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General Chemistry: Atoms First (McMurry/Fay/Pribush) Chapter 16 Thermodynamics: Entropy, Free Energy, and Equilibrium 16.

1 Multiple Choice Questions 1) Which of the following statements is not true? A) The reverse of a spontaneous reaction is always nonspontaneous. B) A spontaneous process always moves toward equilibrium. C) A nonspontaneous process cannot be caused to occur. D) A highly spontaneous process need not occur rapidly. Answer: C Topic: Section 16.1 Spontaneous Processes 2) Which forward reaction is a nonspontaneous process? A) the expansion of a gas into a vacuum B) N2(g) + 3 H2(g) 2 NH3(g) if PH = PN = 1 atm, PNH = 0, and Kp = 4 105 C) 2 NH3(g) N2(g) + 3 H2(g) if PNH = 1 atm, PH = PN = 0, and Kp = 2 10-6 D) none of the above Answer: D Topic: Section 16.1 Spontaneous Processes 3) The chemical system shown below is at equilibrium. Which change in conditions will not result in a spontaneous forward reaction? N2(g) + 3 H2(g) 2 NH3(g) Kp = 4 105 A) adding a catalyst B) adding more H2 C) adding more N2 D) reducing the volume Answer: A Topic: Section 16.1 Spontaneous Processes 4) Classify each of the following processes as spontaneous or nonspontaneous. I. H2O(l) H2O(g) T = 25C, vessel open to atmosphere with 50% relative humidity II. H2O(s) H2O(l) T = 25C, P = 1 atm A) I and II are both spontaneous. B) I is spontaneous and II is nonspontaneous. C) I is nonspontaneous and II is spontaneous. D) I and II are both nonspontaneous. Answer: A Topic: Section 16.1 Spontaneous Processes

5) The reaction A(g) B(g) is spontaneous under standard conditions. Which of the following statements must be true? I. The reaction B(g) A(g) is nonspontaneous under standard conditions. II. A(g) will be completely converted to B(g) if sufficient time is allowed. III. A(g) will be completely converted to B(g) rapidly. A) none of these B) I C) I and II D) I, II, and III Answer: B Topic: Section 16.1 Spontaneous Processes 6) Which of the following processes are spontaneous? I. dissolving more solute in an unsaturated solution II. dissolving more solute in a saturated solution III. dissolving more solute in a supersaturated solution A) none of these B) I C) I and II D) I, II, and III Answer: B Topic: Section 16.1 Spontaneous Processes 7) Which of the following processes is spontaneous? A) a mixture of two gases separating into pure compounds B) reaction of sodium with oxygen C) precipitation of solute from a saturated solution D) water flowing uphill Answer: B Topic: Section 16.1 Spontaneous Processes 8) Entropy is a measure of A) free energy. B) the heat of a reaction. C) molecular randomness. D) the rate of a reaction. Answer: C Topic: Section 16.2 Enthalpy, Entropy, and Spontaneous Processes: A Brief Review 9) For which of the following will the entropy of the system increase? A) condensation of steam B) reaction of magnesium with oxygen to form magnesium oxide C) reaction of nitrogen and hydrogen to form ammonia D) sublimation of dry ice Answer: D Topic: Section 16.2 Enthalpy, Entropy, and Spontaneous Processes: A Brief Review

10) For which process is the sign of S negative in the system? A) 2 H2(g) + O2(g) 2 H2O(g) B) 2 H2O(l) + 2 K(s) 2 K+(aq) +2 OH(aq) + H2(g) C) H2O(s) H2O(g) D) H2O(l) H2O(g) Answer: A Topic: Section 16.2 Enthalpy, Entropy, and Spontaneous Processes: A Brief Review 11) Predict the sign of S of the system for both of the following. I. 2 C(graphite) + O2(g) 2 CO(g) II. C4H10(g) C4H10(l) A) S should be negative for I and negative for II. B) S should be negative for I and positive for II. C) S should be positive for I and negative for II. D) S should be positive for I and positive for II. Answer: C Topic: Section 16.2 Enthalpy, Entropy, and Spontaneous Processes: A Brief Review 12) Sodium reacts violently with water according to the equation: 2 Na(s) + 2 H2O(l) 2 NaOH(aq) + H2(g) The resulting solution has a higher temperature than the water prior to the addition of sodium. What are the signs of and for this reaction? A) H is negative and S is negative. B) H is negative and S is positive. C) H is positive and S is negative. D) H is positive and S is positive. Answer: B Topic: Section 16.2 Enthalpy, Entropy, and Spontaneous Processes: A Brief Review 13) The brown color associated with photochemical smog is due to NO2(g), which is involved in an equilibrium with N2O4(g) in the atmosphere. 2 NO2(g) N2O4(g) Predict the signs of the enthalpy and entropy change for the forward reaction. A) The enthalpy change is negative and the entropy change is negative. B) The enthalpy change is negative and the entropy change is positive. C) The enthalpy change is positive and the entropy change is negative. D) The enthalpy change is positive and the entropy change is positive. Answer: A Topic: Section 16.2 Enthalpy, Entropy, and Spontaneous Processes: A Brief Review

