CHAPTER 9 CHEMICAL EQUILIBRIA

9.2

(a) True (b) False. Changing the rate of a reaction will not affect the value of the equilibrium constant; it merely changes how fast one gets to equilibrium. (c) True (d) False. The standard reaction free energy Gr is not 0 at equilibrium. The reaction free energy Gr , which is dependent upon the concentrations of the products and reactants, is 0 at equilibrium.

9.4

Cl2 decreases from 2.15 to 2.13 bar, PCl3 decreases from 1.28 to 1.26 bar, and PCl5 increases from 0.02 to 0.04 bar. The shapes for the curves can only be determined accurately if the rate law for the reaction is known (see Chapter 13).
2.5 [Cl2] 2 Pressure (bar) 1.5 1 0.5 [PCl5] 0 Time [PCl3]

247

9.6

(a) K =

PNO2 2 PNO PO2

2

(b) K =

PSbCl3 PCl2 PSbCl5

(c) K =

PN2 H4 PN2 PH2 2

9.8

All values should be the same because the same amounts of the substances are present at equilibrium. It doesnt matter whether we begin with reactants or with products; the equilibrium composition will be the same if the same amounts of materials are used. If different amounts had been used, only (e) would be the same in the two containers. A more detailed analysis follows: H2(g) + Br2(g) 2 HBr(g) The equilibrium constant expression for this system is KC = [HBr]2 [H 2 ] [Br2 ]

In terms of the change in concentration, x, of H2 and Br2 that has come about at equilibrium, we may write KC = [2 x]2 [2 x]2 = [0.05 x] [0.05 x] [0.05 x]2 (1)

in the first container, and in terms of the change in concentration, y, of HBr that has come about at equilibrium in the second container, we may write KC = [0.10 y ]2 [0.10 y ]2 = 2 y y y 2 2 2 (2)

Because KC is a constant, and because the relative amounts of starting materials are in the ratio of their stoichiometric factors, we must have
[2 x]2 [0.10 y ]2 = 2 [0.05 x]2 y 2 [2 x] [0.10 y ] = [0.05 x] y 2

248

Cross multiplying:
xy = (0.05 x)(0.10 y ) xy = 0.005 0.05 y 0.10 x + xy y = 0.10 2 x

This may also be seen by solving quadratic equations for Eqs. 1 and 2 for x and y to obtain any value of KC. (a) [Br2 ] = 0.05 x in the first container, [Br2 ] = y /2 in the second container. Because y /2 = 0.05 x satisfies the conditions of Eq. 3, the concentrations and hence the amounts of Br2 are the same in the two cases. (b) [H 2 ] = 0.05 x = y /2 , as above; hence the concentrations of H2 are the same in both systems. (c) Because all concentrations are the same in both cases, this ratio will also be the same. (d) For the same reason as in part (c), this ratio is the same in both cases. (e) This ratio is the equilibrium constant, so it must be the same for both systems. (f) Because all the concentrations and amounts are the same in both cases, and because the volumes and temperatures are the same, the total pressure must be the same: P= (nH2 + nBr2 + nHBr ) RT V

9.10

K = PNH3 PH 2S

For condition 1, K = 0.307 0.307 = 0.0942 For condition 2, K = 0.364 0.258 = 0.0939 For condition 3, K = 0.539 0.174 = 0.0938

9.12

(a)

[Cl ]2 [ClO3 ] [ClO ]3

(b) [CO2]

249

[H + ][CH3 COO ] (c) [CH3 COOH] 9.14 (a) 2 CH4(g) + S8(s) 2 CS2(l) + 4 H2S(g)
Gr = 2 Gf (CS2 , l) + 4 Gf (H 2 S, g) [2 Gf (CH 4 , g)] = 2(65.27 kJ mol1 ) + 4 (33.56 kJ mol1 ) [2 (50.72 kJ mol1 )] = +97.74 kJ mol 1
G = RT ln K

or ln K = ln K = G RT +97 740 J mol1 = 39.4 (8.314 J K 1 mol1 )(298 K)

K = 8 1018 (b) CaC2(s) + 2 H2O(l) Ca(OH)2(s) + C2H2(g)

Gr = Gf (Ca(OH) 2 , s) + Gf (C 2 H 2 , g) [Gf (CaC 2 , s) + 2 Gf (H 2 O, l)] = (898.49 kJ mol1 ) + (+209.20 kJ mol1 ) [(64.9 kJ mol1 ) + 2(237.13 kJ mol 1 )] = 150.1 kJ mol1

ln K =

150 100 J mol1 = +60.6 (8.314 J K 1 mol1 )(298 K)

K = 2 1026 (c) 4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(l) Gr = 4Gf (NO, g) + 6Gf (H 2 O, l) [4Gf (NH 3 , g)] = 4(86.55 kJ mol1 ) + 6(237.13 kJ mol1 ) [4(16.45 kJ mol1 )] = 1010.8 kJ mol1
1010.8 103 J mol1 ln K = = +408 (8.314 J K 1 mol1 )(298 K) K 10177

250

(d) CO2(g) + 2 NH3(g) CO(NH2)2(s) + H2O(l)

Gr = Gf (CO(NH 2 ) 2 , s) + Gf (H 2 O, l) [Gf (CO 2 , g) + 2 Gf (NH 3 , g)] = (197.33 kJ mol1 ) + (237.13 kJ mol1 ) [(394.36 kJ mol1 ) + 2(16.45 kJ mol1 )] = 7.20 kJ mol1
ln K = K = 18 7.20 103 J = +2.91 (8.314 J K 1 mol1 )(298 K)

9.16

(a) Gr = RT ln K = (8.314 J K 1 mol1 )(700 K) ln 54 = 23.2 kJ mol1 (b) Gr = RT ln K = (8.314 J K 1 mol1 )(298 K) ln 0.30 = +2.98 kJ mol1

9.18

G r = G f (CO 2 , g) = 394.36 kJ mol1

G = RT ln K G ln K = RT 394.36 103 J mol1 ln K = = +159.17 (8.314 J K 1 mol1 )(298 K) K = 1.3 1069 In practice, no K will be so precise. A better estimate would be 1 1069 . Because Q < K, the reaction will tend to proceed to produce products.
9.20

The free energy at a specific set of conditions is given by

251

Gr = Gr + RT ln Q Gr = RT ln K + RT ln Q Gr = RT ln K + RT ln pCl5 pCl3 pCl2 (1.33) (0.22)(0.41)

= (8.314 J K 1 mol1 )(503 K) ln 49 + (8.314 J K 1 mol1 )(503 K) ln = 5.0 kJ mol1

Because Gr is negative, the reaction will be spontaneous to form products.

9.22

The free energy at a specific set of conditions is given by

Gr = Gr + RT ln Q Gr = RT ln K + RT ln Q Gr = RT ln K + RT ln [HI]2 [H 2 ] [I 2 ] (2.17) 2 (0.16)(0.25)

= (8.314 J K 1 mol 1 )(700 K) ln 54 + (8.314 J K 1 mol1 )(700 K) ln = 4.5 kJ mol1

Because Gr is positive, the reaction will proceed to form reactants.

