M15 Wils2248 14 Se C15

15 Chemical
Equilibrium
Visualizing Concepts
15.1 (a) kf > kr. According to the Arrhenius equation [14.21], k  A e  E a / R T . As the magnitude
of Ea increases, k decreases. On the energy profile, Ea is the difference in energy
between the starting point and the energy at the top of the barrier. Clearly this
difference is smaller for the forward reaction, so kf > kr.
(b) From the Equation [15.5], the equilibrium constant = k f /k r . Because k f > k r , the
equilibrium constant for the process shown in the energy profile is greater than 1.
15.2 Yes, the system is in equilibrium in boxes 4 and 5. The first box is pure reactant A. As the
reaction proceeds, some A changes to B. In the fourth and fifth boxes, the relative amounts
(concentrations) of A and B are constant. Although the reaction is ongoing the rates of A 
B and B  A are equal, and the relative amounts of A and B are constant.
15.3 Analyze. Given box diagram and reaction type, determine whether K greater or smaller
than one for the equilibrium mixture depicted in the box.
Plan. Assign species in the box to reactants and products. Write an equilibrium expression
in terms of concentrations. Find the relationship between numbers of moles (molecules in
the diagram) and concentration. Calculate K.
Solve. Let red = A, blue = X, red and blue pairs = AX. (The colors of A and X are
arbitrary.) There are 3A, 2B, and 8AX in the box.
M = mol/L. Because each particle represents one mole, we can use numbers of particles in
place of moles in the molarity formula. (The mole is a counting unit for particles, so mol
ratios and particle ratios are equivalent.) V = 1 L, so in this case, [A] = number of A
particles.
[A X] 8 8
K ; [ A X ]  8 / V  8; [ A ]  3/ V  3; [ X ]  2/ V  2 . K    1 .3 3
[A ][X] [ 3 ] [ 2] 6
K is greater than one.
15.4 Analyze/Plan. Given that element A = red and element B = blue, evaluate the species in
the reactant and product boxes, and write the reaction. Answer the remaining questions
based on the balanced equation. Solve.
(a) reactants: 4A 2 + 4B; products: 4A 2 B
balanced equation: A 2 + B  A 2 B
[ A 2 B]
(b) Kc 
[A 2][B]
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15 Chemical Equilibrium Solutions to Exercises
(c) Evaluate concentrations and the value of K for the box in equilibrium, the one on
the right of the diagram. [A 2 B] = 0.4 M; [A 2 ] = 0.1 M; [B] = 0.1 M
[ A 2 B] [ 0 .4]
Kc  = = 40
[A 2][B] [ 0 .1 ] [ 0 .1 ]
(d) n = n(prod) — n(react) = 1 — 2 = —1.
(e) K p  K c (R T ) n , Equation 15.15. Assume a temperature of 25 oC = 298 K.
40
K p  40 [ (0 .0 8 21 )(29 8 )] 1   1 .6 3 5  2
(0 .0 8 21 )(29 8 )
15.5 The reaction A(g) + B(g) ⇌ AB(g) has the larger equilibrium constant. At 40s and 50s, there
are more diatomic products and fewer monoatomic reactants than in the other reaction. An
equilibrium constant is the ratio of concentrations of products to concentrations of reactants at
equilibrium. Another way to say this is that the A(g) + B(g) reaction favors products more
than the X(g) + Y(g) reaction. (The X(g) + Y(g) reaction reaches equilibrium more quickly than
the A(g) + B(g) reaction, but this is a matter of kinetics, not equilibrium constants.)
15.6 Analyze/Plan. The reaction with the largest equilibrium constant has the largest ratio of
products to reactants. Count product and reactant molecules. Calculate ratios and compare.
Solve.
[ C 2H 4X 2 ]
K = . Use numbers of molecules as an adequate measure of concentration.
[ C 2H 4 ] [ X 2 ]
(Although the volume terms don’t cancel, they are the same for all parts. For the purpose of
comparison, we can ignore volume.) Solve.
8
(a) 8 C2H4Cl2, 2 Cl2, 2 C2H4. K = = 2
(2)(2)
6
(b) 6 C2H4Br2, 4 Br2, 4 C2H4. K = = 0.375 = 0.4
(4)( 4)
3
(c) 3 C2H4I2, 7 I2, 7 C2H4. K = = 0.0612 = 0.06
(7)(7)
From the smallest to the largest equilibrium constant, (c) < (b) < (a).
Check. By inspection, there are the fewest product molecules and the most reactant
molecules in (c); most product and least reactant in (a).
15.7 Statement (b) is definitely true. The reaction is a heterogeneous equilibrium for which
K p  PO 2 . The larger volume of vessel B requires that more PbO 2 (s) must decompose to
produce the equilibrium pressure of O 2 (g). (After heating, both vessels will have less than
the 5.0 g PbO 2(s) that was present initially. If the “less” refers to the amount of solid
present initially, statement (a) is also true.)
15.8 Analyze. Given box diagrams, reaction type, and value of K c, determine whether each
reaction mixture is at equilibrium.
Plan. Analyze the contents of each box, express them as concentrations (see
Solution 15.3). Write the equilibrium expression, calculate Q for each mixture, and compare it
to K c. If Q = K, the mixture is at equilibrium. If Q < K, the reaction shifts right (more
product). If Q > K, the reaction shifts left (more reactant).
435
[ A B] 2
Solve. K c  .
[A 2][B2]
For this reaction, n = 0, so the volume terms cancel in the equilibrium expression. In this
case, the number of each kind of particle can be used as a representation of moles (see
Solution 5.3) and molarity.
62
(a) Mixture (i): 1A 2 , 1B 2 , 6AB; Q   36
(1 ) (1 )
Q > K c , the mixture is not at equilibrium.
32
Mixture (ii): 3A 2 , 2B 2 , 3AB; Q   1 .5
(3) (2)
Q = K c , the mixture is at equilibrium.
22
Mixture (iii): 3A 2 , 3B 2 , 2AB; Q   0.44
(3) (3)
Q < K c , the mixture is not at equilibrium.
(b) Mixture (i) proceeds toward reactants.
Mixture (iii) proceeds toward products.
15.9 For the reaction A2(g) + B(g) ⇌A(g) + AB(g), n  0 and K p = K c . We can evaluate the
equilibrium expression in terms of concentration. Also, because n = 0, the volume terms in
the expression cancel and we can use number of particles as a measure of moles and
molarity. The mixture contains 2A, 4AB, and 2A 2 .
[ A ] [ A B] (2)( 4)
Kc    2; B  2
[ A 2 ] [ B ] (2)(B )
2 B atoms should be added to the diagram.
15.10 Analyze. Given the diagram and reaction type, calculate the equilibrium constant K c .
Plan. Analyze the contents of the cylinder. Express them as concentrations, using number of
particles as a measure of moles, and V = 2 L. Write the equilibrium expression in terms of
concentration and calculate K c . Solve.
(a) The mixture contains 2A 2 , 2B, 4AB. [A 2 ] = 2/2 = 1, [B] = 2/2 = 1, [AB] = 4/2 = 2.
[ A B ]2 (2) 2
Kc  2
 4
[ A 2 ] [ B] (1 )(1 ) 2
(b) A decrease in volume favors the reaction with fewer moles of gas. This reaction has
two moles of gas in products and three in reactants, so a decrease in volume favors
products. The number of AB (product) molecules will increase.
Note that a change in volume does not change the value of K c . If V decreases, the
number of AB molecules must increase to maintain the equilibrium value of K c .
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15.11 If temperature increases, K of an endothermic reaction increases and K of an exothermic
reaction decreases. Calculate the value of K for the two temperatures and compare. For this
reaction, n = 0 and K p = K c . We can ignore volume and use number of particles as a
measure of moles and molarity. K c = [A][AB]/[A 2 ][B]
(1) 300 K, 3A, 5AB, 1A 2 , 1B; K c = (3)(5)/(1)(1) = 15
(2) 500 K, 1A, 3AB, 3A 2 , 3B; K c = (1)(3)/(3)(3) = 0.33
K c decreases as T increases, so the reaction is exothermic.
15.12 (a) Exothermic. In both reaction mixtures (orange and blue), [AB] decreases as
T increases.
(b) In the reaction, there are fewer moles of gas in products than reactants, so greater
pressure favors production of products. At any single temperature, [AB] is greater at
P = y than at P = x. Because the concentration of the product, AB, is greater at P =
y, P = y is the greater pressure.
Equilibrium; The Equilibrium Constant (Sections 15.1—15.4)

15.13 Analyze/Plan. Given the forward and reverse rate constants, calculate the equilibrium
constant using Equation 15.5. At equilibrium, the rates of the forward and reverse reactions
are equal. Write the rate laws for the forward and reverse reactions and use their equality
to answer part (b). Solve.
kf 2.5  10 2 min 1
(a) Kc    1.0  10 1
kr 2.5  10 1 min 1
(b) The equilibrium constant is smaller than 1; the equilibrium lies “to the left”. At
equilibrium, the partial pressure of A is greater than the partial pressure of B.
15.14 (a) Reactants predominate at equilibrium. The numeric value of Kc is much less than one,
which means that the denominator of the equilibrium expression is much larger than
the numerator.
(b) The reverse reaction has the greater numeric value of the rate constant. Kc = kf/kr; if
Kc is small, kr is larger than kf and the reverse reaction has the greater rate constant.
15.15 Analyze/Plan. Follow the logic in Sample Exercises 15.1 and 15.5. Solve.
2 2
[I] [SO3 ]
(a) Kc  (b) Kc 
[I 2 ] [SO 2 ] 2 [O 2 ]
[CO] 2 [CO 2 ] [H 2 ]
(c) Kc  (d) Kc 
[CO] [H 2 O] [CO]
[HCO 3 ][H  ] [Zn 2  ]

(e) Kc  (f) Kc 
[CO 2 ] [Fe 2  ]
(g) K c  [Ca 2  ] [Ca32  ]
homogeneous: (a), (b), (d), (e); heterogeneous: (c), (f), (g)
[O] 2 [Si Cl 4 ]
15.16 (a) Kc  (b) Kc 
[O 2 ] [Cl 2 ] 2
437
[HCl] 2 [CO 2 ] 2
(c) Kc  (d) Kc 
[H 2 ] [Cl 2 ] [O 2 ] [CO] 2
[CO32  ] [H+ ] [Fe3+ ] [Ce 3+ ]

(e) Kc  (f) Kc 
[HCO3 ] [Fe 2+ ] [Ce 4+ ]
(g) Kc  [CO 2 ]
homogeneous: (a), (c), (d), (e), (f); heterogeneous: (b), (g)
15.17 Analyze. Given the value of K c or K p , predict the contents of the equilibrium mixture.
Plan. If K c or K p > 1, products dominate; if K c or K p < 1, reactants dominate. Solve.
(a) mostly products (K c > 1)

(b) at low total pressure, mostly reactants (K p < 1)
15.18 (a) the reaction lies to the left, favoring formation of reactants (K c < 1)
(b) at high total pressure, the reaction lies to the right, favoring formation of products
(K p > 1)
15.19 (a) True.

