CHAPTER 17

ENTROPY, GIBBS ENERGY,

AND EQUILIBRIUM
Problem Categories
Biological: 17.83, 17.99, 17.107, 17.115.
Conceptual: 17.9, 17.10, 17.13, 17.14, 17.32, 17.37, 17.40, 17.42, 17.43, 17.44, 17.45, 17.46, 17.49, 17.55, 17.57,
17.58, 17.61, 17.62, 17.65, 17.69, 17.70, 17.75, 17.85, 17.86, 17.89, 17.91, 17.95, 17.101, 17.102, 17.103, 17.105.
Descriptive: 17.36, 17.50a,b, 17.72.
Environmental: 17.50, 17.71, 17.80.
Industrial: 17.56, 17.66, 17.78, 17.82, 17.92.
Organic: 17.87, 17.88.

17.5 (a) increases (b) decreases (c) increases (d) decreases (e) decreases (f) increases
(g) increases

17.6 The probability (P) of finding all the molecules in the same flask becomes progressively smaller as the
number of molecules increases. An equation that relates the probability to the number of molecules is given
by:
 1 N
P   
 2 

where, N is the total number of molecules present.

Using the above equation, we find:
31
(a) P  0.25 (b) P  8  10 (c) P»0

Extending the calculation to a macroscopic system would result in such a small number for the probability
(similar to the calculation with Avogadro’s number above) that for all practical purposes, there is zero
probability that all molecules would be found in the same bulb.

17.9 (a) This is easy. Li(l). The liquid form of any substance always has greater entropy (more microstates).

(b) This is hard. At first glance there may seem to be no apparent difference between the two substances
that might affect the entropy (molecular formulas identical). However, the first has the OH
structural feature which allows it to participate in hydrogen bonding with other molecules. This allows a
more ordered arrangement of molecules in the liquid state. The standard entropy of CH3OCH3 is larger.

(c) This is also difficult. Both are monatomic species. However, the Xe atom has a greater molar mass than
Ar. Xenon has the higher standard entropy.

(d) Same argument as part (c). Carbon dioxide gas has the higher standard entropy (see Appendix 3).

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734 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

(e) O3 has a greater molar mass than O2 and thus has the higher standard entropy.
(f) Using the same argument as part (c), one mole of N2O4 has a larger standard entropy than one mole of
NO2. Compare values in Appendix 3.

Use the data in Appendix 3 to compare the standard entropy of one mole of N2O4 with that of two moles
of NO2. In this situation the number of atoms is the same for both. Which is higher and why?

17.10 In order of increasing entropy per mole at 25°C:

(c) < (d) < (e) < (a) < (b)

(c) Na(s): ordered, crystalline material.

(d) NaCl(s): ordered crystalline material, but with more particles per mole than Na(s).
(e) H2: a diatomic gas, hence of higher entropy than a solid.
(a) Ne(g): a monatomic gas of higher molar mass than H2.
(b) SO2(g): a polyatomic gas of higher molar mass than Ne.

ο
17.11 Using Equation (17.7) of the text to calculate Srxn

ο
(a) Srxn  S °(SO2 )  [S °(O2 )  S °(S)]

ο
Srxn  (1)(248.5 J/K  mol)  (1)(205.0 J/K  mol)  (1)(31.88 J/K  mol)  11.6 J / K  mol

ο
(b) Srxn  S °(MgO)  S °(CO2 )  S °(MgCO3 )

ο
Srxn  (1)(26.78 J/K  mol)  (1)(213.6 J/K  mol)  (1)(65.69 J/K  mol)  174.7 J / K  mol

17.12 Strategy: To calculate the standard entropy change of a reaction, we look up the standard entropies of
reactants and products in Appendix 3 of the text and apply Equation (17.7). As in the calculation of enthalpy
ο
of reaction, the stoichiometric coefficients have no units, so Srxn is expressed in units of J/Kmol.

Solution: The standard entropy change for a reaction can be calculated using the following equation.

ο
Srxn  nS °(products) mS °(reactants)

ο
(a) Srxn  S °(Cu)  S °(H 2 O)  [S °(H 2 )  S °(CuO)]

 (1)(33.3 J/Kmol)  (1)(188.7 J/Kmol)  [(1)(131.0 J/Kmol)  (1)(43.5 J/Kmol)]

 47.5 J/Kmol

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 735

ο
(b) Srxn  S °(Al2 O3 )  3S °(Zn)  [2 S °(Al)  3S °(ZnO)]

 (1)(50.99 J/Kmol)  (3)(41.6 J/Kmol)  [(2)(28.3 J/Kmol)  (3)(43.9 J/Kmol)]

 12.5 J/Kmol

ο
(c) Srxn  S °(CO2 )  2 S °(H 2 O)  [S °(CH 4 )  2 S °(O2 )]

 (1)(213.6 J/Kmol)  (2)(69.9 J/Kmol)  [(1)(186.2 J/Kmol)  (2)(205.0 J/Kmol)]

 242.8 J/Kmol

Why was the entropy value for water different in parts (a) and (c)?

17.13 All parts of this problem rest on two principles. First, the entropy of a solid is always less than the entropy of
a liquid, and the entropy of a liquid is always much smaller than the entropy of a gas. Second, in comparing
systems in the same phase, the one with the most complex particles has the higher entropy.

(a) Positive entropy change (increase). One of the products is in the gas phase (more microstates).

(b) Negative entropy change (decrease). Liquids have lower entropies than gases.

(c) Positive. Same as (a).

(d) Positive. There are two gas-phase species on the product side and only one on the reactant side.

17.14 (a) S < 0; gas reacting with a liquid to form a solid (decrease in number of moles of gas, hence a
decrease in microstates).

(b) S > 0; solid decomposing to give a liquid and a gas (an increase in microstates).

(c) S > 0; increase in number of moles of gas (an increase in microstates).

(d) S < 0; gas reacting with a solid to form a solid (decrease in number of moles of gas, hence a decrease
in microstates).

17.17 Using Equation (17.12) of the text to solve for the change in standard Gibbs energy,

(a) ΔG°  2Gfο (NO) Gfο (N 2 ) Gfο (O2 )  (2)(86.7 kJ/mol)  0  0  173.4 kJ /mol

(b) ΔG°  Gfο [H 2 O( g)] Gfο [H 2 O(l )]  (1)(228.6 kJ/mol)  (1)(237.2 kJ/mol)  8.6 kJ /mol

(c) ΔG°  4Gfο (CO2 )  2Gfο (H 2 O)  2Gfο (C2 H 2 )  5Gfο (O2 )

 (4)(394.4 kJ/mol)  (2)(237.2 kJ/mol)  (2)(209.2 kJ/mol)  (5)(0)  2470 kJ/mol

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736 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

17.18 Strategy: To calculate the standard Gibbs-energy change of a reaction, we look up the standard Gibbs
energies of formation of reactants and products in Appendix 3 of the text and apply Equation (17.12). Note
ο
that all the stoichiometric coefficients have no units so Grxn is expressed in units of kJ/mol. The standard
Gibbs energy of formation of any element in its stable allotropic form at 1 atm and 25°C is zero.

Solution: The standard Gibbs energy change for a reaction can be calculated using the following equation.

ο
Grxn  nGfο (products) mGfο (reactants)

ο
(a) Grxn  2Gfο (MgO)  [2Gfο (Mg)  Gfο (O2 )]

ο
Grxn  (2)(569.6 kJ/mol)  [(2)(0)  (1)(0)]  1139 kJ /mol

ο
(b) Grxn  2Gfο (SO3 )  [2Gfο (SO2 )  Gfο (O2 )]

ο
Grxn  (2)(370.4 kJ/mol)  [(2)(300.4 kJ/mol)  (1)(0)]  140.0 kJ /mol

o
(c) Grxn  4Gfo [CO2 ( g)]  6Gfo [H 2 O(l )] {2Gfo [C2 H6 ( g)]  7Gfo [O2 ( g)]}

ο
Grxn  (4)(394.4 kJ/mol)  (6)(237.2 kJ/mol)  [(2)(32.89 kJ/mol)  (7)(0)]  2935.0 kJ /mol

17.19 Reaction A: First apply Equation (17.10) of the text to compute the Gibbs energy change at 25°C (298 K)

G  H  TS  10,500 J/mol  (298 K)(30 J/Kmol)  1560 J/mol

The 1560 J/mol shows the reaction is not spontaneous at 298 K. The G will change sign (i.e., the reaction
will become spontaneous) above the temperature at which G  0.

H 10500 J/mol
T   350 K
S 30 J/K  mol

Reaction B: Calculate G.