14) What is W in Boltzmann's formula, S = k ln W? A) a fraction indicating the probability of obtaining a result B) a random number C) the number of ways of obtaining the state D) the work times Avogadro's number Answer: C Topic: Section 16.3 Entropy and Probability 15) Which electron on an atom of copper would have the highest value of W in the Boltzmann formula? A) 3s B) 3d C) 4s D) 4p Answer: B Topic: Section 16.3 Entropy and Probability 16) An electron in an oxygen p orbital on which of the following would have the highest entropy? A) CH3CH2OH B) CH3CH2O C) CH3CO2OH D) CH3CO2 Answer: D Topic: Section 16.3 Entropy and Probability 17) What is k in Boltzmann's formula, S = k ln W? A) the degeneracy of the state B) the equilibrium constant for the process C) the universal gas constant divided by Avogadro's number D) the universal gas constant times Avogadro's number Answer: C Topic: Section 16.3 Entropy and Probability 18) The entropy change associated with the expansion of one mole of an ideal gas from an initial volume of Vi to a final volume of Vf at constant temperature is given by the equation, S = R ln (Vf/Vi). What is the entropy change associated with the expansion of three moles of an ideal gas from an initial volume of Vi to a final volume of Vf at constant temperature? A) S = R ln (Vf/Vi) B) S = 3 mol R ln (Vf/Vi) C) S = R ln (Vf 23/Vi) D) S = R ln (Vf 3!/Vi) Answer: B Topic: Section 16.3 Entropy and Probability Algo. Option: algorithmic 4

19) What is the entropy change associated with the expansion of one mole of an ideal gas from an initial volume of V to a final volume of V of 2.50V at constant temperature? A) S = 2.50 R ln (Vf/Vi) B) S = -2.50 R ln (Vf/Vi) C) S = R ln 2.50 D) S = -R ln 2.50 Answer: C Topic: Section 16.3 Entropy and Probability Algo. Option: algorithmic 20) Predict the sign of S for each of the following processes, which occur at constant temperature. I. The volume of 2.0 moles of O2(g) increases from 44 L to 52 L. II. The pressure of 2.0 moles of O2(g) increases from 1.0 atm to 1.2 atm. A) I: S= negative; II: S= negative B) I: S= negative; II: S= positive C) I: S= positive; II: S= negative D) I: S= positive; II: S= positive Answer: C Topic: Section 16.3 Entropy and Probability Algo. Option: algorithmic

21) Assume a heteronuclear diatomic molecule, AB, forms a one-dimensional crystal by lining up along the x-axis. Also assume that each molecule can only have one of six possible orientations, corresponding to atom A facing in either the positive or negative direction along the x-, y-, or z-axis. If the molecules are arranged randomly in the six directions, the molar entropy at absolute zero should be A) R ln 6. B) R ln 66. C) R ln 6! D) 0. Answer: A Topic: Section 16.3 Entropy and Probability 22) The Boltzmann formula is S = k ln W. A perfect crystal has a molar entropy of 0 at absolute zero because A) W = 0. B) W = 1. C) W = NA. D) k = 1. Answer: B Topic: Section 16.3 Entropy and Probability 23) What is the sign of S for each of the following processes? I. The separation of gaseous molecules of UF6, into 238UF6 and 235UF6 at constant temperature and pressure. II. The dissolving of I2(s) in CCl4(l). A) S is negative for I and negative for II. B) S is negative for I and positive for II. C) S is positive for I and negative for II. D) S is positive for I and positive for II. Answer: B Topic: Section 16.3 Entropy and Probability 24) Which has the lowest entropy? A) CH3OH(s, 25C) B) CH3OH(s, 15C) C) CH3OH(l, 15C) D) CH3OH(l, 25C) Answer: A Topic: Section 16.4 Entropy and Temperature

25) Which has the highest entropy in each set? I. H2O(s), H2O(l), H2O(g) at 0.1C, 4.58 atm II. H2O(l) at 0C, H2O(l) at 25C, H2O(l) at 100C (all at 1.0 atm pressure) A) H2O(l) in set I and H2O(l) at 0C in set II B) H2O(s) in set I and H2O(l) at 100C in set II C) H2O(g) in set I and H2O(l) at 0C in set II D) H2O(g) in set I and H2O(l) at 100C in set II Answer: D Topic: Section 16.4 Entropy and Temperature 26) Which provides the greatest increase in entropy? A) H2O (s, 0C) H2O (l, 0C) B) H2O (l, 0C) H2O (l, 25C) C) H2O (g, 0.1C) H2O (s, 0.1C) D) H2O (l, 100C) H2O (g, 100C) Answer: D Topic: Section 16.4 Entropy and Temperature 27) According to the third law of thermodynamics, A) energy is conserved in any transformation of matter. B) the entropy increases for any spontaneous process. C) the entropy of a perfectly ordered, crystalline substance is zero at 0 Kelvin. D) the entropy of the universe increases for any spontaneous process. Answer: C Topic: Section 16.4 Entropy and Temperature 28) Which of the following statements must be true for the entropy of a pure solid to be zero? I. The temperature must be 0 K. II. The solid must be crystalline, not amorphous. III. The solid must be perfectly ordered. IV. The solid must be an element. A) I B) I and II C) I, II, and III D) I, II, III, and IV Answer: C Topic: Section 16.4 Entropy and Temperature 29) Under which of the following conditions would one mole of Ne have the highest entropy, S? A) 27C and 25 L B) 137C and 25 L C) 27C and 35 L D) 137C and 35 L Answer: D Topic: Section 16.4 Entropy and Temperature Algo. Option: algorithmic 7

