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 C has a higher entropy than the sample of solid CO2
(b) Liquid water at the higher temperature (50 C) 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

S = S[NH3(g)] {1/2 S[N2(g)] + 3/2 S[H2(g)]}

S = 1 mol (192.77 J/Kmol) [1/2 mol (191.56 J/Kmol) + 3/2 mol (130.7 J/Kmol)]
S = 99.1 J/K

19.9

(a)

/2 H2(g) + 1/2 Cl2(g) HCl(g)

S = S[HCl(g)] {1/2 S[H2(g)] + 1/2 S[Cl2(g)]}

S = 1 mol (186.2 J/Kmol) [1/2 mol (130.7 J/Kmol) + 1/2 mol (223.08 J/Kmol)]
S = 9.3 J/K
(b) Ca(s) + O2(g) + H2(g) Ca(OH)2(s)
S = S[Ca(OH)2(s)] {S[Ca(s)] + S[O2(g)] + S[H2(g)]}
S = 1 mol (83.39 J/Kmol) [1 mol (41.59 J/Kmol) + 1 mol (205.07 J/Kmol)
+ 1 mol (130.7 J/Kmol]
S = 294.0 J/K
19.11

(a) S = 2 S[AlCl3(s)] {2 S[Al(s)] + 3 S[Cl2(g)]}

S = 2 mol (109.29 J/Kmol) [2 mol (28.3 J/Kmol) + 3 mol (223.08 J/Kmol)]
S = 507.3 J/K
A negative S indicates a decrease in entropy
(b) S = 2 S[CO2(g)] + 4 S[H2O(g)] {2 S[CH3OH()] + 3 S[O2(g)]}
S = 2 mol (213.74 J/Kmol) + 4 mol (188.84 J/Kmol) [2 mol (127.19 J/Kmol)
+ 3 mol (205.07 J/Kmol)]
S = 313.25 J/K

A positive S indicates an increase in entropy

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Chapter 19

19.12

Principles of Reactivity: Entropy and Free Energy

(a) S = 2 S[NaOH(aq) ] + S[H2(g)] {2 S[Na(s)] + 2 S[H2O()]}

S = 2 mol (48.1 J/Kmol) + 1 mol (130.7 J/Kmol) [2 mol (51.21 J/Kmol)
+ 2 mol (69.96 J/Kmol)]
S = 15.4 J/K A negative S indicates a decrease in entropy
(b) S = 2 S[NaCl(aq)] + S[H2O()] + S[CO2(g)] {S[Na2CO3(s)] + 2 S[HCl(aq)]
S = 2 mol (115.5 J/Kmol) + 1 mol (69.95 J/Kmol) + 1 mol (213.74 J/Kmol)
[1 mol (134.79 J/Kmol) + 2 mol (56.5 J/Kmol)]
S = 266.9 J/K

19.17

A positive S indicates an increase in entropy

(a) H < 0, S < 0; depends on T and relative magnitudes of H and S, more favorable at lower T.
(b) H > 0, S < 0; not spontaneous under all conditions

19.19

(a) H = Hf[MgO(s)] + Hf[CO2(g)] Hf[MgCO3(s)]

H = 1 mol (601.24 kJ/mol) + 1 mol (393.509 kJ/mol) 1 mol (1111.69 kJ/mol)
H = 116.94 kJ
S = S[MgO(s)] + S[CO2(g)] S[MgCO3(s)]
S = 1 mol (26.85 J/Kmol) + 1 mol (213.74 J/Kmol) 1 mol (65.84 J/Kmol)
S = 174.75 J/K
(b) G = H TS = 116.94 kJ (298 K)(174.75 J/K)(1 kJ/103 J) = 64.9 kJ
The reaction is predicted to be non-spontaneous at 298 K (G > 0)
(c) The reaction is predicted to be spontaneous at higher temperatures.