G  H  TS  1800 J/mol  (298 K)(113 J/Kmol)  35,500 J/mol

The Gibbs energy change is positive, which shows that the reaction is not spontaneous at 298 K. Since both
terms are positive, there is no temperature at which their sum is negative. The reaction is not spontaneous at
any temperature.

17.20 Reaction A: Calculate G from H and S.

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 737

G  H  TS  126,000 J/mol  (298 K)(84 J/Kmol)  151,000 J/mol

The Gibbs energy change is negative so the reaction is spontaneous at 298 K. Since H is negative and S is
positive, the reaction is spontaneous at all temperatures.

Reaction B: Calculate G.

G  H  TS  11,700 J/mol  (298 K)(105 J/Kmol)  19,600 J

The Gibbs energy change is positive at 298 K which means the reaction is not spontaneous at that
temperature. The positive sign of G results from the large negative value of S. At lower temperatures, the
TS term will be smaller thus allowing the Gibbs energy change to be negative.

G will equal zero when H  TS.

Rearranging,

H 11700 J/mol
T   111 K
S 105 J/K  mol

At temperatures below 111 K, G will be negative and the reaction will be spontaneous.

17.23 Find the value of K by solving Equation (17.14) of the text.

G ο 2.60103 J/mol

Kp  e RT  e (8.314 J/Kmol)(298 K)  e1.05  0.35

17.24 Strategy: According to Equation (17.14) of the text, the equilibrium constant for the reaction is related to
the standard Gibbs energy change; that is, G°  RT ln K. Since we are given the equilibrium constant in
the problem, we can solve for G°. What temperature unit should be used?

Solution: The equilibrium constant is related to the standard Gibbs energy change by the following
equation.

G°  RT ln K

Substitute Kw, R, and T into the above equation to calculate the standard Gibbs energy change, G°. The
14
temperature at which Kw  1.0  10 is 25°C  298 K.

G°  RT ln Kw
14 4 1
G°  (8.314 J/molK)(298 K) ln (1.0  10 )  8.0  10 J/mol  8.0  10 kJ/mol

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738 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

2  2 14
17.25 Ksp  [Fe ][OH ]  1.6  10

14 4
G°  RT ln Ksp  (8.314 J/Kmol)(298 K)ln (1.6  10 )  7.9  10 J/mol  79 kJ/mol

17.26 Use standard Gibbs energies of formation from Appendix 3 to find the standard Gibbs energy difference.

ο
Grxn  2Gfο [H 2 ( g)]  Gfο [O2 ( g)]  2Gfο [H 2 O( g)]

ο
Grxn  (2)(0)  (1)(0)  (2)(228.6 kJ/mol)

ο
Grxn  457.2 kJ /mol  4.572 105 J /mol

We can calculate KP using the following equation. We carry additional significant figures in the calculation to
minimize rounding errors when calculating KP.

G°  RT ln KP
5
4.572  10 J/mol  (8.314 J/molK)(298 K) ln KP

184.54  ln KP

Taking the antiln of both sides,

184.54
e  KP

81
KP  7.2  10

17.27 (a) We first find the standard Gibbs energy change of the reaction.

o
Grxn  Gfo [PCl3 ( g)]  Gfo [Cl2 ( g)] Gfo [PCl5 ( g)]

 (1)(286 kJ/mol)  (1)(0)  (1)(325 kJ/mol)  39 kJ/mol

We can calculate KP using Equation (17.14) of the text.

G ο 39103 J/mol

KP  e RT  e (8.314 J/Kmol)(298 K)  e16  1107

(b) We are finding the Gibbs energy difference between the reactants and the products at their
nonequilibrium values. The result tells us the direction of and the potential for further chemical change.
We use the given nonequilibrium pressures to compute QP.

PPCl PCl (0.27)(0.40)

QP  3 2
  37
PPCl 0.0029
5

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 739

The value of G (notice that this is not the standard Gibbs energy difference) can be found using
Equation (17.13) of the text and the result from part (a).
3
G  G°  RT ln Q  (39  10 J/mol)  (8.314 J/Kmol)(298 K)ln (37)  48 kJ/mol

Which way is the direction of spontaneous change for this system? What would be the value of G if
the given data were equilibrium pressures? What would be the value of QP in that case?

17.28 (a) The equilibrium constant is related to the standard Gibbs energy change by the following equation.

G°  RT ln K

Substitute KP, R, and T into the above equation to the standard Gibbs energy change, G°.

G°  RT ln KP
4
G°  (8.314 J/molK)(2000 K) ln (4.40)  2.464  10 J/mol  24.6 kJ/mol

(b)
Strategy: From the information given we see that neither the reactants nor products are at their standard
state of 1 atm. We use Equation (17.13) of the text to calculate the Gibbs-energy change under non-standard-
state conditions. Note that the partial pressures are expressed as dimensionless quantities in the reaction
quotient QP.

Solution: Under non-standard-state conditions, G is related to the reaction quotient Q by the following
equation.
G  G°  RT ln QP

We are using QP in the equation because this is a gas-phase reaction.

Step 1: G° was calculated in part (a). We must calculate QP. We carry additional significant figures in this
calculation to minimize rounding errors.

PH  PCO (0.66)(1.20)
2O
QP    4.062
PH  PCO (0.25)(0.78)
2 2

4
Step 2: Substitute G°  2.46  10 J/mol and QP into the following equation to calculate G.

G  G°  RT ln QP
4
G  2.464  10 J/mol  (8.314 J/molK)(2000 K) ln (4.062)
4 4
G  (2.464  10 J/mol)  (2.331  10 J/mol)
3
G  1.33  10 J/mol  1.33 kJ/mol

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740 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

17.29 The expression of KP is: K P  PCO

2

Thus you can predict the equilibrium pressure directly from the value of the equilibrium constant. The only
task at hand is computing the values of KP using Equations (17.10) and (17.14) of the text.

3 3
(a) At 25°C, G°  H°  TS°  (177.8  10 J/mol)  (298 K)(160.5 J/Kmol)  130.0  10 J/mol

G o 130.0103 J/mol

PCO  K P  e RT e (8.314 J/Kmol)(298 K)  e52.47  1.61023 atm
2

3 3
(b) At 800°C, G°  H°  TS°  (177.8  10 J/mol)  (1073 K)(160.5 J/Kmol)  5.58  10 J/mol

G ο 5.58103 J/mol

PCO  K P  e RT e (8.314 J/Kmol)(1073 K)  e0.625  0.535 atm
2

What assumptions are made in the second calculation?

17.30 We use the given KP to find the standard Gibbs energy change.

G°  RT ln K
35 5
G°  (8.314 J/Kmol)(298 K) ln (5.62  10 )  2.04  10 J/mol  204 kJ/mol

The standard Gibbs energy of formation of one mole of COCl2 can now be found using the standard Gibbs
energy of reaction calculated above and the standard Gibbs energies of formation of CO(g) and Cl2(g).

ο
Grxn  nGfο (products) mGfο (reactants)

ο
Grxn  Gfο [COCl2 ( g)] {Gfο [CO( g)]  Gfο [Cl2 ( g)]}

204 kJ/mol  (1)Gfο [COCl2 ( g)]  [(1)(137.3 kJ/mol)  (1)(0)]

Gfο [COCl 2 ( g)]  341 kJ /mol

17.31 The equilibrium constant expression is: K P  PH O

2

We are actually finding the equilibrium vapor pressure of water (compare to Problem 17.29). We use
Equation (17.14) of the text.
G  8.6103 J/mol
PH  KP  e RT  e (8.314 J/Kmol)(298 K)  e3.47  3.1102 atm
2O

The positive value of G° implies that reactants are favored at equilibrium at 25°C. Is that what you would
expect?

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 741

17.32 The standard Gibbs energy change is given by:

ο
Grxn  Gfο (graphite) Gfο (diamond)

You can look up the standard Gibbs energy of formation values in Appendix 3 of the text.

ο
Grxn  (1)(0)  (1)(2.87 kJ/mol)  2.87 kJ /mol

Thus, the formation of graphite from diamond is favored under standard-state conditions at 25°C. However,
the rate of the diamond to graphite conversion is very slow (due to a high activation energy) so that it will
take millions of years before the process is complete.

