Chapter 17 - Spontaneity, Entropy, and Free Energy: Answer: C
Chapter 17 - Spontaneity, Entropy, and Free Energy: Answer: C
Chapter 17 - Spontaneity, Entropy, and Free Energy: Answer: C
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2. Ten identical coins are shaken vigorously in a cup and then poured out onto a table top. Which of the
following distributions has the highest probability of occurrence? (T = Tails, H = Heads)
a. T10H0
b. T8H2
c. T7H3
d. T5H5
e. T4H6
ANSWER: d
3. If two pyramid-shaped dice (with numbers 1 through 4 on the sides) were tossed, which outcome has the
highest entropy?
a. The sum of the dice is 3.
b. The sum of the dice is 4.
c. The sum of the dice is 5.
d. The sum of the dice is 6.
e. The sum of the dice is 7.
ANSWER: c
4. A two-bulbed flask contains 7 particles. What is the probability of finding all 7 particles on the left side?
a. 3.50%
b. 2.65%
c. 0.78%
d. 0.14%
e. 1.56%
ANSWER: c
I.
10. A 100-mL sample of water is placed in a coffee cup calorimeter. When 1.0 g of an ionic solid is added, the
temperature decreases from 21.5°C to 20.8°C as the solid dissolves. For the dissolving of the solid
a. ΔH < 0
b. ΔSuniv > 0
c. ΔSsys< 0
d. ΔSsurr > 0
e. none of these
ANSWER: b
12. Assume that the enthalpy of fusion of ice is 6020 J/mol and does not vary appreciably over the temperature
range 270-290 K. If one mole of ice at 0°C is melted by heat supplied from surroundings at 279 K, what is the
entropy change in the surroundings, in J/K?
a. 22.1
b. 21.6
c. 0.0
d. –21.6
e. –22.1
ANSWER: d
13. If the change in entropy of the surroundings for a process at 439 K and constant pressure is –326 J/K, what
is the heat flow absorbed by for the system?
a. 326 kJ
b. 1.35 kJ
c. –143 kJ
d. 113 kJ
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14. The heat of vaporization for 1.0 mole of water at 100.°C and 1.0 atm is 40.55 kJ/mol. Calculate ΔS for the
process H2O(l) → H2O(g) at 100.°C.
a. 109 J/K mol
b. –109 J/K mol
c. 406 J/K mol
d. –406 J/K mol
e. none of these
ANSWER: a
15. A change of state that occurs in a system is accompanied by 61.2 kJ of heat, which is transferred to the
surroundings at a constant pressure and a constant temperature of 300. K. For this process ΔSsurr is:
a. 61.2 kJ/K
b. –61.2 kJ/K
c. –204 J/K
d. 204 J/K
e. 239 kJ/K
ANSWER: d
16. Τhe enthalpy of vaporization of ethanol is 38.56 kJ/mol at its boiling point (78°C). Calculate the value of
ΔSsurr when 1.00 mole of ethanol is vaporized at 78°C and 1.00 atm.
a. 0
b. 4.92 × 102 J/K mol
c. 1.1 × 102 J/K mol
d. –1.1 × 102 J/K mol
e. –4.92 × 102 J/K mol
ANSWER: d
17. ΔSsurr is _______ for exothermic reactions and ______ for endothermic reactions.
a. favorable, unfavorable
b. unfavorable, favorable
c. favorable, favorable
d. unfavorable, unfavorable
e. cannot tell
ANSWER: a
22. Given that ΔHvap is 52.6 kJ/mol, and the boiling point is 83.4°C, 1 atm, if one mole of this substance is
vaporized at 1 atm, calculate ΔSsurr.
a. –148 J/K mol
b. 148 J/K mol
c. 631 J/K mol
23. As long as the disorder of the surroundings is increasing, a process will be spontaneous.
a. True
b. False
ANSWER: False
24. For any given process, ΔSsurr and ΔSsys have opposite signs.
a. True
b. False
ANSWER: False
27. Substance X has a heat of vaporization of 41.4 kJ/mol at its normal boiling point (423°C). For the process
X(l) → X(g) at 1 atm and 423°C calculate the value of ΔSuniv.
