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The reaction proceeds, converting cisbutene into transbutene, but as the concentration of transbutene builds up, the reverse reaction becomes increasingly important until, when the concentration ratio is 3, the rates are equal. Then there is no net change. A plot of concentration vs. time appears similar to Figure 162, with 0.75 bar for the final pressure of transbutene and 0.25 bar for the final pressure of cisbutene:

16.2

The reaction proceeds, converting transbutene into cisbutene, but as the concentration of cisbutene builds up, the reverse reaction becomes increasingly important until, when the concentration ratio is 1/3, the rates are equal. Then there is no net change. A plot of concentration vs. time appears similar to Figure 162, with 0.75 bar for the final pressure of transbutene and 0.25 bar for the final pressure of cisbutene:

16.3

(a) According to the principle of reversibility, every elementary reaction can run in either direction, so as the system approaches equilibrium, the reverse reactions become important:
1 Cl (aq) + ClO2 (aq)

ClO (aq) + ClO (aq)

2 Cl (aq) + ClO3 (aq) ClO (aq) + ClO2 (aq)

(b) The overall reaction is 3 ClO (aq) 2 Cl (aq) + ClO3 (aq) . By inspection, the
equilibrium constant expression is K eq =
[ClO- ]eq [Cl- ]2 3 eq
3 [ClO- ]eq

(c) The overall reaction is the sum of the two elementary steps, so the equilibrium kk constant is the product of the rate ratios of the two steps: K eq = 1 2 k1k2

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(a) According to the principle of reversibility, every elementary reaction can run in either direction, so the decomposition of H2CO is described by the reverse reactions:
3 H2CO HCO + H 2 HCO H + CO 1 2 H H2

(b) The overall reaction is H2 + CO H2CO . By inspection, the equilibrium [H 2CO]eq constant expression is K eq = [H 2 ]eq [CO]eq
(c) The overall reaction is the sum of the three elementary steps, so the equilibrium kk k constant is the product of the rate ratios of the steps: K eq = 1 2 3 k1k2 k3 16.5 A molecular picture of an elementary reaction shows the reactants, the products, and (if necessary) the intermediate collision complex.

16.6

A molecular picture of an elementary reaction shows the reactants, the products, and (if necessary) the intermediate collision complex.

16.7

To test the reversibility of a reaction, set up a system containing the products and observe if reactants form. Here, a solution containing Cl and ClO3 ions should react to form some ClO ions. (If the reaction of ClO to form Cl and ClO3 goes virtually to completion, this experiment may not succeed.)

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To test the reversibility of a reaction, set up a system containing the products and observe if reactants form. Here, if a reactor is charged with formaldehyde gas (H2CO), it should be possible to observe the formation of H2 and CO. (If the reaction between H2 and CO to form H2CO goes virtually to completion, however, this experiment may not succeed.) Equilibrium constant expressions can be written by inspection of the overall stoichiometry, remembering that pure liquids and solids do not appear in the expression. Equilibrium constant expressions contain product concentrations over reactant concentrations raised to their stoichiometric coefficient: ( pIF5 )2 1 eq (a) K eq = (b) K eq = (c) K eq = ( pCO )2 eq 5 5 (pF2 )eq pO2

16.9

( )eq

(d) K eq =

1 (pCO )eq (pH2 )2 eq

(e) K eq =

3 [H 3O+ ]eq [PO 3- ]eq 4

[H 3PO 4 ]eq

16.10 Equilibrium constant expressions can be written by inspection of the overall stoichiometry, remembering that pure liquids and solids do not appear in the expression. Equilibrium constant expressions contain product concentrations over reactant concentrations raised to their coefficient: 3 (pSO2 )eq (pCO2 )eq ( pClF3 )2 eq (a) K eq = (b) K eq = (c) K eq = 3 3 3 ( pH2 S )eq ( pO2 )eq ( pCO )eq (pF2 )eq (pCl2 )eq (d) K eq =
[NH + ]eq 4 [H 3O ]eq [NH 3 ]eq
+

(e) K eq =

1 (pH2 )2 eq

16.11 Equilibrium constant expressions can be written by inspection of the overall stoichiometry, remembering that pure liquids and solids do not appear in the expression:

(a) 2IF5 (g) I2 (s) + 5 F2 (g) (b) P4O10 (s) P4 (s) + 5 O2 (g) (c) BaO (s) + 2 CO (g) BaCO3 (s) + C (s) (d) CH3OH (l) CO (g) + 2 H2 (g)

K eq =

(pF2 )5 eq

K eq = pO2
K eq =

( )5 eq
1

( pIF5 )2 eq

( pCO )2 eq

K eq = (pCO )eq (pH2 )2 eq

(e) PO43 (aq) + 3 H3O+ (aq) H3PO4 (aq) + 3 H2O (l) K eq =

[H 3PO 4 ]eq
3 [H 3O+ ]eq [PO 3- ]eq 4

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16.12 Equilibrium constant expressions can be written by inspection of the overall stoichiometry, remembering that pure liquids and solids do not appear in the expression:

(a) 2 H2O (l) + 2 SO2 (g) 2 H2S (g) + 3 O2 (g) (b) 2 Fe (s) + 3 CO2 (g) Fe2O3 (s) + 3 CO (g) K eq = (c) 2 ClF3 (g) Cl2 (g) + 3 F2 (g)
(d) NH4
+ (aq)

K eq =

3 ( pH2 S )eq ( pO2 )eq

(pSO2 )eq

3 ( pCO )eq 3 (pCO2 )eq

K eq =

3 (pF2 )eq (pCl2 )eq

( pClF3 )2 eq [H 3O+ ]eq [NH 3 ]eq [NH + ]eq 4

+ H2O (l) NH3 (g) + H3

O+ (aq)

K eq =

(e) Sn (s) + 2 H2O (l) SnO2 (s) + 2 H2 (g)

K eq = (pH2 )2 eq

16.13 The standard states of gases are gases at 1 bar, the standard states of solutes are solutions at 1 M, and the standard states of solvents and pure liquids and solids are unit mole fractions, X = 1: (a) p = 1 bar for F2 and IF5, X = 1 for I2 (b) p = 1 bar for O2, X = 1 for P4 and P4O10 (c) p = 1 bar for CO, X = 1 for others (d) p = 1 bar for CO and H2, X = 1 for CH3OH (e) c = 1 M for H3PO4, H3O+, and PO43, X = 1 for H2O 16.14 The standard states of gases are gases at 1 bar, the standard states of solutes are solutions at 1 M, and the standard states of solvents and pure liquids and solids are unit mole fractions, X = 1: (a) p = 1 bar for SO2, O2, and H2S, X = 1 for H2O (b) p = 1 bar for CO and CO2, X = 1 for Fe and Fe2O3 (c) p = 1 bar for each gas (d) c = 1 M for H3O+ and NH4+, P = 1 bar for NH3, X = 1 for H2O (e) p = 1 bar for H2, X = 1 for others 16.15 Your views should be like those in Figure 164, showing two different size samples with equal sized portions of each highlighted to show that equal volumes contain equal numbers of atoms:

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16.16 Your views should be like those in Figure 164, showing two different size samples with equal sized portions of each highlighted to show that equal volumes contain equal numbers of atoms:

16.17 To determine an equilibrium constant at standard temperature from thermodynamic o tables, calculate Goreaction from tabulated values for Gf and then use Equation 163: Go = RT ln Keq

The solubility reaction is LiCl (s) Li+ (aq) + Cl (aq) Keq = Ksp Goreaction = [1 (293.31 kJ/mol) + l (131.0 kJ/mol)] [1 (384.4 kJ/mol)] = 39.91 kJ/mol 4 -1 3.991 x 10 J mol ln Ksp = = 16.11 Ksp = e16.11 = 9.9 x 106 -1 -1 (8.314 J mol K )(298 K)
16.18 To determine an equilibrium constant at standard temperature from thermodynamic o tables, calculate Goreaction from tabulated values for Gf and then use Equation 163: Go = RT ln Keq

The solubility reaction is MgCl2 (s) Mg2+ (aq) + 2 Cl (aq) Keq = Ksp o G reaction = [1 (454.8 kJ/mol) + 2 (131.0 kJ/mol)] [1 (591.8 kJ/mol)] = 125 kJ/mol 4 -1 12.5 x 10 J mol ln Ksp = = 50.45 Ksp = e50.45 = 8.2 x 1021 (8.314 J mol-1 K -1 )(298 K)
16.19 To determine an equilibrium constant at standard temperature from thermodynamic o tables, calculate Goreaction from tabulated values for Gf and then use Equation 163: Go = RT ln Keq (a) Goreaction = [1 (0 kJ/mol) + 1 (394.4 kJ/mol)] [1 (137.2 kJ/mol) + 1 (237.1 kJ/mol)] = 20.1 kJ/mol 2.01 x 10 4 J mol-1 ln Keq = = 8.11 Keq = e8.11 = 3.3 x 103 -1 -1 (8.314 J mol K )(298 K)