17.35 C6H12O6  6O2 ® 6CO2  6H2O G°  2880 kJ/mol

ADP  H3PO4 ® ATP  H2O G°  31 kJ/mol

Maximum number of ATP molecules synthesized:

1 ATP molecule
2880 kJ/mol   93 ATP molecules
31 kJ / mol

17.36 The equation for the coupled reaction is:

glucose  ATP ® glucose 6phosphate  ADP

G°  13.4 kJ/mol  31 kJ/mol  18 kJ/mol

As an estimate:
G ο
ln K 
RT

(18103 J/mol)
ln K   7.3
(8.314 J/K  mol)(298 K)
3
K  1  10

17.37 When Humpty broke into pieces, he became more disordered (spontaneously). The king was unable to
reconstruct Humpty.

17.38 In each part of this problem we can use the following equation to calculate G.

G  G°  RT ln Q
or,
 
G  G°  RT ln [H ][OH ]

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742 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

(a) In this case, the given concentrations are equilibrium concentrations at 25°C. Since the reaction is at
equilibrium, G  0. This is advantageous, because it allows us to calculate G°. Also recall that at
equilibrium, Q  K. We can write:

G°  RT ln Kw

14 4
G°  (8.314 J/Kmol)(298 K) ln (1.0  10 )  8.0  10 J/mol

 
(b) G  G°  RT ln Q  G°  RT ln [H ][OH ]

4 3 4 4
G  (8.0  10 J/mol)  (8.314 J/Kmol)(298 K) ln [(1.0  10 )(1.0  10 )]  4.0  10 J/mol

 
(c) G  G°  RT ln Q  G°  RT ln [H ][OH ]

4 12 8 4
G  (8.0  10 J/mol)  (8.314 J/Kmol)(298 K) ln [(1.0  10 )(2.0  10 )]  3.2  10 J/mol

 
(d) G  G°  RT ln Q  G°  RT ln [H ][OH ]

4 4 4
G  (8.0  10 J/mol)  (8.314 J/Kmol)(298 K) ln [(3.5)(4.8  10 )]  6.4  10 J/mol

ο
17.39 We use Equation (17.7) of the text to calculate Ssoln.

ο
(a) Ssoln  [S °(NH 
4 )  S °(NO3 )]  S °(NH 4 NO3 )

ο
Ssoln  [(1)(112.8 J/K  mol)  (1)(146.4 J/K  mol)]  (1)(151 J/K  mol)  108 J/Kmol

ο
(b) Ssoln  [S °(Fe3 )  3S °(Cl )]  S °(FeCl3 )

ο
Ssoln  [(1)(293.3 J/K  mol)  (3)(56.5 J/K  mol)]  (1)(142.3 J/K  mol)  266.1 J/Kmol

Usually, the solution process leads to an increase in entropy, as in part (a). However, we must also consider
3
hydration. For small, highly charged ions such as Fe , the decrease in entropy due to hydration outweighs
the increase in entropy due to mixing and dissociation. The overall entropy change is negative.

17.40 Because the entropy of the system decreases, the entropy of the surroundings must increase for the reaction to
be spontaneous. Ssurr is positive.

17.41 Only E and H are associated with the first law alone.

17.42 One possible explanation is simply that no reaction is possible, namely that there is an unfavorable Gibbs
energy difference between products and reactants (G  0).

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 743

A second possibility is that the potential for spontaneous change is there (G < 0), but that the reaction is
extremely slow (very large activation energy).

A remote third choice is that the student accidentally prepared a mixture in which the components were
already at their equilibrium concentrations.

Which of the above situations would be altered by the addition of a catalyst?

17.43 We can use data in Appendix 3 of the text to calculate the standard Gibbs energy change for the reaction.
Then, we can use Equation (17.14) of the text to calculate the equilibrium constant, K.

 
AgI(s) ® Ag (aq)  I (aq)

G ο  Gfο (Ag )  Gfο (I ) Gfο (AgI)

G°  (1)(77.1 kJ/mol)  (1)(51.67 kJ/mol)  (1)(66.3 kJ/mol)  91.73 kJ/mol

G°  RT ln K

91.73103 J/mol
ln K    37.024
(8.314 J/K  mol)(298 K)

17
K  8.3  10

This value of K matches the Ksp value in Table 16.2 of the text.

17.44 For a solid to liquid phase transition (melting) the entropy always increases (S  0) and the reaction is
always endothermic (H  0).

(a) Melting is always spontaneous above the melting point, so G < 0.

(b) At the melting point (77.7°C), solid and liquid are in equilibrium, so G  0.

(c) Melting is not spontaneous below the melting point, so G  0.

17.45 For a reaction to be spontaneous, G must be negative. If S is negative, as it is in this case, then the
reaction must be exothermic (why?). When water Gibbszes, it gives off heat (exothermic). Consequently, the
entropy of the surroundings increases and Suniverse  0.

17.46 If the process is spontaneous as well as endothermic, the signs of G and H must be negative and positive,
respectively. Since G  H  TS, the sign of S must be positive (S > 0) for G to be negative.

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744 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

17.47 The equation is: BaCO3(s)  BaO(s)  CO2(g)

G°  Gfο (BaO)  Gfο (CO2 ) Gfο (BaCO3 )

G°  (1)(528.4 kJ/mol)  (1)(394.4 kJ/mol)  (1)(1138.9 kJ/mol)  216.1 kJ/mol

G°  RT ln KP

2.16 105 J/mol

ln K P   87.2
(8.314 J/K  mol)(298 K)

K P  PCO  e87.2  11038 atm

2

17.48 (a) Using the relationship:

H vap
 Svap  90 J/K  mol
Tb.p.

benzene Svap  87.8 J/Kmol

hexane Svap  90.1 J/Kmol

mercury Svap  93.7 J/Kmol

toluene Svap  91.8 J/Kmol

Most liquids have Svap approximately equal to a constant value because the order of the molecules in
the liquid state is similar. The order of most gases is totally random; thus, S for liquid ® vapor should
be similar for most liquids.

(b) Using the data in Table 11.6 of the text, we find:

ethanol Svap  111.9 J/Kmol

water Svap  109.4 J/Kmol

Both water and ethanol have a larger Svap because the liquid molecules are more ordered due to
hydrogen bonding (there are fewer microstates in these liquids).

17.49 Evidence shows that HF, which is strongly hydrogen-bonded in the liquid phase, is still considerably
hydrogen-bonded in the vapor state such that its Svap is smaller than most other substances.

17.50 (a) 2CO  2NO ® 2CO2  N2

(b) The oxidizing agent is NO; the reducing agent is CO.

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 745

(c) G°  2Gfο (CO2 )  Gfο (N 2 )  2Gfο (CO)  2Gfο (NO)

G°  (2)(394.4 kJ/mol)  (0)  (2)(137.3 kJ/mol)  (2)(86.7 kJ/mol)  687.6 kJ/mol

G°  RT ln KP

6.876 105 J/mol

ln K P   277.5
(8.314 J/K  mol)(298 K)
120
KP  3  10

2
PN PCO (0.80)(0.030)2
 1.2 1018
2
(d) QP  2

2 2 5 2 7 2
PCO PNO (5.0 10 ) (5.0 10 )

Since QP << KP, the reaction will proceed from left to right.

(e) H °  2Hfο (CO2 )  Hfο (N 2 )  2Hfο (CO)  2Hfο (NO)

H°  (2)(393.5 kJ/mol)  (0)  (2)(110.5 kJ/mol)  (2)(90.4 kJ/mol)  746.8 kJ/mol

Since H° is negative, raising the temperature will decrease KP, thereby increasing the amount of
reactants and decreasing the amount of products. No, the formation of N2 and CO2 is not favored by
raising the temperature.

17.51 (a) At two different temperatures T1 and T2,

G1ο  H ο  T1S ο  RT ln K1 (1)

G2ο  H ο  T2 S ο  RT ln K2 (2)

Rearranging Equations (1) and (2),

H ο S ο
ln K1   (3)
RT1 R

H ο S ο
ln K2   (4)
RT2 R

Subtracting equation (3) from equation (4) gives,

 H ο S ο   H ο S ο 
    
ln K2  ln K1     
 RT2 R   RT1 R 

K2 H ο  1 1
ln    
K1 R  T1 T2 

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746 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

K2 H ο  T2  T1 
ln   
K1 R  T1T2 
(b) Using the equation that we just derived, we can calculate the equilibrium constant at 65°C.

3
K1  4.63  10 T1  298 K

K2  ? T2  338 K

K2 58.0 103 J/mol  338 K  298 K 

ln   
4.63103 8.314 J/K  mol  (338 K)(298 K) 

K2
ln  2.77
4.63103

Taking the antiln of both sides of the equation,

K2
 e2.77
3
4.6310

K2  0.074

K2  K1, as we would predict for a positive H°. Recall that an increase in temperature will shift the
equilibrium towards the endothermic reaction; that is, the decomposition of N2O4.