(b) False. A single-headed arrow indicates that the reaction “goes to completion,” that the
equilibrium constant is extremely large.
(c) False. The value of the equilibrium constant gives no information about the speed of
a reaction.
15.20 (a) False. The value of n is not zero.

(b) False. Equilibrium constants are not expressed with units.
(c) True. For a gas phase equilibrium, increasing pressure (by decreasing volume) favors
the reaction that produces fewer moles of gas. In this equilibrium, the forward
reaction has fewer moles of gas. When the forward reaction is favored, the value of
K increases.
15.21 Analyze/Plan. Follow the logic in Sample Exercise 15.2. Solve.

2 NO(g) + Br2(g) ⇌ 2 NOBr(g), Kc = 0.013 n  2  3  1
Kp  Kc (RT) n  Kc (RT) 1  K c /RT

0.013
Kp   1.58  10 4  1.6  10 4
(0.08206) (1000)
15.22 2 CO(g) ⇌CO (g) + C(s),

2 KP = 5.80. n  1  2  1
K p  K c (R T ) n ; 5.80 = K c (RT) —1 = K c /RT;
K c = 5.80 RT = 5.80(0.08206)(900) = 428.35 = 428
15.23 Analyze. Given K c for a chemical reaction, calculate K c for the reverse reaction.
Plan. Evaluate which species are favored by examining the magnitude of K c . The
438
equilibrium expressions for the reaction and its reverse are the reciprocals of each other, and
the values of K c are also reciprocal. Solve.
(a) For the reaction as written, K c < 1, which means that reactants are favored. At this
temperature, the equilibrium favors NO and Br 2 .
[ N OB r] 2
(b) K c (fo rw ard )   1 .3  1 0 2
[ N O] 2 [ B r2 ]
[ N O ] 2 [ B r2 ] 1
K c (rev erse)    76 .9 2  77
[ N O B r] 2
1 .3  1 0 2
[ N O ] [ B r2 ] 1 / 2
(c) K c2 (reverse)   (K c (rev erse)) 1 / 2  (76 .9 2) 1 / 2  8 .8
[ N O B r]
15.24 2 H 2 ( g) + S 2 ( g ) ⇌ 2 H 2 S ( g) , K c = 1.08 × 107 at 700 C. n = 2 — 3 = − 1.
(a) K p  K c (R T ) n ; T = 700 C + 273 = 973 K.
1 .0 8  1 0 7
K p  1 .0 8  1 0 7 (R T ) 1   1 .3 5  1 0 5
(0 .0 8 20 6)(9 73)
(b) Mostly H2S. Both Kp and Kc are much greater than one, so the product, H2S, is
favored at equilibrium.
⇌ H S(g);
[ H 2 S]
(c) H 2 ( g) + ½ S 2 (g) 2
K c2 
[ H 2 ] [ S 2 ] 1/ 2
K c 2 = (K c ) 1/2 = (1.08 × 107) 1/2 = 3.29 × 103
K p 2 = (K p ) 1/2 = (1.35 × 105) 1/2 = 368
15.25 Analyze. Given K p for a reaction, calculate K p for a related reaction.

Plan. The algebraic relationship between the K p values is the same as the algebraic
relationship between equilibrium expressions.
PSO3
Solve. Kp   0.184 kPa 0.5
PSO2 × PO1 /2 2
PSO2  PO1 /2 2 1
(a) Kp    5.43 kPa 0.5
PSO3 0.184 kPa 0.5
2
PSO
(b) Kp  3
 0.184 kPa 0.5  3.3856  10 2 = 3.39  10 2 kPa 1
2
PSO 2
 PO2
(c) K p  K c (R T ) n ; n = 2 — 3 = —1; T = 1000 K
K p = K c (RT) —1 = K c /RT; K c = K p (RT)
K c = 3.3856  10—2 kPa—1  8.314 L-kPa/mol-K  1000 K = 281.48 = 281 L/mol
4
PHCl  PO2
15.26 Kp = = 7.62 kPa
PCl2 2  PH2 2O
439
PCl2 2  PH2 2 O 1
(a) Kp    0.1312 = 0.131 kPa 1
4
PHCl  PO2 7.62 kPa
2
PHCl  PO1/22
(b) Kp   (7.62 kPa) 1 / 2  2.76 kPa 0.5
PCl2  PH 2 O
(c) K p  K c (R T ) n ; n = 2.5 — 2 = 0.5; T = 480 C + 273 = 753 K

K p = K c (RT) 1/2, K c = K p /(RT) 1/2 = 2.76 kPa0.5/(8.314 L-kPa/mol-K  753 K)0.5 = 0.0349
L0.5/mol0.5

⇌ Ag (aq) + Cl (aq)
AgCl(s) + —
K c1  1.8  10 10
Ag (aq) + 2 NH (aq) ⇌ [Ag(NH ) ] (aq)
+
3 3 2
+
Kc2  1.6  107
_____________________________________________________________________________________________________
AgCl(s) + 2 NH3(aq) + Ag+(aq) ⇌ [Ag(NH )2] (aq)+ Cl (aq) + Ag (aq)

3
+ — +
AgCl(s) + 2 NH (aq) ⇌ [Ag(NH )2] (aq)+ Cl (aq)

3 3
+ —
Kc  Kc1  Kc2  1.8  10 10  1.6  107  2.9  10 3
15.28 ⇌ 2NOBr(g)
2NO(g) + Br2(g) K1 = 2.0
N (g) + O (g) ⇌ 2NO(g)
1
K2 =
2.1  1 0 30
2 2
2NO(g) + Br (g) + N (g) + O (g) ⇌ 2NOBr(g) + 2NO(g)

2 2 2
N (g) + O (g) + Br (g) ⇌ 2NOBr(g)

2 2 2
1
K c  K 1  K 2  2.0   9 .5 24  1 0 3 1  9 .5  1 0 3 1
2.1  1 0 3 0

(a) K p  PO 2
(b) K c = [Hg(solv)]4[O2 (solv)]
15.30 (a) K p  1 / PS O 2
[ N a2SO 3 ]
(b) Kc 
[ N a 2 O][ S O 2 ]
Calculating Equilibrium Constants (Section 15.5)

15.31 Analyze/Plan. Calculate molarity of reactants and products. Follow the logic in Sample
Exercise 15.7 using concentrations rather than pressures. Solve.
0.050 mol
[CH 3 OH]   0.0050 M
10.00 L
0.850 mol CO 0.750 mol H 2
[CO]   0.085 M ; [H 2 ]   0.075 M
10.00 L 10.00 L
[CH 3 OH] 0.050
Kc    10.46  10.5
[CO] [H 2 ] 2 (0.085)(0.075) 2
[H 2 ] [I 2 ] (5.75  10 4 ) (5.75  10 4 )
15.32 Kc    1.633  10 2  0.0163
[HI] 2 (4.50  10 3 ) 2
440
(a) 2NO(g) + Cl2(g) ⇌ 2NOCl(g)
2
PNOCl (0.350) 2
Kp    61.25  61
2
PNO  PCl2 (0.100) 2 (0.200)
(b) K p  K c (R T ) n ; n = 2 — 3 = —1; K p = K c (RT) —1 = K c /(RT)
K c = K p (RT) = 61.25 (0.08206)(550) = 2.76  103 = 2.8  103
PP C l 5 1 .3 0 atm
15.34 (a) Kp    6 6 .8
PP C l 3  PC l 2 0 .1 24 atm  0 .1 5 7 atm
(b) Because K p > 1, products (the numerator of the K p expression) are favored over
reactants (the denominator of the K p expression).
(c) K p  K c (R T ) n ; n = 1 — 2 = —1; K p = K c (RT) —1 = K c /(RT)