9.24

(a) K =

PSO3 2 PSO2 2 PO2

n

= 3.4

T K = 12.027 K

KC
n

12.027 K KC = T

12.027 K K = 1000 K

(2 3)

3.4 = 2.8 102

(b) K = PNH3 PH2S = 9.4 102

252

 12.02 K KC = T

12.027 K K = 297 K

(2 0)

9.4 102 = 1.5 104

9.26

For the equation written 2 SO 2 (g) + O 2 (g) 2 SO3 (g)

K= PSO3 2 PSO2 PO2
2

Eq. 1

= 2.5 1010

(a) For the equation written SO 2 (g) + 1 2 O 2 (g) SO3 (g) K Eq. 2 = PSO3 PSO2 PO2 1/ 2 = K Eq. 1 = 2.5 1010 = 1.6 105

Eq. 2

(b) For the equation written SO3 (g) SO 2 (g) + 1 2 O 2 (g) This equation is the reverse of Eq. 2, so K Eq. 3 = PSO2 PO2 1/ 2 PSO3 1 K Eq. 1 1 2.5 10
10

Eq. 3

1 K Eq. 2

1 K Eq. 1

K Eq. 2 =

= 6.3 106 Eq. 4

(c) For the equation written 3 SO 2 (g) + 3 2 O 2 (g) 3 SO 3 (g) This equation is
K Eq. 2 = PSO3 3 PSO2 PO2
3 3/ 2

3 2

Eq. 1, so K Eq. 4 = K Eq. 13/ 2

= K Eq. 13/ 2 = (2.5 1010 )3/ 2 = 4.0 1015

9.28

H2(g) + Cl2(g) 2 HCl(g) KC = [HCl]2 [H 2 ][Cl 2 ] (1.45 103 ) 2 [H 2 ](2.45 103 )

K C = 5.1 108

5.1 108 = [H 2 ] =

(1.45 103 ) 2 (5.1 108 )(2.45 103 )

[H 2 ] = 1.7 1012 mol L1

253

9.30

K=

PSbCl3 PCl2 PSbCl5

4

3.5 10
PCl2

(5.02 103 ) PCl2 0.072

(3.5 104 )(0.072) = = 5.0 103 bar 3 5.02 10 [NH 3 ]2 = 0.278 [N 2 ][H 2 ]3

9.32

(a) K C =

[0.122]2 QC = = 0.248 [0.417][0.524]3

(b) QC K C ; therefore the system is not at equilibrium. (c) Because QC < K C , more products will be formed.

9.34

[NH 3 ]2 (a) K C = = 62 [N 2 ][H 2 ]3 [1.12 104 ]2 = 2.95 103 QC = 3 3 3 [2.23 10 ][1.24 10 ] (b) Because QC > K C , ammonia will decompose to form reactants.

9.36

1.00 g I 2 0.830 g I 2 = 0.003 94 mol I 2 ; = 0.003 27 mol I2 1 253.8 g mol 253.8 g mol1
I2(g) 2 I(g)
0.003 94 mol x

2x

0.003 94 mol x = 0.003 27 mol x = 0.000 67 mol; 2 x = 0.0013 mol

0.0013 1.00 = 5.2 104 KC = 0.003 27 1.00

254

9.38

Pressure (Torr) CO(g) + initial final 200

200 88

H2O(g) CO2(g) + H2(g) 200

200 88

0 88

0 88

Note: Because pressure is directly proportional to the number of moles of a substance, the pressure changes can be used directly in calculating the reaction stoichiometry. Technically, to achieve the correct standard state condition, the Torr must be converted to bar (750.1 Torr bar 1 ) ; however, in this case those conversion factors will cancel because there are equal numbers of moles of gas on both sides of the equation.

K=

PCO2 PH2 PCO PH2O

88 88 750.1 750.1 = = 0.62 112 112 750.1 750.1

9.40

(a) The balanced equation is Cl2(g) 2 Cl(g) The initial concentration of Cl2 (g) is Concentration (mol L1 ) initial change equilibrium Cl2(g) 0.0025

0.0050 mol Cl2 = 0.0025 mol L1 2.0 L

2 Cl(g)
0 +2 x +2 x

x
0.0025 x

(2 x) 2 [Cl]2 KC = = = 1.7 103 [Cl2 ] (0.0025 x) 4 x 2 = (1.7 103 )(0.0025 x) 4 x 2 + (1.7 103 ) x (4.25 106 ) = 0 (1.7 103 ) (1.7 103 ) 2 4(4)(4.3 106 ) 2 4 3 (1.7 10 ) 8.47 103 x= 8 3 x = 1.3 10 or + 8.5 104 x=

255

The negative answer is not meaningful, so we choose x = 8.5 104 mol L1 . The concentration of Cl2 is 0.0025 8.5 104

= 0.0017. The concentration of Cl atoms is 2 (8.5 104 )

= 1.7 104 mol L1 . The percentage decomposition of Cl2 is given by 8.5 104 100 = 34% 0.0025 (b) The balanced equation is Br2(g) 2 Br(g) The initial concentration of Br2 (g) is Concentration (mol L1 ) initial change equilibrium KC = Br2(g) 2.5

5.0 mol Br2 = 2.5 mol L1 2.0 L

2 Br(g)
0 +2 x +2 x

x
2.5 x

(2 x) 2 [Br]2 = = 1.7 103 [Br2 ] (2.5 x)

4 x 2 = (1.7 103 )(2.5 x) 4 x 2 + (1.7 103 ) x (4.25 103 ) = 0 (1.7 103 ) (1.7 103 ) 2 4(4)(4.25 103 ) 24 3 (1.7 10 ) 2.608 101 x= 8 2 x = 3.3 10 or + 3.2 102 x= The negative answer is not meaningful, so we choose x = 3.2 102 mol L1 . The concentration of Br2 is 2.5 3.2 102 2.5. The concentration of Br atoms is 2 (3.2 102 ) = 6.4 102 mol L1 . he percentage decomposition of Br2 is given by 3.2 102 100 = 1.3% 2.5 (c) At this temperature, Cl2 and Br2 are equally stable since their equilibrium constants are the same. If we had used the same initial

256

amounts of Cl2 and Br2 in parts (a) and (b), then the percent decomposition would have been the same as well.
9.42

Pressure (bar) initial change final

pBr2 pCl2 pBrCl 2

2 BrCl(g)
1.4 103 2 x 1.4 10 3 2 x

Br2(g) + Cl2(g) 0 +x +x 0 +x +x

K= 32 =

x2 ( x)( x) = (1.4 103 2 x) 2 (1.4 103 2 x) 2 x2 (1.4 103 2 x) 2

32 =

x = 32 (1.4 103 2 x) x = ( 32)(1.4 103 2 x) x + 2 32 x = ( 32)(1.4 103 ) (1 + 2 32) x = ( 32)(1.4 103 )

x= ( 32)(1.4 103 ) (1 + 2 32)

x = 6.4 104

pBr2 = pCl2 = 6.4 104 bar = 0.64 mbar

pBrCl = 1.4 10 3 bar 2 (6.4 10 4 bar) = 1.2 10 4 bar = 0.12 mbar

The percentage decomposition is given by 2 (6.4 104 bar) 100 = 91% 1.4 103 bar

257

9.44

(a) concentration of PCl5 initially = 2.0 g PCl5 1 208.22 g mol PCl5 = 0.032 mol L1 0.300 L Concentration (mol L1 ) PCl5(g) initial change final KC = 0.032