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(b) Goreaction = 2 (394.4 kJ/mol) [1 (0 kJ/mol) + 2 (137.2 kJ/mol)] = 514.4 kJ/mol 5 -1 5.144 x 10 J mol ln Keq = = 207.6 Keq = e207.6 = 1 x 1090 -1 -1 (8.314 J mol K )(298 K) o (c) G reaction = [1 (520.3 kJ/mol) + 2 (137.2 kJ/mol)] [1 (0 kJ/mol) + 1 (1134.4 kJ/mol)] = 339.7 kJ/mol 3.397 x 10 5 J mol-1 ln Keq = = 137.1 Keq = e137.1 = 3 x 1060 -1 -1 (8.314 J mol K )(298 K) o (d) G reaction = [3 (237.1 kJ/mol) + 1 (74.62 kJ/mol)] [6 (0 kJ/mol) + 3 (137.2 kJ/mol)] = 225.1 kJ/mol 2.251 x 10 5 J mol-1 ln Keq = = 90.86 Keq = e90.86 = 2.9 x 1039 (8.314 J mol-1 K -1 )(298 K) 16.20 To determine an equilibrium constant at standard temperature from thermodynamic o tables, calculate Goreaction from tabulated values for Gf and then use Equation 163: Go = RT ln Keq (a) Goreaction = [3 (0 kJ/mol) + 1 (137.2 kJ/mol)] [1 (50.5 kJ/mol) + 1 (237.1 kJ/mol)] = 150.4 kJ/mol 1.504 x 10 5 J mol-1 ln Keq = = 60.7 Keq = e60.7 = 4 x 1027 -1 -1 (8.314 J mol K )(298 K) o (b) G reaction = [4 (87.6 kJ/mol) + 6 (237.1 kJ/mol)] [4 (16.4 kJ/mol) + 5 (0 kJ/mol)] = 1006.6 kJ/mol 1.0066 x 10 6 J mol-1 ln Keq = = 406.3 Keq = e406.3 = 3 x 10176 (8.314 J mol-1 K -1 )(298 K) (c) Goreaction = [2 (237.1 kJ/mol) + 1(0 kJ/mol)] [1 (515.8 kJ/mol) + 2 (0 kJ/mol)] = 41.6 kJ/mol 4 4.16 x 10 J mol-1 ln Keq = = 16.8 Keq = e16.8 = 5.1 x 108 -1 -1 (8.314 J mol K )(298 K) o (d) G reaction = [1 (1015.4 kJ/mol) + 4 (0 kJ/mol)] [3 (0 kJ/mol) + 4 (237.1 kJ/mol)] = 67.0 kJ/mol 4 6.70 x 10 J mol-1 ln Keq = = 27.0 Keq = e27.0 = 5.3 x 1011 -1 -1 (8.314 J mol K )(298 K)

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16.21 To estimate the equilibrium constant at a temperature different from 298 K, calculate Horeaction and Soreaction at 298 K and then use Equations 1410 and 163: Go = Ho TSo Go = RT ln Keq 16.19 (b) Horeaction = 2 (393.5 kJ/mol) [1 (0 kJ/mol) + 2 (110.5 kJ/mol)] = 566.0 kJ/mol o S reaction = 2 (213.8 J/mol K) [1 (205.15 J/mol K) + 2 (197.7 J/mol K)] = 173.0 J/mol K o G reaction, 250K (566.0 kJ/mol) (250 K)(0.1730 kJ/mol K) = 522.8 kJ/mol = 251.5 Keq = e251.5 = 2 x 10109 (8.314 J mol-1 K -1 )(250 K) 16.19 (c) Horeaction = 1 (548.0 kJ/mol) + 2 (110.5 kJ/mol) [1 (0 kJ/mol) + 1(1213.0 kJ/mol)] = 444.0 kJ/mol o S reaction = [1 (72.1 J/mol K) + 2 (197.7 J/mol K)] [1 (5.7 J/mol K) + 1 (112.1 J/mol K)] = 349.7 J/mol K o G reaction, 250K (444.0 kJ/mol) (250 K)(0.3497 J/mol K) = 356.6 kJ/mol ln Keq = ln Keq =

5.228 x 10 5 J mol-1

356.6 x 10 3 J mol-1 (8.314 J mol-1 K -1 )(250 K)

= 171.6

Keq = e171.6 = 3 x 1075

16.22 To estimate the equilibrium constant at a temperature different from 298 K, calculate Horeaction and Soreaction at 298 K and then use Equations 1410 and 163: Go = Ho TSo Go = RT ln Keq 16.20 (c) Horeaction = [2 (285.83 kJ/mol) + 1 (0 kJ/mol)] [1 (577.6 kJ/mol) + 2 (0 kJ/mol)] = 5.9 kJ/mol o S reaction = [2 (69.95 kJ/mol) + 1 (51.2 kJ/mol)] [1 (49.0 J/mol K) + 2 (130.680 J/mol K)] = 119.3 J/mol K o G reaction, 350K (5.9 kJ/mol) (350 K)(0.1193 J/mol K) = 47.7 kJ/mol
(47.7 kJ/mol)(10 3 J/kJ) = 16.4 Keq = e16.4 = 7.5 x 108 (8.314 J/mol K)(350 K) 16.20 (d) Horeaction = [1 (1118.4 kJ/mol) + 4 (0 kJ/mol)] [3 (0 kJ/mol) + 4 (285.83 kJ/mol)] = 24.9 kJ/mol o S reaction = [1 (146.4 J/mol K) + 4 (130.680 J/mol K)] [3 (27.3 J/mol K) + 4 (69.95 J/mol K)] = 307.4 J/mol K o G reaction, 350K (24.9 kJ/mol) (350 K)(0.3074 J/mol K) = 82.7 kJ/mol

ln Keq =

ln Keq =

(82.7 kJ/mol)(10 3 J/kJ) = 28.4 (8.314 J/mol K)(350 K)

Keq = e28.4 = 2.2 x 1012

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16.23 To estimate the equilibrium constant at a temperature different from 298 K, calculate Horeaction and Soreaction at 298 K and then use Equations 1410 and 163: Go = Ho TSo Go = RT ln Keq 16.19 (a) Horeaction = [1 (393.5 kJ/mol) + 1 (0 kJ/mol)] [1 (110.5 kJ/mol) + 1 (241.83 kJ/mol)] = 41.2 kJ/mol o S reaction = [1 (213.8 J/mol K) + 1 (130.680 J/mol K)] [1 (197.7 J/mol K) + 1 (188.835 J/mol K)] = 42.1 J/mol K o G reaction, 395K (41.2 kJ/mol) (395 K)(0.0421 kJ/mol K) = 24.6 kJ/mol ln Keq =

2.46 x 10 4 J mol-1 (8.314 J mol K )(395 K)

-1 -1

= 7.49

Keq = e7.49 = 1.8 x 103

16.19 (d) Horeaction = 1 (20.0 kJ/mol) + 3 (241.83 kJ/mol) [3 (110.5 kJ/mol) + 6(0 kJ/mol)] = 374.0 kJ/mol o S reaction = [1 (226.9 J/mol K) + 3 (188.835 J/mol K)] [3 (197.7 J/mol K) + 6 (130.680 J/mol K)] = 583.8 J/mol K o G reaction, 395K (374.0 kJ/mol) (395 K)(0.5838 J/mol K) = 143.4 kJ/mol ln Keq =

1.434 x 10 5 J mol-1 (8.314 J mol-1 K -1 )(395 K)

= 43.67

Keq = e43.67 = 9.2 x 1018

16.24 To estimate the equilibrium constant at a temperature different from 298 K, calculate Horeaction and Soreaction at 298 K and then use Equations 1410 and 163: Go = Ho TSo Go = RT ln Keq 16.20 (c) Horeaction = [1 (0 kJ/mol) + 2 (241.83 kJ/mol)] [1 (577.6 kJ/mol) + 2 (0 kJ/mol)] = 93.9 kJ/mol o S reaction = [1 (51.2 J/mol K) + 2 (188.835 J/mol K)] [1 (49.0 J/mol K) + 2 (130.680 J/mol K)] = 118.51 J/mol K Goreaction, 425K (93.9 kJ/mol) (425 K)(0.18851 kJ/mol K) = 43.5 kJ/mol ln Keq =

4.35 x 10 4 J mol-1 (8.314 J mol-1 K -1 )(425 K)

= 12.3

Keq = e12.3 = 4.5 x 106

16.20 (d) Horeaction = 1 (1118.4 kJ/mol) + 4 (0 kJ/mol) [3 (0 kJ/mol) + 4 (241.83 kJ/mol)] = 151.1 kJ/mol Soreaction = [1 (146.4 J/mol K) + 4 (130.680 J/mol K)] [3 (27.3 J/mol K) + 4 (188.835 J/mol K)] = 168.1 J/mol K o G reaction, 425K (151.1 kJ/mol) (425 K)(0.1681 J/mol K) = 79.7 kJ/mol ln Keq =

