Therefore, the equilibrium mole fractions are xH = xI = x/n = 9.94 × 10–2; xHI = (n –
2 2
2x)/n = 0.801.
78 n CHAPTER 4

n Equilibrium Constants and Gibbs Energy Changes

4.16. a. ∆G°/J mol–1 = –8.3145 × 283.15 ln (2.19 × 10–3)
∆G° = 14 417 J mol–1 = 14.42 kJ mol–1

b. (C6H5COOH)2 →
←
2C6H5COOH

Initially: 0 0.1 mol dm–3

At equilibrium: x 0.1 – 2x mol dm–3
(0.1 – 2x)2
x = 2.19 × 10–3

4x2 – 0.402 19x + 0.01 = 0

0.402 19 ± 0.001 76 0.402 19 ± 0.041 95
x = 8 = 8
= 0.0555 or 0.04503 mol
Only the second answer is possible, and this leads to
Dimer: 0.045 mol dm–3; Monomer: 0.01 mol dm–3

(0.4)2 × 0.2
4.17. KP at 3000 K = = 0.0889 atm
(0.6)2
∆G°/J mol–1 = –8.3145 × 3000 ln 0.0889
∆G° = 60 370 J mol–1 = 60.4 kJ mol–1

2930
4.18. a. ln Kc = – = –1.136; Kc = 0.321
8.3145 × 310.15
15 500
b. ln Kc = + = 6.01; Kc = 408
8.3145 × 310.15
c. Kc = 0.321 × 408 = 130.9

∆G° = 2.93 – 15.5 = –12.6 kJ mol–1

4.19. a. ∆G° = ∆G°Products – ∆G°Reactants = 2(–16.63) – 0 – (3 × 0) = –33.26 kJ mol–1

KP = exp(–∆G°/RT) = 6.71 × 105 bar–2

b. ∆G° = –32.82 – 209.20 = –242.02 kJ mol–1

KP = 2.5 × 1042 bar–2

c. ∆G° = –32.82 – 68.15 = –100.97 kJ mol–1

KP = 4.9 × 1017 bar–1
 CHEMICAL EQUILIBRIUM n 79

d. ∆G° = –32.82 + (2 × 50.72) = 68.62 kJ mol–1

KP = 9.5 × 10–13

4.20. KP Σv Kc = KP (RT)– Σv Kx = KP P– Σv

a. 6.71 × 105 bar–2 –2 1091.9 (mol dm–3) –2 6.71 × 105

b. 2.5 × 1042 bar–2 –2 4.0682 × 1039 (mol dm–3) –2 2.5 × 1042

c. 4.9 × 1017 bar–1 –1 1.9766 × 1016 (mol dm–3) –1 4.9 × 1017

d. 9.5 × 10–13 0 9.5 × 10–13 9.5 × 10–13

4.21. a. ∆G° = –RT ln K

= –8.3145 × 298.15 ln 10–5
= 28 540 J mol–1 = 28.5 kJ mol–1
∆H° = ∆G° + T∆S° = 28 540 – 298.15 × 41.8
= 16 077 J mol–1 = 16.1 kJ mol–1
b. CO + H2 O →
← CO2 + H2

Initially: 2 2 0 0 mol
At equilibrium: 2–x 2–x x x mol
x2
KP = Kc = = 1.00 × 10–5
(2 – x)2
(Note that the total volume cancels out and so need not be considered.)
x
2 – x = 3.16 × 10 ; x = 6.30 × 10–3
–3

The amounts are therefore

1.994 mol (CO); 1.994 mol (H2O)

6.30 × 10–3 mol (CO2); 6.30 × 10–3 mol (H2)

4.22. For reaction (1)

K1 = exp(–23 800/8.3145 × 310.15)

= 9.81 × 10–5 dm3 mol–1

For reaction (2)
K2 = exp(31 000/8.3145 × 310.15) = 1.66 × 105 mol dm–3
For the coupled reaction (3)
80 n CHAPTER 4

K3 = K1K2 = 16.3

2.9 6.2
4.23. K1 = 90.9 = 0.0319 K2 = 2.9 = 2.138

K(overall) = K1K2 = 0.0682

∆G° = –RT ln K = 8.3145 × 298.15 ln 0.0682

= –6656.8 J mol–1 = –6.66 kJ mol–1
4.24. Let the solubility be c moles per dm3. Then