17.52 We can use data in Appendix 3 of the text to calculate the standard Gibbs energy change for the reaction.
Then, we can use Equation (17.14) of the text to calculate the equilibrium constant, Ksp.

 
AgCl(s) ® Ag (aq)  Cl (aq)

G°  Gfο (Ag )  Gfο (Cl ) Gfο (AgCl)

G°  [(1)(77.1 kJ/mol)  (1)(131.2 kJ/mol)]  (1)(109.7 kJ/mol)  55.6 kJ/mol

G°  RT ln Ksp

55.6 103 J/mol

ln Ksp    22.4
(8.314 J/K  mol)(298 K)

10
Ksp  2  10

This value of Ksp matches the Ksp value in Table 16.2 of the text.

17.53 First, we can calculate the equilibrium constant from the forward and reverse rate constants. Then, Gº can
be calculated from the equilibrium constant.

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 747

kf 0.46
K   31
kr1.5102
G°  RT ln K

G°  (8.314 J/Kmol)(298 K)ln (31)

3
G°  8.5  10 J/mol  8.5 kJ/mol

17.54 The equilibrium reaction is:

 
AgCl(s)  Ag (aq)  Cl (aq)

  10
Ksp  [Ag ][Cl ]  1.6  10

We can calculate the standard enthalpy of reaction from the standard enthalpies of formation in Appendix 3
of the text.
H °  Hfο (Ag )  Hfο (Cl ) Hfο (AgCl)

H°  (1)(105.9 kJ/mol)  (1)(167.2 kJ/mol)  (1)(127.0 kJ/mol)  65.7 kJ/mol

From Problem 17.51(a):

K2 H °  T2  T1 
ln   
K1 R  T1T2 

10
K1  1.6  10 T1  298 K

K2  ? T2  333 K

K2 6.5710 4 J  333 K  298 K 

ln   
1.6 1010 8.314 J/K  mol  (333 K)(298 K) 

K2
ln  2.79
1.6 1010
K2
 e2.79
10
1.6 10
9
K2  2.6  10

The increase in K indicates that the solubility increases with temperature.

17.55 At absolute zero. A substance can never have a negative entropy.

17.56 Assuming that both H° and S° are temperature independent, we can calculate both H° and S°.

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748 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

H °  Hfο (CO)  Hfο (H 2 )  [Hfο (H 2 O)  Hfο (C)]

H°  (1)(110.5 kJ/mol)  (1)(0)]  [(1)(241.8 kJ/mol)  (1)(0)]

H°  131.3 kJ/mol

S°  S°(CO)  S°(H2)  [S°(H2O)  S°(C)]

S°  [(1)(197.9 J/Kmol)  (1)(131.0 J/Kmol)]  [(1)(188.7 J/Kmol)  (1)(5.69 J/Kmol)]

S°  134.5 J/Kmol

It is obvious from the given conditions that the reaction must take place at a fairly high temperature (in order
to have redhot coke). Setting G°  0

0  H°  TS°

1000 J
131.3 kJ/mol 
H ° 1 kJ  976 K  703°C
T 
S ° 134.5 J/K  mol

The temperature must be greater than 703°C for the reaction to be spontaneous.

17.57 (a) We know that HCl is a strong acid and HF is a weak acid. Thus, the equilibrium constant will be less
than 1 (K < 1).

(b) The number of particles on each side of the equation is the same, so S°  0. Therefore H° will
dominate.

(c) HCl is a weaker bond than HF (see Table 9.4 of the text), therefore H° > 0.

17.58 For a reaction to be spontaneous at constant temperature and pressure, G < 0. The process of crystallization
proceeds with more order (less disorder), so S < 0. We also know that

G  H  TS

Since G must be negative, and since the entropy term will be positive (TS, where S is negative), then
H must be negative (H < 0). The reaction will be exothermic.

17.59 For the reaction: CaCO3(s)  CaO(s)  CO2(g) K p  PCO

2

Using the equation from Problem 17.51:

K H ο  1 1  H ο  T2  T1 
ln 2       
K1 R  T1 T2  R  T1T2 

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 749

Substituting,
1829 H ο  1223 K  973 K 
 
ln  
22.6 8.314 J/K  mol  (973 K)(1223 K) 

Solving,
5
H°  1.74  10 J/mol  174 kJ/mol

17.60 For the reaction to be spontaneous, G must be negative.

G  H  TS

Given that H  19 kJ/mol  19,000 J/mol, then

G  19,000 J/mol  (273 K  72 K)(S)

Solving the equation with the value of G  0

0  19,000 J/mol  (273 K  72 K)(S)

S  55 J/Kmol

This value of S which we solved for is the value needed to produce a G value of zero. The minimum value
of S that will produce a spontaneous reaction will be any value of entropy greater than 55 J/Kmol.

17.61 (a) S  0 (b) S < 0 (c) S  0 (d) S  0

17.62 The second law states that the entropy of the universe must increase in a spontaneous process. But the
entropy of the universe is the sum of two terms: the entropy of the system plus the entropy of the
surroundings. One of the entropies can decrease, but not both. In this case, the decrease in system entropy is
offset by an increase in the entropy of the surroundings. The reaction in question is exothermic, and the heat
released raises the temperature (and the entropy) of the surroundings.

Could this process be spontaneous if the reaction were endothermic?

17.63 At the temperature of the normal boiling point the Gibbs energy difference between the liquid and gaseous
forms of mercury (or any other substances) is zero, i.e. the two phases are in equilibrium. We can therefore
use Equation (17.10) of the text to find this temperature. For the equilibrium,

Hg(l)  Hg(g)

G  H  TS  0

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750 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

H  H fο [Hg( g)] H fο [Hg(l )]  60, 780 J/mol  0  60780 J/mol

S  S°[Hg(g)]  S°[Hg(l)]  174.7 J/Kmol  77.4 J/Kmol  97.3 J/Kmol

H 60780 J/mol
Tbp    625 K  352°C
S 97.3 J/K  mol

What assumptions are made? Notice that the given enthalpies and entropies are at standard conditions,
namely 25°C and 1.00 atm pressure. In performing this calculation we have tacitly assumed that these
quantities don’t depend upon temperature. The actual normal boiling point of mercury is 356.58°C. Is the
assumption of the temperature independence of these quantities reasonable?

17.64 Strategy: At the boiling point, liquid and gas phase ethanol are at equilibrium, so G  0. From Equation
(17.10) of the text, we have G  0  H TS or S  H/T. To calculate the entropy change for the
liquid ethanol ® gas ethanol transition, we write Svap  Hvap/T. What temperature unit should we use?

Solution: The entropy change due to the phase transition (the vaporization of ethanol), can be calculated
using the following equation. Recall that the temperature must be in units of Kelvin (78.3°C  351 K).

H vap
Svap 
Tb.p.

39.3 kJ/mol
Svap   0.112 kJ/mol  K  112 J/mol  K
351 K

The problem asks for the change in entropy for the vaporization of 0.50 moles of ethanol. The S calculated
above is for 1 mole of ethanol.

S for 0.50 mol  (112 J/molK)(0.50 mol)  56 J/K

17.65 There is no connection between the spontaneity of a reaction predicted by G and the rate at which the
reaction occurs. A negative Gibbs energy change tells us that a reaction has the potential to happen, but gives
no indication of the rate.

Does the fact that a reaction occurs at a measurable rate mean that the Gibbs energy difference G is
negative?

17.66 For the given reaction we can calculate the standard Gibbs energy change from the standard Gibbs energies
of formation (see Appendix 3 of the text). Then, we can calculate the equilibrium constant, KP, from the
standard Gibbs energy change.

G°  Gfο [Ni(CO)4 ]  [4Gfο (CO)  Gfο (Ni)]

4
G°  (1)(587.4 kJ/mol)  [(4)(137.3 kJ/mol)  (1)(0)]  38.2 kJ/mol  3.82  10 J/mol

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 751

Substitute G°, R, and T (in K) into the following equation to solve for KP.

G°  RT ln KP

G° (3.82 10 4 J/mol)

ln K P  
RT (8.314 J/K  mol)(353 K)
5
KP  4.5  10

17.67 (a) G°  2Gfο (HBr)  [Gfο (H 2 )  Gfο (Br2 )]  (2)(53.2 kJ/mol)  [(1)(0)  (1)(0)]

G°  106.4 kJ/mol

G ο 106.4 103 J/mol

ln K P    42.9
RT (8.314 J/K  mol)(298 K)
18
KP  4  10

(b) G°  Gfο (HBr)  [ 1 Gfο (H 2 )  1 Gfο (Br2 )]  (1)(53.2 kJ/mol)  [( 1 )(0)  ( 1 )(0)]
2 2 2 2

G°  53.2 kJ/mol

G ο 53.2 103 J/mol

ln K P    21.5
RT (8.314 J/K  mol)(298 K)
9
KP  2  10

The KP in (a) is the square of the KP in (b). Both G° and KP depend on the number of moles of reactants and
products specified in the balanced equation.