PCl3(g) +
0 +x +x

Cl2(g) 0 +x +x

x
0.032 x

[PCl3 ][Cl2 ] ( x)( x) x2 = = [PCl5 ] (0.032 x) (0.032 x)

x2 = 0.61 (0.032 x) x 2 = (0.61)(0.032 x) x 2 + (0.61) x 0.020 = 0 (0.61) (0.61) 2 (4)(1)(0.020) x= 2 1 (0.61) 0.67 x= = +0.03 or 0.64 2 1 The negative root is not meaningful, so we choose x = 0.03 mol L1 .
[PCl3 ] = [Cl 2 ] = 0.03 mol L1 ; [PCl5 ] = 0.032 0.03 mol L1 = 0.002 mol L1 . The solution of this

problem again points up the problems with following the significant figure conventions for calculations of this type, because we would use only one significant figure as imposed by the subtraction in the quadratic equation solution. The fact that the equilibrium constant is given to two significant figures, however, suggests that the concentrations could be determined to that level of accuracy. Plugging the answers back into the equilibrium expression gives a value of 0.45, which seems somewhat off from the starting value of 0.61. The closest agreement to the equilibrium expression comes from using [PCl3 ] = [Cl 2 ] = 0.0305 mol L1 and

258

[PCl5 ] = 0.0015 mol L1 ; this gives an equilibrium constant of 0.62.

Rounding these off to two significant figures gives

[PCl3 ] = [Cl 2 ] = 0.030 mol L1 and [PCl5 ] = 0.0015 , which in the

equilibrium expression produces a value of 0.60. The percentage decomposition is given by

0.030 100% = 94% 0.032

9.46

Starting concentration of NH 3 = Concentration (mol L1 ) initial change final 1.6 104 = (0.100 + x)( x) x 2 + 0.100 x 1.6 104 = 0

0.200 mol = 0.100 mol L1 2.00 L

NH4HS(s)

NH3(g)
0.100 +x

+ H2S(g) 0 +x +x

0.100 + x

K C = [NH 3 ][H 2 S] = (0.100 + x)(x)

(+0.100) (+0.100) 2 (4)(1)(1.6 104 ) x= 2 1 0.100 0.1031 = +0.002 or 0.102 x= 2 1 The negative root is not meaningful, so we choose x = 2 103 mol L1 .
[NH 3 ] = +0.100 mol L1 + 2 103 mol L1 = 0.102 mol L1 [H 2 S] = 2 103 mol L1

Alternatively, we could have assumed that x << 0.100, in which case 0.100 x = 1.6 104 or x = 1.6 103.

9.48

The initial concentrations of PCl3 and Cl2 are calculated as follows:

259

[PCl3 ] =

0.200 mol 0.600 mol = 0.0250 mol L1 ; [Cl2 ] = 8.00 L 8.00 L

= 0.0750 mol L1 Concentrations (mol L1 ) PCl5 initial change final 0 +x +x

PCl3(g)
0.0250

Cl2(g) 0.0750

x
0.0250 x

x
0.0750 x

KC =

[PCl3 ][Cl2 ] (0.0250 x)(0.0750 x) = = 33.3 [PCl5 ] (+ x)

x 2 0.100 x + 0.001 875 = 33.3 x x 2 33.40 x + 0.001 875 = 0

x= +33.40 (33.40) 2 (4)(1)(0.001 875) +33.40 33.399 89 = (2)(1) 2

= +5.5 105 or +33.4

The root +33.4 has no physical meaning because it is greater than the starting concentrations of PCl3 and Cl2, so it can be discarded.
[PCl5 ] = 5.5 105 mol L1 ; [PCl3 ] = 0.0250 mol L1

5.5 105 mol L1 = 0.0249 mol L1 ;

[Cl 2 ] = 0.0750 mol L1 5.5 105 mol L1 = 0.0749 mol L1 . Note that

the normal conventions concerning significant figures were ignored in order to obtain a meaningful answer.
9.50

The initial concentrations of N2 and O2 are [N 2 ] = 0.0140 mol 0.240 mol = 0.001 40 mol L1 ; [O 2 ] = 10.0 L 10.0 L

= 0.0214 mol L1 Concentrations (mol L1 ) initial change final N2(g) + 0.001 40 O2(g) 2 NO(g) 0.0214 0

x
0.001 40 x

x
0.0214 x

+2 x +2 x

260

(2 x) 2 [NO]2 = KC = [N 2 ][O 2 ] (0.001 40 x)(0.0214 x)

1.00 105 = 1.00 105 = (2 x) 2 (0.001 40 x)(0.0214 x) 4 x2 x 2 0.0228 x + 3.0 105

4 x 2 = (1.00 105 )( x 2 0.0228 x + 3.0 105 ) 4 x 2 = 1.00 105 x 2 2.28 107 x + 3.0 1010 4 x 2 + 2.28 107 x 3.0 1010 = 0

x=
x=

2.28 107 (2.28 107 ) 2 (4)(4)(3.0 1010 ) (2)(4)

2.28 107 6.93 105 = 8.6 106 or 8.7 106 8

The negative root can be discarded because it has no physical meaning.

[NO] = 2 x = 2(8.6 106 ) = 1.7 105 mol L1 ; the concentrations of N2

and O2 remain essentially unchanged at 0.001 39 mol L1 and 0.0214 mol L1 , respectively.

9.52

The initial concentrations of N2 and H2 are

[N 2 ] = [H 2 ] = 0.20 mol = 0.0080 mol L1 . 25.0 L

At equilibrium, 5.0 % of the N2 had reacted, so 95.0 % of the N2 remains:

[N 2 ] = (0.950)(0.0080 mol L1 ) = 0.0076 mol L1

If 5.0 % reacted, then

0.050 0.200 mol N 2

2 mol NH3 = 0.020 mol NH 3 formed. mol N 2

0.020 mol = 8.0 104 mol L1 . 25.0 L

The concentration of NH 3 formed = The amount of

H 2 reacted = 0.050 0.200 mol N 2

3 mol H 2 = 0.030 mol H 2 used. mol N 2

261

Concentration of H2 present at equilibrium

= 0.200 mol 0.030 mol = 0.0068 mol L1 . 25.0 L

KC =

[NH 3 ]2 (8.0 104 ) 2 = = 2.7 102 [N 2 ][H 2 ]3 (0.0076)(0.0068)3

9.54

Note: The volume of the system is not used because we are given pressures and K. Pressures (bar)N2(g) initial change final
K= PNH3 2 PN 2 PH 2 3

3 H2(g) 0.015
3 x 0.015 3 x

2 NH3(g) 0

0.025

x
0.025 x

+2 x +2 x

(2 x) 2 = 0.036 (0.025 x)(0.015 3 x)3

Solving this explicitly will lead to a high-order equation, so first check to see if the assumption that 3 x << 0.015 can be used to simplify the math: (2 x) 2 = 0.036 (0.025)(0.015)3 4 x 2 = 3.04 109 x = 2.8 105 Comparing x to 0.015, we see that the approximation was justified. At equilibrium, PNH3 = 2 2.8 105 bar = 5.6 105 bar ; the pressures of N2 and H2 remain essentially unchanged.