a. 0
b. 59.5 J/K mol
c. 98 J/K mol
d. –59.5 J/K mol
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28. Substance X has a heat of vaporization of 45.1 kJ/mol at its normal boiling point (423°C). For the process
X(l) → X(g) at 1 atm and 423°C calculate the value of ΔSsurr.
a. 0
b. 64.8 J/K mol
c. 107 J/K mol
d. –64.8 J/K mol
e. –107 J/K mol
ANSWER: d
29. Substance X has a heat of vaporization of 46.7 kJ/mol at its normal boiling point (423°C). For the process
X(l) → X(g) at 1 atm and 423°C calculate the value of ΔS.
a. 0
b. 67.1 J/K mol
c. 110 J/K mol
d. –67.1 J/K mol
e. –110 J/K mol
ANSWER: b
30. Substance X has a heat of vaporization of 45.9 kJ/mol at its normal boiling point (423°C). For the process
X(l) → X(g) at 1 atm and 423°C calculate the value of ΔG.
a. 0 J
b. 65.9 J
c. 109 J
d. –65.9 J
e. –109 J
ANSWER: a
31. Τhe enthalpy of vaporization of methanol is 37.40 kJ/mol at its boiling point (64.7°C). Calculate the value
of ΔS when 1.00 mole of methanol is vaporized at 64.7°C and 1.00 atm.
a. 0
b. 5.78 × 102 J/K mol
c. 1.11 × 102 J/K mol
d. –1.11 × 102 J/K mol
e. –5.78 × 102 J/K mol
ANSWER: c
32. ΔS is _______ for exothermic reactions and ______ for endothermic reactions.
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33. For the process CHCl3(s) → CHCl3(l), ΔH° = 9.17 kJ/mol and ΔS° = 43.9 J/mol/K. What is the melting
point of chloroform?
a. –64 °C
b. 209 °C
c. 130 °C
d. 64 °C
e. –130 °C
ANSWER: a
34. Given that ΔHvap is 66.8 kJ/mol, and the boiling point is 83.4°C, 1 atm, if one mole of this substance is
vaporized at 1 atm, calculate ΔS.
a. –187 J/K mol
b. 187 J/K mol
c. 801 J/K mol
d. –801 J/K mol
e. 0
ANSWER: b
Consider two perfectly insulated vessels. Vessel #1 initially contains an ice cube at 0°C and water at 0°C.
Vessel #2 initially contains an ice cube at 0°C and a saltwater solution at 0°C. In each vessel, consider the
"system" to be the ice, and the "surroundings" to be the liquid.
36. Determine the sign of ΔSsys, ΔSsurr, and ΔSuniv for the contents of
Vessel #1.
ΔSsys ΔSsurr ΔSuniv
a. 0 0 0
b. + – 0
c. + + +
37. Determine the sign of ΔSsys, ΔSsurr, and ΔSuniv for the system (ice/saltwater) in
Vessel #2.
ΔSsys ΔSsurr ΔSuniv
a. 0 0 0
b. + – 0
c. + + +
d. + – +
e. + 0 +
ANSWER: d
38. The melting point of water is 0°C at 1 atm pressure because under these conditions:
a. ΔS for the process H2O(s) → H2O(l) is positive.
b. ΔS and ΔSsurr for the process H2O(s) → H2O(l) are both positive.
c. ΔS and ΔSsurr for the process H2O(s) → H2O(l) are equal in magnitude and
opposite in sign.
d. ΔG is positive for the process H2O(s) → H2O(l).
e. None of these is correct.
ANSWER: c
a. I
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42. A mixture of hydrogen and chlorine remains unreacted until it is exposed to ultraviolet light from a burning
magnesium strip. Then the following reaction occurs very rapidly:
H2(g) + Cl2(g) → 2HCl(g) ΔG = –45.54 kJ
ΔH = –44.12 kJ
ΔS = –4.76 J/K
Which of the following is consistent with this information?
a. The reactants are thermodynamically more stable than the products.
b. The reaction has a small equilibrium constant.
c. The ultraviolet light raises the temperature of the system and makes the
reaction more favorable.
d. The negative value for ΔS slows down the reaction.
e. The reaction is spontaneous, but the reactants are kinetically stable.