17.68 We carry additional significant figures throughout this calculation to minimize rounding errors. The
equilibrium constant is related to the standard Gibbs energy change by the following equation:

G°  RT ln KP
5
2.12  10 J/mol  (8.314 J/molK)(298 K) ln KP

38
KP  6.894  10

We can write the equilibrium constant expression for the reaction.

K P  PO
2

PO  ( K P )2
2

PO  (6.894 1038 )2  4.81075 atm

2

This pressure is far too small to measure.

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752 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

17.69 Talking involves various biological processes (to provide the necessary energy) that lead to a increase in the
entropy of the universe. Since the overall process (talking) is spontaneous, the entropy of the universe must
increase.

17.70 Both (a) and (b) apply to a reaction with a negative G° value. Statement (c) is not always true. An
endothermic reaction that has a positive S° (increase in entropy) will have a negative G° value at high
temperatures.

17.71 (a) If G° for the reaction is 173.4 kJ/mol,

173.4 kJ/mol
then, Gfο   86.7 kJ /mol
2

(b) G°  RT ln KP

3
173.4  10 J/mol  (8.314 J/Kmol)(298 K)ln KP

31
KP  4  10

(c) H° for the reaction is 2  Hfο (NO)  (2)(86.7 kJ/mol)  173.4 kJ/mol

Using the equation in Problem 17.51:

K2 173.4 103 J/mol  1373 K  298 K 

ln   
4 1031 8.314 J/mol  K  (1373 K)(298 K) 

7
K2  3  10

(d) Lightning promotes the formation of NO (from N2 and O2 in the air) which eventually leads to the
formation of nitrate ion (NO
3 ), an essential nutrient for plants.

17.72 We write the two equations as follows. The standard Gibbs energy change for the overall reaction will be the
sum of the two steps.

CuO(s)  Cu(s)  1 O2(g) G°  127.2 kJ/mol

2
C(graphite)  1 O2(g)  CO(g) G°  137.3 kJ/mol
2

CuO  C(graphite)  Cu(s)  CO(g) G°  10.1 kJ/mol

We can now calculate the equilibrium constant from the standard Gibbs energy change, G°.

G° (10.1103 J/mol)

ln K  
RT (8.314 J/K  mol)(673 K)

ln K  1.81

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 753

K  6.1
17.73 Using the equation in the Chemistry in Action titled “The Efficiency of Heat Engines” in Section 17.4 of the
text:
T2  T1 2473 K 1033 K
Efficiency    0.5823
T2 2473 K

The work done by moving the car:

2
mgh  (1200 kg)(9.81 m/s )  h  heat generated by the engine.

The heat generated by the gas:

3
3.1 kg 1000 g 1 mol 5510 10 J
1.0 gal      1.5108 J
1 gal 1 kg 114.2 g 1 mol

The maximum use of the energy generated by the gas is:

8 7
(energy)(efficiency)  (1.5  10 J)(0.5823)  8.7  10 J

Setting the (useable) energy generated by the gas equal to the work done moving the car:
7 2
8.7  10 J  (1200 kg)(9.81 m/s )  h

3
h  7.4  10 m

17.74 As discussed in Chapter 17 of the text for the decomposition of calcium carbonate, a reaction favors the
formation of products at equilibrium when

G°  H°  TS° < 0

If we can calculate H° and S°, we can solve for the temperature at which decomposition begins to favor
products. We use data in Appendix 3 of the text to solve for H° and S°.

H °  Hfο [MgO(s )]  Hfο [CO2 ( g)] Hfο [MgCO3 (s )]

H°  601.8 kJ/mol  (393.5 kJ/mol)  (1112.9 kJ/mol)  117.6 kJ/mol

S°  S°[MgO(s)]  S°[CO2(g)]  S°[MgCO3(s)]

S°  26.78 J/Kmol  213.6 J/Kmol  65.69 J/Kmol  174.7 J/Kmol

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754 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

For the reaction to begin to favor products,

H°  TS° < 0

or
H °
T
S °

117.6 103 J/mol

T
174.7 J/K  mol

T  673.2 K

17.75 (a) The first law states that energy can neither be created nor destroyed. We cannot obtain energy out of
nowhere.

(b) If we calculate the efficiency of such an engine, we find that Th  Tc, so the efficiency is zero! See
Chemistry in Action titled “The Efficiency of Heat Engines” in Section 17.4 of the text.

17.76 (a) G°  Gfο (H 2 )  Gfο (Fe 2 )  [Gfο (Fe)  2Gfο (H )]

G°  (1)(0)  (1)(84.9 kJ/mol)  [(1)(0)  (2)(0)]

G°  84.9 kJ/mol

G°  RT ln K
3
84.9  10 J/mol  (8.314 J/molK)(298 K) ln K

14
K  7.6  10

(b) G°  Gfο (H 2 )  Gfο (Cu2 )  [Gfο (Cu)  2Gfο (H )]

G°  64.98 kJ/mol

G°  RT ln K
3
64.98  10 J/mol  (8.314 J/molK)(298 K) ln K

12
K  4.1  10

The activity series is correct. The very large value of K for reaction (a) indicates that products are
highly favored; whereas, the very small value of K for reaction (b) indicates that reactants are highly
favored.

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 755

kf
17.77 2NO  O2  2NO2
kr

G°  (2)(51.8 kJ/mol)  [(2)(86.7 kJ/mol)  0]  69.8 kJ/mol

G°  RT ln K
3
69.8  10 J/mol  (8.314 J/molK)(298 K)ln K

12 1
K  1.7  10 M

kf
K
kr

7.1109 M 2 s1
1.71012 M 1 
kr

3 1 1
kr  4.2  10 M s

17.78 (a) It is a “reverse” disproportionation redox reaction.

(b) G°  (2)(228.6 kJ/mol)  [(2)(33.0 kJ/mol)  (1)(300.4 kJ/mol)]

G°  90.8 kJ/mol

3
90.8  10 J/mol  (8.314 J/molK)(298 K) ln K

15
K  8.2  10

Because of the large value of K, this method is efficient for removing SO2.

(c) H°  [(2)(241.8 kJ/mol)  (3)(0)]  [(2)(20.15 kJ/mol)  (1)(296.1 kJ/mol)]

H°  147.2 kJ/mol

S°  [(2)(188.7 J/Kmol)  (3)(31.88 J/Kmol)]  [(2)(205.64 J/Kmol)  (1)(248.5 J/Kmol)]

S°  186.7 J/Kmol

G°  H°  TS°

Due to the negative entropy change, S°, the Gibbs energy change, G°, will become positive at
higher temperatures. Therefore, the reaction will be less effective at high temperatures.

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756 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

17.79 (1) Measure K and use G°  RT ln K

(2) Measure H° and S° and use G°  H°  TS°

17.80 2O3  3O2

G°  3Gfο (O2 )  2Gfο (O3 )  0  (2)(163.4 kJ/mol)

G°  326.8 kJ/mol

3
326.8  10 J/mol  (8.314 J/molK)(243 K) ln KP

70
KP  1.8  10

Due to the large magnitude of K, you would expect this reaction to be spontaneous in the forward direction.
However, this reaction has a large activation energy, so the rate of reaction is extremely slow.

17.81 First convert to moles of ice.

1 mol H 2 O(s )
74.6 g H 2 O(s )  4.14 mol H 2 O(s )
18.02 g H 2 O(s )

For a phase transition:

Hsys
Ssys 
T
(4.14)(6010 J/mol)
Ssys   91.1 J /K  mol
273 K

Hsys
Ssurr 
T
(4.14)(6010 J/mol)
Ssurr   91.1 J /K  mol
273 K

Suniv  Ssys  Ssurr  0

This is an equilibrium process. There is no net change.

17.82 Heating the ore alone is not a feasible process. Looking at the coupled process:

Cu2S ® 2Cu  S G°  86.1 kJ/mol

S  O2 ® SO2 G°  300.4 kJ/mol
Cu2S  O2 ® 2Cu  SO2 G°  214.3 kJ/mol

Since G° is a large negative quantity, the coupled reaction is feasible for extracting sulfur.