K c = K p (RT) = 66.8(0.08206  450) = 2.5  103
15.35 Analyze/Plan. Calculate the concentrations of reactants and products and follow the logic
in Sample Exercise 15.8. Solve.
(a) First calculate the change in [H2]; the concentration of H2 decreased from the initial
value (0.030) to the equilibrium value (0.010 mol/L). From the stoichiometry of the
reaction, calculate the changes in the other pressures. Finally, calculate the
equilibrium pressures
2NO(g) + 2H2(g) ⇌ N2(g) + 2H2O(g)

initial 0.070 M 0.030 M 0 M 0.130 M
change —0.020 M —0.020 M +0.020/2 M +0.020 M
equil. 0.050 M 0.010 M 0.010 M 0.150 M
[N 2 ] [H 2 O] 2 (0.010)(0.150) 2
(b) Kc    900  9.0  10 2
[NO] 2 [H 2 ] 2 (0.050) 2 (0.010) 2
15.36 (a) Calculate the initial concentrations of H 2 (g) and Br 2 (g) and the equilibrium
concentration of H 2 (g). M = mol/L.
1 m ol H 2 1
[ H 2 ] init  1 .3 74 g H 2    0 .3 4 0 79  0 .3 41 M
2.0 1 5 9 g H 2 2.0 0 L
1 m o l B r2 1
[ B r2 ]  70 .3 1 g B r2    0 .21 9 9 8  0 .220 M
1 5 9 .8 1 g B r2 2.0 0 L
1 m ol H 2 1
[ H 2 ] eq u il  0 .5 6 6 g H 2    0 .1 40 3 8  0 .1 40 M
2.0 1 5 9 g H 2 2.0 0 L
H2(g) + Br2(g) ⇌ 2HBr(g)

initial 0.34079 M 0.21998 M 0
change —0.20041 M —0.20041 M +2(0.20041) M
equil. 0.14038 M 0.01957 M 0.40082 M
The change in H 2 is (0.34079 — 0.14038 = 0.20041 = 0.200). The changes in [Br 2 ] and
441
[HBr] are set by stoichiometry, resulting in the equilibrium concentrations shown in
the table.
[ H B r] 2 (0 .40 0 8 2) 2 (0 .4 0 1 ) 2
(b) Kc     5 8 .48  5 8
[ H 2 ] [ B r2 ] (0 .1 40 3 8) (0 .0 1 9 5 7) (0 .1 40) (0 .0 20)
The equilibrium concentration of Br2 has 3 decimal places and 2 sig figs, so the
value of Kc has 2 sig figs.
15.37 Analyze/Plan. Follow the logic in Sample Exercise 15.8, using partial pressures, rather than
concentrations. Solve.
8.314 L  kPa 550 K

(a) PH2O  0.713 mol    326.03 kPa  326.0 kPa
mol  K 10.00 L
8.314 L  kPa 550 K

PH2  0.443 mol    202.57 kPa  202.6 kPa
mol  K 10.00 L
8.314 L  kPa 550 K

PCO2  0.886 mol    405.14 kPa  405.1 kPa
mol  K 10.00 L
(b) Partial pressure and number of moles are proportional.

The partial pressure of H2 decreased from the initial value 202.6 kPa to the
equilibrium value 182 kPa.
CO2(g) + H2(g) ⇌ CO(g) + H2O(g)

initial 405.1 kPa 202.6 kPa 0 326.0 kPa
change —20.6 kPa —20.6 kPa +20.6 kPa +20.6 kPa
equil. 384.5 kPa 182 kPa 20.6 kPa 346.6 kPa
Equilibrium partial pressure:

P(H2O) = 346.6 kPa
P(CO2) = 384.5 kPa
P(CO) = 20.6 kPa
PH2O  PCO (346.6)(20.6)

(c) Kp    0.102  0.10
PCO2  PH2 (384.5)(182)
K p  K c (R T ) n ; n = 2 — 2 = 0; K p = K c (RT) ;
0
(d) K c = K p = 0.10
15.38 (a) N2O4(g) ⇌ 2NO2(g)
initial 1.500 atm 1.000 atm
change +0.244 atm —0.488 atm
equil. 1.744 atm 0.512 atm
The change in PN O 2 is (1.000 — 0.512) = —0.488 atm, so the change in PN 2 O 4 is
+(0.488/2) = +0.244 atm.
442
PN2 O 2 (0 .5 1 2) 2
(b) Kp    0 .1 5 0 3  0 .1 5 0
PN 2 O 4 (1 .744)
(c) K p  K c (R T ) n ; n = 2 — 1 = 1; K p = K c (RT) 1 = K c (RT)

K c = K p /(RT) = 0.1503/(0.08206  298) = 6.15 × 10—3
15.39 Analyze/Plan. Follow the logic in Sample Exercise 15.8. mM = 10—3 M

X(aq) Y(aq) XY(aq)
+ ⇌
initial 1.0 mM 1.0 mM 0
change —0.80 mM —0.80 mM +0.80 mM
equil. 0.20 mM 0.20 mM 0.80 mM
[XY] (0 .8 0  1 0 3 )
Kc    2.0  1 0 4
[ X ] [ Y ] (0 .20  1 0 3 ) (0 .20  1 0 3 )
15.40 The initial concentrations of drug candidate and protein are the same in the two
experiments, and the two reactions have the same stoichiometry. At equilibrium, the
concentration of B-protein complex is greater than the concentration of A-protein complex,
so drug B is the better choice for further research. Calculation of equilibrium constants for
the two reactions confirms this conclusion.
A(aq) protein(aq) ⇌ A-protein(aq)
+
initial 2.00 × 10—6 mM 1.50 × 10—6 mM 0
change —1.00 × 10—6 mM —1.00 × 10—6 mM +1.00 × 10—6 mM
equil. 1.00 × 10—6 mM 0.50 × 10—6 mM 1.00 × 10—6 mM
[ A -p ro tein] (1 .0 0  1 0 6 )
Kc    2.0  1 0 6
[ A ] [ p ro tein] (1 .0 0  1 0 6 ) (0 .5 0  1 0 6 )
B(aq) protein(aq) B-protein(aq)

+ ⇌
initial 2.00 × 10—6 mM 1.50 × 10—6 mM 0
change —1.40 × 10—6 mM —1.40 × 10—6 mM +1.40 × 10—6 mM
equil. 0.60 × 10—6 mM 0.10 × 10—6 mM 1.40 × 10—6 mM
[ B  p ro tein] (1 .40  1 0 6 )
Kc    2.3  1 0 7
[ B] [ p ro tein] (0 .6 0  1 0 6 ) (0 .1 0  1 0 6 )
443
Applications of Equilibrium Constants (Section 15.6)
15.41 (a) The value of Qc at this point in the reaction is zero, as there are zero products
( Qc 
[products]
[reactant]
; zero in the numerator of the equilibrium expression).
(b) As the reaction proceeds, products are formed, and reactants are consumed, thus, the
value of Qc will increase.
(c) The reaction must be at equilibrium.
15.42 (a) If Q c > K c , the reaction will proceed in the direction of more reactants, to the left.
(b) Q c = 0 if the concentration of any product is zero.
15.43 Analyze/Plan. Follow the logic in Sample Exercise 15.9. We are given molarities, so we
calculate Q directly and decide on the direction to equilibrium. Solve.
[ C O] [ C l 2 ]
Kc   2.1 9  1 0 1 0 at 1 0 0 C
[ C O C l2 ]
(1.0  10 4 ) (7.2  10 6 )
(a) Q   7.2  10 6 ; Q  Kc
(1.0  10 4 )
The reaction will proceed left to attain equilibrium.
(2.2  10 7 ) (3.0  10 6 )
(b) Q   3.0  10 11 ; Q  K c
(2.2  10 2 )
The reaction will proceed right to attain equilibrium.
(7.2  10 6 )(7.2  10 6 )
(c) Q   5.18  10 9 ; Q  K c
(0.0100)
The reaction will proceed left to attain equilibrium.
15.44 Calculate the reaction quotient in each case, compare with

2
PNH
Kp  3
 4.39  10 9
PN 2  PH3 2
(9930 kPa) 2
(a) Q   1.3  10 7
(4560) (5570) 3
Because Q > K p , the reaction will shift toward reactants to achieve equilibrium.
(5780) 2
(b) Q  
(14490) (0) 3
Because Q > K p , reaction must shift toward reactants to achieve equilibrium. There
must be some H 2 present to achieve equilibrium. In this example, the only source of
H 2 is the decomposition of NH 3 .
(1320) 2
(c) Q   1.1  10 9
(2740)(8310) 3
Q is only slightly less than Kp, so the reaction will shift slightly toward products to
achieve equilibrium.
444
15.45 Analyze/Plan. We are given concentrations, so write the KC expression and solve for [Cl2].
Change molarity to partial pressure using the ideal gas equation and the definition of
molarity. Solve.
[SO 2 ] [Cl 2 ] K [SO 2 Cl 2 ] (0.090)(0.100)
Kc   0.090; [Cl 2 ]  c   0.120 M
[SO 2 Cl 2 ] [SO 2 ] 0.075
0.120 mol 8.314 L  kPa

PCl2  [Cl 2 ]  RT    393 K  392.09 kPa  392.1 atm
L mol  K
2
PSO
15.46 Kp  3
; PSO3  Kp  PSO
2
 PO2  (0.0035)(18.24) 2 (50.66)  58.991  7.7 kPa
2
PSO 2
 PO2 2
15.47 Analyze/Plan. Follow the logic in Sample Exercise 15.10. In each case, change masses to
molarities, solve for the equilibrium molarity of the desired component, and calculate mass
of that substance present at equilibrium. Solve.
[ B r] 2
Kc   1 .04  1 0 3
[ B r2 ]
1.50 g Br2 1 mol Br2

[Br2 ]    0.009387  0.00939 M
1.00 L 159.8 g Br2
[Br] = (K c [Br 2 ]) 1/2 = [(1.04  10 —3)(0.009387)] 1/2 = (9.762  10 —6)1/2 = 0.003124 = 0.00312 M
0.003124 mol Br 79.90 g Br
 1.00 L   0.2496 g  0.250 g Br(g)
L mol
[Br] 2 (0.003124) 2
Check. Kc    1.04  10 3
[Br2 ] (0.009387)
[HI] 2
15.48 Kc   55.3
[H 2 ] [I 2 ]
1.30 g H 2 1 mol H 2
[H 2 ]    0.06448  0.0645 M
10.0 L 2.016 g H 2
21.0 g I 2 1 mol I 2
[I 2 ]    0.008274  0.00827 M
10.0 L 253.8 gI 2
[HI] = (K c [H2][I2]) 1/2 = [(55.3)(0.06448)(0.008274)] 1/2 = (0.02950)1/2 = 0.1718 M = 0.172 M

0.1718 mol HI 127.9 g HI
 10.0 L   219.73 g  220 g HI (g)
L mol
[HI] 2 (0.1718) 2
Check. Kc    55.3
[H 2 ] [I 2 ] (0.06448)(0.008274)
15.49 Analyze/Plan. Follow the logic in Sample Exercise 15.10. In each case, change masses to
molarities, solve for the equilibrium molarity of the desired component, and calculate mass
of that substance present at equilibrium. Solve.
[ I] 2
Kc   3.1  1 0 5
[ I2 ]
445
30.0 mg I 10 3 g 1 mol I
[I]     4.728  10 5 M  4.73  10 5 M
5.00 L 1 mg 126.9 g I
[I] 2 (4.728  10 5 ) 2
[I 2 ]    7.211  10 5 M  7.2  10 5 M
Kc 3.1  10 5
7.211  10 5 mol I2 253.8 g I 2