7.97 x 10 4 J mol-1 (8.314 J mol K )(425 K)

474
-1 -1

= 22.6

Keq = e22.6 = 6.5 x 109

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16.25 Use Le Chtelier's principle to determine the effect on an equilibrium position caused by adding one reagent: In reactions (a), (b), and (d), CO is a reactant, so adding CO causes the reaction to go to the right, forming products; in reaction (c), CO is a product, so adding CO causes the reaction to proceed to the left, forming reactants. 16.26 Use Le Chtelier's principle to determine the effect on an equilibrium position caused by adding one reagent. Note, however, that pure liquids and solids do not appear in equilibrium constant expressions, so changing their amounts do not affect the equilibrium position. In all four reactions of Problem 16.20, H2O is a liquid reactant, so adding H2O has no effect on the equilibrium position. 16.27 Use Le Chtelier's principle to determine the effect on an equilibrium position caused by a change in conditions: (a) Solid reactants do not appear in the equilibrium constant expression, so adding PbCl2 has no effect. (b) Addition of water dilutes the solution, reducing the concentrations of the product ions, so more of the solid will dissolve. (c) Addition of NaCl increases the concentration of one of the product ions, Cl, so some solid will precipitate. (d) Addition of KNO3 does not change the concentrations in the equilibrium constant expression, so adding this solid has no effect. 16.28 Use Le Chtelier's principle to determine the effect on an equilibrium position caused by a change in conditions: (a) Increasing the temperature causes the equilibrium position to shift in the endothermic direction. The reaction is exothermic in the forward direction, so increasing the temperature shifts the equilibrium position in the direction of reactants, and the amount of SO3 decreases. (b) Addition of O2 increases the concentration of one of the reactants, so more SO3 will form. (c) Addition of Ar gas leaves the concentrations of all reagents unchanged, so this addition has no effect on the amount of SO3 present. 16.29 Use Le Chtelier's principle to determine what changes in conditions will drive an equilibrium in any given direction. This reaction can be driven to the left by removing SO2, removing Cl2, adding SO2Cl2, or increasing the temperature. 16.30 Use Le Chtelier's principle to determine what changes in conditions will drive an equilibrium in any given direction. This reaction can be driven to the left by removing PCl5, adding Cl2, adding PCl3, or decreasing the temperature.

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16.31 To calculate an equilibrium constant when amounts are available, we generally must convert amounts data into concentrations or pressures using stoichiometric reasoning, then complete an amounts table and substitute into the equilibrium constant expression. In this problem, however, the equilibrium constant expression contains p2 in the numerator and denominator, so units cancel and amounts can be used directly. Set up an amounts table, using the fact that the change is 0.49 mol for CO: Reaction: H2 + CO2

H2O +

CO

Initial amount (mol) 1.00 1.00 0 0 Change in amount (mol) 0.49 0.49 + 0.49 + 0.49 Equilibrium amount (mol) 0.51 0.51 0.49 0.49 Now substitute into the equilibrium constant expression and evaluate K: ( pH 2 O )eq ( pCO )eq (nH 2 O )eq (nCO )eq (0.49)2 Keq = = 0.92 = = ( pH 2 )eq ( pCO2 )eq (nH 2 )eq (nCO2 )eq (0.51)2 16.32 To calculate an equilibrium constant from experimental data, complete a concentration table using concentration or pressures using stoichiometric reasoning. Then substitute into the equilibrium constant expression. We are given initial pressures in bar. Use the fact that the change is 0.93 bar for Cl2: Reaction: 4 HCl +

O2

2 Cl2 +

2 H2O

Initial pressure (bar) 2.30 1.00 0 0 Change in pressure (bar) 1.86 0.465 + 0.93 + 0.93 Equilibrium pressure (bar) 0.44 0.535 0.93 0.93 Now substitute into the equilibrium constant expression and evaluate K: Keq =

( pH 2 O )2 ( pCl2 )2 eq eq
4 ( pHCl )eq ( pO2 )eq

(0.93)2 (0.93)2 (0.44)4 (0.535)

= 37

16.33 To calculate an equilibrium constant when experimental data concerning amounts are available, identify the reaction, convert amounts data into concentration using stoichiometric reasoning, then complete a concentration table and substitute into the equilibrium constant expression. For solutes, concentrations must be in mol/L. 0.0500 mol [C2H5CO2H]initial = = 0.100 M 0.500 L To complete the concentration table, use stoichiometric reasoning and the fact that the change is 1.15 x 103 M for H3O+ (The concentration of water is not needed, because water is the solvent): Reaction: H2 O +

C2H5CO2H
0.100 1.15 x 103 0.099 476

C2H5CO2 + 0 + 1.15 x 103 1.15 x 103

H3O+ 0 +1.15 x 103 1.15 x 103

Initial conc. (M) Change in conc. (M) Equilibrium conc. (M)

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Now substitute into the equilibrium constant expression and evaluate K: [C2 H 5CO- ]eq [H 3O+ ]eq (1.15 x 10-3 )2 2 Ka = = 1.3 x 105 = [C2 H 5CO2 H]eq (0.099) 16.34 To calculate an equilibrium constant when experimental data concerning concentrations are available, identify the reaction, then complete a concentration table and substitute into the equilibrium constant expression. To complete the concentration table, use stoichiometric reasoning and the fact that the change is 6.5 x 103 M for H3O+ (The concentration of water is not needed, because water is the solvent): Reaction:

H2O + HCNO

CNO +

H3O+

Initial conc. (M) 0.20 0 0 3 3 Change in conc. (M) 6.5 x 10 + 6.5 x 10 + 6.5 x 103 Equilibrium conc. (M) 0.19 6.5 x 103 6.5 x 103 Now substitute into the equilibrium constant expression and evaluate Keq: Keq = Ka =

[CNO- ]eq [H 3O+ ]eq [HCNO]eq

(6.5 x 10-3 )2 = 2.2 x 104 (0.19)

16.35 To calculate concentrations at equilibrium from initial conditions, set up a concentration table. For a gas phase reaction, concentrations must be expressed in bar. Let x = change in pH 2 : Reaction: H2 +

Br2

2 HBr

Initial pressure (bar) 0 0 10.0 Change in pressure (bar) +x +x 2x Equilibrium pressure (bar) x x 10.0 2x Now substitute into the equilibrium constant expression and solve for x: (pHBr )2 (10.0 - 2x)2 eq Keq = = 1.6 x 105 = ( pH 2 )eq ( pBr2 )eq (x)(x) To simplify, assume that 2x << 10.0: (10.0)2 1.6 x 105 = so (x)2 x = 2.5 x 102 = ( pH 2 )eq = ( pBr2 )eq x2 =

100 1.6 x 10
5

= 6.25 x 104

(pHBr)eq = 10.0 2(2.5 x 102) = 10.0 bar 2(2.5 x 102) = 0.050 << 10.0, so the approximation is valid.

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16.36 To calculate concentrations at equilibrium from initial conditions, set up a concentration table. For a gas phase reaction, concentrations must be expressed in bar. Let x = change in pCO : Reaction: CO +

Cl2

COCl2

Initial pressure (bar) 0 0 0.250 Change in pressure (bar) +x +x x Equilibrium pressure (bar) x x 0.250 x Now substitute into the equilibrium constant expression and solve for x: (pCOCl2 )eq 0.250 - x = Keq = = 1.5 x 108; assume that x << 0.250 2 (pCO )eq (pCl2 )eq x 1.5 x 108 =

0.250 x
2

x = 4.1 x 105

1.5 x 10 ( pCO )eq = ( pCl2 )eq = 4.1 x 105 bar

so

x2 =

0.250
8

= 1.67 x 109

(pCOCl2 )eq = 0.250 4.1 x 105 = 0.250 bar

4.1 x 105 << 0.250, so the approximation is valid. 16.37 To calculate concentrations at equilibrium from initial conditions, set up a concentration table. For a gas phase reaction, concentrations must be expressed in bar. Let x = change in pCO2 : Reaction: FeO (s) +

CO (g)

CO2 (g) +

Fe (s)

Initial pressure (bar) excess 5.0 0 Change in pressure (bar) x +x Equilibrium pressure (bar) 5.0 x x Now substitute into the equilibrium constant expression and solve for x: (pCO2 )eq x = Keq = = 0.403 ( pCO )eq (5.0 -x) x = (0.403)(5.0 x) = 2.015 0.403 x (pCO2 )eq = 1.4 bar x = 1.436 so 1.403 x = 2.015 ( pCO )eq = 5.0 1.4 = 3.6 bar

16.38 This problem describes an equilibrium reaction. We are asked to determine the equilibrium pressures of all the gases. To calculate pressures at equilibrium from initial conditions, set up a concentration table, write the K expression, and solve for the pressures: Let x = change in [N2]: Reaction: Initial pressure (bar) Change in pressure (bar) Equilibrium pressure (bar) N2 +