ANSWER: e
43. For a particular chemical reaction ΔH = 5.8 kJ and ΔS = –23 J/K. Under what temperature condition is the
reaction spontaneous?
a. When T < –252 K.
b. When T < 252 K.
c. The reaction is spontaneous at all temperatures.
d. The reaction is not spontaneous at any temperature.
e. When T > 252 K.
ANSWER: d
44. For a certain process at 355 K, ΔG = –12.1 kJ and ΔH = –9.2 kJ. Therefore, ΔS for the process is
a. 0 J/K mol
b. 8.2 J/K mol
45. Consider the freezing of liquid water at –10°C. For this process what are the signs for ΔH, ΔS, and ΔG?
ΔH ΔS ΔG
a. + – 0
b. + – –
c. – + 0
d. – + –
e. – – –
ANSWER: e
46. For the process of a certain liquid vaporizing at 1 atm, ΔH°vap = 68.5 kJ/mol and ΔS°vap= 74.1 J/mol K.
Assuming these values are independent of T, what is the normal boiling point of this liquid?
a. 924 °C
b. 1197 °C
c. 651 °C
d. 0.924 °C
e. none of these
ANSWER: c
47. For the reaction A + B → C + D, ΔH° = +40 kJ and ΔS° = +50 J/K. Therefore, the reaction under standard
conditions is
a. spontaneous at temperatures less than 10 K
b. spontaneous at temperatures greater than 800 K
c. spontaneous only at temperatures between 10 K and 800 K
d. spontaneous at all temperatures
e. nonspontaneous at all temperatures
ANSWER: b
50. As O2(l) is cooled at 1 atm, it freezes at 54.5 K to form Solid I. At a lower temperature, Solid I rearranges to
Solid II, which has a different crystal structure. Thermal measurements show that ΔH for the I →II phase
transition is –743.11 J/mol, and ΔS for the same transition is -17.0 J/K mol. At what temperature are Solids I
and II in equilibrium?
a. 13.6 K
b. 43.7 K
c. 19.8 K
d. 98.2 K
e. They can never be in equilibrium because they are both solids.
ANSWER: b
51. At constant pressure, the following reaction 2NO2(g) → N2O4(g) is exothermic. The reaction (as written) is
a. always spontaneous
b. spontaneous at low temperatures, but not high temperatures
c. spontaneous at high temperatures, but not low temperatures
d. never spontaneous
e. cannot tell
ANSWER: b
52. Given that ΔHvap is 63.2 kJ/mol, and the boiling point is 83.4°C, 1 atm, if one mole of this substance is
vaporized at 1 atm, calculate ΔG.
a. –177 J
b. 177 J
c. 758 J
d. –758 J
e. 0 J
ANSWER: e
The following questions refer to the following reaction at constant 25°C and 1 atm.
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56. Given the following data, calculate the normal boiling point for formic acid (HCOOH).
ΔHf°(kJ/mol) S°(J/mol K)
HCOOH(l) -410. 130.0
HCOOH(g) -363 250.8
a. 0.39 °C
b. 389 °C
c. 662 °C
d. 279 °C
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57. The following reaction takes place at 120°C: H2O(l) → H2O(g) ΔH = 44.0 kJ/mol ΔS = 0.119 kJ/mol K
Which of the following must be true?
a. The reaction is not spontaneous.
b. The reaction is spontaneous.
c. ΔG = 0
d. ΔG < 0
e. Two of these.
ANSWER: e
When ignited, solid ammonium dichromate decomposes in a fiery display. This is the reaction for a "volcano"
demonstration. The decomposition produces nitrogen gas, water vapor, and chromium(III) oxide. The
temperature is constant at 25°C.
Substance ΔHf° (kJ/mol) S° (kJ/mol K)
Cr2O3(g) –1147 0.08120
H2O(l) –242 0.1187
N2(g) 0 0.1915
(NH4)2Cr2O7(s) –22.5 0.1137
62. For which of the following processes would ΔS° be expected to be most positive?
a. O2(g) + 2H2(g) → 2H2O(g)
b. H2O(l) → H2O(s)
c. NH3(g) + HCl(g) → NH4Cl(g)
d. 2NH4NO3(s) → 2N2(g) + O2(g) + 4H2O(g)
e. N2O4(g) → 2NO2(g)
ANSWER: d
a. I
b. I, IV
c. I, III, IV
d. II, IV
e. II
ANSWER: a
68. When a stable diatomic molecule spontaneously forms from its atoms, what are the signs of ΔH°, ΔS°, and
ΔG°?