 5.00 L   0.0915 g  0.092 g I 2 (g)
L mol I 2
[I] 2 (4.728  10 5 ) 2
Check. Kc    3.1  10 5
[I 2 ] 7.211  10 5
gR T
15.50 P V  nR T ; P 
MM V
1.17 g SO3 8.314 L-kPa 700 K

PSO3     42.53 = 42.5 kPa
80.06 g/mol mol-K 2.00 L
0.105 g O 2 8.314 L-kPa 700 K

PO2     9.548 = 9.55 kPa
32.00 g/mol mol-K 2.00 L
2
PSO
Kp  3.0  10 2  3
; PSO2  PSO
2
/(K p ) (PO2 )  0.5
2
PSO 2
 PO2 3
PSO2  [(42.53) 2 /(3.0  10 2 ) (9.548)]0.5 = 0.7947 = 0.79
MM PV 64.06 g SO 2 mol-K 0.7947 kPa  2.00 L

g SO 2    
RT mol SO 2 8.314 L-kPa 700 K
= 0.01749 = 0.018 g SO 2
Check. K p = (42.53)2 / ((0.7947)2  9.548) = 3.0  102
15.51 Analyze/Plan. Follow the logic in Sample Exercise 15.11. Because molarity of NO is given
directly, we can construct the equilibrium table straight away. Solve.
2NO(g) ⇌ N2(g) + O2(g) Kc 

x2
 2.4  103
(250  2 x ) 2
initial 0.250 M 0 0
change —2x +x +x
equil. 0.250 — 2x +x +x
x
 2.4  103  48.99
0.175  2x
x = (0.250 — 2x)48.99 = 12.247 — 97.98x; 98.98x = 12.247, x = 0.1237 = 0.12 M
[N 2 ] = [O 2 ] = 0.1237 M; [NO] = 0.250 — 2(0.1237) = 0.002527 = 0.003 M
Check. K c = (0.1237) 2/(0.002527) 2 = 2.4  10 3
446
15.52 [Br 2 ] = 0.25 mol/3.0 L = 0.08333 = 0.083 M; [Cl 2 ] = 0.55 mol/3.0 L = 0.1833 = 0.18 M
[ B rC l] 2
Br2(g) Cl2(g) 2BrCl(g) Kc   7.0
+ ⇌ [ B r2 ] [ C l 2 ]
initial 0.083 M 0.18 M 0

change —x —x +2x
equil. (0.083 — x) (0.18 — x) +2x
(2x ) 2
7.0  ; 4x2 = 7.0(0.0153 — 0.2666x + x2); 0 = 0.1069 — 1.8662x + 3x2
(0 .0 8 3 3 3  x) (0 .1 8 3 3  x )
1 .8 6 6 2  (  1 .8 6 6 2) 2  4(3)(0 .1 0 6 9)
x  0 .0 6 3 8 7  0 .0 6 4 M
2(3)
(The 0.56 M quadratic solution is not chemically meaningful.)
[BrCl] = 2x = 0.1277 = 0.13 M; [Br 2 ] = 0.08333 — 0.06387 = 0.01946 = 0.019 M
[Cl 2 ] = 0.1833 — 0.06387 = 0.1195 = 0.12 M
Check. K c = (0.1277) 2/(0.01946)(0.1195) = 7.0125 = 7.0
15.53 Analyze/Plan. Write the K p expression, substitute the stated pressure relationship, and solve
for PB r2 . Solve.
PBr2  PNO
2 2
PNOBr 1
Kp  2
; PBr2  K p  2
; PNO  PNOBr
PNOBr PNO 2
2
PNOBr 1
PBr2  Kp  = Kp  = K p  4  51.2  4  204.8  205 kPa
 PNOBr 
2
1 1/4
2
15.54 K c = [NH 3 ][H 2 S] = 1.2  10 —4. Because of the stoichiometry, equilibrium concentrations of
H 2 S and NH 3 will be equal; call this quantity y. Then, y 2 = 1.2  10 —4, y = 0.010954 = 0.011
M.
15.55 (a) CaSO4(s) ⇌ Ca 2+

(aq) + SO42—(aq) K c  [ C a 2  ] [ S O 4 2  ]  2.4  1 0 5
At equilibrium, [Ca 2+] = [SO 4 2—] = x

K c = 2.4  10 —5 = x 2; x = 4.9  10 —3 M Ca 2+ and SO 4 2—
(b) A saturated solution of CaSO 4 (aq) is 4.9  10 —3 M.
1.4 L of this solution contain:
4.9  1 0 3 m o l 1 3 6 .1 4 g C aS O 4
 1 .4 L   0 .9 3 3 7  0 .9 4 g C aS O 4
L m ol
A bit more than 1.0 g CaSO 4 is needed to have some undissolved CaSO 4 (s) in
equilibrium with 1.4 L of saturated solution.
447
15.56 (a) Analyze/Plan. If only PH 3 BCl 3 (s) is present initially, the equation requires that the
equilibrium concentrations of PH 3 (g) and BCl 3 (g) are equal. Write the K c expression
and solve for x = [PH 3 ] = [BCl 3 ]. Solve.
K c = [PH 3 ][BCl 3 ]; 1.87  10 —3 = x 2; x = 0.043243 = 0.0432 M PH 3 and BCl 3
(b) Because the mole ratios are 1:1:1, mol PH 3 BCl 3 (s) required = mol PH 3 or BCl 3
produced.
0 .0 43 2 43 m o l P H 3
 0 .25 0 L  0 .0 1 0 8 1  0 .0 1 0 8 m o l P H 3  0 .0 1 0 8 m o l P H 3 B C l 3
L
1 5 1 .2 g P H 3 B C l 3
0 .0 1 0 8 1 m o l P H 3 B C l 3   1 .6 3 46  1 .6 3 g P H 3 B C l 3
1 m o l P H 3 B C l3
In fact, some PH 3 BCl 3 (s) must remain for the system to be in equilibrium, so a bit
more than 1.63 g PH 3 BCl 3 is needed.
15.57 Analyze/Plan. Follow the approach in Solution 15.51. Calculate [IBr] from mol IBr and
construct the equilibrium table.
Solve. [IBr]initial = 1.00 mol/5.00 L = 0.200 M
[I2]initial = [Br2]initial = 0 M
[IBr] 2 (0.200  2x) 2

I2 (g) + Br2 (g) ⇌ 2IBr (g) Kc 
[I 2 ][Br2 ]

x2
initial 0 0 0.200
change +x +x —2x
equil. x x (0.200 — 2x)
(0.200  2x) 2  0.200  2x 

2
   Kc
x2  x 
0.200  2x
 K c  310  17.607
x
0.200  2x  17.607x
0.200  19.607x
0.200
x=  0.01020  0.0102 M
19.607
[IBr]equil. = 0.200 — 2x = 0.200 — 0.0204 = 0.1795 = 0.180 M
[I 2 ] equil = [Br2 ] equil = x = 0.0102 M
15.58 CaCrO4(s) ⇌ Ca 2+
(aq) + CrO42—(aq) K c  [ C a 2  ] [ C rO 4 2  ]  7.1  1 0 4
At equilibrium, [Ca 2+] = [CrO 4 2—] = x

K c = 7.1  10 —4 = x 2, x = 0.0266 = 0.027 M Ca 2+ and CrO 4 2—
448
15.59 Analyze/Plan. Follow the logic in sample Exercise 15.11, using torr in place of M. We are
given Kp, so we use pressure in torr directly in the equilibrium expression.
Equilibrium pressures in kPa: PCH3I = PHI = x
CH4(g) + I2(g) ⇌ CH3I(g) + HI(g)
initial 13.3 6.67 0 0
change —x —x +x +x
equil. 13.3 — x 6.67 — x +x +x
PCH3 I  PHI x 2
Kp    1.95  10 4
PCH4  PI2 (13.3  x)(6.67  x)
x 2  (1.95  10 4 )(88.711  19.97x + x 2 )  0.0172986  0.00389 415 x  0.0000195 x 2
0.9 9981 x 2  0.00389415 x  0.0172 98 6  0
Solving the quadratic equation
(negative solution is chemically not meaningful.)
x = 0.1296 kPa
Equilibrium pressures in kPa: PCH3I = PHI = x = 0.1296 kPa
PCH4 = 13.3 — 0.1296 = 13.1704 = 13.2 kPa
PI2 = PCH4 = 6.67 — 0.1296 = 6.5404 = 6.54 kPa
PCH3 I  PHI 0.1296  0.1296
Check: Kp    1.95  10 4
PCH4  PI2 13.2  6.54
15.60
CH3COOH(solv) + CH3CH2OH(solv) ⇌ CH3COOCH2CH3(g) + H2O(solv)
initial 0.275 M 3.85 M 0 M 0 M
change —x M —x M +x M +x M
equil. 0.275—x M 3.85—x M +x M +x M
x2
K c  6.6 8  ; x 2  6.68(1 .059  4.1 25 x  x 2 )
(0.275  x)(3.85  x)
27.56  (  27.56) 2  4(5.68)(7.072)

0  5.6 8 x 2  27.56 x  7.072; x   0.271 85  0 .272 M
2(5.68)
(The 4.58 M quadratic solution is not chemically meaningful.)