Cr(OH)3(s) →
← Cr 3+ + 3OH–
c 3c
Then the value of the solubility product is Ksp = c(3c)3 = 27c4. Therefore,

c = (Ksp/27)1/4 = 3.2 × 10–8 mol dm–3.

n Temperature Dependence of Equilibrium Constants

4.25. a. Zero
b. ∆G° = 0; ∆H° > 0; ∴ ∆S° > 0
c. Kc = KP(RT)–Σν = (0.0831 × 298.15)–1

= 0.0404 mol dm–3

∆G° = –8.3145 × 298.15 ln 0.0404 = 7955 J mol–1
= 7.96 kJ mol–1
d. KP > 1 bar

e. ∆G° < 0

4.26. a. Yes
b. Yes
c. ∆S° > 0

4.27. a. ∆G° = –32.82 – 68.15 = –100.97 kJ mol–1

∆H°= –84.68 – 52.26 = –136.94 kJ mol–1
–136 940 + 100 970
∆S° = 298.15 = –120.6 J K–1 mol–1

Standard state is 1 bar

 CHEMICAL EQUILIBRIUM n 81

∆G° +100 970

b. ln (KP/bar–1) = – RT = = 40.73
8.3145 × 298.15
KP = 4.89 × 1017 bar–1

c. Kc = KP (RT) = 4.89 × 1017 × 0.0831 × 298.15

= 1.21 × 1019 dm3 mol–1

d. ∆G° = –RT ln Kc = –8.3145 × 298.15 ln (1.21 × 1019)

= –108 925 J mol–1 = –108.9 kJ mol–1

∆H° –∆G° –136 940 + 108 925
e. ∆S° = T = 298.15 = –93.96 J K–1 mol–1

f. ∆G°(100 °C) = ∆H° – T∆S° = –136 940 + (373.15 ×120.6)

= –91 938 J mol–1
–∆G° 91 938
ln (KP/bar–1) = RT = = 29.63
8.3145 × 373.15
KP(100°C) = 7.38 × 1012 bar–1

4.28. a. 2H2(g) + O2(g) →

← 2H2O(g)
∆f G° = 2∆f G°H O –2∆f G°H – ∆f G°O
2 2 2

= 2(–228.57) – 2(0) – 0 = –457.14 kJ mol–1

∆f H° = 2∆f H°H O – 2∆f H°H – ∆f H°O
2 2 2

= 2(–241.82) – 2(0) –0 = – 483.64 kJ mol–1

∆G° = ∆H° – T∆S°
– 457.14 – (– 483.64)
∆f S° = – 298.15 = –0.08888 kJ mol–1= –88.88 J K–1 mol–1

b. ∆G° = –RT ln KP°

457 140 J mol–1

ln (KP° /bar–1) = = 184.4
8.3145 J K–1 mol–1 298.15 K
KP° = 1.222 × 1080 bar–1

c. ∆G(2000°C)/kJ mol–1 = ∆f H° – 2273.15 ∆f S°

= – 483.64 – 2273.15 (–0.08888)
= –281.6 kJ mol–1
281 600
ln (KP/bar–1) = = 14.90
8.3145 × 2273.15
KP = 2.96 × 106 bar–1
82 n CHAPTER 4

4.29. ∆rG° = 2∆fG°(O3, g) – 3∆fG °(O2, g)

= 2(163.2) – 3(0) = 326.4 kJ mol–1.

K = exp(–∆rG°/RT) = exp[–326 400 /(8.3145 × 400)]

= 3.371 × 10–43.

∆H° – ∆G° –20 100 + 31 000

4.30. a. ∆S° = T = 310.15
= 35.1 J K–1 mol–1
31 000
b. ln Kc = = 12.02
8.3145 × 310.15
Kc = 1.66 × 105 mol dm–3

c. ∆G°(25°C) = –20 100 – (298.15 × 35.1)

= –30 570 J mol–1
30 570
ln Kc = = 12.33
8.3145 × 298.15
Kc = 2.27 × 105 mol dm–3

4.31. a. ∆H° = –165.98 + 146.44 = –19.54 kJ mol–1

∆S° = 306.4 – 349.0 = – 42.6 J K–1 mol–1
∆G° = –19 540 + (42.6 × 298.15)
= –6839 J mol–1 = –6.84 kJ mol–1
6839
b. ln KP = = 2.759; KP = 15.78
8.3145 × 298.15
If partial pressure of neopentane = x bar, partial pressure of n-pentane = (1 – x) bar
x
1 – x = 15.78
x = 15.78 – 15.78x; x = 0.940
1 – x = 0.060
Thus P(neopentane) = 0.940 bar and P(n-pentane) = 0.060 bar.

