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Chapter 19

Principles of Reactivity: Entropy and Free Energy

Chapter 19
Principles of Reactivity: Entropy and Free Energy
SOLUTIONS TO STUDY QUESTIONS
19.1

(a) The CO2 vapor at 0 ºC has a higher entropy than the sample of solid CO2
(b) Liquid water at the higher temperature (50 ºC) has a higher entropy
(c) Ruby has a higher entropy than pure alumina
(d) The sample of N2(g) at the lower pressure (1 bar) has a higher entropy

19.4

(a) NaCl(g) has a higher entropy than NaCl(s) or NaCl(aq)
(b) H2S(g) has a higher entropy than H2O(g)
(c) C2H4(g) has a higher entropy than N2(g)
(d) H2SO4(aq) has a higher entropy than H2SO4()

19.8

∆Sº = Sº[NH3(g)] – {1/2 Sº[N2(g)] + 3/2 Sº[H2(g)]}
∆Sº = 1 mol (192.77 J/K·mol) – [1/2 mol (191.56 J/K·mol) + 3/2 mol (130.7 J/K·mol)]
∆Sº = –99.1 J/K

19.9

(a)

/2 H2(g) + 1/2 Cl2(g) → HCl(g)

1

∆Sº = Sº[HCl(g)] – {1/2 Sº[H2(g)] + 1/2 Sº[Cl2(g)]}
∆Sº = 1 mol (186.2 J/K·mol) – [1/2 mol (130.7 J/K·mol) + 1/2 mol (223.08 J/K·mol)]
∆Sº = 9.3 J/K
(b) Ca(s) + O2(g) + H2(g) → Ca(OH)2(s)
∆Sº = Sº[Ca(OH)2(s)] – {Sº[Ca(s)] + Sº[O2(g)] + Sº[H2(g)]}
∆Sº = 1 mol (83.39 J/K·mol) – [1 mol (41.59 J/K·mol) + 1 mol (205.07 J/K·mol)
+ 1 mol (130.7 J/K·mol]
∆Sº = –294.0 J/K
19.11

(a) ∆Sº = 2 Sº[AlCl3(s)] – {2 Sº[Al(s)] + 3 Sº[Cl2(g)]}
∆Sº = 2 mol (109.29 J/K·mol) – [2 mol (28.3 J/K·mol) + 3 mol (223.08 J/K·mol)]
∆Sº = –507.3 J/K
A negative ∆Sº indicates a decrease in entropy
(b) ∆Sº = 2 Sº[CO2(g)] + 4 Sº[H2O(g)] – {2 Sº[CH3OH()] + 3 Sº[O2(g)]}
∆Sº = 2 mol (213.74 J/K·mol) + 4 mol (188.84 J/K·mol) – [2 mol (127.19 J/K·mol)
+ 3 mol (205.07 J/K·mol)]
∆Sº = 313.25 J/K

A positive ∆Sº indicates an increase in entropy

Copyright © 2006 Thomson Learning, Inc. All rights reserved.