30) Which has the highest standard molar entropy at 25C? A) Al(s) B) Al(l) C) Al(g) D) All three should have a standard molar entropy of zero. Answer: C Topic: Section 16.5 Standard Molar Entropies and Standard Entropies of Reaction 31) Which has the highest standard molar entropy at 25C? A) F2(g) B) Cl2(g) C) Br2(g) D) I2(g) Answer: D Topic: Section 16.5 Standard Molar Entropies and Standard Entropies of Reaction 32) Which of the following gas molecules has the greatest standard molar entropy at 25C? A) C2H2 B) CH2CH2 C) CH3CH3 D) All have the same entropy. Answer: C Topic: Section 16.5 Standard Molar Entropies and Standard Entropies of Reaction 33) Which substance has the highest standard molar entropy at 25C ? A) C(graphite) B) C2H4(g) C) CH3OH(l) D) MgCO3(s) Answer: B Topic: Section 16.5 Standard Molar Entropies and Standard Entropies of Reaction 34) Which one of the following has the lowest standard molar entropy, S, at 25C?" A) C8H18(s) B) C8H18(l) C) C12H26(s) D) C12H26(l) Answer: A Topic: Section 16.5 Standard Molar Entropies and Standard Entropies of Reaction Algo. Option: algorithmic

35) Calculate S for the following reaction. N2(g) + 2 O2(g) 2 NO2(g)

A) -156.5 J/K B) -121.5 J/K C) 15.5 J/K D) 636.5 J/K Answer: B Topic: Section 16.5 Standard Molar Entropies and Standard Entropies of Reaction 36) S = 198.7 J/K for the reaction shown below. Calculate S for NH3(g). N2(g) + 3 H2(g) 2 NH3(g)

A) 61.7 J/Kmol B) 123.4 J/Kmol C) 192.3 J/Kmol D) 384.6 J/Kmol Answer: C Topic: Section 16.5 Standard Molar Entropies and Standard Entropies of Reaction 37) Calculate S for the formation of one mole of solid sodium bromide from the elements at 25C.

A) -116.7 J/K B) -81.2 J/K C) -40.5 J/K D) 86.8 J/K Answer: C Topic: Section 16.5 Standard Molar Entropies and Standard Entropies of Reaction

38) The standard molar entropy for Br2(g) is 245.46 J/(mol K) at 25C. Given that S = 104.58 J/K for the dissociation of one mole of Br2(g) into Br(g) at 25C, find the standard molar entropy for Br(g) at 25C. A) 70.44 J/(mol K) B) 140.08 J/(mol K) C) 175.02 J/(mol K) D) 350.04 J/(mol K) Answer: C Topic: Section 16.5 Standard Molar Entropies and Standard Entropies of Reaction 39) Which of the three laws of thermodynamics provides a criterion for spontaneity? A) the first law of thermodynamics B) the second law of thermodynamics C) the third law of thermodynamics D) both the second and third laws of thermodynamics Answer: B Topic: Section 16.6 Entropy and the Second Law of Thermodynamics 40) Which of the following is a criterion for spontaneity that holds for any process? A) G < 0 B) G > 0 C) Stotal < 0 D) Stotal > 0 Answer: D Topic: Section 16.6 Entropy and the Second Law of Thermodynamics 41) According to the second law of thermodynamics, all reactions proceed spontaneously in the direction that increases the entropy of the A) surroundings. B) system. C) system surroundings D) system + surroundings Answer: D Topic: Section 16.6 Entropy and the Second Law of Thermodynamics 42) For a process to be at equilibrium, it is necessary that A) Ssys = Ssurr. B) Ssys = - Ssurr. C) Ssys = 0. D) Ssys = 0 and Ssurr = 0. Answer: B Topic: Section 16.6 Entropy and the Second Law of Thermodynamics

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43) For a spontaneous process A) energy and entropy are conserved. B) energy is conserved and the entropy of the system and surroundings increases. C) the energy of the system and the surroundings decreases and the entropy of the system and surroundings increases. D) both the energy and the entropy of the system and surroundings decrease. Answer: B Topic: Section 16.6 Entropy and the Second Law of Thermodynamics 44) For the process CaCO3(calcite) CaCO3(aragonite) H = -0.21 kJ, S = -4.2 J/K Assuming that the surroundings can be considered a large heat reservoir at 25C, calculate Ssurr and Stotal for the process at 25C and 1 atm pressure. Is the process spontaneous at 25C and 1 atm pressure? A) Ssurr = 4.2 J/K, total = 0, not spontaneous B) Ssurr = 0.7 J/K, Stotal = -3.5 J/K, not spontaneous C) Ssurr = -0.7 J/K, Stotal = -4.9 J/K, spontaneous D) Ssurr = -0.7 J/K, Stotal = -4.9 J/K, not spontaneous Answer: B Topic: Section 16.6 Entropy and the Second Law of Thermodynamics 45) During perspiration, A) the entropy of the water evaporated decreases and the entropy of the body decreases. B) the entropy of the water evaporated decreases and the entropy of the body increases. C) the entropy of the water evaporated increases and the entropy of the body decreases. D) the entropy of the water evaporated increases and the entropy of the body increases. Answer: C Topic: Section 16.6 Entropy and the Second Law of Thermodynamics 46) A hot penny is dropped into cold water inside a polystyrene foam cup. Assuming negligible heat loss to the atmosphere and the cup, A) the decrease in entropy of the penny is equal to the increase in entropy of the water. | Spenny | = | Swater | B) the decrease in entropy of the penny is less than the increase in entropy of the water. | Spenny | < | Swater | C) the decrease in entropy of the penny is more than the increase in entropy of the water. | Spenny | > | Swater | D) the entropy of both the penny and the water increases. Answer: B Topic: Section 16.6 Entropy and the Second Law of Thermodynamics