4.32. a. Slope of plot of ln Kc against 1/T is

=
ln 3 1.0986 
= –6836
 1 – 1  1.607 × 10– 4
313.15 298.15
From Eq. 4.73,
∆H° = 6836 × 8.3145 = 56 840 J mol–1
 CHEMICAL EQUILIBRIUM n 83

= 56.8 kJ mol–1
b. –56.8 kJ mol–1

4.33. a. Slope of plot of ln Kc against 1/T is

ln 1.45 0.372
– =– = –6724.6 K
1 1 5.532 × 10–5
298.15 – 303.15
∆H° = 6724.6 × 8.3145 = 55 910 J mol–1
= 55.9 kJ mol–1
At 25 °C, ∆G° = –RT ln 1.00 × 10–14
= –8.3145 × 298.15 × (–32.236)
= 79 912 J mol–1
∆H° – ∆G° 55 910 – 79 912
∆S° = T = 298.15
= –80.5 J K–1 mol–1
b. The difference between the reciprocals of the absolute temperatures corresponding to 25 °C and
37 °C is
3.3540 × 10–3 – 3.2242 × 10–3 = 1.298 × 10– 4
The slope of the plot ln Kw against 1/T was –6724.6 K, and in going from 25 °C to 37 °C
ln Kw is thus increased by
6724.6 × 1.298 × 10– 4 = 0.873
At 25°C, ln Kw is –32.244 and at 37 °C it is therefore
–32.244 + 0.873 = – 31.371
Kw at 37 °C is therefore 2.38 × 10–14 mol2 dm–6.
4.34. a. At 400 °C,
4844
log10(KP/bar) = 7.55 – 673.15 = 0.354

KP = 2.259 bar

∆G°/kJ mol–1 = –8.3145 × 673.15 ln 2.259

∆G° = – 4549 J mol–1 = –4.55 kJ mol–1
From Figure 4.2 (b),
∆H° = 4844 × 8.3145 × 2.303 J mol–1
= 92 750 J mol–1
= 92.75 kJ mol–1
92 800 + 4549
∆S° = 673.15 J K–1 mol–1
84 n CHAPTER 4

= 144.6 J K–1 mol–1

b. Kc = 2.259 × (0.0831 × 673.15)–1
= 0.0404 mol dm–3
∆G°/kJ mol–1 = –8.3145 × 673.15 ln 0.0404
∆G° = 17 960 J mol–1 = 17.96 kJ mol–1
c. I2 + cyclopentene →
← 2HI + cyclopentadiene
0.1 – x 0.1 – x 2x x
4x3
= 0.0404
(0.1 – x)2
For a very approximate solution, neglect x in comparison with 0.1:
4x3 = 0.0404 × (0.1)2 = 4.04 × 10– 4
x3 = 1.01 × 10– 4
x = 0.0466
For a better solution, calculate 4x3/(0.1 – x)2 at various x values:

x 0.0466 0.04 0.03 0.0350

4x3 0.1419 0.0711 0.022 0.0406
(0.1 – x)2
x = 0.0350
Final concentrations are
[I2] = 0.0650 M;
[cyclopentene] = 0.0650 M; [HI] = 0.0700 M;
[cyclopentadiene] = 0.0350 M

4.35. ∆H° = –283.66 + 110.53 = –173.13 kJ mol–1

∆G° = –166.27 + 137.17 = –29.10 kJ mol–1
–173 130 + 29 100
∆S° = 298.15 = – 483.1 J K–1 mol–1