353

not spontaneous under all conditions 19.1 J/K·mol) + 1 mol (130.21 (a) ∆Hº = 2 ∆Hfº[PbO(s)] = 2 mol (–219 kJ/mol) = –438 kJ ∆Sº = 2 Sº[(PbO(s)] – {2 Sº[Pb(s)] + Sº[O2(g)]} ∆Sº = 2 mol (66.8 J/K·mol) – [1 mol (192.75 J/K (b) ∆Gº = ∆Hº – T∆Sº = 116.84 J/K·mol) ∆Sº = 174.96 J/K·mol)] ∆Sº = –15.36 kJ/mol)] = –86.79 J/K·mol) + 2 mol (56.9 kJ The reaction is predicted to be non-spontaneous at 298 K (∆Gº > 0) (c) The reaction is predicted to be spontaneous at higher temperatures.61 kJ ∆Sº = Sº[NH4NO3(aq)] – {Sº[NH3(g)] + Sº[HNO3(aq)]} ∆Sº = 1 mol (259.509 kJ/mol) – 1 mol (–1111. (b) ∆Hº > 0.74 J/K·mol) – [1 mol (134.24 kJ/mol) + 1 mol (–393.77 J/K·mol) + 1 mol (146.5 J/K·mol)] ∆Sº = 266.5 J/K·mol) – [2 mol (64.81 J/K·mol) + 1 mol (205.9 kJ Reaction (a) is product-favored and enthalpy-driven.94 kJ ∆Sº = Sº[MgO(s)] + Sº[CO2(g)] – Sº[MgCO3(s)] ∆Sº = 1 mol (26.87 kJ/mol) – [1 mol (–45. All rights reserved.74 J/K·mol) – 1 mol (65. ∆Sº < 0.17 A positive ∆Sº indicates an increase in entropy (a) ∆Hº < 0.Chapter 19 19.95 J/K·mol) + 1 mol (213. depends on T and relative magnitudes of ∆H and ∆S.61 kJ – (298 K)(–79. more favorable at lower T.4 J/K)(1 kJ/103 J) = –62. ∆Sº < 0. .4 J/K·mol)] = –79.19 (a) ∆Hº = ∆Hfº[MgO(s)] + ∆Hfº[CO2(g)] – ∆Hfº[MgCO3(s)] ∆Hº = 1 mol (–601.4 J/K ∆Gº = ∆Hº – T∆Sº = –86.9 J/K 19. 354 Copyright © 2006 Thomson Learning.69 kJ/mol) ∆Hº = 116. 19.07 J/K·mol)] = –201.7 J/K ∆Gº = ∆Hº – T∆Sº = –438 kJ – (298 K)(–201.4 J/K A negative ∆Sº indicates a decrease in entropy (b) ∆Sº = 2 Sº[NaCl(aq)] + Sº[H2O()] + Sº[CO2(g)] – {Sº[Na2CO3(s)] + 2 Sº[HCl(aq)] ∆Sº = 2 mol (115.90 kJ/mol) + 1 mol (–207. Inc.5 J/K·mol) + 1 mol (69. Reaction (b) is product-favored and enthalpy-driven.12 Principles of Reactivity: Entropy and Free Energy (a) ∆Sº = 2 Sº[NaOH(aq) ] + Sº[H2(g)] – {2 Sº[Na(s)] + 2 Sº[H2O()]} ∆Sº = 2 mol (48.21 J/K·mol) + 2 mol (69.75 J/K)(1 kJ/103 J) = 64.7 J/K·mol) – [2 mol (51.7 J/K)(1 kJ/103 J) = –378 kJ (b) ∆Hº = ∆Hfº[NH4NO3(aq)] – {∆Hfº[NH3(g)] + ∆Hfº[HNO3(aq)]} ∆Hº = 1 mol (–339.94 kJ – (298 K)(174.85 J/K·mol) + 1 mol (213.

355 . All rights reserved.1 J/K·mol)] = 168.7 kJ ∆Sº = Sº[CS2(g)] – {Sº[C(graphite)] + 2 Sº[S(s)]} ∆Sº = 1 mol (237.0 J/K ∆Gfº = ∆Hº – T∆Sº = 116.93 kJ – (298 K)(–154.6 kJ Appendix L value 66.6 J/K·mol) + 2 mol (32.7 kJ – (298 K)(168. Copyright © 2006 Thomson Learning.93 kJ/mol) = –425.6 J/K ∆Gfº = ∆Hº – T∆Sº = –425.087 J/K·mol) + 1/2 mol (130.0 J/K)(1 kJ/103 J) = 66.135 J/K·mol) + 1/2 mol (223.7 kJ/mol) = 116.08 J/K·mol)] = 77. Inc.75 kJ (c) /2 I2(s) + 1/2 Cl2(g) → ICl(g) 1 ∆Hº = ∆Hfº[ICl(g)] = 1 mol (17.93 kJ ∆Sº = Sº[NaOH(s)] – {Sº[Na(s)] + 1/2 Sº[O2(g)] + 1/2 Sº[H2(g)]} ∆Sº = 1 mol (64.23 Principles of Reactivity: Entropy and Free Energy (a) C(graphite) + 2 S(s) → CS2(g) ∆Hº = ∆Hfº[CS2(g)] = 1 mol (116.95 J/K)(1 kJ/103 J) = –5.51 kJ – (298 K)(77.72 kJ Appendix L value –5.8 J/K·mol) – [1 mol (5.Chapter 19 19.73 kJ Reactions (b) and (c) are product-favored.95 J/K ∆Gfº = ∆Hº – T∆Sº = 17.61 kJ (b) Na(s) + 1/2 O2(g) + 1/2 H2(g) → NaOH(s) ∆Hº = ∆Hfº[NaOH(s)] = 1 mol (–425.51 kJ ∆Sº = Sº[ICl(g)] – {1/2 Sº[I2(s)] + 1/2 Sº[Cl2(g)]} ∆Sº = 1 mol (247.9 kJ Appendix L value –379.51 kJ/mol) = 17.46 J/K·mol) – [1 mol (51.56 J/K·mol) – [1/2 mol (116.6 J/K)(1 kJ/103 J) = –379.7 J/K·mol)] ∆Sº = –154.21 J/K·mol) + 1/2 mol (205.