19.21

(a) H = 2 Hf[PbO(s)] = 2 mol (219 kJ/mol) = 438 kJ

S = 2 S[(PbO(s)] {2 S[Pb(s)] + S[O2(g)]}
S = 2 mol (66.5 J/Kmol) [2 mol (64.81 J/Kmol) + 1 mol (205.07 J/Kmol)] = 201.7 J/K
G = H TS = 438 kJ (298 K)(201.7 J/K)(1 kJ/103 J) = 378 kJ
(b) H = Hf[NH4NO3(aq)] {Hf[NH3(g)] + Hf[HNO3(aq)]}
H = 1 mol (339.87 kJ/mol) [1 mol (45.90 kJ/mol) + 1 mol (207.36 kJ/mol)] = 86.61 kJ
S = S[NH4NO3(aq)] {S[NH3(g)] + S[HNO3(aq)]}
S = 1 mol (259.8 J/Kmol) [1 mol (192.77 J/Kmol) + 1 mol (146.4 J/Kmol)] = 79.4 J/K
G = H TS = 86.61 kJ (298 K)(79.4 J/K)(1 kJ/103 J) = 62.9 kJ
Reaction (a) is product-favored and enthalpy-driven.
Reaction (b) is product-favored and enthalpy-driven.

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Chapter 19

19.23

Principles of Reactivity: Entropy and Free Energy

(a) C(graphite) + 2 S(s) CS2(g)

H = Hf[CS2(g)] = 1 mol (116.7 kJ/mol) = 116.7 kJ
S = S[CS2(g)] {S[C(graphite)] + 2 S[S(s)]}
S = 1 mol (237.8 J/Kmol) [1 mol (5.6 J/Kmol) + 2 mol (32.1 J/Kmol)] = 168.0 J/K
Gf = H TS = 116.7 kJ (298 K)(168.0 J/K)(1 kJ/103 J) = 66.6 kJ
Appendix L value 66.61 kJ
(b) Na(s) + 1/2 O2(g) + 1/2 H2(g) NaOH(s)
H = Hf[NaOH(s)] = 1 mol (425.93 kJ/mol) = 425.93 kJ
S = S[NaOH(s)] {S[Na(s)] + 1/2 S[O2(g)] + 1/2 S[H2(g)]}
S = 1 mol (64.46 J/Kmol) [1 mol (51.21 J/Kmol) + 1/2 mol (205.087 J/Kmol)
+ 1/2 mol (130.7 J/Kmol)]
S = 154.6 J/K
Gf = H TS = 425.93 kJ (298 K)(154.6 J/K)(1 kJ/103 J) = 379.9 kJ
Appendix L value 379.75 kJ
(c)

/2 I2(s) + 1/2 Cl2(g) ICl(g)

H = Hf[ICl(g)] = 1 mol (17.51 kJ/mol) = 17.51 kJ

S = S[ICl(g)] {1/2 S[I2(s)] + 1/2 S[Cl2(g)]}
S = 1 mol (247.56 J/Kmol) [1/2 mol (116.135 J/Kmol) + 1/2 mol (223.08 J/Kmol)] = 77.95 J/K
Gf = H TS = 17.51 kJ (298 K)(77.95 J/K)(1 kJ/103 J) = 5.72 kJ
Appendix L value 5.73 kJ
Reactions (b) and (c) are product-favored.

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Chapter 19

19.24

Principles of Reactivity: Entropy and Free Energy

(a) Ca(s) + O2(g) + H2(g) Ca(OH)2(s)

H = Hf[Ca(OH)2(s)] = 1 mol (986.09 kJ/mol) = 986.09 kJ
S = S[Ca(OH)2(s)] {S[Ca(s)] + S[O2(g)] + S[H2(g)]}
S = 1 mol (83.39 J/Kmol) [1 mol (41.59 J/Kmol) + 1 mol (205.07 J/Kmol) + 1 mol (130.7
J/Kmol)]
S = 294.0 J/K
Gf = H TS = 986.09 kJ (298 K)(294.0 J/K)(1 kJ/103 J) = 898.5 kJ
Appendix L value 898.43 kJ
(b) 1/2 Cl2(g) Cl(g)
H = Hf[Cl(g)] = 1 mol (121.3 kJ/mol) = 121.3 kJ
S = S[Cl(g)] 1/2 S[Cl2(g)]
S = 1 mol (165.19 J/Kmol) 1/2 mol (223.08 J/Kmol) = 53.65 J/K
Gf = H TS = 121.3 kJ (298 K)(53.65 J/K)(1 kJ/103 J) = 105.3 kJ
Appendix L value 105.3 kJ
(c) 2 Na(s) + C(graphite) + 3/2 O2(g) Na2CO3(s)
H = Hf[Na2CO3(s)] = 1 mol (1130.77 kJ/mol) = 1130.77 kJ
S = S[Na2CO3(s)] {2 S[Na(s)] + S[C(graphite)]+ 3/2 S[O2(g)]}
S = 1 mol (134.79 J/Kmol) [2 mol (51.21 J/Kmol) + 1 mol (5.6 J/Kmol)
+ 3/2 mol (205.07 J/Kmol)]
S = 280.84 J/K
Gf = H TS = 1130.77 kJ (298 K)(280.84 J/K)(1 kJ/103 J) = 1047.08 kJ
Appendix L value 1048.08 kJ
Reactions (a) and (c) are product-favored.