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 757


17.83 Since we are dealing with the same ion (K ), Equation (17.13) of the text can be written as:

G  G°  RT ln Q
 400 mM 
G  0  (8.314 J/mol  K)(310 K) ln  
 15 mM 
3
G  8.5  10 J/mol  8.5 kJ/mol

17.84 First, we need to calculate H° and S° for the reaction in order to calculate G°.

H°  41.2 kJ/mol S°  42.0 J/Kmol

Next, we calculate G° at 300°C or 573 K, assuming that H° and S° are temperature independent.

G°  H°  TS°

3
G°  41.2  10 J/mol  (573 K)(42.0 J/Kmol)
4
G°  1.71  10 J/mol

Having solved for G°, we can calculate KP.

G°  RT ln KP
4
1.71  10 J/mol  (8.314 J/Kmol)(573 K) ln KP

ln KP  3.59

KP  36

Due to the negative entropy change calculated above, we expect that G° will become positive at some
temperature higher than 300°C. We need to find the temperature at which G° becomes zero. This is the
temperature at which reactants and products are equally favored (KP  1).

G°  H°  TS°

0  H°  TS°

3
H ° 41.2  10 J/mol
T 
S ° 42.0 J/K  mol

T  981 K  708°C

This calculation shows that at 708°C, G°  0 and the equilibrium constant KP  1. Above 708°C, G° is
positive and KP will be smaller than 1, meaning that reactants will be favored over products. Note that the
temperature 708°C is only an estimate, as we have assumed that both H° and S° are independent of
temperature.

Using a more efficient catalyst will not increase KP at a given temperature, because the catalyst will speed up
both the forward and reverse reactions. The value of KP will stay the same.

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758 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

17.85 The process is: ethanol(l)  ethanol(g). The equilibrium constant for this process is:

KP  Pethanol(g)

In this case, the vapor pressure of ethanol is equal to the equilibrium constant. We can solve for KP from
G°. We assume that both H° and S° are temperature independent.

H °  Hfο [ethanol( g)] Hfο [ethanol(l )]

4
H°  (1)(235.1 kJ/mol)  (1)(276.98 kJ/mol)]  41.9 kJ/mol  4.19  10 J/mol

S°  S°[ethanol (g)]  S°[ethanol(l)]

S°  [(1)(282.7 J/Kmol)  (1)(161.0 J/Kmol)]  121.7 J/K·mol

Next, we solve for G°.

4 3
G°  H°  TS°  4.19  10 J/mol  (298 K)(121.7 J/Kmol)  5.6  10 J/mol

G°  RT ln KP

5.6 103 J/mol

ln K P    2.3
(8.314 J/K  mol)(298 K)

KP  Pethanol(g)  0.1 atm

The vapor pressure of ethanol at 25°C is 0.1 atm.

17.86 Energy must be supplied from the surroundings to dissociate the reactant molecules into atoms. The kinetic
energy of the surrounding molecules decreases and therefore the entropy of the surrounding molecules
decreases. Ssurr is negative.

17.87 (a) G° for CH3COOH:

5
G°  (8.314 J/molK)(298 K) ln (1.8  10 )
4
G°  2.7  10 J/mol  27 kJ/mol

G° for CH2ClCOOH:

3
G°  (8.314 J/molK)(298 K) ln (1.4  10 )
4
G°  1.6  10 J/mol  16 kJ/mol

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 759

(b) The TS° is the dominant term.


(c) The breaking of the OH bond in ionization of the acid and the forming of the OH bond in H3O .

 
(d) The CH3COO ion is smaller than CH2ClCOO and can participate in hydration to a greater extent,
leading to a more ordered solution.

17.88 butane ® isobutane

G°  Gfο (isobutane) Gfο (butane)

G°  (1)(18.0 kJ/mol)  (1)(15.9 kJ/mol)

G°  2.1 kJ/mol

For a mixture at equilibrium at 25°C:

G°  RT ln KP
3
2.1  10 J/mol  (8.314 J/molK)(298 K) ln KP

KP  2.3

P mol isobutane
K P  isobutane 
Pbutane mol butane

mol isobutane
2.3 
mol butane

This shows that there are 2.3 times as many moles of isobutane as moles of butane. Or, we can say for every
one mole of butane, there are 2.3 moles of isobutane.

2.3 mol
mol % isobutane  100%  70%
2.3 mol  1.0 mol

By difference, the mole % of butane is 30%.

Yes, this result supports the notion that straight-chain hydrocarbons like butane are less stable than branched-
chain hydrocarbons like isobutane.

17.89 At the temperature of the normal boiling point the Gibbs energy difference between the liquid and gaseous
forms of bromine (or any other substances) is zero (i.e., the two phases are in equilibrium). We can therefore
use Equation (17.10) of the text to find this temperature. For the equilibrium,

Br2(l)  Br2(g)

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760 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

G  H  TS  0

H  H fο [Br2 ( g)] H fο [Br2 (l )]  30.91 kJ/mol  0  3.09110 4 J/mol

S  S°[Br2(g)]  S°[Br2(l)]  245.3 J/Kmol  152.3 J/Kmol  93.0 J/Kmol

4
H 3.09110 J/mol
Tbp    332 K  59°C
S 93.0 J/K  mol

17.90 We use Equation (17.7) of the text to determine Sº for the one species not listed in each reaction.

ο
(a) Srxn  S °[Na(l )]  S °[Na(s )]

48.64 J/K  mol  (1)S °[Na(l )]  (1)(51.05 J/K  mol)

S°[Na(l)]  99.69 J/Kmol

ο
(b) Srxn  S °[S2 Cl2 ( g)] {2 S °[S(monoclinic)]  S °[Cl2 ( g)]}

43.4 J/K  mol  (1)S °[S2 Cl2 ( g)]  [(2)(32.55 J/K  mol)  (1)(223.0 J/K  mol)]

S°[S2Cl2(g)]  331.5 J/Kmol

ο
(c) Srxn  {S °[Fe 2 (aq )]  2 S °[Cl (aq )]}  S °[FeCl2 (s )]

118.3 J/K  mol  (1)(113.39 J/K  mol)  (2)(56.5 J/K  mol)  (1)S°[FeCl2 (s )]

S°[FeCl2(s)]  117.9 J/Kmol

17.91 Heat is absorbed by the rubber band, so H is positive. Since the contraction occurs spontaneously, G is
negative. For the reaction to be spontaneous, S must be positive meaning that the rubber becomes more
disordered upon heating. This is consistent with what we know about the structure of rubber; The rubber
molecules become more disordered upon contraction (See the Figure in the Chemistry in Action Essay in
Section 17.7 of the text).

17.92 We can calculate KP from G°.

G°  [(1)(394.4 kJ/mol)  (0)]  [(1)(137.3 kJ/mol)  (1)(255.2 kJ/mol)]

G°  1.9 kJ/mol

3
1.9  10 J/mol  (8.314 J/molK)(1173 K) ln KP

KP  1.2

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 761

Now, from KP, we can calculate the mole fractions of CO and CO2.

PCO
KP  2
 1.2 PCO  1.2 PCO
PCO 2

PCO PCO 1
CO     0.45
PCO  PCO PCO  1.2 PCO 2.2
2

CO  1  0.45  0.55

2

We assumed that G° calculated from Gfο values was temperature independent. The Gfο values in
Appendix 3 of the text are measured at 25°C, but the temperature of the reaction is 900°C.

17.93 G°  RT ln K

and,

G  G°  RT ln Q

Substituting,

G  RT ln K  RT ln Q
G  RT(ln Q  ln K)
Q 
G  RT ln  
 K 

If Q  K, G  0, and the net reaction will proceed from right to left (see Figure 14.5 of the text).

If Q < K, G < 0, and the net reaction will proceed from left to right.

If Q  K, G  0. The system is at equilibrium.

17.94 For a phase transition, G  0. We write:

G  H  TS

0  H  TS

Hsub
Ssub 
T

Substituting H and the temperature, (78°  273°)K  195 K, gives

Hsub 62.4 103 J/mol

Ssub    3.20 102 J/K  mol
T 195 K

This value of Ssub is for the sublimation of 1 mole of CO2. We convert to the S value for the sublimation
of 84.8 g of CO2.

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762 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

1 mol CO2 3.20 102 J

84.8 g CO2    617 J /K
44.01 g CO2 K  mol

17.95 The second law of thermodynamics states that the entropy of the universe increases in a spontaneous process
and remains unchanged in an equilibrium process. Therefore, the entropy of the universe is increasing with
time, and thus entropy could be used to determine the forward direction of time.