39 J/K·mol) – [1 mol (41.08 J/K·mol) = 53.21 J/K·mol) + 1 mol (5.09 kJ/mol) = –986.07 J/K·mol)] ∆Sº = –280.77 kJ/mol) = –817.59 J/K·mol) + 1 mol (205.38 kJ/mol) + 1 mol (–394.0 J/K ∆Gfº = ∆Hº – T∆Sº = –986.54 kJ product-favored (b) ∆Gºrxn = –(2 ∆Gfº[CuO(s)]) = –[2 mol (–128.24 Principles of Reactivity: Entropy and Free Energy (a) Ca(s) + O2(g) + H2(g) → Ca(OH)2(s) ∆Hº = ∆Hfº[Ca(OH)2(s)] = 1 mol (–986.3 kJ Appendix L value 105.25 (a) ∆Gºrxn = 2 ∆Gfº[KCl(s)] = 2 mol (–408.359 kJ/mol) – 1 mol ∆Gfº[BaCO3(s)] ∆Gfº[BaCO3(s)] = –1134.07 J/K·mol) + 1 mol (130.3 kJ ∆Sº = Sº[Cl(g)] – 1/2 Sº[Cl2(g)] ∆Sº = 1 mol (165.4 kJ/mol 356 Copyright © 2006 Thomson Learning.7 kJ = 1 mol (–520.65 J/K ∆Gfº = ∆Hº – T∆Sº = 121.09 kJ ∆Sº = Sº[Ca(OH)2(s)] – {Sº[Ca(s)] + Sº[O2(g)] + Sº[H2(g)]} ∆Sº = 1 mol (83.0 J/K)(1 kJ/103 J) = –898. All rights reserved.79 J/K·mol) – [2 mol (51.09 kJ – (298 K)(–294.3 kJ/mol) = 121. Inc.27 ∆Gºrxn = ∆Gfº[BaO(s)] + ∆Gfº[CO2(g)] – ∆Gfº[BaCO3(s)] 219.84 J/K)(1 kJ/103 J) = –1047.23 kJ/mol) + 6 mol (–228.37 kJ/mol) = –1101.08 kJ Appendix L value –1048.3 kJ – (298 K)(53.65 J/K)(1 kJ/103 J) = 105.84 J/K ∆Gfº = ∆Hº – T∆Sº = –1130.Chapter 19 19.43 kJ (b) 1/2 Cl2(g) → Cl(g) ∆Hº = ∆Hfº[Cl(g)] = 1 mol (121.14 kJ product-favored 19.5 kJ Appendix L value –898.77 kJ/mol) = –1130.3 kJ (c) 2 Na(s) + C(graphite) + 3/2 O2(g) → Na2CO3(s) ∆Hº = ∆Hfº[Na2CO3(s)] = 1 mol (–1130.77 kJ ∆Sº = Sº[Na2CO3(s)] – {2 Sº[Na(s)] + Sº[C(graphite)]+ 3/2 Sº[O2(g)]} ∆Sº = 1 mol (134.3 kJ/mol)] = 256.08 kJ Reactions (a) and (c) are product-favored.7 J/K·mol)] ∆Sº = –294. 19.77 kJ – (298 K)(–280.19 J/K·mol) – 1/2 mol (223.59 kJ/mol) – 4 mol (–16.6 kJ reactant-favored (c) ∆Gºrxn = 4 ∆Gfº[NO2(g)] + 6 ∆Gfº[H2O(g)] – 4 ∆Gfº[NH3(g)] ∆Gºrxn = 4 mol (51.6 J/K·mol) + 3/2 mol (205. .