0.271 85 m o l ethyl acetate 88.1 0 g ethyl acetate
 1 5.0 L   359.25  359 g ethyl acetate
L m ol
LeChâtelier’s Principle (Section 15.7)

(a) No effect. Catalysts do not affect equilibria.
(b) Shift equilibrium to the left; CO2 is a product, so the reaction will proceed in the
reverse direction.
449
(c) Shift equilibrium to the right; CO is a reactant, so the reaction will proceed in the
forward direction.
(d) Shift equilibrium to the left. The reaction is exothermic, so the equilibrium constant
will decrease with increasing temperature.
(e) Shift equilibrium to the left. A decrease in pressure (caused by an increase in volume)
shifts the reaction in the direction that produces more gas molecules (partial pressure
of all gases is initially cut to half; reaction quotient larger than equilibrium constant.)
(f) No effect. The noble gas would not alter the partial pressures of any of the reacting
components and therefore would not cause a shift in equilibrium.
15.62 4 NH3(g) + 5 O2(g) ⇌ 4 NO(g) + 6 H O(g) 2
(a) increase [NH3], increase yield NO

(b) increase [H2O], decrease yield NO
(c) decrease [O2], decrease yield NO
(d) decrease container volume, decrease yield NO (fewer moles gas in reactants)
(e) add catalyst, no change
(f) increase temperature, decrease yield NO (reaction is exothermic)
15.63 Analyze/Plan. Given certain changes to a reaction system, determine the effect on KP, if
any. Only changes in temperature cause changes to the value of KP. Solve.
(a) no effect (b) no effect (c) increase equilibrium constant
(d) no effect (e) decrease equilibrium constant
15.64 (a) The reaction must be endothermic (+H) if heating increases the fraction of products.
(b) There must be more moles of gas in the products if increasing the volume of the
vessel increases the fraction of products.
15.65 Analyze/Plan. Use Hess’s law,  H    H of p ro d u cts   H of reactants, to calculate Ho.

According to the sign of H, describe the effect of temperature on the value of K. According
to the value of n, describe the effect of changes to container volume. Solve.
(a)  H    H of N O 2 (g)   H of N 2 O (g)  3  H of N O (g)
H  = 33.84 kJ + 81.6 kJ — 3(90.37 kJ) = —155.7 kJ
(b) Because the reaction is exothermic, the equilibrium constant will decrease with
increasing temperature.
(c) A change in volume at constant temperature will affect the fraction of products in
the equilibrium mixture because n does not equal zero. An increase in container
volume would favor reactants, whereas a decrease in volume would favor products.
15.66 (a)  H   H of C H 3 O H (g)  H of C O (g)  2 H of H 2 (g)

= —201.2 kJ — (—110.5 kJ) — 0 kJ
= —90.7 kJ
(b) The reaction is exothermic; an increase in temperature would decrease the value of K
and decrease the yield. A low temperature is needed to maximize yield.
450
(c) Increasing total pressure would increase the partial pressure of each gas, shifting the
equilibrium toward products. The extent of conversion to CH 3 OH increases as the
total pressure increases.
15.67 For this reaction, there are more moles of product gas than moles of reactant gas. An
increase in total pressure increases the partial pressure of each gas, shifting the equilibrium
toward reactants. An increase in pressure favors formation of ozone.
15.68 (a) Low temperature. For an exothermic reaction such as this, decreasing temperature
increases the value of K and the amount of products at equilibrium.
(b) No. Because there are equal numbers of moles of gas in the products and reactants, the
equilibrium yield of products cannot be changed by changing pressure.
15.69 (a) Endothermic. Bond breaking is always an endothermic process.
(b) The equilibrium constant increases. For an endothermic reaction, heat is a “reactant.”
An increase in temperature and heat favors the forward reaction and the value of Kc
increases.
(c) The forward rate constant increases by a larger amount than the reverse rate
constant. If Kc = kf/kr and the value of Kc increases, the value of kf must increase by
a greater amount than the value of kr.
15.70 False. When the temperature of an exothermic reaction increases, the rate constants of both
the forward and the reverse reactions increase, but the value of the reverse rate constant
increases by a greater amount.
Additional Exercises
15.71 (a) Because both the forward and reverse processes are elementary steps, we can write
the rate laws directly from the chemical equation.
rate f = k f [CO][Cl 2 ] = rate r = k r [COCl][Cl]
k f [ C O C l] [ C l]
 K
kr [ C O] [ C l 2 ]
k f 1 .4  1 0 28 M 1 s 1
Kc    1 .5  1 0 3 9
kr 9 .3  1 0 1 0 M 1 s 1
For a homogeneous equilibrium in the gas phase, we usually write K in terms of

partial pressures. In this exercise, concentrations are more convenient because the rate
constants are expressed in terms of molarity. For this reaction, the value of K is the
same regardless of how it is expressed, because there is no change in the moles of
gas in going from reactants to products.
(b) Because the K is quite small, reactants are much more plentiful than products at
equilibrium.
451
⇌ 2 B(g),
[B] 2
15.72 3 A(g) Kc =  1
[A]3
[A]3 = [B]2; [A] = [B]2/3; [B] = [A]3/2
15.73 CH 4 (g) + H 2 O(g)  CO(g) + 3 H 2 (g)
PC O  PH3 2 g RT
Kp  ;P ; T  1 000 K
PC H 4  PH 2 O MM V
8 .6 2 g 0 .0 8 20 6 L -atm 1 0 0 0 K
PC O     5 .0 5 0 7  5 .0 5 atm
28 .0 1 g/ m o l m o l-K 5 .0 0 L
2.6 0 g 0 .0 8 20 6 L -a tm 1 0 0 0 K
PH 2     21 .1 6 6 3  21 .2 atm
2.0 1 6 g/ m o l m o l-K 5 .0 0 L
43 .0 g 0 .0 8 20 6 L -atm 1 0 0 0 K
PC H 4     43 .9 9 73  44.0 atm
1 6 .0 4 g/ m o l m o l-K 5 .0 0 L
48 .4 g 0 .0 8 20 6 L -a tm 1 0 0 0 K
PH 2 O     44.0 8 1 1  44.1 atm
1 8 .0 2 g/ m o l m o l -K 5 .0 0 L
(5 .0 5 0 7) (21 .1 6 6 3) 3
Kp   24.6 9 49  24.7
( 43 .9 9 73) ( 44.0 8 1 1 )
K p  K c (R T ) n , K c = K p / (R T ) n ; n = 4 — 2 = 2
K c = (24.6949)/[(0.08206)(1000)] 2 = 3.6673  10 —3 = 3.67  10 —3
2.00 mol
15.74 [SO 2 Cl 2 ]   0.200 mol/L
5.00 L
The change in [SO2 Cl 2 ] = 0.40(0.200 M) = 0.080 M
⇌
[ S O 2 ] [ C l2 ]
SO2Cl2(g) SO2(g) + Cl2(g) Kc 
[ S O 2 C l2 ]
initial 0.200 M 0 0
change —0.080 M +0.080 M +0.080 M
equil. 0.120 M +0.080 M +0.080 M
[SO 2 ] [Cl 2 ] (0.080) 2

(a) Kc    0.05333  0.053
[SO 2 Cl 2 ] 0.120
(b) K p  K c (R T ) n ; n = 2 — 1 = 1;
K p = (0.05333 mol/L)(8.314 L⋅kPa/mol⋅K)(310 K) = 137.4 kPa = 137 kPa
(c) Decrease. There are more moles of gas in the products, so decreasing the container
volume will shift equilibrium toward reactant.
2.00 mol
(d) [SO 2 Cl 2 ]   2.00 mol/L. Let x equal the change in [SO2 Cl 2 ].
1.00 L
The equilibrium concentrations are: [SO2 Cl 2 ] = (2.00 — x); [SO2 ] = [Cl 2 ] = x
452
[SO 2 ] [Cl 2 ] x2
Kc    0.05333; solving the quadratic, x = 0.301 = 0.30 mol/L
[SO 2 Cl 2 ] 2.00  x
(We expect the decomposition to be greater than 5%, so we must use the quadratic
formula to solve for x.)
% decomposition = (0.30/2.00)  100 = 15%; the decrease in volume shifts the
equilibrium toward the reactant, as expected.
15.75 (a) Exothermic. The values of Kc in the table decrease as temperature increases; the
reverse reaction is favored. This is the case if heat is a “product” of the reaction.
(b)  H rxn
o
  n  H of (p ro d u cts)   n H of (reactants). Be careful with coefficients,
states, and signs.
 H rxn
o
 2  H of N H 3 (g)  3 H of H 2 (g)  H of N 2 (g)
= 2(—46.19 kJ) — 3(0 kJ) — 0 kJ = —92.38 kJ
Yes, the calculated value of H is negative, which agrees with the prediction from
part (a) that the reaction is exothermic.
(c) [NH3] = 0.025 mol/1.00 L = 0.025 M
[ N H 3 ]2
⇌
N2
3 H2 2 NH3 Kc   0.05 8
+ [ N 2 ] [ H 2 ]3
initial 0 M 0 M 0.0250 M
change +x M +3x M —2x M
equil. x M 3x M (0.0250 — 2x) M
(0 .0 25 0  2x) 2 (0 .0 25 0  2x) 2
K c  0 .0 5 8   . T ake the sq u are ro o t o f b o th sid es.
(x)(3x) 3 9x 4
0 .0 25 0  2x
0 .240 8 3  ; 0 .722 49x 2  2x  0 .0 25 0  0 ; x = 0 .0 1 244 = 0 .0 1 2 M
3x 2
[NH3] at equilibrium = 0.025 — 2(0.01244) = 0.000120 = 1.2  10—4 M
or, [NH3] at equilibrium = 0.025 — 2(0.012) = 0.001 M
In this case, intermediate rounding changes the result by an order of magnitude.