29 100
ln KP = = 11.74
8.3145 × 298.15
KP = 1.25 × 105 bar–3

4.36. ∆H° = –207.4 + 104.6 = –102.8 kJ mol–1

∆G° = –111.3 + 37.2 = –74.1 kJ mol–1
–102 800 + 74 100
∆S° = 298.15 = –96.3 J K–1 mol–1
 CHEMICAL EQUILIBRIUM n 85

4.37. a. Kc = 95/5 = 19

∆G°/J mol–1 = –8.3145 × 298.15 ln 19

∆G° = –7299 J mol–1 = –7.30 kJ mol–1
10– 4
b. ∆G/J mol–1 = –7299 + 8.3145 × 298.15 ln
10–2
∆G = (–7299 – 11 416) J mol–1 = –18 714 J mol–1
= –18.7 kJ mol–1
The reaction will therefore go from left to right.

4.38. a. ∆H° = –110.53 – 241.82 + 393.51 = 41.16 kJ mol–1

∆G° = –137.17 – 228.57 + 394.36 = 28.62 kJ mol–1
41 160 – 28 620
∆S° = 298.15 = 42.06 J K–1 mol–1

28 620
b. ln KP = – = –11.55
8.3145 × 298.15
KP = 9.68 × 10–6
c. From the data in Table 2.1,
∆d = 28.41 + 30.54 – 44.22 – 27.28
= –12.55 J K–1 mol–1
∆e = 10–3(4.10 + 10.29 – 8.79 – 3.26)
= 2.34 × 10–3 J K–2 mol–1
∆f = 104(– 4.6 + 0 + 86.2 – 5.0)
= 76.6 × 104 J K–1 mol–1
Then, from Eq. 2.52,
∆H°T/J mol–1 = 41 160 – 12.55[(T/K) – 298.15] + 1.17 × 10–3[(T/K)2 – 298.152] –

76.6 × 104 T/K – 298.15

1 1
 
= 47 367 – 12.55(T/K) + 1.17 × 10–3(T/K)2 – 76.6 × 104/(T/K)
∆H °
d. ln K = ∫
RT 2
dT

 47 367 12.55 −3 76.6 × 10 

4
∫  (T / K ) 2 T / K
1
− + × −
3 
= 8.3145 1 . 17 10 d (T / K )
 ( T / K ) 
38.3 × 104
= 8.3145– (T/K) – 12.55 ln (T/K) + 1.17 × 10–3 (T/K) +
1 47 367
+I
 (T/K)2 
86 n CHAPTER 4

5697 4.61 × 104

= – T/K – 1.51 ln (T/K) + 1.41 × 10– 4 (T/K) + +I
(T/K)2
I is obtained from the fact that at 298.15, ln K = –11.55
I = –11.55 + 19.11 + 8.60 – 0.042 – 0.519 = 15.60
5697 4.61 × 104
ln K = 15.60 – T/K – 1.51 ln (T/K) + 1.41 × 10– 4 (T/K) +
(T/K)2
e. ln KP at 1000 K

5697 4.61 × 104

= 15.60 – 1000 – 1.51 ln 1000 + 0.141 +
10002
= –0.34
KP (1000 K) = 0.71

4.39. Partial pressures at 1395 K are:

CO: 0.000 140 atm; CO2: (1 – 0.000 140) atm; O2: 0.000 070 atm

(0.000 140)2 × 0.000 070

KP = = 1.372 × 10–12 atm = 1.39 × 10–12 bar
(0.9999)2
At 1443 K,
(0.000 250)2 × 0.000 125
KP = = 7.814 × 10–12 atm = 7.92 × 10–12 bar
(0.999 75)2
At 1498 K,
(0.000 471)2 × 0.000 2355
KP = = 5.227 × 10–11 atm = 5.30 × 10–11 bar
(0.999 529)2
Then
T/K 1012KP/atm 104/(T/K) ln(1012KP/atm)

1395 1.372 7.168 0.3163

1443 7.814 6.930 2.0559
1498 52.27 6.676 3.956
From a plot of ln (KP/atm) against 1/(T/K),

slope = –7.39 × 104 K and ∆H° = –R × slope = 609 kJ mol–1.