262

9.56

Concentrations (mol L1 ) CH3COOH + C2H5OH initial change final

KC = =

CH3COOC2H5 + H2O
0 +x +x 0.015 +x 0.015 + x

0.024

0.059

x
0.024 x

x
0.059 x

[CH 3 COOC2 H 5 ][H 2 O] ( x)(0.015 + x) = [CH 3 COOH][C2 H5 OH] (0.024 x)(0.059 x)

x 2 + 0.015 x x 2 0.083 x + 0.0014 x 2 + 0.015 x x 2 0.083 x + 0.001 42

4.0 =

4.0 x 2 0.332 x + 0.005 68 = x 2 + 0.015 x 3.0 x 2 0.347 x + 0.005 68 = 0 x= (0.347) (0.347) 2 (4)(3.0)(0.005 68) (2)(3.0) = + 0.347 0.228 6.0

x = 0.0958 or 0.0198

The root 0.0958 is meaningless because it is larger than the initial concentration of acetic acid and ethanol, so the value 0.0198 is chosen. The equilibrium concentration of the product ester is, therefore, 0.0198 mol L1 . The numbers can be confirmed by placing them into the equilibrium expression:

KC =

[CH3 COOC2 H 5 ][H 2 O] (0.0198)(0.015 + 0.0198) = 4.1 = [CH 3 COOH][C2 H5 OH] (0.024 0.0198)(0.059 0.0198)

This is reasonably good agreement, given the nature of the calculation. Given that the KC value is reported to only two significant figures, the best report of the concentration of ester will be 0.020 mol L1 . PPCl5 PPCl3 PCl2

9.58

K=

3.5 104 =

1.3 102 (9.56) PCl2

263

PCl2

1.3 102 = = 3.9 104 bar 4 (9.56)(3.5 10 )

9.60

We use the reaction stoichiometry to calculate the amounts of substances present at equilibrium: Amounts (mol) CO(g) + initial change final 1.000 H2O(g) 1.000 CO2(g) + H2(g) 0 +x 0.665 0 +x +x

x
1.000 x

x
1.000 x

(a) Because x = 0.665 mol, there will be ( 1.000 0.665 ) mol = 0.335 mol CO; 0.335 mol H2O; 0.665 mol H2. The concentrations are easy to calculate because V = 10.00 L:
[CO] = [H 2 O] = 0.0335 mol L1 ; [CO 2 ] = [H 2 ] = 0.0665 mol L1

(b) K C =

[CO 2 ][H 2 ] (0.0665) 2 = = 3.94 [CO][H 2 O] (0.0335) 2

0.100 mol = 0.0100 mol L1 10.0 L

9.62

The initial concentration of H 2 S = The final concentration of H 2 =

0.0285 mol = 0.002 85 mol L1 10.0 L

Concentrations (mol L1 ) 2 H2S(g) 2 H2(g) + S2(g) initial change final 0.0100

2 x 0.0100 2 x

0
+2 x

0 +x +x

0.002 85

Thus, 2 x = 0.002 85 mol L1 or x = 0.001 42 mol L1 At equilibrium:

264

[H 2 S] = 0.0100 mol L1 0.002 85 mol L1 = 0.0072 mol L1 [H 2 ] = 0.002 85 mol L1 [S2 ] = 0.001 42 mol L1 KC = (0.002 85) 2 (0.001 42) = 2.22 104 2 (0.0072)

9.64

The initial concentration of PCl5 =

0.865 mol = 1.73 mol L1 0.500 L

Concentrations (mol L1 ) PCl5(g) initial change final

KC = [PCl3 ][Cl2 ] [PCl5 ]

PCl3(g) + Cl2(g) 0 +x +x 0 +x +x

1.73

x
1.73 x

( x)( x) x2 = 1.80 = (1.73 x) (1.73 x) (1.80)(1.73 x) = x 2

x 2 + 1.80 x 3.114 = 0 1.80 (1.80) 2 (4)(1 3.114) 1.80 3.96 x= = (2)(1) 2 x = +1.08 or 2.88

The negative root is not physically meaningful and can be discarded. The concentrations of PCl3 and Cl2 are, therefore, 1.08 mol L1 at equilibrium, and the concentration of PCl5 is 1.73 mol L1 1.08 mol L1 = 0.65 mol L1 . These numbers can be checked by substituting back into the equilibrium expression: KC = [PCl3 ][Cl2 ] [PCl5 ]

(1.08) 2 = 1.79 (0.65) which compares well to KC (1.80).

265

9.66

We use the ideal gas relationship to find the initial concentration of HCl(g) at 25C:

PV RT 1 atm 1.00 bar (4.00 L) 1.013 25 bar n= = 0.176 mol (0.082 06 L atm K 1 mol 1 )(273 K) n=
[HCl] = 0.176 mol = 0.0147 mol L1 12.00 L

Concentrations (mol L1 ) 2 HCl(g) + I2(s) 2 HI(g) + Cl2(g) initial change final [HI]2 [Cl2 ] KC = [HCl]2 1.6 10
34

0.0147
2 x 0.147 2 x

0
+2 x +2 x

0 +x +x

(2 x) 2 ( x) = (0.0147 2 x) 2

Because the equilibrium constant is very small, we will assume that x << 0.0147: 1.6 10 x3 = x=
34

4 x3 = (0.0147) 2

(1.6 1034 )(0.0147) 2 4 (1.6 1034 )(0.0147) 2 = 2.1 1013 4

At equilibrium: [HI] = 2 2.1 1013 = 4.2 1013

[Cl 2 ] = 2.1 10 13

[HCl] = 0.0147 mol L1

266

9.68

25.6 g 1 17.03 g mol initial [NH3] = = 0.301 mol L1 5.00 L

Concentrations (mol L1 ) initial change final

[N 2 ][H 2 ]3 KC = [NH 3 ]2 ( x)(3 x)3 = 0.395 (0.301 2 x) 2 27 x 4 = 0.395 (0.301 2 x) 2
27 x 4 = 0.395 (0.301 2 x) 2 3 3 x2 = 0.628 (0.301 2 x)

2 NH3(g) 0.301

N2(g) 0 +x +x

3 H2(g) 0

2 x
0.301 2 x

+3x +3x

3 3 x 2 = (0.628)(0.301 2 x) = 0.189 1.26 x 5.20 x 2 + 1.26 x 0.189 = 0 1.26 (1.26) 2 (4)(5.20)(0.189) 1.26 2.34 = (2)(5.20) 10.4 x = + 0.105 or 0.396 x= The negative root is discarded because it is not physically meaningful. Thus, at equilibrium we should have
[N 2 ] = 0.105 mol L1 ; [H 2 ] = 0.315 mol L1 ; [NH 3 ] = 0.091 mol L1 .

9.70

2 HCl(g) H 2 (g) + Cl2 (g) K= PH2 PCl2 PHCl

2

= 3.2 1034

(Eq. 1) (Eq. 2)

At equilibrium, PTotal = PH 2 + PCl2 + PHCl = 3.0 bar .