However, by either method, a very small concentration of NH3(g) is present at
equilibrium.
PB r2  PN2 O gR T
15.76 (a) Kp  ;P ; T  1 0 0 C  273  3 73 K
PN2 O B r MM V
4.1 9 g 0 .0 8 20 6 L -atm 3 73
PB r2     0 .1 6 0 5 1  0 .1 6 1 atm
1 5 9 .8 g/ m o l m o l-K 5 .0 0 L
3 .0 8 g 0 .0 8 20 6 L -atm 3 73
PN O     0 .6 28 28  0 .6 28 atm
3 0 .0 1 g/ m o l m o l-K 5 .0 0 L
3 .22 g N O B r 0 .0 8 2 0 6 L -atm 3 73
PN O B r     0 .1 79 3 6  0 .1 79 atm
1 0 9 .9 g/ m o l m o l-K 5 .0 0 L
453
(0 .1 6 0 5 1 ) (0 .6 28 28) 2
Kp   1 .9 6 9 5  1 .9 7 K p  K c (R T ) n ,  n  3  2  1
(0 .1 79 3 6) 2
K c = K p /RT = 1.9695/(0.08206)(373) = 0.064345 = 0.0643

(b) Pt  PB r2  PN O  PN O B r  0 .1 6 0 5 1  0 .6 28 28  0 .1 79 3 6  0 .9 6 8 1 5  0 .9 6 8 a tm
(c) All NO and Br2 present at equilibrium came from the decomposition of the original
NOBr. The mass of original NOBr is the sum of the masses of all compounds at
equilibrium.
Original g NOBr = 4.19 gBr 2 + 3.08 g NO + 3.22 g NOBr = 10.49 g
15.77 (a) A(g) ⇌ 2B(g) + 2C(g)

initial 100 kPa 0 0
change —25 kPa +25 kPa +50 kPa
equil. 75 kPa 25 kPa 50 kPa
P t o t a l = p A + p B + p C = 7 5 + 2 5 + 5 0 = 15 0 k Pa
PB  (PC ) 2
(b) Kp 
PA
25  (50) 2
Kp   833.33  833.3
75
(c) Increasing the volume of the flask favors the reaction with more moles of gas. Doing
the reaction in a larger flask maximizes the yield of B.
2
PNH
15.78 (a) Kp  3
 4.23  10 7 ; T  300 C  273  573 K
PN 2  PH3 2
gRT 1.05 g 8.314 L-kPa 573 K

PNH3      293.7= 294 kPa
MM  V 17.03 g/mol mol-K 1.00 L
N2(g) + 3 H2(g) ⇌ 2 NH3(g)

initial 0 0 ?
change x 3x —2x
equil. x kPa 3x kPa 293.7 kPa
(Remember, only the change line reflects the stoichiometry of the reaction.)
(293.7) 2 7 (293.7) 2
Kp   4.23  10 ; 27 x 4
 ; x 4  7.5527x10 9
(x) (3x) 3 4.23  10 7
x  294.8 = 295 kPa  PN 2 ; PH2  3x  884.4 = 884 kPa
MM  PV 28.02 g N 2 mol-K 294.8 kPa  1.00 L

gN2      1.73 g N 2
RT mol N 2 8.314 L-kPa 573 K
2.016 g H 2 mol-K 884.4 kPa  1.00 L
gH2     0.374 g H 2
mol H 2 8.314 L-kPa 573 K
454
(b) The initial PNH3  293.7 kPa + 2  294.8 kPa = 883.3 = 883 kPa
17.03 g NH 3 mol-K 883.3 kPa  1.00 L
g NH3     3.16 g NH 3
mol NH 3 8.314 L-kPa 573 K
(c) Pt  PN 2  PH 2  PNH3  294.8 kPa + 884.4 kPa + 293.7 kPa

= 1472.9 = 1473 kPa = 1.473MPa
15.79 2IBr (g ⇌ I 2 (g) + Br 2 (g)

initial 5.07 kPa 0 0
change —2x +x +x
equil. (5.07 — 2x) x x
PI2  PBr2 x2
Kp  8.5  10 3   ; taking the square root of both sides
2
PIBr (0.50  2x) 2
x
 (8.5  10 3 ) 1 / 2  0.0922; x  0.0922(5.07  2x)
5.07  2x
x + 0.184 x = 0.4675; 1.184 x = 0.4675; x = 0.3948 = 3.9  10 —1
At equilibrium, PI2  PBr2  x  0.395 kPa
P I Br at equilibrium = 5.07 — (2  0.395) = 4.28 kPa
Check.
PI2  PBr2 0.395 2
Kp  2
 2
 8.5  10 3 ; the calculated concentrations are sel f-consist ent.
PIBr (4 .28)
15.80 (a) K p = 0.052; K p  K c (R T ) n ; n = 2 — 0 = 2; K c = K p /(RT) 2

K c = 0.052/[0.08206)(333)] 2 = 6.964  10 —5 = 7.0  10 —5
(b) PH 3 BCl 3 is a solid and its concentration is taken as a constant, C.
0.0500 g BCl 3 mol BCl3
[BCl3 ]    2.8449  10 4  2.84  10 4 mol/L BCl3
1.500 L 117.17 g BCl3
PH3BCl3 ⇌ PH3 BCl3

+
initial C 0 M 2.84  10 —4 M
change +x M +x M
equil. C +x M (2.84  10 —4 + x) M
K c  [ P H 3 ] [ B C l 3 ] ; 6 .9 6 4  1 0 5  x(2.8 4  1 0 4  x); x 2  2.8 4  1 0 4 x  6 .9 6 4  1 0 5  0

 2.84  1 0 4  [ (2.84  1 0 4 ) 2  4(1 )(  6.964  1 0 5 )] 1 / 2
x  0 .0 0 8 20 4  8 .2  1 0 3 M P H 3
2(1 )
−
Check. Kc = (8.2  10 —3) ( 2.84  10 —4 + 8.2  10 —3) = 7.0 × 10 5.
15.81 K p  PNH3  PH2 S ; Pt  62.21 kPa

If the equilibrium amounts of NH 3 and H 2 S are solely due to the decomposition of
455
NH 4 HS(s), the equilibrium pressures of the two gases are equal, and each is 1/2 of the total
pressure.
PNH3  PH 2 S  62.21 kPa / 2 = 31.105 = 31.10 kPa
K p = (31.105 kPa)2 = 967.52 = 968 kPa2
gRT 5.37 g 8.314 L  kPa 1100 K

15.82 Initial PSO3      111.52  111.5 kPa
MM V 80.07 g/mol mol  K 5.00 L
2 SO3 (g) ⇌ 2 SO2 (g) + O2 (g)

initial 111.5 kPa 0 0
change —2x +2x +x
equil. 111.5 — 2x 2x x
Pt = 111.5 — 2x + 2x + x = 111.5 + x
111.5 + x = 157
x = 157 — 111.5 = 45.5 kPa
2 SO3 (g) ⇌ 2 SO2 (g) + O2 (g)
equil. 111.5 — 2x 2x x
20.5 kPa 91 kPa 45.5 kPa
2
PSO  PO2 (91) 2 (45.5)
Kp  2
2
  896.6
PSO 3
(20.5) 2
K p  K c (R T ) n ; n = 3 — 2 = 1;
K c = K p /RT = 896.6/[(8.314)(1000)] = 0.107
15.83 Note: Kp has a unit, Kp = 2.6  10—3 kPa—1 (in the question).
P2
In general, the reaction quotient is of the form Q  2 N O C l .
PN O  PC l 2
2
PNOCl (0.20) 2
(a) Q    5.0
2
PNO  PCl2 (0.20) 2 (0.20)
Q > K p . The mixture is not at equilibrium. It will shift to the left and produce more
reactants as it moves toward equilibrium.
2
PNOCl (0.020) 2
(b) Q    0.043
2
PNO  PCl2 (0.25) 2 (0.15)
Q < K p . The mixture is not at equilibrium. It will shift to the right and produce
more products as it moves toward equilibrium.
2
PNOCl (0.050) 2
(c) Q    0.26
2
PNO  PCl2 (0.15) 2 (0.43)
Q = K p . The mixture is at equilibrium.
g CO2 1
15.84 K c  [ C O 2 ]  0 .0 1 0 8; [ C O 2 ]  
44.0 1 g/ m o l 1 0 .0 L
In each case, calculate [CO 2 ] and determine the position of the equilibrium.
456
4.25 g 1
(a) [CO2]    9 .6 5 7  1 0 3  9 .6 6  1 0 3 M
44.0 1 g/ m o l 1 0 .0 L
Q = 9.66  10 —3 < K c . The reaction proceeds to the right to achieve equilibrium and
the amount of CaCO 3 (s) decreases.
5 .6 6 g C O 2 1
(b) [CO2]    0 .0 1 29 M
44.0 1 g/ m o l 1 0 .0 L
Q = 0.0129 > K c . The reaction proceeds to the left to achieve equilibrium and the
amount of CaCO 3 (s) increases.
(c) 6.48 g CO 2 means [CO 2 ] > 0.0129 M; Q > 0.0129 > K c , the amount of CaCO 3
increases.
15.85 CO2(g) + H2(g) ⇌ CO(g) + H2O(g)
initial 1.50 mol 1.50 mol 0 0
change −x −x +x +x
equil. (1.50 − x)mol (1.50 − x)mol x x
Since n = 0, the volume terms cancel and we can use moles in place of molarity in the K
expression.
[ C O] [ H 2 O] x2
Kc = 0.802 = 
[ C O 2 ] [ H 2 O] (1 .5 0  x) 2
Take the square root of both sides.
(0.802)1/2 = x/(1.50 — x); 0.8955(1.50 — x) = x
1.3433 = 1.8955x, x = 0.7087 = 0.709 mol
[CO] = [H2O] = 0.7087 mol/3.00 L = 0.236 M
[CO2] = [H2] = (1.50 — 0.709)mol/3.00 L = 0.264 M
25 .0 g C O 2 1
15.86 (a) [CO2] =  = 0.18935 = 0.189 M
44.0 1 g/ m o l 3 .0 0 L
C(s) + CO2(g) ⇌ 2CO(g)

initial excess 0.189 0
change − x − x +2x
equil. 0.189− x +2x
[ C O ]2 (2 x) 2
; 4x = 1.9(0.189 − x); 4x + 1.9x — 0.36 = 0.
2 2
Kc = 1.9 = =
[CO2] 0 .1 8 9  x
Solve the quadratic for x.