3 H2
3.0 3 x 3.0 3 x

2 NH3 0 + 2x 2x

5.0 x 5.0 x 478

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Now substitute into the equilibrium constant expression and solve for x: Keq = 2.81 x 105 = 2.81 x 105 = x = 3.08 x

(2x)2 = ; Assume that 3x << 3.0: 3 ( pN 2 )eq ( pH 2 )eq (5.0 x)(3.0 3x)3
3

(pNH 3 )2 eq

4x 2 (5.0)(3.0)

4x2 = (5.0)(3.0)3(2.81 x 105) = 3.79 x 103

(pNH 3 )eq = 2(3.08 x 102) = 6.2 x 102 bar

102

3(3.08 x 102) = 0.09, about 3% of 3.0, so 3 x is << 3.0 and the approximation is valid. 16.39 To identify species in solution, first identify the nature of the solute. Strong acids, strong bases, and salts generate ions, while all other substances remain molecular: (a) weak acid, major species are H2O and CH3CO2H; (b) salt, major species are H2O, NH4+ and Cl; (c) salt, major species are H2O, K+ and Cl; (d) salt, major species are H2O, Na+ and CH3CO2; and (e) strong base, major species are H2O, Na+ and OH. 16.40 To identify species in solution, first identify the nature of the solute. Strong acids, strong bases, and salts generate ions, while all other substances remain molecular: (a) weak acid, major species are H2O and HClO; (b) salt, major species are H2O, Ca2+ and Br; (c) salt, major species are H2O, K+ and ClO; (d) strong acid, major species are H2O, H3O+ and NO3; and (e) weak acid, major species are H2O and HCN. 16.41 The equilibria among major species depend on the nature of the species. The proton transfer reaction of water always plays a role:

H2O (l) + H2O (l) H3O+ (aq) + OH (aq) (a) weak acid equilibrium: CH3CO2H (aq) + H2O (l) CH3CO (aq) + H3O+ (aq) (b) ammonium ion is the weak conjugate acid of NH3: NH4+ (aq) + H2O (l) NH3 (aq) + H3O+ (aq) (c) There are no equilibria other than the water equilibrium. (d) acetate ion is the weak conjugate base of acetic acid: CH3CO2 (aq) + H2O (l) CH3CO2H (aq) + OH (aq) (e) There are no equilibria other than the water equilibrium.
16.42 The equilibria among major species depend on the nature of the species. The proton transfer reaction of water always plays a role:

H2O (l) + H2O (l) H3O+ (aq) + OH (aq) (a) weak acid equilibrium: HClO (aq) + H2O (l) ClO (aq) + H3O+ (aq) (b) There are no equilibria other than the water equilibrium.
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(c) ClO ion is the conjugate base of HClO, so is a weak base:

ClO (aq) + H2O (l) HClO (aq) + OH (aq) (d) There are no equilibria other than the water equilibrium. (e) weak acid equilibrium: HCN (aq) + H2O (l) CN (aq) + H3O+ (aq)
16.43 To identify species in solution, first identify the nature of the solute. Strong acids, strong bases, and salts generate ions, while all other substances remain molecular: (a) major species are (CH3)2CO (acetone) and H2O; (b) salt, major species are H2O, K+, and Br; (c) strong base, major species are H2O, Li+, and OH; and (d) strong acid, major species are H2O, H3O+, and HSO4. 16.44 To identify species in solution, first identify the nature of the solute. Strong acids, strong bases, and salts generate ions, while all other substances remain molecular: (a) salt, major species are H2O, Na+, and HCO3; (b) major species are CH3OH (methanol) and H2O; (c) strong acid, major species are H2O, H3O+, and Br; and (d) weak acid, major species are C6H5CO2H (benzoic acid) and H2O. 16.45 Equilibrium constant expressions have the concentrations of the products in the numerator and the concentrations of the reactants in the denominator with each concentration raised to the power of its stoichiometric coefficient. Remember to omit liquids and solids from the expressions. If the reaction involves a weak acid (or base) reacting with water, Keq will be related to Ka (or Kb if a base). If the reaction involves a solid, Keq will be related to Ksp: 1 1 [ClO- ][H 3O+ ] 2 (a) Keq = = Ka (b) Keq = = 3+ 3 K sp [HClO2 ] [Fe ][OH ] (c) Keq =

[HCN] 1 - ][H O+ ] = K [CN a 3

16.46 Equilibrium constant expressions have the concentrations of the products in the numerator and the concentrations of the reactants in the denominator with each concentration raised to the power of its stoichiometric coefficient. Remember to omit liquids and solids from the expressions. If the reaction involves a weak acid (or base) reacting with water, Keq will be related to Ka (or Kb if a base). If the reaction involves a solid, Keq will be related to Ksp: (a) Keq = [Ag + ]2 [SO2- ] = Ksp 4
[H 3O+ ][H 2 PO- ] 4 = 1 K a1 [H 3PO 4 ] [HCO2 H] 1 (c) Keq = = + [HCO2 ][H 3O ] K a

(b) Keq =

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16.47 To identify the spectator ions, first determine the reaction (if any) that occurs when the solutions are mixed. Species that do not participate in the reaction are spectator ions:

(a) CH3CO2H + OH CH3CO2 + H2O; spectator ion: Na+ (b) 3 Ca2+ + 2 PO 3- Ca3(PO4)2; spectator ions: Cl and K+ 4 (c) H3O+ + OH 2 H2O; spectator ions: K+ and NO 3
16.48 To identify the spectator ions, first determine the reaction (if any) that occurs when the solutions are mixed. Species that do not participate in the reaction are spectator ions:

(a) Fe3+ + 3 OH Fe(OH)3; spectator ions: Cl and Na+ (b) NH3 + H3O+ NH + + H2O; spectator ion: NO 4 3 (c) H3O+ + CH3CO2 CH3CO2H + H2O; spectator ions: K+ and ClO 4
16.49 Equilibrium constant expressions are determined by the stoichiometry of the overall reaction, with pure liquids, solids, and solvent omitted from the expression. Equilibrium constant expressions have the concentrations of the products in the numerator and the concentrations of the reactants in the denominator, with each concentration raised to the power of its stoichiometric coefficient: (a) Keq = ( pCO2 )eq (pH 2 O )eq (c) Keq = (b) Keq =
4 3 ( pNH 3 )eq (pO2 )eq

(pN 2 )2 eq

( pCH 3CHO )2 eq (pC2 H 4 )2 (pO2 )eq eq

(d) Keq = [Ag + ]2 [SO2- ]eq eq 4

(e) Keq = ( pH 2 S )eq ( pNH 3 )eq 16.50 Equilibrium constant expressions are determined by the stoichiometry of the overall reaction, with pure liquids, solids, and solvent omitted from the expression. Equilibrium constant expressions have the concentrations of the products in the numerator and the concentrations of the reactants in the denominator, with each concentration raised to the power of its stoichiometric coefficient: (a) Keq = (c) Keq =
4 (pNO )eq 4 ( pNH 3 )eq (pO2 )5 eq

(b) Keq = (d) Keq =

[CN - ]eq [H 3O+ ]eq [HCN]eq

[OH - ]eq [HSO- ]eq 4 [SO2- ]eq 4

1 [NH + ]2 [SO2- ]eq 4 eq 4

3 (pO2 )eq

(e) Keq =

(pO 3 )2 eq

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16.51 This problem describes an equilibrium reaction. We are asked to determine the equilibrium pressures of all the gases. To calculate pressures at equilibrium from initial conditions, set up a concentration table, write the Keq expression, and solve for the pressures. For a gas phase reaction, concentrations must be expressed in bar. p1 p2 pT ( 3.00 bar ) (273 + 352) K = 6.29 bar p2 = 1 2 = = T1 T2 T1 ( 298 K ) Reaction:

COCl2

CO

Cl2

Initial pressure (bar) 6.29 0 0 x x Change in pressure (bar) + + x Equilibrium pressure (bar) 6.29 x x x Now substitute into the equilibrium constant expression and solve for x : Keq = 8.3 x 104 = 8.3 x 104 =

(pCO )eq ( pCl2 )eq ( pCOCl2 )eq

(x)2 ; Assume that x << 6.29: 6.29 x

x2 x2 = (6.29)(8.3 x 104) = 5.22 x 103 6.29 ( pCOCl2 )eq = 6.29 7.2 x 102 = 6.22 bar x = 7.2 x 102 bar = (pCO )eq = ( pCl2 )eq
7.2 x 102 is 1.1% of 6.29, so x is << 6.29 and the approximation is valid. 16.52 To calculate concentrations at equilibrium from initial conditions, set up a concentration table. For a gas phase reaction, concentrations must be expressed in bar. We know the pressure of Cl2 gas at 298 K, from which we can calculate the initial pressure at 1200 K: p1 p2 pT ( 0.57 bar ) (1200 K ) = 2.3 bar p2 = 1 2 = = T1 T2 T1 ( 298 K ) Let x = change in pCl2 : Reaction:

Cl2 (g)

2Cl (g)

Initial pressure (bar) 2.3 0 Change in pressure (bar) x + 2x Equilibrium pressure (bar) 2.3 x 2x Now substitute into the equilibrium constant expression and solve for x: (pCl )2 (2x)2 eq Keq = = 2.5 x 105; assume x << 2.3 = ( pCl2 )eq (2.3 -x) 4x2 = (2.5 x 105)(2.3) = 5.75 x 105 x2 = 1.44 x 105 (pCl )eq = 3.8 x 103 bar ( pCl2 )eq = 2.3 bar x = 3.8 x 103 0.0038 << 2.3, so the approximation is valid.