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72. The reaction is allowed to proceed until all substances involved have reached their equilibrium
concentrations. Under those conditions, what is ΔG for the reaction?
a. –1.35 × 105 kJ
b. 98.7 kJ
c. –25.2 kJ
d. 135 kJ
e. 0
ANSWER: e
75. The standard free energy of formation of NaCl(s) is –384.0 kJ/mol. ΔG° for the reaction 2NaCl(s) → 2Na(s)
+ Cl2(g) is:
a. –384.0 kJ
b. 768.0 kJ
c. 384.0 kJ
d. –768.0 kJ
e. none of these
ANSWER: b
76. Consider the following hypothetical reaction at 310 K. Standard free energies of formation are given in
parentheses.
B → C ΔG° = –33.6 kJ/mol
(176.4
(?)
kJ/mol)
Calculate the standard free energy of formation of compound B.
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77. For the reaction ΔH° = 126.4 kJ/mol and ΔS° = –74.9 J/K mol.
At 379°C, what is ΔG ?
a. 154.8 kJ/mol
b. 49.0 kJ/mol
c. 175.2 kJ/mol
d. 77.6 kJ/mol
e. 157.3 kJ/mol
ANSWER: c
79. Of ΔS, ΔSsurr, ΔSuniv, and ΔG, which are state functions?
a. ΔS, ΔSsurr, ΔSuniv, and ΔG are all state functions.
b. Only ΔS, ΔSuniv, and ΔG are state functions.
c. Only ΔS and ΔG are state functions.
d. Only ΔS, ΔSsurr, and ΔSuniv are state functions.
e. Only ΔSuniv and ΔG are state functions.
ANSWER: c
81. The standard molar free energies of formation of NO2(g) and N2O4(g) at 25°C are 51.84 and 98.00 kJ/mol,
respectively. What is the value of ΔG for the reaction written as follows at 25°C if the pressures of both gases
are 1.88 atm?
2NO2 N2O4
a. –4.12
b. 4.12
c. –7.24
d. –5.68
e. –5.81
ANSWER: c
82. Elemental sulfur exists in two crystalline forms, rhombic and monoclinic. From the following data, calculate
the equilibrium temperature at which monoclinic sulfur and rhombic sulfur are in equilibrium.
ΔHf° (kJ/mol) S° (J/K mol)
S (rhombic) 0 31.880
S (monoclinic) 0.30 32.546
a. 450 K
b. 200 K
c. –200
K
d. –450
K
e. 0 K
ANSWER: a
83. Given the following data (ΔHf, S°, respectively) for N2O4(l) -20. kJ/mol, 209.0 J/K mol, and N2O4(g) 10.
kJ/mol, 303.8 J/K mol. Above what temperature (in °C) is the vaporization of N2O4 liquid spontaneous?
a. Above –178 °C.
b. Above –230 °C.
c. Above 3 °C.
d. Above 30. °C.
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84. The reaction 2H2O(g) → 2H2(g) + O2(g) has a positive value of ΔG°. Which of the following statements
must be true?
a. The reaction is slow.
b The reaction will not occur. (When H2O(g) is introduced into a flask, no O2 or
.
H2 will form even over a long period of time.)
c. The reaction is exothermic.
d The equilibrium lies far to the right.
.
e. None of these is true.
ANSWER: e
86. The acid dissociation constant for a weak acid HX at 25°C is 1.9 10–6. Calculate the free energy of
formation for X–(aq) at 25°C. The standard free energies of HX(aq) and H+(aq) at 25°C are –245.4 kJ/mol and
0, respectively.
a. –243 kJ/mol
b. 278 kJ/mol
c. 0
d. –213 kJ/mol
e. –278 kJ/mol
ANSWER: d
87. The standard molar free energies of formation of NO2(g) and N2O4(g) at 25°C are 51.840 and
98.065 kJ/mol, respectively. What is the value of Kp (in atm) for the reaction written as follows at 25°C?