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47) At constant pressure and temperature, which statement is true? A) All reactions for which H < 0 are spontaneous. B) All reactions for which S < 0 are spontaneous. C) All reactions for which G < 0 are spontaneous. D) All reactions for which K < 1 are spontaneous. Answer: C Topic: Section 16.7 Free Energy 48) Why is the sign of G rather than the sign of Stotal generally used to determine the spontaneity of a chemical reaction? A) G can be used for processes that occur under any conditions. B) G involves thermodynamic functions of the system only. C) Free energy is easier to understand than entropy. D) Entropy is based on probability and is therefore less reliable. Answer: B Topic: Section 16.7 Free Energy 49) Other than only PV work, what reaction conditions must be satisfied for the sign of G to be used as a criterion for spontaneity? A) constant volume and pressure B) constant temperature and pressure C) constant temperature and volume D) constant volume only Answer: B Topic: Section 16.7 Free Energy 50) For the reaction 3 C2H2(g) C6H6(l) at 25C, the standard enthalpy change is -631 kJ and the standard entropy change is -430 J/K. Calculate the standard free energy change at 25C. A) 948 kJ B) -503 kJ C) -618 kJ D) -1061 kJ Answer: B Topic: Section 16.7 Free Energy 51) For a particular process G is less than H. Therefore A) S is positive. B) S is negative. C) S is zero. D) S is negative if H is positive and S is positive if H is negative. Answer: A Topic: Section 16.7 Free Energy

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52) For a particular process, G = H at a given temperature and pressure. Therefore, A) S is positive if H is positive and negative is H is negative. B) S is negative if H is positive and positive if H is negative. C) S is zero. D) S = G/T. Answer: C Topic: Section 16.7 Free Energy 53) The solubility of manganese(II) fluoride in water is 6.6 g/mL at 40C and 4.8 g/L at 100C. Based on these data, what is the sign of H and S for the process below? MnF2(s) Mn2+(aq) + 2 F-(aq) A) H is negative but the sign of S cannot be determined from this information. B) H is negative and S is definitely negative. C) H is positive but the sign of S cannot be determined from this information. D) H is positive and S is definitely negative. Answer: A Topic: Section 16.7 Free Energy 54) At 25C, H = 1.895 kJ and S = -3.363 J/K for the transition C(graphite) C(diamond) Based on these data A) graphite cannot be converted to diamond at 1 atm pressure. B) diamond is more stable than graphite at all temperatures at 1 atm. C) diamond is more stable than graphite below 290C and graphite is more stable than diamond above 290C. D) graphite is more stable than diamond below 290C and diamond is more stable than graphite above 290C. Answer: A Topic: Section 16.7 Free Energy 55) For bromine, Hvap = 30.91 kJ/mol and Svap = 93.23 JK-1mol-1 at 25C. What is the normal boiling point for bromine? A) 25C B) 58C C) 124C D) 332C Answer: B Topic: Section 16.7 Free Energy

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56) Consider the reaction: N2(g) + 3 F2(g) 2 NF3(g) H = -249 kJ and S = -278 J/K at 25C Calculate G and state whether the equilibrium composition should favor reactants or products at standard conditions. A) G = -332 kJ; the equilibrium composition should favor products. B) G = -332 kJ; the equilibrium composition should favor reactants. C) G = -166 kJ; the equilibrium composition should favor products. D) G = -166 kJ; the equilibrium composition should favor reactants. Answer: C Topic: Section 16.7 Free Energy 57) Which statement is true about the formation of CaCO3(s) from CaO(s) and CO2(g) at 1.00 atm? CaO(s) + CO2(g) CaCO3(s) H = -178.7 kJ and S = -150.4 J/K A) The reaction is spontaneous at all temperatures. B) The reaction is spontaneous at high temperatures. C) The reaction is spontaneous at low temperatures. D) The reaction is not spontaneous at any temperature. Answer: C Topic: Section 16.7 Free Energy 58) The signs of G, H, and S at 25C are shown below for three reactions.

Which reaction could go in the reverse direction at high temperature? A) I B) II C) III D) I and II Answer: C Topic: Section 16.7 Free Energy 59) For the evaporation of water during perspiration on a hot, dry day, A) H is positive and TS = H. B) H is positive and TS > H. C) H is positive and TS < H. D) H is negative and TS is positive. Answer: B Topic: Section 16.7 Free Energy

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60) For the reaction below G = + 33.0 kJ, H = + 92.2 kJ, and S = + 198.7 J/K. Estimate the temperature at which this reaction becomes spontaneous. 2 NH3(g) N2(g) + 3 H2(g) A) 0.464 K B) 166 K C) 298 K D) 464 K Answer: D Topic: Section 16.7 Free Energy 61) Calculate the standard free energy change at 25C for the reaction 2 NO(g) + O2(g) 2 NO2(g).