∆G°(1395 K) = –8.3145 × 1395 ln (1.372 × 10–12)
= 316.8 kJ mol–1
∆H° – ∆G°
∆S° = T = 209 J K–1 mol–1

(standard state 1 atm)

 CHEMICAL EQUILIBRIUM n 87

4.40. Suppose that there are present x mol of I2 and y mol of I:

y
x + 2 = 1.958 × 10–3

(x + y) mol RT
P = V
At 800° C
558.0 (x + y)0.082 05 dm3 atm K–1 mol–1
760.0 atm = × 1073.15 K
249.8 × 10–3 dm3
x + y = 2.0829 × 10–3
y
2 = 0.1249 × 10 ; y = 2.498 × 10– 4
–3

x = 1.833 × 10–3
Degree of dissociation,
x 1.833 × 10–3
α=1– =1– = 0.0638
1.958 × 10–3 1.958 × 10–3
At 1000°C, x + y = 2.3535 × 10–3
y
2 = 3.955 × 10 ; y = 7.91 × 10– 4
–4

x = 1.5625 × 10–3; α = 0.202

At 1200°C, x + y = 2.7715 × 10–3
y
2 = 8.135 × 10 ; y = 1.627 × 10–3
–4

x = 1.1445 × 10–3; α = 0.415

a. α = 0.0638, 0.202, 0.415 at the three temperatures
b. At 800 °C,
(2.498 × 10– 4 mol)2
Kc =
1.833 × 10–3 mol × 0.2498 dm3
= 1.363 × 10– 4 mol dm–3
At 1000 °C,
(7.91 × 10– 4)2
Kc =
1.5625 × 10–3 × 0.2498
= 16.0 × 10– 4 mol dm–3
At 1200 °C,
(1.627 × 10–3)2
Kc =
1.1445 × 10–3 × 0.2498
= 92.59 × 10– 4 mol dm–3
88 n CHAPTER 4

c. KP = Kc (RT)Σν (Eq. 4.26)

= KcRT since Σν = 1
At 800 °C, KP

= 1.363 × 10– 4 mol dm–3 × 100 dm3 m–3 × 8.3145 J K–1 mol–1 × 1073.15 K
= 1.216 kPa = 9.12 Torr = 0.0122 bar
At 1000 °C, KP = 16.97 kPa
At 1200 °C, KP = 113.4 kPa

d. 104Kc
T/K 104Kc/mol dm–3 104/(T/K) ln
mol dm–3
1073.15 1.363 9.318 0.310
1273.15 16.03 7.855 2.774
1473.15 92.59 6.788 4.528
Slope of a plot of ln(Kc/mol dm–3) against 1/(T/K) is –1.67 × 104 K–1.

∆U° = 139 kJ mol–1

∆H° = ∆U° + RT = 139 000 + (8.3145 × 1273.15)
= 149 586 J mol–1 = 150 kJ mol–1
e. At 1000°C, KP = 16.97 kPa = 0.169 bar.

∆G° = –(8.3145 × 1273.15 J mol–1) ln(0.169/bar)

= 18 819 J mol–1
= 18.8 kJ mol–1
(standard state: 1 bar)
∆H° – ∆G°
∆S° = T = 103.0 J K–1 mol–1

4.41. ∆G° = –RT ln K° = –8.3145 × 300 ln 5.7 × 10–3

= 12 889 J mol–1 = 12.9 kJ mol–1
ln (5.7 × 10–3/7.8 × 10– 4) 1.989
Slope of plot = =
(1/300) – (1/340) 3.922 × 10– 4
= 5071 K
∆H° = –8.3145 × 5071 = –42 160 J mol–1 = –42.16 kJ mol–1
∆S° = (∆H° – ∆G°)/T = –183 J K–1 mol–1

4.42. ∆G° = ∆H° – T∆S° = –85 200 + 300 × 170.2

= –34 140 J mol–1
 CHEMICAL EQUILIBRIUM n 89

Kc = exp(34 140/8.3145 × 300)

= 8.8 × 105
The equilibrium constant is equal to unity when ∆G° is equal to zero.
0 = –85 200 + T × 170.2
T = 500.6 K

4.43. ∆G° = –8.3145 × 310.15 × ln 1.66 × 105

= –30 996 J mol–1
∆H° – ∆G° –20 100 + 31 996
∆S° = T = 310.15
= 35.13 = 35.1 J K–1 mol–1
At 25 °C, ∆G° = ∆H° – T∆S° = –20 100 – (298.15 × 35.1)
= –30 565 J mol–1
= –8.3145 × 298.15 ln Kc
30 565
ln Kc = = 12.33
8.3145 × 298.15
Kc = 2.26 × 105 mol dm–3