2NO2 N2O4
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88. Given that ΔGf° for NH3 = –16.673 kJ/mol, calculate the equilibrium constant for the following reaction at
298 K:
N2(g) + 3H2(g) 2NH3(g)
a. 7.00 × 105
b. 8.37 × 102
c. 1.01
d. 4.73 × 1069
e. 5.86 × 108
ANSWER: a
90. Determine ΔG° for the weak acid, HF, at 25°C. (Ka = 7.17 × 10–4)
a. 1.5 kJ
b. 177 kJ
c. 7.79 kJ
d. 1.78 kJ
e. 17.9 kJ
ANSWER: e
93. For the following reaction, CO2(g) + 2H2O(g) CH4(g) + 2O2(g), ΔH° = 803 kJ which of the following
will increase K?
a. decrease number of moles of methane
b. increase volume of system
c. increase the temperature of system
d. all of the above
e. none of the above
ANSWER: c
94. For a particular reaction the equilibrium constant is 0.0124 at 370.°C and ΔH° is +16.0 kJ at 25°C.
Assuming ΔH° and ΔS° are temperature independent, calculate ΔS° for the reaction.
a. 6.74 J/K
b. –6.74 J/K
c. –11.6 J/K
d. 11.6 J/K
e. none of these
ANSWER: c
96. Consider the following hypothetical reaction (at 310.2 K). Standard free energies in kJ/mol are given in
parentheses.
A B + C ΔG° = ?
(-32.2) (207.8) (-237.0)
What is the value of the equilibrium constant for the reaction at 310.2 K?
a. 0.31
b. 1.0
c. 8.3 × 104
d. 273
e. 0.42
ANSWER: a
99. The standard free energy of formation of nitric oxide, NO, at 1000. K (roughly the temperature in an
automobile engine during ignition) is 78.4 kJ/mol. Calculate the equilibrium constant for the reaction
N2(g) + O2(g) 2NO(g)
at 1000. K.
a. 1.57 × 105
b. 8.03 × 10–5
c. –14.8
d. 6.45 × 10-9
e. 0.948
ANSWER: d
100. Consider the reaction 2NO2(g) N2O4(g); ΔH° = –56.8 kJ and ΔS° = –175 J/K. In a container (at 298
K) N2O4(g) and NO2(g) are mixed with initial partial pressures of 2.4 atm and 0.42 atm, respectively. Which of
the following statements is correct?
a. Some N2O4(g) will decompose into NO2(g).
b. Some NO2(g) will dimerize to form N2O4(g).
c. The system is at equilibrium at these initial pressures.
d. The final total pressure must be known to answer this question.
e. None of these.
ANSWER: a
Consider the gas phase reaction NO + O2 NO2 for which ΔH° = –57.05 kJ and K = 1.54 × 106 at 25°C.
105. For this system at equilibrium, how will raising the temperature affect the amount of NO present?
a. The amount of NO will increase.
b. The amount of NO will decrease.
c. The amount of NO will remain the same.
d. Cannot be determined.
e. Answer depends on the value of K.
ANSWER: a
106. What would be the effect on the amount of NO present of compressing the equilibrium system to a smaller
volume, while keeping the temperature constant?
a. The amount of NO will increase.
b. The amount of NO will decrease.
109. The equilibrium constant of a certain reaction was measured at various temperatures to give the plot shown
below. What is ΔS° for the reaction in J/mol ⋅ K?
a. 0.20
b. 3.0
c. 25
d. –50.
e. –8.3 × 103
ANSWER: c
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110. Consider a weak acid, HX. If a 0.10 M solution of HX has a pH of 4.04 at 25°C, what is ΔG° for the acid's
dissociation reaction at 25°C?
a. –40.4 kJ
b. 3.39 kJ
c. 0
d. –3.39 kJ
e. 40.4 kJ
ANSWER: e
111. For the reaction CO(g) + 2H2(g) CH3OH(g) ΔG°700K = –13.456 kJ. The Kp for this reaction at 700. K
is:
a. 10.1
b. 1.00
c. 1.54
d. 2.31
e. none of these
ANSWER: a
112. For the reaction 2HF(g) H2(g) + F2(g), ΔG° = 38.3 kJ, at 1000 K. If, at this temperature, 5.00 moles of
HF(g), 0.500 moles of H2(g), and 0.75 moles of F2(g) are mixed in a 1.00-L container:
a. Some HF will decompose (to yield H2 and F2).
b. The system is at equilibrium.
c. Some HF will be formed (from H2 and F2).
d. Not enough data are given to answer this question.
e. None of these (A-D).