 1 .9  (1 .9) 2  4( 4)(  0 .3 6)
x = = 0.14505 = 0.15 M
2(4)
[CO] = 2x = 2(0.14505) = 0.2901 = 0.29 M
0.2901 m o l C O 28.01 g C O
 3.00 L × = 24.38 = 24 g CO
L m ol
457
(b) The amount of C(s) consumed is related to x. Change M to mol to g C.
0 .1 45 0 5 m o l
× 3.00 L × 12.01 g = 5.226 = 5.2 g C consumed
L
(c) A smaller vessel at the same temperature increases the total pressure of the mixture.
The equilibrium shifts to form fewer total moles of gas, which favors reactants. The
yield of CO product will be smaller in a smaller vessel.
(d) The two Kc values are 0.133 at 298 K and 1.9 at 1000 K. The reaction is endothermic,
because K is larger at higher temperature.
PC O 2
15.87 Kp   6.0  1 0 2
PC O
If P C O is 20 kPa, PC O 2 can never exceed 101.3 kPa — 20 kPa = 81 kPa. Then Q = 81/20 =
4.1. Because this is far less than K, the reaction will shift in the direction of more product.
Reduction will therefore occur.
15.88 The anecdote tells us that increasing the volume of the reaction container, the furnace, had
no effect on the amount of unreacted CO(g), the amount of CO(g) expelled. This is true for
reactions that have the same number of moles of gaseous products and reactants, as this
one does. It also means that K p = K c .
15.89 (a) CCl4(g) ⇌ C(s) + 2 Cl2(g)

initial 202.7 kPa 0
change —x +2x
equil. 202.7 kPa — x 2x
PCl2 2 (2x) 2
Kp  77  
PCCl4 (202.7  x)
15607.9 — 77x = 4x 2; 4x 2 + 77x — 15607.9 = 0

Using the quadratic formula, a = 4, b = 77, c = —15607.9
 77  (77) 2  4(4) (  15607.9)

77  505.6
x  
 53.58 = 54 kPa
2(4) 8
x 53.58
Fraction CCl 4 reacted    0.264  26%
202.7 kPa 202.7
(b) PCl2  2x  2(53.58)  107 kPa
PCCl4  202.7  x  202.7 - 53.58 = 149 kPa
PPCl5 (20.3)
15.90 (a) Q    7.9  10 3
PPCl3  PCl2 (50.7) (50.7)
7.9  10—3 (Q) > 8.59  10—4 (K), the reaction proceeds to the left.
(b) PCl3(g) + Cl2(g) ⇌ PCl5(g)

initial 50.7 kPa 50.7 kPa 20.3 kPa
change +x +x —x
458
equil. 50.7 kPa + x 50.7 kPa + x 20.3 kPa — x
(Because the reaction proceeds to the left, PP C l 5 must decrease and PP C l 3 and PC l 2
must increase.)
(20.3  x) (20.3  x)
Kp  8.59  10 4  ; 8.59  10 4 
(50.7  x) (50.7  x) (2570.5  101.4x  x 2 )
8.59  10 4 (2570.5 + 101.4 x + x 2) = 20.3 — x; —18.092 + 1.0871 x + 8.59  10 4 x 2 = 0
 1.0871  (1.0871) 2  4(8.59  10 4 ) ( 18.092)  1.0871  1.1153

x  4
  16.4 kPa
2(8.59  10 ) 1.718  10 3
PPCl3  PCl2 = 50.7 kPa + 16.4 kPa = 67.1 kPa
PPCl5  20.3 kPa - 16.4 kPa = 3.9 kPa
To two decimal places, the pressures are 67, 67, and 4 kPa, respectively. When
substituting into the K p expression, pressures to three decimal places yield 8.66  10—4
kPa—1 which is close to Kp.
(c) Increasing the volume of the container favors the process where more moles of gas
are produced, so the reverse reaction is favored and the equilibrium shifts to the left;
the mole fraction of Cl 2 increases.
(d) For an exothermic reaction, increasing the temperature decreases the value of K; more
reactants and fewer products are present at equilibrium and the mole fraction of Cl 2
increases.
15.91 Analyze/Plan. Calculate the equilibrium pressures of H2, I2, and HI; use them to calculate Kp.
Set up a new equilibrium table and calculate new equilibrium pressures. Solve.
P RT 8.314 L-kPa 773 K kPa
    642.7
n V mol-K 10.00 L mol
kPa
PH2  PI2  0.150 mol  642.7  96.4 kPa
mol
kPa
PHI  1.000 mol  642.7  642.7 kPa
mol
⇌
2
PHI (642.7) 2
H2(g) + I2(g) 2HI(g); Kp    44.44  44.4
PH2  PI2 (96.4) 2
642.7 kPa
PHI (added)  0.100 mol   64.27 kPa
mol
H2(g) + I2(g) ⇌ 2HI(g)
initial 96.4 96.4 (642.7 + 64.27)
change +x +x —2x
equil. (96.4 + x) atm (96.4 + x) (706.97 — 2x)
(706.97  2x) 2
Kp  44.44  . Take the square root of both sides:
(96.4  x) 2
459
706.97  2x
6.666  ; 6.666(96.4  x)  706.97  2x; 642.602  6.666x  706.97  2x;
96.4  x
8.666x  64.37; x  7.43
PH2  PI2  96.4  7.43  103.83  103.83 kPa; PHI  706.97  2(7.73)  692.11 kPa
(692.11) 2
Check.  44.4
(103.8) 2
15.92 (a) Because the volume of the vessel = 1.00 L, mol = M. The reaction will proceed to
the left to establish equilibrium.
A(g) 2B(g) ⇌ 2 C(g)
+
initial 0 M 0 M 1.00 M
change +x M +2 x M —2 x M
equil. x M 2 x M (1.00 — 2 x) M
At equilibrium, [C] = (1.00 — 2x) M, [B] = 2x M.
(b) x must be less than 0.50 M (so that [C], 1.00 —2 x, is not less than zero).
[ C] 2 (1 .0 0  2x) 2
(c) Kc  ;  0 .25
[ A ] [ B] 2 (x) (2x) 2
1.00 — 4x + 4x 2 = 0.25(4x) 3; x 3 — 4x 2 + 4x — 1 = 0
(d)
(e) From the plot, x  0.383 M

[A] = x = 0.383 M; [B] = 2 x = 0.766 M
[C] = 1.00 — 2x = 0.234 M
Using the K c expression as a check:
(0 .23 4) 2
K c  0 .25;  0 .24; the estim ated valu es are reaso nab le.
(0 .3 8 3) (0 .76 6) 2
PO2  PCO
2
15.93 Kp  2
 1  10 11 ; PO2  (0.03) (101.3 kPa)  3.04 kPa
PCO 2
460
PCO  (0.002) (101.3 kPa)  0.20 kPa; PCO2  (0.12) (101.3 kPa)  12.2 kPa
(3.04)(0.20) 2
Q  2
 8.2  10 4  8  10 4
(0.12)
Because Q > K p , the system will shift to the left to attain equilibrium. Thus, a catalyst that
promoted the attainment of equilibrium would result in a lower CO content in the exhaust.
k f 1 .8  1 0 3 M 1 s 1
15.94 (a) At 700 K: K c    0 .0 28 5 7  0 .0 29
k r 6 .3  1 0 2 M 1 s 1
k f 0 .0 9 7 M 1 s 1
(b) At 800 K: K c    0 .0 3 73 1  0 .0 3 7
kr 2.6 M 1 s 1
The value of Kc increases when the temperature increases. The reaction is

endothermic.
Integrative Exercises
− −
15.95 Calculate the initial [IO4 ], and then construct an equilibrium table to determine [H4IO6 ] at
equilibrium.
0 .9 0 5 M  25 .0 m L
M c  V c  Md  L d ;  Md  0 .0 45 25  0 .0 45 3 M IO 4 
5 0 0 .0 m L
−
I O 4 (aq) + 2H 2 O ( l) ⇌ −
H 4 I O 6 (aq)
initial 0.0453 M 0
change −x +x
equil. 0.0453 − x +x
[ H 4 IO 6  ] x
K c  3.5  1 0 2  

[ IO 4 ] (0.0453  x)
−
Because Kc is relatively large and [I O 4 ] is relatively small, we cannot assume x is small
relative to 0.0453.
0.035(0.04525 — x) = x; 0.001584 — 0.035 x = x; 0.001584 = 1.035 x
−
x = 0.001584/1.035 = 0.001530 = 0.0015 M H 4 IO 6 at equilibrium
15.96 (a) CoO(s) + H2(g) ⇌ Co(s) + H2O(g) K 1 = 67

CO(g) + H2O(g) ⇌ H2(g) + CO2(g) 1/K2 = 1/0.14
CoO(s)+H2(g)+CO(g)+H2O(g) ⇌ Co(s)+H O(g)+H (g)+CO (g)2 2 2 K c = K 1 /K 2