267

And, since the atomic ratio Cl:H is 1:3 ,

moles Cl 1 nHCl + 2nCl2 = = moles H 3 nHCl + 2nH2

nHCl + 2nH2 = 3(nHCl + 2nCl2 ) nH2 = nHCl + 3nCl2 Pgas ngas at T ,V constant so PH2 = PHCl + 3PCl2 (Eq. 3)

We now have three equations in three unknowns, so we can rearrange and substitute to find each partial pressure. Substituting equation 3 into equation 2 gives
PTotal = 4 PCl2 + 2 PHCl = 3.0 bar

PHCl =

3.0 bar 2 PCl2 2

3.0 bar + PCl2 2

Substitution back into equation 3 gives

PH 2 =

Using these two expressions for partial pressures in equation 1 gives

3.0 + PCl2 PCl2 2 = 3.2 1034 K= 2 3.0 2 PCl2 2

Since the equilibrium constant is so small, we would expect the partial pressure of chlorine to be very low at equilibrium, so we can neglect it to simplify this expression. 3.0 PCl2 2 K = 3.2 1034 2 3.0 2 PCl2 = (1.5)(3.2 1034 ) = 4.8 1034 bar PHCl = PH2 = 1.5 bar

268

9.72

(a) According to Le Chateliers principle, an increase in the partial pressure CO 2 will shift the equilibrium to the left, increasing the partial pressure of CH 4 . (b) According to Le Chateliers principle, a decrease in the partial pressure of CH 4 will shift the equilibrium to the left, decreasing the partial pressure of CO2. (c) The equilibrium constant for the reaction is unchanged, because it is unaffected by any change in concentration. (d) According to Le Chateliers principle, a decrease in the concentration of H2O will shift the equilibrium to the right, increasing the concentration of CO2.

9.74

The questions can all be answered qualitatively using Le Chateliers principle: (a) Adding a reactant will promote the formation of products; the amount of HI should increase. (b) I2 is solid and already present in excess in the original equilibrium. Adding more solid will not affect the equilibrium so the amount of Cl2 will not change. (c) Removing a product will shift the reaction toward the formation of more products; the amount of Cl2 should increase. (d) Removing a product will shift the reaction toward the formation of more products; the amount of HCl should decrease. (e) The equilibrium constant will be unaffected by changes in the concentrations of any of the species present. (f) Removing the reactant HCl will cause the reaction to shift toward the production of more reactants; the amount of I2 should increase. (g) As in (e), the equilibrium constant will be unaffected by the changes to the system.

269

9.76

Increasing the total pressure on the system by decreasing its volume will shift the equilibrium toward the side of the reaction with fewer numbers of moles of gaseous components. If the total number of moles of gas is the same on the product and reactant sides of the balanced chemical equation, then changing the pressure will have little or no effect on the equilibrium distribution of species present. (a) decrease in the amount of NO2; (b) increase in the amount and concentration of NO; (c) decrease in the amount of HI; (d) decrease in the amount of SO2; (e) increase in the amount and concentration of NO2. (Note that it is not possible to predict whether or not the concentration will increase, decrease, or remain the same in cases where the amount of the substance is decreasing. More specific information about the extent of the changes in the amount and the volume is needed in those cases.)

9.78

(a) The partial pressure of SO3 will decrease when the partial pressure of SO2 is decreased. According to Le Chateliers principle, a decrease in the partial pressure of a reactant will shift the equilibrium to the left, decreasing the partial pressure of the products, in this case SO3. (b) When the partial pressure of SO2 increases, the partial pressure of O2 will decrease. According to Le Chalteliers principle, an increase in the partial pressure of a reactant shifts the equilibrium toward products, decreasing the partial pressure of the other reactant, O2.

9.80

If a reaction is exothermic, raising the temperature will tend to shift the reaction toward reactants, whereas if the reaction is endothermic, a shift toward products will be observed. For the specific reactions given, raising the temperature should favor products in (a) and reactants in (b) and (c).

9.82

Even though numbers are given, we do not need to do a calculation to answer this qualitative question. Because the equilibrium constant is larger at lower temperatures (4.0 1024 at 298 K vs. 2.5 1010 at 500 K, see

270

Table 9.2, page 334) , more products will be present at the lower

temperature. Thus we expect more SO3 to be present at 25C than at 500 K, assuming that no other changes occur to the system (the volume is fixed and no reactants or products are added or removed from the vessel).
9.84

To answer this question, we must calculate Q: Q= [ClF]2 (0.92) 2 = = 15 [Cl2 ][F2 ] (0.18)(0.31)

Because Q K, the system is not at equilibrium, and because Q < K, the reaction will proceed to produce more products so ClF will tend to form.
9.86

(a) HgO(s) Hg(l) + 1 2 O 2 (g) H r = [H f (HgO, s)] H r = [90.83 kJ mol1 ] H r = +90.83 kJ mol1 S r = S (Hg, l) + 1 2 S (O 2 , g) [ S (HgO, s)]
1 S r = 76.02 J K 1 mol 1 + 1 mol1 2 205.14 J K

[70.29 J K 1 mol1 ] S r = 108.30 J K 1 mol1 At 298 K: Gr(298 K) = 90.83 kJ (298 K)(108.30 J K 1 )/(1000 J kJ 1 ) = 58.56 kJ mol1 Gr(298 K) = RT ln K ln K = = Gr(298 K) RT 58 560 J = 23.6 (8.314 J K 1 )(298 K)

K = 6 1011 At 373 K:
G r(373 K) = 90.83 kJ (373 K)(108.3 J K 1 )/(1000 J kJ 1 ) = 50.4 kJ mol1

271

ln K =

50 400 J = 16.3 (8.314 J K 1 )(373 K)

K = 8 108 (b) propene (C3H6, g) cyclopropane (C3H6, g) H r = H f (cyclopropane, g) [H f (propene, g)] H r = 53.30 kJ mol1 [(20.42 kJ mol1 )] H r = +32.88 kJ mol1 S r = S (cyclopropane, g) [ S (propene, g)] S r = 237.4 J K 1 mol1 [266.6 J K 1 mol1 ] S r = 29.2 J K 1 mol1 At 298 K:

Gr(298 K) = 32.88 kJ mol1 (298 K)( 29.2 J K 1 mol1 )/(1000 J kJ 1 ) Gr(298 K) ln K = = = 41.58 kJ mol1 = RT ln K

Gr(298 K) RT 41 580 J = 16.8 (8.314 J K 1 )(298 K)

K = 5 108 At 373 K: Gr(373 K) = 32.88 kJ mol1 (373 K)( 29.2 J K 1 mol1 )/(1000 J kJ 1 ) = 43.8 kJ mol1 ln K = 43 800 J = 14.1 (8.314 J K 1 )(373 K)

K = 7 107

9.88

We can think of the vaporization of a liquid as an equilibrium reaction, e.g., for substance A, A(l ) A( g ) . This reaction has an equilibrium constant expression K = PA . Since PA is the pressure of the gas above a

272

liquid, it is the equilibrium vapor pressure of that liquid. Therefore, the vapor pressure varies with temperature in the same way that this equilibrium constant varies with temperature.