A) -4.7 kJ B) -72.6 kJ C) -157.8 kJ D) -532.6 kJ Answer: B Topic: Section 16.8 Standard Free-Energy Changes for Reactions 62) For any thermodynamic function Y, Y for a reaction refers to the change in Y for the process in which A) the mixed reactants at 1 atm go to equilibrium at 1 atm. B) the separate reactants at 1 atm go to equilibrium at 1 atm. C) the separate reactants in their standard states are completely converted to separate products in their standard states. D) the spontaneous reaction occurs. Answer: C Topic: Section 16.8 Standard Free-Energy Changes for Reactions 63) Which of the following is true? A) As a reaction at constant temperature and pressure goes to equilibrium, |G| decreases. B) The larger G, the faster the reaction. C) The standard state for solutes is the pure solute at 1 atm. D) When a reaction reaches equilibrium, G = 0. Answer: A Topic: Section 16.8 Standard Free-Energy Changes for Reactions

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64) Which statement is true concerning the standard states of F2(g) and C6H12O6(aq)? A) The standard state for F2(g) is the pure gas at 1 atm and for C6H12O6(aq) is the pure solid at 1 atm. B) The standard state for F2(g) is the pure gas at 1 mol/L and for C6H12O6(aq) is the pure solid at 1 atm. C) The standard state for F2(g) is the pure gas at 1 atm and for C6H12O6(aq) is the solution at a concentration of 1 mol/L. D) The standard state for F2(g) is the pure gas at 1 mol/L and for C6H12O6(aq) is the solution at a concentration of 1 mol/L. Answer: C Topic: Section 16.8 Standard Free-Energy Changes for Reactions 65) Calculate the standard free energy for the reaction given. 2 CH3OH(l) + 3 O2(g) 2 CO2(g) + 4 H2O(l)

A) -465.2 kJ B) -797.8 kJ C) -1404.8 kJ D) -2069.8 kJ Answer: C Topic: Section 16.9 Standard Free Energies of Formation 66) Which is the lowest at 25C? A) Gf for H2O (s) B) Gf for H2O (l) C) Gf for H2O (g) D) 1/2Gf for O2 (g) plus Gf for H2O (g) Answer: B Topic: Section 16.9 Standard Free Energies of Formation 67) Which of the following is zero at 25C? A) Gf for N2(g) B) Gf for H2O (l) C) S for N2 (g) D) S for H2O (l) Answer: A Topic: Section 16.9 Standard Free Energies of Formation

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68) A positive value of Gf for a solid compound at 25C means the A) compound cannot exist at 25C and 1 atm. B) compound must be a liquid or a gas at 25C and 1 atm. C) process of forming the compound from the elements is exothermic. D) process of forming the compound from the stable elements at 25C and 1 atm is nonspontaneous. Answer: D Topic: Section 16.9 Standard Free Energies of Formation 69) At 25C, Gf is -620 kJ/mol for SiCl4(g) and -592 kJ/mol for MgCl2(s). Calculate G for the reaction, and determine if the reaction is spontaneous at 25C if the pressure of SiCl4(g) is 1 atm. A) G = 28 kJ; the process is spontaneous. B) G = 28 kJ; the process is nonspontaneous. C) G = -564 kJ; the process is spontaneous. D) G = -564 kJ; the process is nonspontaneous. Answer: C Topic: Section 16.9 Standard Free Energies of Formation 70) Which of the following are unstable with respect to their constituent elements at 25C?

A) C8H18(l), CH3OH(l) B) C8H18(l), C2H2(g) C) C2H2(g) D) CH3OH(l) Answer: C Topic: Section 16.9 Standard Free Energies of Formation 71) In general, as a reaction goes to equilibrium A) G decreases. B) Gf decreases. C) G goes to zero. D) G decreases. Answer: C Topic: Section 16.10 Free-Energy Changes and the Composition of the Reaction Mixture

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72) At 25C, G = -198 kJ for the reaction, NO(g) + O3(g) NO2(g) + O2(g). Calculate G under the following conditions:

A) -159 kJ B) -167 kJ C) -198 kJ D) -236 kJ Answer: A Topic: Section 16.10 Free-Energy Changes and the Composition of the Reaction Mixture 73) For a reaction at constant temperature, as Q increases A) G and G increase. B) G and G decrease. C) G increases, but G remains constant. D) G decreases, but G remains constant. Answer: C Topic: Section 16.10 Free-Energy Changes and the Composition of the Reaction Mixture 74) At high temperatures boron carbide vaporizes according to the equation B4C(s) 4 B(g) + C(s) Which equation describes the relationship between G and G for this reaction? A) G = G + R T ln (pB [C]/[B4C]) B) G = G + R T ln pB C) G = G + 4 R T ln pB D) G = G - 4 R T ln pB Answer: C Topic: Section 16.10 Free-Energy Changes and the Composition of the Reaction Mixture