17.96 First, let’s convert the age of the universe from units of years to units of seconds.

365 days 24 h 3600 s

(13109 yr)    4.11017 s
1 yr 1 day 1h

31
The probability of finding all 100 molecules in the same flask is 8  10 . Multiplying by the number of
seconds gives:
31 17 13
(8  10 )(4.1  10 s)  3  10 s

17.97 Equation (17.10) represents the standard Gibbs-energy change for a reaction, and not for a particular
compound like CO2. The correct form is:
G°  H°  TS°

For a given reaction, G° and H° would need to be calculated from standard formation values (graphite,
oxygen, and carbon dioxide) first, before plugging into the equation. Also, S° would need to be calculated
from standard entropy values.

C(graphite)  O2(g) ® CO2(g)

17.98 We can calculate Ssys from standard entropy values in Appendix 3 of the text. We can calculate Ssurr from
the Hsys value given in the problem. Finally, we can calculate Suniv from the Ssys and Ssurr values.

Ssys  (2)(69.9 J/Kmol)  [(2)(131.0 J/Kmol)  (1)(205.0 J/Kmol)]  327 J/Kmol

Hsys (571.6 103 J/mol)

Ssurr    1918 J / K  mol
T 298 K

Suniv  Ssys  Ssurr  (327  1918) J/Kmol  1591 J/Kmol

17.99 H° is endothermic. Heat must be added to denature the protein. Denaturation leads to more disorder (an
increase in microstates). The magnitude of S° is fairly large (1600 J/Kmol). Proteins are large molecules
and therefore denaturation would lead to a large increase in microstates. The temperature at which the process
favors the denatured state can be calculated by setting G° equal to zero.

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 763

G°  H°  TS°

0  H°  TS°

H ο 512 kJ/mol
T   320 K  47°C
ο 1.60 kJ/K  mol
S

17.100 q and w are not state functions. Recall that state functions represent properties that are determined by the state
of the system, regardless of how that condition is achieved. Heat and work are not state functions because
they are not properties of the system. They manifest themselves only during a process (during a change).
Thus their values depend on the path of the process and vary accordingly.

17.101 (d) will not lead to an increase in entropy of the system. The gas is returned to its original state. The entropy
of the system does not change.

17.102 Since the adsorption is spontaneous, G must be negative (G < 0). When hydrogen bonds to the surface
of the catalyst, the system becomes more ordered (S < 0). Since there is a decrease in entropy, the
adsorption must be exothermic for the process to be spontaneous (H < 0).

17.103 (a) An ice cube melting in a glass of water at 20°C. The value of G for this process is negative so it must
be spontaneous.

(b) A “perpetual motion” machine. In one version, a model has a flywheel which, once started up, drives a
generator which drives a motor which keeps the flywheel running at a constant speed and also lifts a
weight.

(c) A perfect air conditioner; it extracts heat energy from the room and warms the outside air without using
any energy to do so. (Note: this process does not violate the first law of thermodynamics.)

(d) Same example as (a).

(e) A closed flask at 25°C containing NO2(g) and N2O4(g) at equilibrium.

17.104 (a) Each CO molecule has two possible orientations in the crystal,

CO or OC
1
If there is no preferred orientation, then for one molecule there are two, or 2 , choices of orientation. Two

molecules have four or 2 choices, and for 1 mole of CO there are 2 N A choices. From Equation (17.1) of
2

the text:
S  k ln W
23
S  (1.381023 J/K) ln 26.02210

S  (1.381023 J/K)(6.022 1023 /mol) ln 2

S  5.76 J/Kmol

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764 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

(b) The fact that the actual residual entropy is 4.2 J/Kmol means that the orientation is not totally random.

17.105 The analogy is inappropriate. Entropy is a measure of the dispersal of molecules among available energy
levels. The entropy of the room is the same whether it is tidy or not.

17.106 We use data in Appendix 3 of the text to calculate H° and S°.

H °  H vap  Hfο [C6 H6 ( g)] Hfο [C6 H6 (l )]

H°  82.93 kJ/mol  49.04 kJ/mol  33.89 kJ/mol

S°  S°[C6H6(g)]  S°[C6H6(l)]

S°  269.2 J/Kmol  172.8 J/Kmol  96.4 J/Kmol

We can now calculate G° at 298 K.

G°  H°  TS°

1 kJ
G°  33.89 kJ/mol  (298 K)(96.4 J/K  mol)
1000 J

G°  5.2 kJ/mol

H° is positive because this is an endothermic process. We also expect S° to be positive because this is a
liquid ® vapor phase change. G° is positive because we are at a temperature that is below the boiling point of
benzene (80.1°C).


17.107 (a) A  B ® C  xH

From Equation (17.13) of the text and using the chemical standard state of 1 M, we write

x
 [C]  [H ] 
  
1 M  1 M 
 
G  G°  RT ln
 [A]  [B] 
 
1 M 1 M 

For the biological standard state, we write

 x
 [C]  [H ] 
  
1 M   1107 M 
 
G  G°' RT ln
 [A]  
 [B] 

1 M  1 M 

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 765

We set the two equations equal to each other.

x  x
     [C]  [H ] 
 [C]  [H ]    
1 M  1 M  1 M 1107 M 
   
G°  RT ln  G°' RT ln
     
 [A]  [B]   [A]  [B] 
1 M 
1 M  1 M 
1 M 

  x  x
 [H ]   [H ] 

G°  RT ln    G°' RT ln  
 1 M 
7
110 M 

 x   x
 [H ] 
G°  G°' RT ln    RT ln  [H ] 
1107 M   1 M 
 

 [H ] x
 
 7 
 110 M 
G°  G°' RT ln  
 [H ] 

 

 1 M 

 1 
G°  G°'  xRT ln   (1)
 110 
7


For the reverse reaction, C  xH ® A  B, we can show that

 1 
G°  G°'  xRT ln   (2)
 110 
7

(b) To calculate G°' , we use Equation (2) from part (a). Because x  1, Equation (2) becomes

1
G°  G°' (1)(8.314 J/mol  K)(298 K) ln
1107

G°  G°' 39.93 kJ/mol

or
G°'  21.8 kJ/mol  39.93 kJ/mol  18.1 kJ /mol

We now calculate G using both conventions.

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766 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

Chemical standard state:

 P 
 [NAD ] 
  H2 


 1 M 1 atm 
G  G°  RT ln
 [NADH]  [H ] 
  
 1 M  1 M 
 

(4.6 103 )(0.010)

G  21.8103 J/mol  (8.314 J/mol  K)(298 K) ln
(1.5102 )(3.0 105 )

G  10.3 kJ/mol

Biological standard state:

   
 [NAD ]  PH2 
  
 1 M 1 atm 
G  G°' RT ln
 
 [NADH]  [H ] 
  
 1 M 1107 M 
 

(4.6 103 )(0.010)

G  18.1103 J/mol  (8.314 J / mol  K)(298 K) ln
(1.5102 )(3.0 105 / 1107 )

G  10.3 kJ/mol

As expected, G is the same regardless of which standard state we employ.

17.108 We can calculate G° at 872 K from the equilibrium constant, K1.

G°  RT ln K

G°  (8.314 J/mol  K)(872 K) ln(1.80 104 )

4
G°  6.25  10 J/mol  62.5 kJ/mol

We use the equation derived in Problem 17.51 to calculate H°.

K H ο  1 1
ln 2    
K1 R  T1 T2 

0.0480 H ο  1 1 
ln    
1.80 104 8.314 J/mol  K  872 K 1173 K 

H°  157.8 kJ/mol

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 767

Now that both G° and H° are known, we can calculate S° at 872 K.

G°  H°  TS°

3 3
62.5  10 J/mol  (157.8  10 J/mol)  (872 K)S°

S°  109 J/Kmol

17.109 First, calculate the equilibrium constant, KP, from the G° value.

G°  RT ln K P
3.4 103 J/mol  (8.314 J/mol  K)(298 K) ln K P
ln K P  1.4
KP  4

Next, calculate the QP value for each reaction mixture and compare the value to KP calculated above. The
problem states that the partial pressures of the gases in each frame are equal to the number of A2, B2, and AB
molecules times 0.10 atm.
2
PAB
(a) QP 
PA  PB
2 2

(0.3)2
QP   1.5
(0.3)(0.2)

(0.6)2
(b) QP   6.0
(0.2)(0.3)

(0.4)2
(c) QP   4.0
(0.2)(0.2)

(1) Reaction mixture (c) is at equilibrium (Q  K). G  0.