K 2 H r 1 1 = The vant Hoff equation, ln , (see 16, page 354), K1 R T1 T2

gives the temperature dependence of K. To make this equation fit the special case of vapor pressure all we need to do is substitute P for K
and H vap for H r .
P2 H vap 1 1 ln = P R T1 T2 1

This relationship is known as the Clausius-Clapeyron equation (see

> 0 , vapor pressure increases with equation 4, page 285). Since H vap

temperature.
9.90

Recall Gr = RT ln K = H r T S r and K = 10 pK and ln

K 2 H r 1 1 = K1 R T1 T2

, the vant Hoff equation (see equation 16,

page 354). Rearranging and plugging in values, K 1013.8330 R H r = ln 2 = ln 15.136 K1 1 1 10 T1 T2 = (3.000)(7.381 104 J mol1 ) = 221.4 kJ mol1
H r S = R ln K + T
r

8.314 J K 1 mol1 1 1 293 K 303 K

= (8.314 J K 1 mol1 ) ln(1015.136 ) + = 465.9 J K 1 mol1

221.4 103 J mol1 293 K

273

The sign on S r is positive because of the randomization that occurs as deuterons dissociate and redistribute throughout the liquid. From the results above, the autoprotolysis constant of heavy water at 25C is
K 2 H r 1 1 = ln K1 R T1 T2 221.4 103 J mol1 1 1 15.136 ln K 2 = + ln10 1 1 8.314 J K mol 293 K 298 K = 33.327

K D, 298 K = 3.359 1015 or pK D, 298 K = 14.474

Since pK H, 298 K = 14.00 for regular water < pK D, 298 K = 14.474 , substitution of D for H causes reactants, i.e., the associated molecules, to be favored more in heavy water than in regular water even though we expect D and H to be chemically equivalent. We can suggest that this observation is another example of the kinetic isotope effect where the zero-point energy of the O-D bond is lower than that of the O-H bond (see the solutions to Exercises 17.55 and 17.85 for further discussion). If bond dissociation is the rate-limiting step in the mechanism, and if only the vibrational energy of the ground state of the water molecules is changed appreciably, then the activation barrier for dissociation is bigger in heavy water since the zero-point energy is lower due to the heavier mass of D. This increase in the activation energy for bond dissociation causes the rate of dissociation to decrease while the rate of association is not changed appreciably. The position of equilibrium then favors the associated D 2 O molecules more than it does in the H 2 O molecules. (a) H r = [2H f (O3 , g)] = [2(142.7 kJ mol1 )] = 285.4 kJ mol1

9.92

274

S r = 3S (O 2 , g) [2S (O3 , g)] = 3(205.14 J K 1 mol1 ) [2(238.93 J K 1 mol1 )] = 137.56 J K 1 mol1 At 298 K: Gr(298 K) = 285.4 kJ mol1 (298 K)(137.56 J K 1 mol1 )/(1000 J kJ 1 ) = 326.4 kJ mol1 or directly from Gf values Gr = 2Gf (O3 , g) = 2(163.2 kJ mol1 ) = 326.4 kJ mol1 (b) Gr(298 K) = RT ln K ln K = Gr(298 K) RT 326 390 J = = +132 (8.314 J K 1 )(298 K)

K = 1057 The equilibrium constant for the decomposition of ozone to oxygen is extremely large, making this process extremely favorable. Note: The presence of ozone in the upper atmosphere is largely due to kinetic factors that inhibit the decomposition; however, in the presence of a suitable catalyst, this process should occur extremely readily.

9.94

2.50 g 1 92.02 g mol = 0.0136 mol L1 ; [NO 2 ] = [N 2 O4 ] = 2.00 L = 0.003 59 mol L1 Concentration (mol L1 ) initial change final N2O4(g) 0.0136

0.330 g 1 46.01 g mol 2.00 L

2 NO2(g) 0.003 59

x
0.0136 x

+2 x 0.003 59 + 2 x

275

[NO 2 ]2 K = [N 2 O 4 ] 4.66 103 = (0.003 59 + 2 x) 2 0.0136 x

(4.66 103 )(0.0136 x) = (0.003 59 + 2 x) 2 6.34 105 4.66 103 x = 4 x 2 + 1.44 102 x + 1.29 105 4 x 2 + 1.91 102 x 5.05 105 = 0 Solving by using the quadratic equation gives x = 1.89 103.

[N 2 O 4 ] = 0.0136 mol L1 1.89 103 mol L1 = 0.012 mol L1 [NO 2 ] = 0.003 59 mol L1 + 2 (1.89 103 mol L1 ) = 0.0074 mol L1
These numbers can be checked by substituting them into the equilibrium expression:
(0.0074) 2 ? = 4.66 103 0.012
4.6 103 = 4.66 103

9.96

We can write an equilibrium expression for the interconversion of each pair of isomers: 2-methyl propene cis-2-butene K1 2-methyl propene trans-2-buteneK2 cis-2-butene trans-2-butene ratios. The Ks can be obtained from the Gr s for each interconversion:
G1 = 65.86 kJ mol1 58.07 kJ mol1 = 7.79 kJ mol1 G2 = 62.97 kJ mol1 58.07 kJ mol1 = 4.90 kJ mol1 G3 = 62.97 kJ mol1 65.86 kJ mol1 = 2.89 kJ mol1

K3

We need to calculate only two of these values in order to determine the

276

Gr RT G1 7790 J mol1 = = 3.14; K1 = 0.043 ln K1 = RT (8.314 J K 1 mol1 )(298 K) Gr = RT ln K ; ln K = ln K 2 = ln K 3 = G2 4900 J mol1 = = 1.98; K 2 = 0.14 RT (8.314 J K 1 mol1 )(298 K) G3 2890 J mol1 = = +1.17; K 3 = 3.2 RT (8.314 J K 1 mol1 )(298 K)

Each K gives a ratio of two of the isomers:

K1 =
[cis -2-butene] [trans -2-butene] [trans -2-butene] ; K2 = ; K3 = [2-methylpropene] [2-methylpropene] [cis -2-butene]

We will choose to use the first two Ks to calculate the final answer:
[cis -2-butene] = 0.043 [2-methylpropene] [trans -2-butene] = 0.14 [2-methylpropene]

If we let the number of moles of 2-methylpropene = 1, then there will be 0.14 mol trans-2-butene and 0.043 mol cis-2-butene. The total number of moles will be 1 mol + 0.14 mol + 0.043 mol = 1.18 mol. The percentage of each will be % 2-methylpropene = % cis -2-butene = 1 mol 100% = 85% 1.18 mol

0.043 mol 100% = 4% 1.18 mol 0.14 mol 100% = 12% 1.18 mol

% trans -2-butene =

(The sum of these should be 100% but varies by 1%, due to limitations in the use of significant figures/rounding conventions.) The relative amounts are what we would expect, based upon the free energies of formation (the more negative or less positive value corresponding to the thermodynamically more stable compound), which indicate that the most stable compound is the 2-methylpropene followed by trans-2-butene with cis-2-butene being the least stable isomer. We can use K3 as a check of these numbers:

277

0.14 [ -2-butene] trans ? K 3 = 3.2 = = V 0.043 [cis -2-butene] V 3.2 3.3

9.98

A initial 10.00 atm change final

2B
0 atm +2 x +2 x

3C 0 atm +3 x +3 x PB 2 PC 3 PA

x
10.00 x

The equilibrium expression is K =

We can also write Ptotal = 10.00 x + 2 x + 3 x = 10.00 + 4 x = 15.76 x = 1.44 atm PA = 8.56 atm; PB = 2.88 atm; PC = 4.32 atm (2.88) 2 (4.32)3 K= = 78.1 8.56 G = RT ln K = (8.314 J K 1 mol1 )(298 K)ln(78.1) = 10.8 kJ mol1

9.100 (a) First we calculate the initial pressure of the gas at 127C using the

ideal gas relationship: PV = nRT m PV = RT M P= mRT MV (10.00 g)(0.082 06 L atm K 1 mol1 )(298 K) = (17.03 g mol1 )(4.00 L) = 3.59 atm