4.44. ∆G° = –8.3145 × 300 × ln 7.2 × 10–5

= 23 793 J mol–1
∆H° – ∆G° 40 000 – 23 793
∆S° = T = 300
= 54.02 J K–1 (standard state: 1 mol dm–3)
The equilibrium constant is unity when ∆G° is zero:
0 = ∆H° – T∆S°
∆H° 40 000
T = = 54.02
∆S°
= 740 K

4.45. ∆G° = –RT ln Kc = –8.3145 × 300 ln (4.5 × 104)

= –26 725 J mol–1

∆H° – ∆G° – 40 200 + 26 725
∆S° = T = 300
= – 44.9 J K–1 mol–1
The equilibrium constant is unity when ∆G° = 0.
90 n CHAPTER 4

∆G° = 0 = –40 200 + (44.9 × T)

T = 895 K

4.46. For the equilibrium

Br2(l) = Br2(g)

the vapor pressures are the equilibrium constants. The corresponding ∆G° values (standard state:
1 bar) are
∆G°(331.35 K) = –RT ln 1 = 0
∆G°(282.45 K) = – 8.3145 × 282.45 (J mol–1) ln 0.1334
= 4730.7 J mol–1
We can therefore set up two simultaneous equations:
0 = ∆H° – (331.35 K) ∆S°
4730.7 J mol–1 = ∆H° – (282.45 K) ∆S°
Subtraction gives
∆S° = 4730.7 J mol–1/48.9 K = 96.74 J K–1 mol–1
∆H° = 96.74 J K–1 mol–1 × 331.35 K = 32 055 J mol–1
At 25°C,
∆G° = 32 055 – (96.74 × 298.15) J mol–1
= 3212 J mol–1
The vapor pressure at 25°C is the corresponding equilibrium constant:
P = KP = exp(–3212/8.3145 × 298.15)
= 0.274 bar

4.47. For the reaction, ∆G° = 2 × 162.3 = 324.6 kJ mol–1

Then
KP = exp(–∆G° /RT) = exp(–324 600/8.3145 × 298.15)

= 1.36 × 10–57 bar–1 (The unit arises from the standard state of 1 bar.)
Σν for the reaction is 2 – 3 = –1. From Eq. 4.26,
Kc = KP (RT)–Σν

1.36 × 10–57 bar–1 (8.3145 × 298.15 J)

=
1.00000 × 105 Pa bar–1
= 3.37 × 10–59 m3 mol–1 (since J Pa–1 = m3)
= 3.37 × 10–56 dm3 mol–1
From Eq. 4.32,
 CHEMICAL EQUILIBRIUM n 91

Kx = KP P–Σν, so that at 2 bar pressure,

Kx = 1.36 × 10–57 bar–1 × 2 bar = 2.72 × 10–57

This equilibrium constant (Eq. 4.31) is x(O3)2/x(O2)3, and since it is so small, x(O2) is almost
exactly unity. Thus
x(O3)2 = 2.72 × 10–57
and
x(O3) = 5.22 × 10–29

4.48. At 500 K, by Eq. 2.46,

∆H° = ∆H°(300 K) + ∆CP(500 – 300)

= –9600 –(7.11 × 200) = –11 022 J mol–1

For the entropy change at 500 K, the corresponding equation is
T2∆C
∫T P dT
∆S°(T2) = ∆S°(T1) + T
1

= ∆S°(T1) + ∆CP ln (T2/T1)

At 500 K, ∆S° is therefore

∆S° = 22.18 – 7.11 ln(500/300) = 18.55 J K–1 mol–1
Therefore
∆G° = –11 022 – 18.55 × 500 = –20 297 J mol–1
The equilibrium constant KP is therefore

exp(20 297/8.3145 × 500) = 131.9

Since the reaction involves no change in the number of molecules, Kc and Kx also have this value
(see Eqs. 4.26 and 4.32), and they are not affected by the pressure.
Let the mole fraction of HI be x; then the mole fractions of H2 and I2 are both (1 – x)/2, and the
expression for Kx is therefore

Kx = 4x2/(1 – x)2 = 131.9

Taking square roots
11.48 = 2x/(1 – x)
whence x = 0.85
Pressure has no effect on the above values.