357 . (c) While many spontaneous processes are exothermic. When a solid is dissolved in water the ions are dispersed throughout the solution. (b) Product-favored reactions can occur at any rate.21 J/K·mol) + 1 mol (223. All rights reserved. Based on the third law of thermodynamics.81 In a solid the particles have fixed positions in the solid lattice. 1 bar).07 J/K·mol)] = –121.2 kJ ∆Sº = Sº[Hg()] + Sº[S(g)] – Sº[HgS(s)] ∆Sº = 1 mol (76.2 kJ/mol) = 337. (d) Endothermic processes can be spontaneous at high temperatures.29 Principles of Reactivity: Entropy and Free Energy (a) ∆Sº = 2 Sº[NO2(g)] – {Sº[N2(g)] + 2 Sº[O2(g)]} ∆Sº = 2 mol (240.6 J/K·mol) + 1 mol (205. 19. Increasing the temperature will make the reaction more reactant-favored (d) ∆Sº = 2 Sº[Na(s)] + Sº[Cl2(g)] – 2 Sº[NaCl(s)] ∆Sº = 2 mol (51.28 J/K Entropy-favored. Increasing the temperature will make the reaction more product-favored 19.7 J/K·mol) – [1 mol (38. The only exception to this is the entropy of the solvation process.2 J/K·mol) + 1 mol (213. A substance cannot have S = 0 J/K·mol at standard conditions (25 ºC.83 J/K·mol) – 1 mol (82. All substances have positive entropy values at temperatures above 0 K.Chapter 19 19. Increasing the temperature will make the reaction more reactant-favored (b) ∆Sº = 2 Sº[CO(g)] – {2 Sº[C(graphite)] + Sº[O2(g)]} ∆Sº = 2 mol (197.04 J/K·mol) – [1 mol (191. Copyright © 2006 Thomson Learning. endothermic processes can be spontaneous at high temperatures. When water molecules are constrained to a more ordered arrangement in a solution than in pure water.1 J/K Entropy-favored.02 J/K·mol) + 1 mol (167. Increasing the temperature will make the reaction more product-favored (c) ∆Sº = Sº[CaCO3(s)] –{Sº[CaO(s)] + Sº[CO2(g)]} ∆Sº = 1 mol (91. negative values of entropy cannot occur.5 J/K ∆Gº = 0 = ∆Hº – T∆Sº = 337.74 J/K·mol)] = –160.31 HgS(s) → Hg() + S(g) ∆Hº = ∆Hfº[S(g)] – ∆Hfº[HgS(s)] = 1 mol (278.98 kJ/mol) – 1 mol (–58. 19.08 J/K·mol) – 2 mol (72.5 J/K)(1 kJ/103 J) T = 2088 K or greater 19.07 J/K·mol)] = 179.2 kJ – T(161.76 The entropy of a pure crystal is zero at 0 K. not necessarily a fast rate.11 J/K·mol) = 181.74 (a) The entropy of the universe increases in all product-favored reactions.2 J/K Entropy-disfavored. a higher degree of order results and entropy is negative.56 J/K·mol) + 2 mol (205.4 J/K·mol) = 161. Inc.674 J/K·mol) – [2 mol (5.62 J/K Entropy-disfavored.

82 358 Principles of Reactivity: Entropy and Free Energy ∆Hº ∆Sº ∆Gº (a) + + + (b) – + – (c) – + – Copyright © 2006 Thomson Learning.Chapter 19 19. All rights reserved. . Inc.