278

P P 1 = 2 T1 T2 P2 3.59 atm = 298 K 400 K

P2 = 4.82 atm or 4.88 bar (1 atm = 1.01325 bar) From Table 9.1 we find that the equilibrium constant is 41 for the equation N 2 (g) + 3 H 2 (g) 2 NH 3 (g) Although this exercise technically begins with pure ammonia and allows it to dissociate into N2(g) and H2(g), we can use the same expression. pressure (bar) initial change final
(4.88 2 x) 2 = 41 ( x)(3 x)3 (4.88 2 x) 2 = 41 27 x 4 4.88 2 x 3 3 x2 = 41

N 2 (g) 0 +x +x

3 H2(g) 0

2 NH3(g) 4.88

+3x +3x

2 x
4.88 2 x

4.88 2 x = 3 123 x 2 33.3 x 2 + 2 x 4.88 = 0 x = 0.354

PNH3 = 4.17 bar or 4.11 atm; PN 2 = 0.354 bar or 0.349 atm; PH 2 = 1.06 bar

or 1.05 atm Ptotal = 4.11 atm + 0.349 atm + 1.05 atm = 5.51 atm (b) The equilibrium constant can be calculated from G at 400 K, which can be obtained from H and S . The values are

279

H = 2(46.11 kJ mol1 ) = 92.22 kJ mol1 S = 2(192.45 J K 1 mol 1 ) [(191.61 J K 1 mol1 ) + 3(130.68 J K 1 mol1 )] = 198.75 J K 1 mol1 G = (92.22 kJ mol1 )(1000 J K 1 ) (400 K)(198.75 J K 1 mol1 ) = 12.72 kJ mol1 = 12720 J mol1

K = e G / RT = e+12720 Jmol

/ (8.314 J K 1 mol1 )(400K )

= 46

This is reasonably good agreement considering the logarithmic nature of these calculations. For comparison, the G value calculated from K = 41 at 400 K is 12.34 kJ mol1 .

9.102 (a) pressure (bar)

2 AsH3(g) 2 As(s) + 3 H2(g)

initial change final

0.52 2 x 0.52 2 x +3x +3x

At equilibrium, total pressure = 0.64 bar.

0.64 = 0.52 2 x + 3x = 0.52 + x x = 0.12 bar

PAsH3 = 0.52 bar 2(0.12 bar) = 0.28 bar PH 2 = 3(0.12 bar) = 0.36 bar

(b) Find the number of moles of AsH 3 that decomposed and relate it to the mass of As. n= (0.24 bar)(1.00 L) PV = RT (0.0831 L bar K 1 mol1 )(298 K)

= 9.69 103 mol AsH3 decomposed 2 mol As 74.9 g As mass As = (9.69 103 mol AsH 3 ) 2 mol AsH 3 1 mol As = 0.73 g As

280

(c) K =

3 PH 2 2 PAsH 3

(0.36)3 = 0.60 (0.28) 2

9.104 The free energy change for the reaction is calculated from the equation
G = G + RT ln Q = RT ln K + RT ln Q

In order to determine the range of Cl2 pressures that we need to examine, we will first calculate the equilibrium pressures of the gases present. Br2(g) initial change final
0.2 = 0.2 =

Cl2(g) 1.00 bar

2 BrCl(g) 0 2x 2x

1.00 bar

x
1.00 x

x
1.00 x

PBrCl 2 (2 x) 2 = PBr2 PCl2 (1.00 x) 2 2x 1.00 x

x = 0.183 0.2

In other words, equilibrium will be reached when PBrCl = 2 x = 0.36 bar , at the point on the graph where G = 0.
100 0 delta G (kJ per mol) -100 -200 -300 -400 -500 -600 -700 0 0.1 0.2 0.3 0.4 0.5

Pressure of BrCl (bar)

281

Notice that the free energy change for the reaction is most negative the farther the system is from equilibrium and that the value approaches 0 as equilibrium is attained.
9.106 The graph is generated for ln K vs. 1/T according to the relationship
ln K = H 1 S + R T R H S is the slope and is the intercept. R R

where

20 16 12 ln K 8 4 0 0 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035 1/T (1/K) y = -5398.4x +17.899 R = 0.99213

H = 5398 K R H = 44.9 kJ mol1 S = 17.9 R S = 149 J K 1 mol1 Because the reaction involves breaking only the NN bond, the enthalpy of reaction should be an approximation of the NN bond strength. Notice that this value is considerably less than the average 163 kJ mol1 value for NN bonds given in Table 2.2. Therefore it is a very weak NN bond.

282

9.108 (a) Since we are only using two temperatures, it really is not necessary to

make graphs in order to determine H and S . We can easily substitute into the vant Hoff equation, ln

K 2 H r 1 1 = , for each K1 R T1 T2

halogen to get H , then use it to find S from

G = H T S = RT ln K . A spread sheet will work well.

(b) & (c) Results from our spread sheet based on the relationships given above and data from Table 9.2 are given below. The S values are for the reactions X2(g) 2 X(g), so we can calculate the standard molar entropies for the atomic species using data from Appendix 2A and the relationship S = 2 S m (X, g) S m (X 2 , g).
S

Halogen Fluorine Chlorine Bromine Iodine

S (X 2 , g)

S (X, g)

1 1 kJ mol 1 J K mol

1 1 J K 1 mol 1 J K mol

164 256 195 163

126 160 110 152

202.78 223.07 245.46 260.69

164 192 178 206

9.110 The general form of this type of equation is

ln K = H r R 1 S r + R T

which is easily derived from the relationships Gr = RT ln K and Gr = H r T S r . By inspection, we can see that for the original expression to be valid,

H r = 21 700, which gives H r R = +(21 700 K)(8.314 J K 1 mol1 )/(1000 J kJ 1 ) = 180 kJ mol1

283

9.112 (a) K =

1 PPH3 PBCl3
K 19.2 = n ( RT ) [(0.08314 L bar K 1 mol 1 )(333 K)]2

(b) K = K c ( RT ) n
Kc =

= 1.48 104

(c) The initial pressure of PH3 is: nRT (0.0128 mol)(0.08314 L bar K 1 mol1 )(333 K) = PPH3 = 0.500 L V = 0.7088 bar pressure (bar) PH3(g) initial change equilibrium K = 19.2 = 0.7088 +x + BCl3(g) 0 +x

PH3BCl3(s)

0.7088 + x

1 1 = PPH3 PBCl3 (0.7088 + x) x

x 2 + 0.7088 x 0.05208 = 0

0.7088 (0.7088) 2 + 4(0.05208) x= 2 = 0.06712 (negative root isn't physically possible) So PPH3 = 0.7088 + 0.06712 = 0.7759 bar and cPH3 =
PPH3 RT

0.7759 bar = 0.0280 mol L1 (0.08314 L bar K 1 mol1 )(333 K)

(d) K increases as T increases, so the equilibrium position is shifting toward products with the addition of heat. The reaction is endothermic. (e) K = K c ( RT ) n
Kc = K 26.2 = n ( RT ) [(0.08314 L bar K 1 mol 1 )(343 K)]2

= 2.13 104

284

(f) PH 3 has a lone pair of electrons to donate in order to form an adduct with BCl3 , which can be an electron acceptor. Therefore PH 3 is a Lewis base while BCl3 is a Lewis acid.
9.114 (a) The values of the standard free energies of formation are

Compound BCl3(g) BBr3(g) BCl2Br(g) BClBr2(g)

G f (kJ mol 1 )

387.969 236.914 338.417 287.556

(b) A number of equilibrium reactions are possible including 2 BCl2Br(g) BCl3(g) + BClBr2(g) 2 BClBr2(g) BBr3(g) + BCl2Br(g) 2 BCl3(g) + BBr3(g) 3 BCl2Br(g) BCl3(g) + 2 BBr3(g) 3 BClBr2(g) (c) BCl3 because it is the most stable as determined by its G f value. (d) No. Although the equilibrium reaction given in the exercise would require that these two partial pressures be equal, there are other equilibria occurring as in (b) that will cause the values to be unequal. (e) We will solve this problem graphically rather than by writing a computer program to solve a system of simultaneous equations. Standard free energies of formation are only used to get equilibrium constants for two essential reactions from K = e
Gr RT

and

Gr = n prods G f mreacts G f .