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75) At 2600 K, G = 775 kJ for the vaporization of boron carbide: B4C(s) 4 B(g) + C(s) Find G and determine if the process is spontaneous if the reaction vessel contains 4.00 mol B4C(s), 0.400 mol of C(s), and B(g) at a partial pressure of 1.0 10-5 atm. At this temperature, R T = 21.6 kJ. A) G = -270 kJ; spontaneous. B) G = -270 kJ; nonspontaneous. C) G = -220 kJ; spontaneous. D) G = -220 kJ; nonspontaneous. Answer: C Topic: Section 16.10 Free-Energy Changes and the Composition of the Reaction Mixture 76) G = G for a reaction A) if Q = K. B) if Q = 1. C) at STP. D) at the start of the reaction. Answer: B Topic: Section 16.10 Free-Energy Changes and the Composition of the Reaction Mixture 77) What is the relationship between G and the GF for the reaction below? MgF2(s) Mg2+(aq) + 2 F-(aq) A) G = {Gf [Mg2+ (aq)] + 2 Gf [F- (aq)] - Gf [MgF2 (s)]} + RT ln ([Mg2+] [F-]2/ [MgF2]) B) G = {Gf [Mg2+ (aq)] + 2 Gf [F- (aq)] - Gf [MgF2 (s)]} + RT ln ([Mg2+] [F-])2) C) G = {Gf [Mg2+ (aq)] + 2 Gf [F- (aq)]} + RT ln ([Mg2+] [F-]2) D) G = {Gf [Mg2+ (aq)] + 2 Gf [F- (aq)] - Gf [MgF2 (s)]} + RT ln Ksp Answer: B Topic: Section 16.10 Free-Energy Changes and the Composition of the Reaction Mixture 78) If Q increases A) G increases and the reaction becomes more spontaneous. B) G increases and the reaction becomes less spontaneous. C) G decreases and the reaction becomes more spontaneous. D) G decreases and the reaction becomes less spontaneous. Answer: B Topic: Section 16.10 Free-Energy Changes and the Composition of the Reaction Mixture

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79) What is the relationship between G, Qp, and Kp for a reaction involving gases? A) G = Qp/Kp B) G = Kp/Qp C) G = RTln(Qp/Kp) D) G = RTln(Kp/Qp) Answer: C Topic: Section 16.11 Free Energy and Chemical Equilibrium 80) When equilibrium is reached at constant temperature and pressure, A) Q = 1. B) G = 0. C) S is maximized. D) G is minimized. Answer: D Topic: Section 16.11 Free Energy and Chemical Equilibrium 81) Calculate Ksp for PbI2 at 25C based on the following data:

A) 4 10-31 B) 8 10-18 C) 9 10-9 D) 5 10-5 Answer: C Topic: Section 16.11 Free Energy and Chemical Equilibrium 82) At high temperatures, boron carbide vaporizes according to B4C(s) 4 B(g) + C(s) At 2500 K, the equilibrium pressure of B(g) is 0.0342 mm Hg over a mixture of 0.300 mol B4C(s) and 0.500 mol C(s). Calculate for this process. A) 832 kJ B) 799 kJ C) 281 kJ D) 247 kJ Answer: A Topic: Section 16.11 Free Energy and Chemical Equilibrium

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83) Solid NaHCO3 is heated to 90C. At equilibrium the total pressure of the gases produced is 0.545 atm. Calculate G at 90C for the reaction 2 NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g). A) -7.85 kJ B) -3.67 kJ C) +3.67 kJ D) +7.85 kJ Answer: D Topic: Section 16.11 Free Energy and Chemical Equilibrium 84) What is K if G = -18.0 kJ for a reaction at 25? A) 1.4 103 B) 1.2 102 C) 8.1 10-3 D) 7.3 10-4 Answer: A Topic: Section 16.11 Free Energy and Chemical Equilibrium 85) If G is negative for a reaction, A) K < 0. B) K = 0. C) K is between 0 and 1. D) K > 1. Answer: D Topic: Section 16.11 Free Energy and Chemical Equilibrium 86) If G is positive for a reaction, A) K < 0. B) K = 0. C) K is between 0 and 1. D) K > 1. Answer: C Topic: Section 16.11 Free Energy and Chemical Equilibrium 87) For the following reaction find Kp at 25C and indicate whether Kp should increase or decrease as the temperature rises. NH4HS(s) H2S(g) + NH3(g)H = 83.47 kJ and G = 17.5 kJ at 25C. A) Kp = 8.6 10-4 and Kp should increase as the temperature rises. B) Kp = 8.6 10-4 and Kp should decrease as the temperature rises. C) Kp = 1.2 103 and Kp should increase as the temperature rises. D) Kp = 1.2 103 and Kp should decrease as the temperature rises. Answer: A Topic: Section 16.11 Free Energy and Chemical Equilibrium

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88) If G is small and positive, A) the forward reaction is spontaneous and the system is far from equilibrium. B) the forward reaction is spontaneous and the system is near equilibrium. C) the reverse reaction is spontaneous and the system is far from equilibrium. D) the reverse reaction is spontaneous and the system is near equilibrium. Answer: D Topic: Section 16.11 Free Energy and Chemical Equilibrium 89) In figure (1) below argon atoms, represented by unshaded spheres, and neon atoms, represented by shaded spheres, are in separate compartments. Figure (2) shows the equilibrium state of the system after the stopcock separating the two compartments is opened. Assuming that argon and neon behave as ideal gases, what are the signs (+, -, or 0) of H, S, and G for this process?