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16.53 At equilibrium, a molecular picture should show the presence of both reactants and products, in relative amounts that are determined by the value of the equilibrium constant. Set up a "concentration" table to determine how many of each species are present at equilibrium: Initial 12 12 0 0 Change x x +x + x Equilibrium 12 x 12 x x x Substitute in the equilibrium constant expression and solve for x: x (x)2 Keq = 25 = ; Taking the square root of each side gives 5 = 2 (12 x) (12 - x) (60 5 x ) = x 6 x = 60 and x = 10 The molecular picture should show (12 10) = 2 of each reactant and 10 of each product:

16.54 At equilibrium, a molecular picture should show the presence of both reactants and products, in relative amounts that are determined by the value of the equilibrium constant. Set up a "concentration" table to determine how many of each species are present at equilibrium: Initial 12 12 0 Change x x +2x Equilibrium 12 x 12 x 2x Substitute in the equilibrium constant expression and solve for x: 2x (2x)2 Keq = 4 = ; Taking the square root of each side gives 2 = (12 x) (12 - x)(12 - x) x) = 2x x = 24 and x = 6 2(12 4 The molecular picture should show (12 6) = 6 of each reactants, and 2(6) = 12 product molecules:

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16.55 At equilibrium between a solute and solution, the rate at which molecules leave the surface of the solute equals the rate at which molecules are captured from solution at the surface of the solute. Adding more solute to a solution that is saturated increases the total surface area, so the overall rate at which molecules enter the solution becomes greater. However, the rate at which molecules are captured also becomes greater. The rate per unit surface area is unchanged, so the concentration of chloroform in the aqueous solution remains the same. 16.56 At equilibrium between a solid salt and solution, the rate at which ions leave the surface of the solid equals the rate at which ions are captured from solution at the surface of the solid. Adding solid to a solution at equilibrium increases the total surface area, so the overall rate at which ions leave becomes greater. However, the rate at which ions are captured also becomes greater. The rate per unit surface area is unchanged, so the concentration of sodium chloride in the aqueous solution remains the same. 16.57 To calculate equilibrium pressures, set up a concentration table. In this problem, the table can be short, because two of the three equilibrium pressures are provided: Reaction: Br2 (g) +

I2 (g)

2 IBr (g)

Equilibrium pressure (bar) 0.512 0.327 Substitute into the equilibrium constant expression and solve for x : (pIBr )2 x2 eq 322 = = (0.512)(0.327) (pBr2 )eq (pI2 )eq x2 = (322)(0.512)(0.327) = 53.91 ( pIBr )eq = 7.34 bar x = 7.34

16.58 To calculate equilibrium pressures, set up a concentration table. In this problem, the table can be short, because one equilibrium pressure is provided and the others must be stoichiometrically related: Reaction: C (s) +

2 H2O (g)

CO2 (g) +

2 H2 (g) 2x

Equilibrium pressure (bar) x 2.80 x 102 Substitute into the equilibrium constant expression and solve for x: 0.38 =

(pCO2 )eq (pH 2 )2 eq (pH 2 O )2 eq

x(2x)2 (280)2

4x3 = (0.38)(280)2 = 2.98 x 104 x3 = 7.4 x 103, x = 19.5 (pCO2 )eq = 20. bar (pH 2 )eq = 2(19.5) = 39 bar

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16.59 To determine an equilibrium constant at standard temperature from thermodynamic tables, calculate Goreaction from tabulated values for Gof. To estimate the equilibrium constant at a temperature different from 298 K, calculate Horeaction and Soreaction at 298K and then use Equations 1410 and 163: Go = Ho TSo Go = RT ln Keq At 298 K: Goreaction = 1 (99.8 kJ/mol) 2 (51.3 kJ/mol) = 2.8 kJ/mol ln Keq = At 525 K: Horeaction = 1 (11.1 kJ/mol) 2 (33.2 kJ/mol) = 55.3 kJ/mol Soreaction = 1 (304.4 J/mol K) 2 (240.1 J/mol K) = 175.8 J/mol K -3 175.8 J 10 kJ Goreaction (55.3 kJ/mol) (525 K) = 37.0 kJ/mol 1 mol K 1 J ln Keq = = 8.48 Keq = e8.48 = 2.1 x 104 (8.314 J mol-1 K -1 )(525 K) Notice that the exothermic reaction has a smaller Keq at higher temperature.

2.8 x 10 3 J mol-1 (8.314 J mol-1 K -1 )(298 K) Keq = e1.1 = 3.0

= 1.1

3.70 x 10 4 J mol-1

16.60 To determine an equilibrium constant at standard temperature from thermodynamic tables, calculate Goreaction from tabulated values for Gof. To estimate the equilibrium constant at a temperature different from 298 K, calculate Horeaction and Soreaction at 298K and then use Equations 1410 and 163: Go = Ho TSo Go = RT ln Keq At 298 K: Goreaction = 4 (87.6 kJ/mol) [2 (103.7 kJ/mol) + 1 (0 kJ/mol)] = 143.0 kJ/mol 3 -1 143.0 x 10 J mol ln Keq = = 57.7; Keq = e57.7 = 8.7 x 1026 -1 -1 (8.314 J mol K )(298 K) At 825 K: Horeaction = 4 (91.3 kJ/mol) [2 (81.6 kJ/mol) + 1 (0 kJ/mol)] = 202.0 kJ/mol Soreaction = 4 (210.8 J/mol K) [2 (220.0 J/mol K) + 1 (205.152 J/mol K)] = 198.0 J/mol K -3 198.0 J 10 kJ Goreaction (202.0 kJ/mol) (825 K) = 38.7 kJ/mol 1 mol K 1 J

(8.314 J mol K )(825 K) Notice that the endothermic reaction has a larger Keq at higher temperature.
485

ln Keq =

38.7 x 10 3 J mol-1
-1 -1

= 5.64

Keq = e5.64 = 3.6 x 103

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16.61 (a) The general weak base reaction is B + H2O BH+ + OH, and B = (CH3)3N: [(CH 3 )3NH + ]eq [OH - ]eq (CH3)3NH+ + OH (CH3)3N + H2O Kb = [(CH 3 )3N]eq (b) The general weak acid reaction is HA + H2O A + H3O+, and HA = HF: [F - ]eq [H 3O+ ]eq F + H3O+ HF + H2O Ka = [HF]eq
(c) A solubility reaction involves solid dissolving to produce ions:

CaSO4 (s) Ca2+(aq) + SO42(aq)

Ksp = [Ca 2+ ]eq [SO 4 2- ]eq

16.62 (a) The general weak acid reaction is HA + H2O A + H3O+, and HA = Cl3CCO2H:
Cl3CCO2H + H2O Cl3CCO2 + H3

O+

Ka =

[Cl3CCO2- ]eq [H 3O+ ]eq [Cl3CCO2 H]eq

(b) The general weak base reaction is B + H2O BH+ + OH, and B = (C6H5)NH2: [(C6 H 5 )NH + ]eq [OH - ]eq 3 (C6H5)NH2 + H2O (C6H5)NH3+ + OHKb = [(C6 H 5 )NH 2 ]eq
(c) A solubility reaction involves solid dissolving to produce ions:

Ca(OH)2 (s) Ca2+(aq) + 2OH(aq)

Ksp = [Ca 2+ ]eq [OH - ]2 eq

16.63 To predict effects of changes on equilibrium position, apply Le Chtelier's principle: The system will respond in the direction that reduces the effect of the change. The reaction in

Example 1614 is: 2 NO (g) + O2 (g) 2 NO2 (g): (a) NO2 is a product, so reducing its pressure causes the reaction to proceed to the right. (b) There are more moles of gas on the reactant side, doubling the volume causes the reaction to proceed to the left. (c) Adding Ar does not change any of the pressures in the equilibrium expression, so this change has no effect.
16.64 To predict effects of changes on equilibrium position, apply Le Chtelier's principle: The system will respond in the direction that reduces the effect of the change. The reaction in

Example 1612 is: HA + H2O A + H3O+, where HA is benzoic acid and A is the conjugate base, benzoate anion: (a) Adding sodium benzoate will increase the concentration of benzoate anion (A) in the solution, causing the reaction to proceed to the left. Increasing the volume of the solution will reduce the concentrations of all solutes. (b) There are more moles of solutes on the product side, so the reaction will proceed to the right. (c) Adding NaCl does not change any concentrations in the equilibrium expression, so this change has no effect.
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16.65 To estimate the equilibrium constant at a temperature different from 298 K, calculate Horeaction and Soreaction at 298 K and then use Equations 1410 and 163: Go = Ho TSo Go = RT ln Keq