In order to solve this part of the problem, first we need to figure out the independent reactions between the four species. If we consider BCl3 and BBr3 as pure species in terms of the halogens atoms, then the mixed species BClBr2 and BCl2Br can be made from the pure species by these two reactions: 285

(1) BCl3 + 2 BBr3 3 BClBr2 (2) 2 BCl3 + BBr3 3 BCl2Br

871 K1 = exp = 1.421 8.314 298.15 2399 K 2 = exp = 2.632 8.314 298.15

All other reactions between the species can be derived from these two essential reactions, so there are only two independent reactions for the system. Let so
PBCl3 = x , and PBBr3 = y then K1 =

PBClBr2 3 xy 2

and K 2 =

PBCl2 Br 3 x2 y

PBClBr2 = K11/ 3 x1/ 3 y 2 / 3 , and PBCl2 Br = K 21/ 3 x 2 / 3 y1/ 3

Atom balances are determined by the initial composition of the system. Balancing B atoms we get
o o PBCl + PBBr = PBCl3 + PBCl2Br + PBClBr2 + PBBr3 3 3 o o = PBBr = 1 bar are the initial pressures. Balancing Cl atoms where PBCl 3 3

and Br atoms gives us

o 3PBCl = 3PBCl3 + 2 PBCl2Br + PBClBr2 3 o 3PBBr = PBCl2Br + 2 PBClBr2 + 3PBBr3 3

(Notice that the B balance is not an independent condition because it is implied by the Cl and Br balances.) In terms of x and y, the Cl balance and Br balance can be written as Cl balance: Br balance:
3 x + 2 K 21 / 3 x 2 / 3 y1/ 3 + K11/ 3 x1/ 3 y 2 / 3 = 3

K 21/ 3 x 2 / 3 y1/ 3 + 2 K11/ 3 x1/ 3 y 2 / 3 + 3 y = 3

Subtracting the second equation from the first equation, dividing the resulting equation by y, and also using this new definition x y
1/ 3

we arrive at following equation in terms of z:

3 z 3 + K 21/ 3 z 2 K11 / 3 z 3 = 0

286

3 z 3 + 1.381z 2 1.124 z 3 = 0

This cubic equation can be solved graphically by noting where f ( z ) = 3z 3 + 1.381z 2 1.124 z 3 crosses 0. The only real root is

z = 0.975 .
25 20 15 10 5 0 -3 -2 -1 -5 -10 -15 -20 -25 0 1 2 3

z
Substituting x = z 3 y back into the Cl balance equation gives
y= = 3 3z + 2K
3 3 1/ 3 2 2

z + K11/ 3 z

3 3(0.975) + 2(1.381)(0.975) 2 + (1.124)(0.975) = 0.461

Then x = z 3 y = (0.975)3 (0.461) = 0.428 And finally: PBClBr2 = ( (1.421)(0.428)(0.461) 2 )

1/ 3

= 0.506 = 0.606

PBCl2 Br = ( (2.632)(0.428)2 (0.461) )

1/ 3

287

The results can be summarized as:

PBCl3 = 0.428 bar PBBr3 = 0.461 bar PBCl2 Br = 0.606 bar PBClBr2 = 0.506 bar

Note that in part (c) we predicted that BCl3 is the most abundant species in the equilibrated mixture. However, this calculation reveals that it is the least abundant species at equilibrium given the stated initial conditions. The result is simply non-intuitive. What we need to recognize is that the formation reactions and their corresponding values of free energy of reaction describe equilibria between the elements B(s), Cl2(g), and Br2(l) and the boron trihalides under standard conditions. In our mixture the compounds are certainly not in equilibrium with their elements in their standard states, so the prediction in part (c) fails. Also note that in this system, B(s) and Br2(l) cannot exist at same time, because the equilibrium constant of B(s) + 1.5 Br2(l) BBr3(g) is very large, while the actual pressure of BBr3(g) is way below this equilibrium constant. B(s) may exist from a microscopic amount of decomposition of BCl3(g), so Br2(l) can not exist. This condition further prevents BCl2Br and BClBr2 from decomposing into their elements, so only BCl3(g) may decompose to a small extent. Clearly, this small amount of Cl2(g) is far below standard conditions.
9.116 (a) Find Q to see if the reaction is at equilibrium.

cyclohexane (C) Q=

methylcyclohexane (M)

[M] 0.100 = = 5.00 > K = 0.140 [C] 0.0200

The reaction will proceed to the left to form more reactant.

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(b) initial change equil

K=

[C] 0.0200 +x

[M] 0.100

x
0.100 x

0.0200 + x

[M] 0.100 x = = 0.140 [C] 0.0200 + x 0.100 x = (0.140)(0.0200 + x) 1.140 x = 9.72 102 x = 8.53 102

[M] = 0.100 0.0853 = 0.0147 = 0.015 M [C] = 0.0200 + 0.0853 = 0.1053 M (c) At equilibrium, [C] = 0.100 M. The total concentration of all species is 0.120 M. Therefore, [M] = 0.020 at equilibrium. K 50C = [M] 0.100 = = 5.0 [C] 0.020

(d) As the temperature increased, K also increased resulting in the reaction forming more products: C + heat reaction is endothermic.
9.118 Refer to Grahams Law of Effusion, equation 19, page 144, which states

M. Therefore, the

that the ratio of the rates of effusion of two gases, both at the same temperature, is equal to the square-root of the inverse ratio of their molar masses.

Rate of effusion of H 2 = Rate of effusion of HI =

M HI M H2 127.9 g mol1 2.016 g mol1

= 7.97 This treatment suggests that H2 effuses ~8 times faster than HI. However, it is also important to note that the partial pressure of each gas affects the collision frequency of the molecules with the pinhole. Therefore, an expression that takes this dependence into account is
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Rate of effusion of H 2 PH 2 = Rate of effusion of HI PHI

M HI M H2

The partial pressure of hydrogen is 0.7 atm, or 0.69 bar. The partial pressure of HI can be found from
2 PHI PH2

K=

PHI = K PH2 = (0.345 0.69)1/ 2 = 0.49 bar

Rate of effusion of H 2 PH2 = Rate of effusion of HI PHI M HI 0.69 bar 127.9 g mol1 = M H2 0.49 bar 2.016 g mol1

= 11 = 10 (to 1 sig fig) So hydrogen effuses ten times as fast as hydrogen iodide under these conditions.

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