A) H = +, S = -, G = + B) H = 0, S = +, G = C) H = 0, S = -, G = + D) H = -, S = +, G = Answer: B Topic: Key Concept Problems

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90) In figure (1) below oxygen molecules, represented by unshaded spheres, and chlorine molecules, represented by shaded spheres, are in separate compartments. Figure (2) shows the equilibrium state of the system after the stopcock separating the two compartments is opened. Assuming the oxygen and the chlorine behave as ideal gases, what are the signs (+, -, or 0) of H, S, and G for this process?

A) H = +, S = -, G = + B) H = 0, S = +, G = C) H = 0, S = -, G = + D) H = -, S = +, G = Answer: B Topic: Key Concept Problems 91) The figure represents the spontaneous deposition of iodine in which iodine vapor, I2(g), becomes crystalline iodine solid I2(s): I2(g): I2(s). What are the signs (+ or -) of H, S, and G for this process?

A) H = +, S = +, G = + B) H = +, S = +, G = C) H = -, S = -, G = + D) H = -, S = -, G = Answer: D Topic: Key Concept Problems

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92) The figure represents the spontaneous evaporation of nitrogen in which liquid nitrogen, N2(l), becomes gaseous nitrogen, N2(g): N2(l) N2(g). What are the signs (+ or -) of H, S, and G for this process?

A) H = +, S = +, G = + B) H = +, S = +, G = C) H = -, S = -, G = + D) H = -, S = -, G = Answer: B Topic: Key Concept Problems 93) An ideal gas is expanded at constant temperature. What are the signs (+, -, or 0) of H, S, and G for this system?

A) H = +, S = -, G = + B) H = 0, S = +, G = C) H = 0, S = -, G = + D) H = -, S = +, G = Answer: B Topic: Key Concept Problems

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94) The figure above represents the nonspontaneous reaction O2(g) 2O(g). What are the signs (+ or -) of H, S, and G for this process? A) H = +, S = +, G = + B) H = +, S = +, G = C) H = -, S = -, G = + D) H = -, S = -, G = Answer: A Topic: Key Concept Problems 95) The figure above represents the reaction O2(g) 2O(g), which is nonspontaneous at 25C. How will the spontaneity of this reaction vary with temperature? This reaction is A) nonspontaneous at all temperatures. B) nonspontaneous at high temperatures and spontaneous at low temperatures. C) spontaneous at high temperatures and nonspontaneous at low temperatures. D) spontaneous at all temperatures. Answer: C Topic: Key Concept Problems The figure below represents the spontaneous reaction of H2 (shaded spheres) with O2 (unshaded spheres) to produce gaseous H2O.

96) What are the signs (+, or -) of H, S, and G for this process? A) H = +, S = +, G = + B) H = +, S = +, G = C) H = -, S = -, G = + D) H = -, S = -,G = Answer: D Topic: Key Concept Problems

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97) How will the spontaneity of this reaction vary with temperature? This reaction is A) nonspontaneous at all temperatures. B) nonspontaneous at high temperatures and spontaneous at low temperatures. C) spontaneous at high temperatures and nonspontaneous at low temperatures. D) spontaneous at all temperatures. Answer: B Topic: Key Concept Problems Consider the reaction 2A(g) A2(g). The following pictures represent two possible initial states and the equilibrium state of the system.

98) For initial state 1 what is the relationship between the reaction quotient, Qp, and the equilibrium constant, Kp? A) Qp < Kp B) Qp = Kp = 1 C) Qp = Kp 1 D) Qp > Kp Answer: A Topic: Key Concept Problems 99) For initial state 2 what is the relationship between the reaction quotient, Qp, and the equilibrium constant, Kp? A) Qp < Kp B) Qp = Kp = 1 C) Qp = Kp 1 D) Qp > Kp Answer: D Topic: Key Concept Problems

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100) What are the signs (+ or -) of H, S, and G when the system spontaneously goes from initial state 1 to the equilibrium state? A) H = +, S = +, G = + B) H = +, S = +, G = C) H = -, S = -, G = + D) H = -, S = -, G = Answer: D Topic: Key Concept Problems 101) What are the signs (+ or -) of H, S, and G when the system spontaneously goes from initial state 2 to the equilibrium state? A) H = +, S = +, G = + B) H = +, S = +, G = C) H = -, S = -, G = + D) H = -, S = -, G = Answer: B Topic: Key Concept Problems Consider the following gas-phase reaction of A2 (shaded spheres) and B2 (unshaded spheres): A2(g) + B2(g) 2 AB(g) G = +25 kJ

102) Which of the above reaction mixtures has the least spontaneous forward reaction? A) (1) B) (2) C) (3) D) (4) Answer: D Topic: Key Concept Problems 103) Which of the above reaction mixtures has the most spontaneous forward reaction? A) (1) B) (2) C) (3) D) (4) Answer: A Topic: Key Concept Problems

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104) Which of the above reaction mixtures is G of reaction = G ? A) (1) B) (2) C) (3) D) (4) Answer: C Topic: Key Concept Problems