(2) Reaction mixture (a) has a negative G value. Because Q < K, the system will shift right, toward
products, to reach equilibrium. This shift corresponds to a negative G value. The value of G could
also be calculated using Equation (17.13) of the text.

G  G°  RT ln Q  2.4 kJ/mol

(3) Reaction mixture (b) has a positive G value. Because Q  K, the system will shift left, toward
reactants, to reach equilibrium. This shift corresponds to a positive G value.

G  G°  RT ln Q  1.0 kJ/mol

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768 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

17.110 We can solve for the minimum partial pressure of N2 by first assuming that the system is at equilibrium. From
the given value of KP we write:

2
PNH
KP  3

PN  PH3
2 2

(2.1102 )2
2.4 103 
PN (1.52)3
2

PN  0.052 atm
2

For the reaction to proceed spontaneously in the forward direction, the nitrogen gas pressure must be slightly
larger than 0.052 atm.

An alternative way to solve this problem is to use Equation (17.13) of the text. We first set G  0, calculate
G° from the KP value, and then solve for pressure of nitrogen gas. We again obtain 0.052 atm for the
pressure of nitrogen gas. A slight increase in the nitrogen pressure (from 0.052 atm) will result in G < 0 so
the reaction is spontaneous in the forward direction.

17.111 The van’t Hoff equation has the form of a straight line,

H °
ln K w  C
RT
y  mx  b

where the slope equals H°/R. We plot ln Kw vs. 1/T and determine the slope of the line.

ln Kw 1/T (K )
1

34.4 3
3.66  10
33.5 3
3.53  10
32.2 3
3.36  10
31.2 3
3.19  10
30.5 3
3.10  10

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 769

The slope of the plot equals H°/R.

H °
6838.1 K  
8.314 J/mol  K
4
H°  5.69  10 J/mol  56.9 kJ/mol

17.112 The missing distributions are as follows:

17.113 Basic approach:

· Calculate S° and H°.
· Assume that S° and H° are independent of temperature.
· Calculate the temperature at which G°  0.

From the data in Appendix 3, we can calculate the enthalpy and entropy of the reaction.

S°  94.56  (193.0  187.0)  285.4 J/K  mol

H°  315.4  [(46.3)  (92.3)]  176.8 kJ/mol

To estimate the temperature at which the reaction is no longer spontaneous, we write

G°  H°  TS°  0

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770 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

Solving for temperature gives

H ° –176.8 kJ/mol 1000 J/kJ

T   620 K or 350°C
S ° –285.4 J / K  mol

The temperature must be above 350°C for the reaction not to be spontaneous.

17.114 Basic approach:

· Estimate heat of vaporization of diethyl ether using Trouton’s rule, which is described in Problem 17.48.
· Note that KP for the vaporization of a liquid at a certain temperature is equal to the vapor pressure of the
liquid at that temperature, and recall that the vapor pressure of a liquid is equal to 760 mmHg at its normal
boiling point.
· Derive the equation for the relationship between Hvap, Tb, and KP, or simply apply the general equation
given in Problem 17.51 to the vaporization of diethyl ether, and solve for the vapor pressure at 20°C.

Trouton’s rule states that the ratio of the molar heat of vaporization of a liquid (Hvap) to its boiling point is
approximately 90 J/K  mol, or

H vap
 90 J/K  mol
Tb

Converting the boiling point of diethyl ether from Celsius to Kelvin, plugging that into the rearranged
equation gives

H vap  (90 J/K  mol)(Tb )  (90 J/K  mol)(308 K)(1 kJ/1000 J)  28 kJ/mol

The equilibrium constant, KP, for the vaporization of a liquid at a certain temperature is equal to the vapor
pressure of the liquid at that temperature. Therefore we can apply the equation you derived in Problem 17.51
to solve for the vapor pressure of diethyl ether at 20°C.

Rewriting that equation in terms of the parameters of this problem gives

P H vap  T2  T1 
ln 2   
P1 R  T2T1 

Letting subscript 1 correspond to 34.6°C  308 K (the normal boiling point of diethyl ether) and subscript 2
correspond to 20°C  293 K, and recalling that the vapor pressure of any liquid at its normal boiling point is
1 atm  760 mmHg, we can solve for P2, the vapor pressure of diethyl ether at 20°C.

P2 28 kJ/mol  298 K  308 K 

ln     0.37
760 mmHg 8.314 J/K  mol(1 kJ/1000 J)  308 K  298 K 

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 771

P2  e0.37 (760 mmHg)  520 mmHg

The vapor pressure of diethyl ether decreases when the temperature is lowered, as expected, but note that the
vapor pressure at 20°C is still quite high. The high vapor pressure of diethyl ether at modest temperatures
must be considered in the laboratory because the highly flammable vapors can be a hazard when using this
solvent in proximity to an open flame or spark.

17.115 Basic approach:


· Determine the concentration of H (aq) in blood from the pH.

· Use the ratio of protonated and neutral nicotine along with [H ] to solve for K.
· CalculateG° from K.


Blood is buffered at pH  7.4, so the concentration of H (aq) in blood is

[H ]  10pH  107.4  4.0 108 M

Since 90% of the nicotine in the bloodstream is protonated

[nicotine-H ] 90

[nicotine] 10

and

[nicotine-H ] 90
K   2.3108
 8
[nicotine][H ] 10(4.0 10 )

Assuming a normal body temperature of 37°C  310 K,

1 kJ
G°  RT ln K  [(8.314 J/K  mol)(310 K) ln (2.3108 )]  5.0 101 kJ/mol
1000 J

17.116 Basic approach:

· Calculate the number microstates for the initial and final distributions using the equation for combinations.
· Calculate S from Equation (17.3).

Because C(n,r) gives the number of ways to distribute n objects between two bins, this function can be used
to calculate the number of microstates (W) corresponding to the distribution of n molecules between two
flasks. For the initial distribution, the number of microstates is given by

n! 20! 20 1918 1

Wi    1
r !(n  r )! 0!(20  0)! 1(20 1918 1)!

as expected because there is only one way to put all 20 molecules in the left flask. For the final distribution,
the number of microstates is given by

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772 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM

n! 20! 20! 2.431018

Wf      2 105
r !(n  r )! 10!(20 10)! (10!)2 6 2
(3.6310 )

The change in entropy can be calculated from Equation (17.3)

W  2 105 

S  k ln f  (1.381023 J/K) ln    2 1022 J/K
Wi  1 


This value is roughly an order of magnitude greater than the S calculated for the analogous process depicted
in Figure 17.2 involving only 4 molecules. Imagine the magnitude of S for such a process involving moles
of molecules!

17.117 Basic approach:

· Estimate H° for the formation of H¾On¾H(g) from the elements H2(g) and O2(g) reactions using
average bond enthalpies.
· Consider the expected trend in S°.
· Determine the value of n for which G°  H°T S° becomes positive.

We can use average bond enthalpies from Table 9.4 to estimate H° for the general reaction

H2(g)  /2O2(g) ® H¾On¾H(g)

n

H°  BE(reactants)  BE(products)

 [BE(H¾H)  /2BE(OO)]  [2BE(H¾O)  (n1)BE(O¾O)]
n

So for n  1

H°  [BE(H¾H)  /2BE(OO)]  [2BE(H¾O)  (0)BE(O¾O)]

1

 (436.4 kJ/mol)  /2(498.7 kJ/mol)  2(460 kJ/mol)

1

 234 kJ/mol

n2

H°  [BE(H¾H)  BE(OO)]  [2BE(H¾O)  BE(O¾O)]

 (436.4 kJ/mol)  (498.7 kJ/mol)  2(460 kJ/mol)  (142 kJ/mol)
 127 kJ/mol

n3

H°  [BE(H¾H)  /2BE(OO)]  [2BE(H¾O)  2BE(O¾O)]

3

 (436.4 kJ/mol)  /2(498.7 kJ/mol)  2(460 kJ/mol)  2(142 kJ/mol)

3

 20 kJ/mol

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 CHAPTER 17: ENTROPY, GIBBS ENERGY, AND EQUILIBRIUM 773

As n increases, the reaction becomes less exothermic, hence less favored based on enthalpy. Furthermore, as
n increases, S° is expected to become more negative because the number of moles of reactant is increasing,
but the number of moles of product stays the same; therefore, we would expect that the reaction is also
becoming increasingly less favored based on entropy as n increases. Given the small negative value of H°
when n  3, it is reasonable to expect that the reaction

H2(g)  /2O2(g) ® H¾O¾O¾O¾H(g)

3

is nonspontaneous or very close to being nonspontaneous.

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