ANSWER: c
113. If the temperature of the system is raised, the ratio of the partial pressure of PCl5 to the partial pressure of
PCl3 will
a. increase
b. decrease
c. stay the same
d. impossible to tell without more information
e. none of these
114. When some Cl2(g) is added at constant volume and temperature, the ratio of the partial pressure of PCl5 to
the partial pressure of PCl3 will
a. increase
b. decrease
c. stay the same
d. impossible to tell without more information
e. none of these
ANSWER: a
115. When the volume is decreased at constant temperature, the ratio of the partial pressure of PCl5 to the
partial pressure of PCl3 will
a. increase
b. decrease
c. stay the same
d. impossible to tell without more information
e. none of these
ANSWER: a
116. Water gas, a commercial fuel, is made by the reaction of hot coke carbon with steam.
C(s) + H2O(g) CO(g) + H2(g)
When equilibrium is established at 816°C the concentrations of CO, H2, and H2O are 4.00 × 10–2, 4.00 × 10–2,
and 1.00 × 10–2 mole/liter, respectively. Calculate the value of ΔG° for this reaction at 816°C.
a. 12.4 kJ
b. –12.55 kJ
c. 54.25 kJ
d. 16.59 kJ
e. none of these
ANSWER: d
The equilibrium constant Kp (in atm) for the dissociation reaction of Cl2 2Cl was measured as a function of
temperature (in K). A graph of ln Kp versus 1/T for this reaction gives a straight line with a slope of –
1.427 × 104 and an intercept of 14.51.
117. From these data, which of the following statements is true?
a. The reaction is exothermic.
b. The reaction is endothermic.
c. The reaction rate is high
119. For a certain process, at 300. K, ΔG = –48.7 kJ and ΔH = –7.0 kJ. If the process is carried out reversibly,
the amount of useful work that can be performed is
a. –55.7 kJ
b. –7.0 kJ
c. –41.7 kJ
d. –48.7 kJ
e. 41.7 kJ
ANSWER: d
120. For a certain process, at 300. K, ΔG = –14.5 kJ and ΔH = –7.0 kJ. If the process is carried out so that no
useful work is performed, ΔG is
a. 14.5 kJ
b. 7.0 kJ
c. 0
d. –7.0 kJ
e. –14.5 kJ
ANSWER: e
127. Which item (a, b or c) in each of the three groups below has the lowest entropy?
128. In which of the following pairs is the substance with the HIGHER entropy listed first?
I. NaCl(s), NaCl(aq)
II. CO(g), CO2(g)
III. 1 mole of H2(g) at 25°C; 1 mole of H2(g) at 50°C
a. I only
b. II only
c. III only
d. all of them
e. none of them
ANSWER: e
131. Which of the following processes should show the greatest increase in entropy?
a. C6H6(l) + 15/2 O2(g) → 6 CO2(g) + 3 H2O(g)
b. 2 NO2(g) → N2O4(g)
c. C2H4(g) + H2(g) → C2H6(g)
d. BaS(s) + 2 NaNO3(s) → Ba(NO3)2(s) + Na2S(s)
e. This cannot be predicted without additional information.
ANSWER: a
132. In which of the following reactions do you expect to have the largest increase in entropy?
a. I2(s) → I2(g)
b. 2IF(g) → I2(g) + F2(g)
c. Mn(s) + O2(g) → MnO2(s)
d. Hg(l) + S(s) → HgS(s)
e. CuSO4(s) + 5H2O(l) → CuSO4.H2O(s)
ANSWER: a
134. For the reaction, X + Y → A + B, ΔGo is –1324 kJ. Which one of the following statements is NOT valid
concerning the reaction?
a. The reaction is thermodynamically favorable.
b. The reaction is spontaneous as written.
c. The products are more stable than the reactants.
d. The reaction will proceed rapidly from left to right.
e. Three of these statements are valid.
ANSWER: d