The solubility reaction is LiCl (s) Li+ (aq) + Cl (aq) o H reaction = [1 (167.1 kJ/mol) + 1 (278.47 kJ/mol)] [1 (408.6 kJ/mol)] = 36.97 kJ/mol o S reaction = [1 (56.5 J/mol K) + 1 (12.2 J/mol K)] [1 (59.3 J/mol K)] = 9.4 J/mol K Goreaction, 373K (36.97 kJ/mol) (373 K)(0.0094 kJ/mol K) = 40.5 kJ/mol
ln Keq =

4.05 x 10 4 J mol-1
-1 -1

(8.314 J mol K )(373 K) From Problem 16.17, at 298 K, Keq = 9.9 x 106; LiCl is less soluble at high temperature.
16.66 To estimate the equilibrium constant at a temperature different from 298 K, calculate Horeaction and Soreaction at 298 K and then use Equations 1410 and 163: Go = Ho TSo Go = RT ln Keq

= 13.06

Keq = e13.06 = 4.7 x 105

The solubility reaction is MgCl2 (s) Mg2+ (aq) + 2 Cl (aq) Horeaction = [2 (167.1 kJ/mol) + 1 (467.0 kJ/mol)] [1 (641.3 kJ/mol)] = 159.9 kJ/mol Soreaction = [2 (56.5 J/mol K) + 1 (137 J/mol K)] [1 (89.6 J/mol K)] = 113.6 J/mol K o G reaction, 373K (159.9 kJ/mol) (373 K)(0.1136 kJ/mol K) = 117.5 kJ/mol
ln Keq = = 37.9 (8.314 J mol-1 K -1 )(373 K) Keq = e37.9 = 2.9 x 1016; from Problem 16.18, at 298 K, Keq = 8.2 x 1021 By this estimate, MgCl2 is less soluble at high temperature than at low. 16.67 To calculate an equilibrium constant from initial and equilibrium conditions, set up a concentration table: Reaction:

1.175 x 10 5 J mol-1

CCl4 (g)

2 Cl2 (g) +

C (s)

Initial pressure (bar) 1.00 0 Change in pressure (bar) x + 2x Equilibrium pressure (bar) 1.00 x 2x The problem gives the total equilibrium pressure, which is the sum of partial pressures: 1.35 bar = (1.00 x) + 2 x = 1.00 + x, from which x = (1.35 1.00) = 0.35 Substitute into the equilibrium constant expression and calculate K:
[(2)(0.35)]2 0.70 2 Keq = = 0.75 = = (pCCl4 )eq (1.00 0.35) 0.65 (pCl2 )2 eq

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16.68 When the volume of a gas system changes, all partial pressures change proportionally. This generates a new set of "initial" conditions that form the starting point for a new concentration table. When volume doubles, pressure is cut in half: 0.65 0.70 pCCl4 = pCl2 = = 0.325 bar = 0.35 bar 2 2 To return to equilibrium, pCl2 increases. Reaction:

CCl4 (g)

2 Cl2 (g) +

C (s)

Initial pressure (bar) 0.325 0.35 Change in pressure (bar) x + 2x Equilibrium pressure (bar) 0.325 x 0.35 + 2x Substitute into the equilibrium constant expression and solve for x: (0.35 + 2x)2 0.75 = , from which (0.75)(0.325 x) = (0.35 + 2x)2 (0.325 x) 0.24375 0.75 x = 0.1225 + 1.40 x + 4 x2 4 x2 + 2.15 x 0.12125 = 0

b b 2 4ac 2.15 (2.15)2 4(4)(0.12125) = x= = 0.0515 2a 2(4) ( pCCl4 )eq = (0.325 0.0515) = 0.27 bar ( pCl2 )eq = [0.35 + 2(0.0515)] = 0.45 bar
ptotal = 0.72 bar. This pressure is larger than the pressure that would result from expansion without reaction, in conformity with Le Chtelier's Principle. 16.69 To determine an equilibrium constant at standard temperature from thermodynamic o tables, calculate Goreaction from tabulated values for Gf ; to estimate the equilibrium constant at a temperature different from 298 K, calculate Horeaction and Soreaction at 298 K and then use Equations 1410 and 163: Go = Ho TSo Go = RT ln Keq (a) Goreaction = 1 (210.7 kJ/mol) [1 (31.8 kJ/mol) + 1 (178.6 kJ/mol)] = 63.9 kJ/mol 4 6.39 x 10 J mol-1 ln Keq = = 25.8 Keq = e25.8 = 1.6 x 1011 (8.314 J mol-1 K -1 )(298 K) (b) When the equilibrium pressure is 1.00 bar, Keq = 1, ln(Keq) = 0 and Goreaction = 0 0 = Ho TSo TSo =Ho and T =
H o S o

Horeaction = 1 (265.4 kJ/mol) [1 (61.4 kJ/mol) + 1 (224.3 kJ/mol)] = 102.5 kJ/mol o S reaction = 1 (191.6 J/mol K) [1 (175.0 J/mol K) + 1 (146.0 J/mol K)] = 129.4 J/mol K 3 102.5 kJ 10 J 1 mol K T= = 792 K 1 mol 1 kJ 129.4 J 488

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(c)

Go

3 129.4 J 10 kJ = 33.4 kJ/mol reaction, 1050 K (102.5 kJ/mol) (1050 K) 1 mol K 1 J

= 3.83 (8.314 J mol-1 K -1 )(1050 K) Keq = e3.83 = 2.2 x 102 Notice that Keq decreases as T increases for this exothermic reaction. 16.70 To calculate concentrations at equilibrium from initial conditions, set up a concentration table. For a gas phase reaction, concentrations must be expressed in bar. Use the ideal gas equation to calculate the initial pressure of PCl5 gas:
L atm (2.00 g)(0.08206 mol K )(390 K) nRT mRT = 0.1025 atm = = V MM V (208.22 g mol-1 )(3.00 L) Convert from atm to bar: 1.013 bar 0.1025 atm = 0.1038 bar 1 atm Let x = change in pCl2 :

ln Keq =

3.34 x 10 4 J mol-1

p=

Reaction:

PCl5 (g)

PCl3 (g) +

Cl2 (g)

Initial pressure (bar) 0.1038 0 0 Change in pressure (bar) x +x +x Equilibrium pressure (bar) 0.1038 x x x Now substitute into the equilibrium constant expression and solve for x: ( pPCl3 )eq ( pCl2 )eq (x)2 Keq = = 1.83 x 103 = ( pPCl5 )eq (0.1038 x) x2 = (1.83 x 103)(0.1038 x) = 1.90 x 104 (1.83 x 103)x x2 + (1.83 x 103)x 1.90 x 104 = 0 x= x=

b b 2 4ac (1.83 x 10-3 ) (1.83 x 10-3 )2 + 4(1.90 x 10-4 ) = 2a 2(3.72)

(1.83 x 10-3 ) + (2.76 x 10-2 ) (1.83 x 10-3 ) (7.63 x 10-4 ) = = 1.29 x 102 2 2 ( pPCl3 )eq = ( pCl2 )eq = 1.29 x 102 bar ( pPCl5 )eq = 0.1038 0.0129 = 0.0909 bar

16.71 (a) The equilibrium constant expression for a reaction can be written by inspection of the stoichiometry of the reaction, omitting pure liquids, solids, and solvents:
K eq = [CO2- ]eq 3 (pCO2 )eq [OH - ]2 eq

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(b) Use Le Chtelier's Principle to predict the effect of changes on a system at equilibrium. Dissolving Na2CO3 leads to an increase in the concentration of CO32, so the equilibrium shifts to the left and the pressure of CO2 increases. (c) At first glance, it may appear that HCl will not affect this equilibrium, but recall that HCl is a strong acid which generates H3O+ in solution. This, in turn, will react with OH, reducing the concentration of a reactant. Again the equilibrium shifts to the left and the pressure of CO2 increases. 16.72 To relate an equilibrium constant to rate constants for elementary steps, set forward and reverse reaction rates equal to each other, rearrange to obtain equilibrium expressions, and then multiply the expressions:

H2SO4 SO3 + H2O

k1[H2SO4]eq = k1[SO3]eq[H2O]eq

Rate constants: k1, k1 k1 [SO 3 ]eq [H 2O]eq = k1 [H 2SO 4 ]eq Rate constants: k2, k2 [C6 H 6SO 3 ]eq k2 = k2 [SO 3 ]eq [C6 H 6 ]eq Rate constants: k3, k3
]