4.49. Values of ∆G° and of K[= exp(–∆G°/RT)u] are

Temperature
θ /°C T/K ∆G°/kJ mol–1 K
92 n CHAPTER 4

40.0 313.15 3.98 0.22

42.0 315.15 2.20 0.43
44.0 317.15 0.42 0.85
46.0 319.15 –1.36 1.67
48.0 321.15 –3.14 3.24
50.0 323.15 – 4.93 6.27
∆G° = ∆H° – T∆S° = 0 when T = 317.6 and K = 44.4°C
At this temperature there will be equal concentrations of P and D.

n Binding to Protein Molecules

4.50. If the concentration of M is [M], that of sites occupied and unoccupied is n[M]. The association
reactions may be formulated in terms of the sites, S,
Ks
S+A→
← SA
[SA]
Ks = [S][A]

where [S] is the concentration of unoccupied sites and [SA] is the concentration of occupied sites.
The total concentration of sites, n[M], is
 1 
n[M] = [S] + [SA] = [SA] K [A] + 1
 s 
The average number of occupied sites per molecule is the total concentration of occupied sites
divided by the total concentration of M:

– [SA] n nKs[A]
ν = [M] = 1 = 1 + K [A]
s
Ks[A] + 1

4.51. The total concentration of the molecule M is

[M]0 = [M] + [MA] + [MA2] + . . . + [MAn]
The total concentration of occupied sites is the total concentration of bound A molecules:
[A]b = [MA] + 2[MA2] + . . . + n[MAn]
Expressing every term in terms of [A]:
[M]0 = [M]{1 + K1[A] + K1K2[A]2 + . . . + (K1K2 . . . Kn)[A]n}

[A]b = [M]{K1[A] + 2K1K2[A]2 + . . . + n(K1K2 . . . Kn)[A]n}

Thus
 CHEMICAL EQUILIBRIUM n 93

– [A]b K1[A] + 2K1K2[A]2 + . . . + n(K1K2 . . . Kn)[A]n

ν = [M] =
0 1 + K1[A] + K1K2[A]2 + . . . + (K1K2 . . . Kn)[A]n

4.52. With K1 = nKs, K2 = (n – 1)Ks/2,

K3 = (n – 2)Ks/3 . . . Kn = Ks/n, the preceding equation becomes
2 n
– nKs[A] + n(n – 1)K s [A]2 + . . . + nKs [A]n
ν = 2 n
1 + nKs[A] + n(n –1)K s [A]2/2 + . . . + K s [A]n

nKs[A] {1 + (n – 1)Ks[A] + . . . + Kns–1[A]n–1}

= 2 n
1 + nKs[A] + n(n – 1)K s [A]2/2 + . . . + K s [A]n

The coefficients are the binomial coefficients,

nKs[A](1 + Ks[A]) n–1
–
ν =
(1 + Ks[A])n

nKs[A]
= 1 + K [A]
s
–
which are the expressions obtained in Problem 49. To test the equation, plot 1/ν against 1/[A]:
1 1 1
– = n + nKs[A]
ν
– –
One of the intercepts is 1/n. Alternatively, plot ν against ν /[A]:
–
– ν
ν = n – K [A]
s

4.53. If Kn is very much larger than K1, K2, and so on, the equation obtained in Problem 51 reduces as
follows:

– n(K1K2 . . . Kn)[A]n
ν =
1 + (K1K2 . . . Kn)[A]n

nK[A]n
=
1 + K[A]n
where K = K1K2 . . . Kn is the overall equilibrium constant for the binding of n molecules:
K
nA + M →
← MAn
–
The fraction of sites occupied, θ, is ν /n:
K[A]n
θ= or
1 + K[A]n
θ
= K[A]n
1–θ
94 n CHAPTER 4

The slope of a plot of ln {θ/(1 – θ)} against [A] is thus n. If the sites are identical and independent
(Problem 50), the slope is 1. Intermediate behavior can give nonlinear plots; the maximum slope of
a Hill plot cannot be greater than n.