CoO(s) + CO(g) ⇌ Co(s) + CO (g) 2 K c = 4.8 × 102
(b) Based on the results of part (a), CO(g) is a stronger reducing agent than H2(g) at 823
K. In the first reaction above, H2(g) reduces CoO(s) and the value of K is 67. In the
fourth reaction, CO(g) reduces CoO(s) and the value of K is 480. The much larger
equilibrium constant for the fourth reaction indicates that products are more favored
than the products in the first reaction.
461
1 m o l C o O (s)
(c) 5 .0 0 g C o O (s )   0 .0 6 6 727  0 .0 6 6 7 m o l C o O (s )
74.9 3 2 g C o O (s )
PV 1 .0 0 atm 2.5  1 0 1 L
n   = 0 .0 1 0 223 = 0 .0 1 0 m o l C O
R T 0 .0 8 20 6 L -atm / m o l-K 29 8 K
(d)
CoO(s) + CO(g) ⇌ Co(s) + CO2(g)
initial 0.0667 mol 0.010 mol 0 mol 0 mol

change —x mol —x mol x mol x mol
equil. 0.0667 — x mol 0.0102 — x mol x mol x mol
67 [CO2] x
Kc    ; 478 .5 7(0 .0 1 0  x) = x
0 .1 4 [ C O (g)] 0 .0 1 0 2  x
4.7857 — 478.57 x = x; 4.7857 = 479.57 x; x = 0.009979 = 0.010 mol
At equilibrium, mol CoO(s) = 0.0667 — 0.009979 = 0.05672 = 0.057 mol CoO(s)
g CoO(s) = 0.05672 mol CoO  74.932 g/mol = 4.250 = 4.3 g CoO(s)
[Note that the equilibrium concentration of CO is essentially zero. With an

equilibrium constant of 4.8  102, the reaction “goes to completion” and CO is the
limiting reactant.]
15.97 Consider the energy profile for an exothermic reaction.
The activation energy in the forward direction, Eaf, equals Eu and the activation energy in the
reverse reaction, Ear, equals Eu — H. (The same is true for an endothermic reaction because
the sign of H is the positive and Ear < Eaf.) For the reaction in question,
k f A f e  E af / R T
K 
k r A r e  E ar / R T
Because the ln form of the Arrhenius equation is easier to manipulate, we will consider ln K.
k  E af  E 
ln K  ln  f   ln k f  ln k r   ln A f   ar  ln A r 
 kr  RT  RT 
Substituting E u for E a f and (E u — H) for E a r
462
E u  (E u  H )  E u  (E u  H )
ln K   ln A f    ln A r  ; ln K   ln A f  ln A r
RT  RT  RT
 H A
ln K   ln f
RT Ar
For the catalyzed reaction, E c at < E u and E a f = Ecat , E a r = E c at — H. The catalyst does not
change the value of H.
E cat  (E cat  H )
ln K cat   ln A f  ln A r
RT
 H ln A f
ln K cat  
RT Ar
Thus, assuming A f and A r are not changed by the catalyst, ln K = ln K c at and K = K c at.
15.98 (a) For the reaction SO2(l) ⇌ SO2(g), K p  PS O 2 . From the phase diagram, as T
increases PS O 2 and K p increase. For an endothermic reaction, K increases as T
increases. The phase diagram tells us that the vaporization of SO2(l) is an
endothermic process.
(b) Read PS O 2 from the liquid-gas line on the phase diagram at 0 oC and 100 oC. Note
that the pressure axis of the phase diagram is logarithmic with respect to pressure,
but linear with respect to logP. In terms of logP, the axis labels would be 1, 2, 3 and
4. The logP values at 0 oC and 100 oC are approximately 2.25 and 3.4. The values of
2.25 3.4
PS O 2 and K p are 10 and 10 , 180, and 2500 kPa, respectively.
(c) It is not possible to calculate an equilibrium constant between the gas and liquid phases
in the supercritical region, because they do not exist separately in this region. That is, the
gas and liquid phases are indistinguishable in the supercritical region.
(d) Gases are most ideal at high temperature and low pressure. The red dot at slightly
greater than 240 oC is the point where SO2(g) most closely approaches ideal behavior.
(e) The point near 15 oC is the one at the lowest temperature, but it is also at low
pressure. In general, the closer the pressure and temperature conditions are to the
point of phase transition, the less ideal the behavior of the gas (because it is nearly a
liquid). This describes the point near 115 oC and 2000 kPa, which is at relatively high
pressure and near the liquid-gas line.
15.99 (a) The larger rate constant is kr. Kc = kf/kr and the value of Kc is much less than one
(3.1 × 10—4). The value of kr must be larger than the value of kf.
kf k 0.27s 1
(b) Kc  ; kr  f   870.97  8.7  1 0 2
kr K c 3.1  1 0 4
(c) The forward reaction is bond breaking, which is always endothermic.

(d) The reverse rate constant kr will increase. An increase in temperature causes both kr
and kf to increase. For an endothermic reaction, we expect the value of Kc to increase
with an increase in temperature, so the increase in kf will be greater than the
increase in kr.
463
15.100 (a) H 2 O(l) ⇌ H O(g);

2 K p  PH 2 O
(b) At 30C, the vapor pressure of H 2 O(l) is 31.82 torr. K P  PH 2 O  3 1 .8 2 to rr

K p = 31.82 torr  1 atm/760 torr = 0.041868 = 0.04187 atm
(c) From part (b), the value of K p is the vapor pressure of the liquid at that
temperature. By definition, vapor pressure = atmospheric pressure = 1 atm at the
normal boiling point. K p = 1 atm
15.101 (a) VSEPR indicates that each O atom has four electron domains about it and thus
adopts tetrahedral geometry. One O atom has two covalent bonds to H and two
hydrogen bonds to H atoms on the second water molecule. The O atom on the
second water molecule has two nonbonding electron pairs. The water dimer is not
symmetrical.
(b) Hydrogen-bonding is the intermolecular interaction involved in water dimer

formation.
(c) Water dimer formation is exothermic, because the value of K decreases as temperature
increases.
15.102 The O2-binding reaction occurs in aqueous solution, so we will write a Kc expression. The
amount of O2(g) will appear as a pressure. By convention, reactions which involve gaseous
and aqueous substances have mixed equilibrium expressions written in terms of both
pressures and molar concentrations.
[ H b -(O 2 ) 4 ]
Kc 
PO4 2  [ H b]
The P50 value is the partial pressure at which 50% of the hemoglobin is saturated with
O2(g). At this partial pressure, the concentrations of O2-bound hemoglobin and free
hemoglobin are equal, [Hb — (O2)4] = [Hb]. Substitute the two P50 values into the Kc
expression and compare the values for fetal and adult hemoglobin.
1 1
at P50, KcF  4
  0.0244 kPa 4 ;
PO2 (2.53 kPa) 4
1 1
KcA  4
  6.16  10 3 kPa 4
PO2 (3.57 kPa) 4
Comparing the two values, KcF /KcA = 0.0244 / 6.16  10—3 ≈ 4. The equilibrium constant for
O2-binding by fetal hemoglobin is approximately four times that by adult hemoglobin.
464

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15 Chemical

K is greater than one.

Q > K c , the mixture is not at equilibrium.

Q = K c , the mixture is at equilibrium.

Q < K c , the mixture is not at equilibrium.

(b) Mixture (i) proceeds toward reactants.

Mixture (iii) proceeds toward products.

2 B atoms should be added to the diagram.

K c decreases as T increases, so the reaction is exothermic.

Equilibrium; The Equilibrium Constant (Sections 15.1—15.4)

[HCO 3 ][H  ] [Zn 2  ]

[CO32  ] [H+ ] [Fe3+ ] [Ce 3+ ]

homogeneous: (a), (c), (d), (e), (f); heterogeneous: (b), (g)

(a) mostly products (K c > 1)

15.19 (a) True.

15.20 (a) False. The value of n is not zero.

15.21 Analyze/Plan. Follow the logic in Sample Exercise 15.2. Solve.

Kp  Kc (RT) n  Kc (RT) 1  K c /RT

15.22 2 CO(g) ⇌CO (g) + C(s),

K p  K c (R T ) n ; 5.80 = K c (RT) —1 = K c /RT;

K c = 5.80 RT = 5.80(0.08206)(900) = 428.35 = 428

15.24 2 H 2 ( g) + S 2 ( g ) ⇌ 2 H 2 S ( g) , K c = 1.08 × 107 at 700 C. n = 2 — 3 = − 1.

(a) K p  K c (R T ) n ; T = 700 C + 273 = 973 K.

K p 2 = (K p ) 1/2 = (1.35 × 105) 1/2 = 368

15.25 Analyze. Given K p for a reaction, calculate K p for a related reaction.

(c) K p  K c (R T ) n ; n = 2 — 3 = —1; T = 1000 K

K p = K c (RT) —1 = K c /RT; K c = K p (RT)

K c = 3.3856  10—2 kPa—1  8.314 L-kPa/mol-K  1000 K = 281.48 = 281 L/mol

(c) K p  K c (R T ) n ; n = 2.5 — 2 = 0.5; T = 480 C + 273 = 753 K

15.27 Analyze/Plan. Follow the logic in Sample Exercise 15.4. Solve.

AgCl(s) + 2 NH3(aq) + Ag+(aq) ⇌ [Ag(NH )2] (aq)+ Cl (aq) + Ag (aq)

AgCl(s) + 2 NH (aq) ⇌ [Ag(NH )2] (aq)+ Cl (aq)

Kc  Kc1  Kc2  1.8  10 10  1.6  107  2.9  10 3

2NO(g) + Br (g) + N (g) + O (g) ⇌ 2NOBr(g) + 2NO(g)

N (g) + O (g) + Br (g) ⇌ 2NOBr(g)

15.29 Analyze/Plan. Follow the logic in Sample Exercise 15.5. Solve.

(b) K c = [Hg(solv)]4[O2 (solv)]

Calculating Equilibrium Constants (Section 15.5)

(b) K p  K c (R T ) n ; n = 2 — 3 = —1; K p = K c (RT) —1 = K c /(RT)

K c = K p (RT) = 61.25 (0.08206)(550) = 2.76  103 = 2.8  103

(c) K p  K c (R T ) n ; n = 1 — 2 = —1; K p = K c (RT) —1 = K c /(RT)

2NO(g) + 2H2(g) ⇌ N2(g) + 2H2O(g)

H2(g) + Br2(g) ⇌ 2HBr(g)

8.314 L  kPa 550 K

8.314 L  kPa 550 K

8.314 L  kPa 550 K

(b) Partial pressure and number of moles are proportional.

CO2(g) + H2(g) ⇌ CO(g) + H2O(g)

Equilibrium partial pressure:

PH2O  PCO (346.6)(20.6)

(c) K p  K c (R T ) n ; n = 2 — 1 = 1; K p = K c (RT) 1 = K c (RT)

15.39 Analyze/Plan. Follow the logic in Sample Exercise 15.8. mM = 10—3 M

B(aq) protein(aq) B-protein(aq)

(c) The reaction must be at equilibrium.

15.44 Calculate the reaction quotient in each case, compare with

0.120 mol 8.314 L  kPa

1.50 g Br2 1 mol Br2

[HI] = (K c [H2][I2]) 1/2 = [(55.3)(0.06448)(0.008274)] 1/2 = (0.02950)1/2 = 0.1718 M = 0.172 M

7.211  10 5 mol I2 253.8 g I 2