SO3 + C6H6 C6H6SO3

k2[SO3]eq[C6H6]eq = k2[C6H6SO3]eq

C6H6SO3 + H2O C6H5SO3 + H3O+

k3[C6H6SO3]eq[H2O]eq = k3[H3 O+]
eq[C6H5SO3 eq

+ k3 [H 3O ]eq [C6 H 5SO 3 ]eq = k3 [H 2O]eq [C6 H 6SO 3 ]eq

Multiply these three expressions and cancel concentration terms:

[H 3O+ ]eq [C6 H 5SO- ]eq k1k2 k3 3 = Keq = k1k2 k3 [C6 H 6 ]eq [H 2SO 4 ]eq
16.73 To find an equilibrium total pressure, it is necessary to calculate equilibrium partial pressures of all gaseous participants. First determine the initial pressures of the gases, using the ideal gas equation: L atm nRT (0.494 mol)(0.08206 mol K )(1020 + 273 K) p= = 52.4 atm = V 1.00 L 1.013 bar Convert from atm to bar: 52.4 atm = 53.1 bar 1 atm Set up a concentration table, write the equilibrium expression and solve for the pressure: Reaction: Initial pressure (bar) Change in pressure (bar) Equilibrium pressure (bar) C (s) +

CO2 (g)
53.1 x 53.1 x

2 CO (g) 53.1 +2x 53.1 + 2 x

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Substitute into the equilibrium constant expression and solve for x : (53.1 + 2x)2 167.5 = (167.5)(53.1 x ) = (53.1 + 2 x )2 (53.1 x) 8894 167.5 x = 2820 + 212.4 x + 4 x 2 4 x 2 + 379.9 x 6074 = 0

b b 2 4ac 379.9 (379.9)2 4(4)(6074) 379.9 491.4 = = = 13.9 2a 2(4) 8 Rule out the negative value, which would give a negative pressure: ( pCO2 )eq = 53.1 13.9 = 39.2 bar ( pCO )eq = 53.1 + 2(13.9) = 80.9 bar

x =

Ptotal = 39.2 + 80.9 = 1.20 x 102 bar 16.74 To calculate an equilibrium constant from initial and equilibrium conditions, set up a concentration table: Reaction:

2 Ef (g) + 3 N2 (g)

2 EfN3 (g)

Initial pressure (bar) 0.75 1.00 0 Change in pressure (bar) 2x 3x +2x Equilibrium pressure (bar) 0.75 2 x 1.00 3 x 2x The problem gives the total equilibrium pressure, which is the sum of partial pressures: 0.85 = (0.75 2 x) + (1.00 3 x) + 2 x = 1.75 3 x 3 x = (1.75 0.85) = 0.90 and x = 0.30 pEf = 0.75 2(0.30) = 0.15 bar pN 2 = 1.00 3(0.30) = 0.10 bar
pEfN 3 = 2(0.30) = 0.60 bar

Ptotal = 0.15 + 0.10 + 0.60 = 0.85 bar, which matches the experimental pressure. Substitute into the equilibrium constant expression and calculate Keq: Keq =
[EfN 3 ]2 eq
3 [Ef]2 [N 2 ]eq eq

(0.60)2 (0.15)2 (0.10)3

= 1.6 x 104

16.75 To determine the volume that will contain a single molecule of SnH4 we first need to find the equilibrium pressure of the gas. To calculate equilibrium pressures, set up a concentration table: Reaction: Sn (s) +

2 H2 (g)

SnH4 (g)

Initial pressure (bar) 200 0 Change in pressure (bar) 2 x +x Equilibrium pressure (bar) 200 2 x x Because Keq is very small, we assume that 2x << 200: [SnH 4 ]eq x 1.1 x 1033 = = x = (1.1 x 1033)(200)2 = 4.4 x 1029 [H 2 ]2 (200)2 eq [SnH4]eq = 4.4 x 1029 bar (a very small pressure) 491

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To calculate the volume that would be expected to contain a single molecule, use pV = nRT # = nNA V RT = # pN A First, convert the pressure from bar to atm: 1 atm p = (4.4 x 1029 bar) = 4.3 x 1029 atm 1.013 bar V/1 molecule =
L atm (0.08206 mol K )(298 K) RT = 9.4 x 105 L = pN A (6.022 x 10 23 mol-1 )(4.3 x 10-29 bar)

16.76 (a) Follow the fivestep procedure for solving equilibrium problems: 1.) The species are acetic acid (A) and its dimer (A2)

2.) The reaction is 2 A (g) A2 (g) (pA2 )eq 3.) Keq = =3.72 (pA )2 eq
4.) The total pressure at equilibrium is given, Ptotal = 0.75 bar. Let x = pA2 and pA = 0.75 x 5.) Substitute into the equilibrium constant expression and solve for x : x 3.72 = (0.75 - x)2 Solve for x using the quadratic equation. x = (3.72)(0.75 x)2 = (3.72)( x 2 1.50 x + 0.563) = 3.72 x 2 5.58 x + 2.093 0 = 3.72 x 2 6.58 x + 2.093

b b 2 4ac 6.58 (6.58)2 4(3.72)(2.093) 6.58 43.296 31.144 = x= = 2a 2(3.72) 7.44 6.58 3.49 x= = 1.35 or 0.415 7.44 Rule out 1.35, which would give a negative pressure for the monomer. ( pA2 )eq = 0.415 bar
(b) The reaction to form the dimer is exothermic, so raising the temperature will shift the equilibrium position to the left. The equilibrium constant is lower at 200 oC.

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16.77 This molecular picture illustrates starting conditions and equilibrium conditions. The symbols indicate BG3 as the starting material and G2 and GB as products. Count numbers of symbols to determine initial and equilibrium concentrations. Set up a concentration table using numbers of symbols:

Reaction Initial Change Equilibrium

15 12 3

0 +12 12

0 +12 12

(a) From the amounts of change, the stoichiometry is 1:1, so the net reaction is

; (b) Use numbers of symbols at equilibrium to calculate the equilibrium constant: [BG]eq [G 2 ]eq (12)(12) K eq = = = 48 [BG 3 ]eq (3) 16.78 To calculate concentrations at equilibrium from initial conditions, set up a concentration table. For a gas phase reaction, concentrations must be expressed in bar. Let x = change in [H2]: Reaction: Initial pressure (bar) Change in pressure (bar) Equilibrium pressure (bar) H2 +

F2
3.00 x 3.00 x

2 HF 0 + 2x 2x

3.00 x 3.00 x

Now substitute into the equilibrium constant expression and solve for x: Keq = 115 =

(pHF )2 eq ( pH 2 )eq ( pF2 )eq

(2x)2 4x 2 = (3.00 -x)(3.00 -x) (9.00 - 6.00x +x 2 )

4x2 = (115)(9.00 6.00x + x2) = 1035 690 x + 115 x2 0 = 111 x2 690 x + 1035

b b 2 4ac 690 (690)2 4(111)(1035) 690 16560 = = = 3.69 or 2.53 2a 2(111) 222 The initial pressures are 3.00 bar, so a change of 3.69 bar is impossible; thus, x = 2.53 ( pH 2 )eq = ( pF2 )eq = 3.00 2.53 = 0.47 bar
(pHF )eq = 2(2.53) = 5.06 bar

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16.79 (a) To calculate an equilibrium constant from initial and equilibrium conditions, set up a concentration table: Reaction: C (s) +

CO2 (g)

2 CO (g)

Initial pressure (bar) 0.464 0 Change in pressure (bar) x + 2x Equilibrium pressure (bar) 0.464 x 2x The problem gives the equilibrium pressure, which is the sum of partial pressures: 0.746 bar = (0.464 x) + 2 x = 0.464 + x, from which x = (0.746 0.464) = 0.282 Substitute into the equilibrium constant expression and calculate K: (pCO )2 [(2)(0.282)]2 0.564 2 eq Keq = = 1.75 = = (pCO2 )eq (0.464 0.282) 0.182 (b) Applying the ideal gas equation, the pressure of CO2 will be multiplied by 3 if the container is compressed to one third of its initial volume: pCO2 = 3(0.464 bar) = 1.392 bar Set up a new concentration table using this as the initial pressure: Reaction:

C (s) + CO2 (g)

2 CO (g)

Initial pressure (bar) 1.392 0 Change in pressure (bar) x + 2x Equilibrium pressure 1.392 x 2x (bar) Write the equilibrium expression and solve for the pressures of the gases: (pCO)2 (2x)2 4x 2 eq Keq = 1.75 = = = (pCO 2 )eq 1.392 x 1.392 x x = 0.592 pCO = 2x = 2(0.592 bar) = 1.184 bar pCO2 = 1.392 bar x = 1.392 bar 0.592 bar = 0.800 bar The total pressure at equilibrium is the sum of the partial pressures: Peq = 1.184 bar + 0.800 bar = 1.98 bar (final result rounds to 3 significant figures) 16.80 (a) To calculate an equilibrium constant when experimental data concerning amounts are available, convert amounts data into concentration using stoichiometric reasoning, then complete an amounts table and substitute into the equilibrium constant expression. Generally, pressures in bar are required for gasphase reactions, but in this problem, the equilibrium constant expression contains p2 in the numerator and denominator, so units cancel and amounts can be used directly. Set up a concentration table, using the change of 0.182 mol for I2: Reaction: Initial amount (mol) Change in amount (mol) Equilibrium amount (mol) 2 HI