19.25

(a) Grxn = 2 Gf[KCl(s)] = 2 mol (408.77 kJ/mol) = 817.54 kJ

product-favored
(b) Grxn = (2 Gf[CuO(s)]) = [2 mol (128.3 kJ/mol)] = 256.6 kJ
reactant-favored
(c) Grxn = 4 Gf[NO2(g)] + 6 Gf[H2O(g)] 4 Gf[NH3(g)]
Grxn = 4 mol (51.23 kJ/mol) + 6 mol (228.59 kJ/mol) 4 mol (16.37 kJ/mol) = 1101.14 kJ
product-favored

19.27

Grxn = Gf[BaO(s)] + Gf[CO2(g)] Gf[BaCO3(s)]

219.7 kJ = 1 mol (520.38 kJ/mol) + 1 mol (394.359 kJ/mol) 1 mol Gf[BaCO3(s)]
Gf[BaCO3(s)] = 1134.4 kJ/mol

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Chapter 19

19.29

Principles of Reactivity: Entropy and Free Energy

(a) S = 2 S[NO2(g)] {S[N2(g)] + 2 S[O2(g)]}

S = 2 mol (240.04 J/Kmol) [1 mol (191.56 J/Kmol) + 2 mol (205.07 J/Kmol)] = 121.62 J/K
Entropy-disfavored. Increasing the temperature will make the reaction more reactant-favored
(b) S = 2 S[CO(g)] {2 S[C(graphite)] + S[O2(g)]}
S = 2 mol (197.674 J/Kmol) [2 mol (5.6 J/Kmol) + 1 mol (205.07 J/Kmol)] = 179.1 J/K
Entropy-favored. Increasing the temperature will make the reaction more product-favored
(c) S = S[CaCO3(s)] {S[CaO(s)] + S[CO2(g)]}
S = 1 mol (91.7 J/Kmol) [1 mol (38.2 J/Kmol) + 1 mol (213.74 J/Kmol)] = 160.2 J/K
Entropy-disfavored. Increasing the temperature will make the reaction more reactant-favored
(d) S = 2 S[Na(s)] + S[Cl2(g)] 2 S[NaCl(s)]
S = 2 mol (51.21 J/Kmol) + 1 mol (223.08 J/Kmol) 2 mol (72.11 J/Kmol) = 181.28 J/K
Entropy-favored. Increasing the temperature will make the reaction more product-favored

19.31

HgS(s) Hg() + S(g)

H = Hf[S(g)] Hf[HgS(s)] = 1 mol (278.98 kJ/mol) 1 mol (58.2 kJ/mol) = 337.2 kJ
S = S[Hg()] + S[S(g)] S[HgS(s)]
S = 1 mol (76.02 J/Kmol) + 1 mol (167.83 J/Kmol) 1 mol (82.4 J/Kmol) = 161.5 J/K
G = 0 = H TS = 337.2 kJ T(161.5 J/K)(1 kJ/103 J)
T = 2088 K or greater

19.74

(a) The entropy of the universe increases in all product-favored reactions.

(b) Product-favored reactions can occur at any rate, not necessarily a fast rate.
(c) While many spontaneous processes are exothermic, endothermic processes can be spontaneous at high
temperatures.
(d) Endothermic processes can be spontaneous at high temperatures.

19.76

The entropy of a pure crystal is zero at 0 K. A substance cannot have S = 0 J/Kmol at standard conditions
(25 C, 1 bar). All substances have positive entropy values at temperatures above 0 K. Based on the third
law of thermodynamics, negative values of entropy cannot occur. The only exception to this is the entropy
of the solvation process. When water molecules are constrained to a more ordered arrangement in a
solution than in pure water, a higher degree of order results and entropy is negative.

19.81

In a solid the particles have fixed positions in the solid lattice. When a solid is dissolved in water the ions
are dispersed throughout the solution.

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Chapter 19

19.82

358

Principles of Reactivity: Entropy and Free Energy

(a) +

(b)

(c)

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