H2

I2 0 + 0.182 0.182

1.00 2(0.182) 0.636 494

0 + 0.182 0.182

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Chapter 16

Now substitute into the equilibrium constant expression and evaluate Keq: Keq =

( pH 2 )eq ( pI2 )eq ( pHI )2 eq

(nH 2 )eq (nI2 )eq (nHI )2 eq

(0.182)2 (0.636)2

= 0.0819

(b) To estimate the equilibrium constant at a temperature different from 298 K, calculate Horeaction and Soreaction at 298 K and then use Equations 1410 and 163: Go = Ho TSo Go = RT ln Keq Horeaction = [1 (0 kJ/mol) + 1 (62.4 kJ/mol)] 2 (26.5 kJ/mol) = 9.4 kJ/mol Soreaction = [1 (130.680 J/mol K) + 1 (260.7 J/mol K)] 2 (206.6 J/mol K) = 21.82 J/mol K o G reaction, 625 C 9.4 kJ/mol) (625 + 273 K)(0.02182 kJ/mol K) = 29.0 kJ/mol ln Keq =

29.0 x10 3J mol-1

(8.314 J mol-1 K -1 )(898 K) Keq = e3.88 = 0.021

= 3.88

(c) As in part (a), we can make use of the fact that both numerator and denominator of the equilibrium constant expression contain p2, so units cancel and we can work directly with moles. Construct a concentration table, write the equilibrium expression, and solve for the pressures. Reaction: 2 HI

H2

I2 0 +x x

Initial amount (mol) 1.00 0 Change in amount (mol) 2x +x Equilibrium amount (mol) 1.00 2x x Use the Keq expression to calculate the amount of H2 formed: Keq =

( pH 2 )eq ( pI2 )eq ( pHI )2 eq

(x)2 (1.00-2x)2

= 0.021

Take the square root of both sides: x = 0.145 so x = 0.145 0.290 x (1.00 2x ) 1.290 x = 0.145 from which x = 0.112 mol and (1.00 2x) = 0.776 mol Use the ideal gas equation to calculate the partial pressures, which we leave in atm: L atm nRT (0.112 mol)(0.08206 mol K )(898 K) pH 2 = pI2 = = 8.25 atm = V 1.00 L L atm nRT (0.776 mol)(0.08206 mol K )(898 K) pHI = = 57.2 atm = V 1.00 L

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16.81 This problem describes an equilibrium reaction pertinent to smog. Use standard procedures to determine the partial pressures of each pollutant. The equilibrium constant expression is dimensionless because it has p2 in both numerator and denominator, so we can use any convenient units. Begin by converting all the initial pressures to the same units, ppm. Because Keq is so large, take the reaction to completion and then determine the equilibrium pressures: Reaction: O3 + NO2 O2 + NO Initial (ppm) 1.5 0 6.5 x 103 2.1 x 105 Change (ppm) 6.5 x 103 6.5 x 103 +6.5 x 103 +6.5 x 103 5 Completion (ppm) 0 1.5 2.1 x 10 6.5 x 103 Use these values as the initial values in a new concentration table, write the equilibrium expression, and solve for the equilibrium pressures: Reaction: O3 + NO

O2

NO2

Initial (ppm) 0 1.5 2.1 x 105 6.5 x 103 Change (ppm) +x +x x x 5 Equilibrium (ppm) x 1.5 + x 2.1 x 10 6.5 x 103 x The equilibrium expression is: pO2 pNO2 (2.1 x 10 5 )(6.5 x 10 3 x) Keq = 6.0 x 1034 = ; assume x << 6.5 x 103 = pO 3 pNO x(1.5 + x) x = 1.5 x 1032 (assumption is valid) Convert ppm to bar, using the fact that 1 ppm = 1 part in 106 and standard atmospheric pressure is 1.01325 bar: pO 3 = (1.5 x 1032 ppm)(1 atm)(106/ppm)(1.01325 bar) = 1.5 x 1038 bar pNO = (1.5 ppm)(1 atm)(106/ppm)(1.01325 bar) = 1.5 x 106 bar pNO2 = (6.5 x 103 ppm)(1 atm)(106/ppm)(1.01325 bar) = 6.6 x 109 bar
pO2 = (2.1 x 105 ppm)(1 atm)(106/ppm)(1.01325 bar) = 0.21 bar

16.82 (a) This problem describes an equilibrium reaction pertinent to sulfuric acid synthesis. Use standard procedures to determine the partial pressures of each gas. Because K is large, take the reaction to completion and then determine the equilibrium pressures. Since information is given about both reactants this is a limiting reactant problem. Divide the pressures by the stoichiometric coefficients to determine the limiting reactant: 0.350 O2: 0.762 bar SO2: = 0.175 bar (LR) 2 Use a concentration table to determine the pressures at completion: Reaction: 2 SO2 + 2 SO3 O2 Initial (bar) 0.350 0.762 0 Change (bar) 0.350 (0.350)/2 + 0.350 Completion (bar) 0 0.587 0.350 496

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Use these values in a new concentration table, write the equilibrium expression, and solve for the equilibrium pressures: Reaction: Initial (bar) Change (bar) Equilibrium (bar) 2 SO2 + 0 +2x 2x

O2
0.587 +x 0.587 + x

2 SO3 0.350 2x 0.3502x

The equilibrium expression is: 2 pSO (0.350 2x)2 Keq = 5.60 x 104 = 2 3 = ; assume 2x<<0.350 pSO pO2 (2x)2 (0.587 + x)
2

5.60 x 104 = x2 =

(0.350)

(2x)2 (0.587) (0.350)2

4

; rearrange to get: = 9.32 x 107 from which

4(5.60 x 10 )(0.587) x = 9.65 x 104 Now solve for the partial pressures of the three gases: pSO2 = 2(9.65 x 104) = 1.93 x 103 bar
pO2 = 0.587 + 9.65 x 104 = 0.588 bar pSO 3 = 0.350 2(9.65 x 104) = 0.348 bar

(b) To estimate Keq using thermodynamic values, use the equation: Go = RT ln Keq Gfo for SO2, O2, and SO3 are 300.1, 0.00, and 371.1 kJ/mol respectively. Goreaction = 2 (371.1 kJ/mol) [1 (0.000 kJ/mol) + 2 (300.1 kJ/mol)] = 142.0 kJ/mol G o 1.42 x 10 5 J mol-1 ln Keq = = 57.3 = RT (8.314 J mol-1K -1 )(298 K) Keq = e57.3 = 7.7 x 1024 Based on this result, the reaction should be run at lower temperature to improve the yield. (c) Although the reaction is thermodynamically more favorable at lower temperatures, the reaction is kinetically very slow. Therefore, it must be run at higher temperatures (700 K) to speed up the reaction while still being thermodynamically favorable.

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16.83 The molecular picture of the equilibrium conditions shows 4 O2, 5 SO3, and 5 SO2 molecules. From this, calculate the "equilibrium constant" for the reaction:
K eq = [SO 3 ]2 eq [SO2 ]2 [O2 ]eq eq = (5)2 (5)2 (4) = 0.25

(a) To determine what happens under the new conditions, compare amounts of molecules with equilibrium amounts. Equilibrium conditions show 4 O2, 5 SO3, and 5 SO2 molecules. The new picture shows 4 O2, 3 SO3, and 5 SO2 molecules. The amounts of reactants are the same as before, but there are fewer product molecules, so Q < Keq and the reaction will proceed to the right, forming additional SO3. (b) To determine the effect of temperature, compare amounts of molecules at equilibrium for the two temperatures. Equilibrium conditions at 1100 K: 4 O2, 5 SO3, and 5 SO2 molecules Equilibrium conditions at 1300 K: 5 O2, 3 SO3, and 7 SO2 molecules The equilibrium shifts to the left, forming additional reactant molecules, when temperature increases. According to Le Chtelier's principle, the reaction shifts in the endothermic direction (absorbs heat) when temperature increases. Therefore, the forward reaction is exothermic. (c) To determine what happens under the new conditions, compare amounts of molecules with equilibrium amounts. Equilibrium conditions show 4 O2, 5 SO3, and 5 SO2 molecules. The new picture shows 4 O2, 9 SO3, and 9 SO2 molecules. Qualitative reasoning is insufficient to decide what happens, because the number of molecules of a reactant and a product both have increased. Compare Q for the second set of conditions with Keq calculated from the equilibrium conditions:
K eq = [SO 3 ]2 eq [SO2 ]2 [O2 ]eq eq = (5)2 (5)2 (4) = 0.25 and

Q=

[SO 3 ]2 [SO2 ]2 [O2 ]

(9)2 (9)2 (4)

= 0.25 ;

The two values are identical, so the new conditions represent equilibrium, and no change will occur.

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