105) According to the diagram above, the forward reaction is A) nonspontaneous at d and e, and spontaneous at f. B) nonspontaneous at d, at equilibrium at e, and spontaneous at f. C) spontaneous at d, at equilibrium at e, and nonspontaneous at f. D) spontaneous at d, e, and f. Answer: C Topic: Key Concept Problems 106) According to the diagram above, A) G is positive and the equilibrium composition is rich in products. B) G is positive and the equilibrium composition is rich in reactants. C) G is negative and the equilibrium composition is rich in products. D) G is negative and the equilibrium composition is rich is reactants. Answer: B Topic: Key Concept Problems

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107) According to this diagram, A) G is positive and is equal to a - b. B) G is positive and is equal to b - c. C) G is negative and is equal to b - c. D) G is negative and is equal to a - c. Answer: A Topic: Key Concept Problems 108) The following pictures represent three equilibrium mixtures for the interconversion of A, B, and C molecules (unshaded spheres) into X, Y, and Z molecules (shaded spheres), respectively. What is the sign of G for each of the three reactions?

A) G (1) = -; G (2) = +; G (3) = 0 B) G (1) = -; G (2) = 0; G (3) = + C) G (1) = 0; G (2) = -; G (3) = + D) G (1) = +; G (2) = 0; G (3) = Answer: B Topic: Key Concept Problems 16.2 Algorithmic Questions 1) The entropy change associated with the expansion of one mole of an ideal gas from an initial volume of Vi to a final volume of Vf at constant temperature is given by the equation, S = R ln (Vf/Vi). What is the entropy change associated with the expansion of three moles of an ideal gas from an initial volume of Vi to a final volume of Vf at constant temperature? A) S = R ln (Vf/Vi) B) S = 3 mol R ln (Vf/Vi) C) S = R ln (Vf 23/Vi) D) S = R ln (Vf 3!/Vi) Answer: B Topic: Section 16.3 Entropy and Probability Algo. Option: algorithmic

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2) What is the entropy change associated with the expansion of one mole of an ideal gas from an initial volume of V to a final volume of 4.50 V at constant temperature? A) S = 4.50 R ln (Vf/Vi) B) S = -4.50 R ln (Vf/Vi) C) S = R ln 4.50 D) S = -R ln 4.50 Answer: C Topic: Section 16.3 Entropy and Probability Algo. Option: algorithmic 3) Predict the sign of S for each of the following systems, which occur at constant temperature I. The volume of 2.0 moles of O2(g) increases from 44 L to 52 L. II. The pressure of 2.0 moles of O2(g) increases from 1.0 atm to 1.2 atm. A) I: S = negative; II: S = negative B) I: S = negative; II: S = positive C) I: S = positive; II: S = negative D) I: S = positive; II: S = positive Answer: C Topic: Section 16.3 Entropy and Probability Algo. Option: algorithmic 4) Under which of the following conditions would one mole of He have the highest entropy, S? A) 17C and 15 L B) 127C and 15 L C) 17C and 25 L D) 127C and 25 L Answer: D Topic: Section 16.4 Entropy and Temperature Algo. Option: algorithmic 5) Which one of the following would be expected to have the lowest standard molar entropy, S, at 25C? A) C10H22(s) B) C10H22(l) C) C14H30(s) D) C14 OH(l) Answer: A Topic: Section 16.5 Standard Molar Entropies and Standard Entropies of Reaction Algo. Option: algorithmic

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16.3 Short Answer Questions 1) Chemical and physical changes can be classified as spontaneous or nonspontaneous. At 25C and 1 atm pressure the decomposition of water into hydrogen and oxygen is classified as ________, and the melting of ice is classified as ________. Answer: nonspontaneous, spontaneous Topic: Section 16.1 Spontaneous Processes 2) The sign (+ or ) of H is ________ and the sign (+ or ) of S is ________ for the evaporation of water. Answer: +, + Topic: Section 16.2 Enthalpy, Entropy, and Spontaneous Processes: A Brief Review 3) A 1.0 mole sample of gas at STP has a ________ entropy than 1.0 mole of gas at 273 K and 835 mm Hg. Answer: higher Topic: Section 16.3 Entropy and Probability 4) The entropy of water at 25 is ________ than the entropy of water at 35C. Answer: less than Topic: Section 16.4 Entropy and Temperature 5) Standard molar entropies, S, in J/Kmol, are given below each reactant and product in the reaction shown below. The standard entropy of reaction, S, for this reaction is ________ J. CH4(g) + 2 O2(g) CO2(g) + 2 H2O(l) 186.2 205.0 213.6 69.9 Answer: 242.8 Topic: Section 16.5 Standard Molar Entropies and Standard Entropies of Reaction 6) A reaction for which H = + 98.8 kJ and S = + 141.5 J/K is ________ (spontaneous or nonspontaneous) at low temperatures and ________ (spontaneous or nonspontaneous) at high temperatures. Answer: nonspontaneous, spontaneous Topic: Section 16.7 Free Energy 7) A reaction has G = + 21.5 kJ/mol, H = + 25.0 kJ/mol, and S = + 15.0 J/molK can become spontaneous at a temperature of ________ K. Answer: 1670 Topic: Section 16.7 Free Energy 8) Acetylene, C2H2, has a standard enthalpy of formation, H = 226.7 kJ/mol, and a standard entropy change for its formation from its elements, S = 58.8 J/Kmol. The standard free energy of formation of acetylene is ________ kJ/mol. Answer: + 209.2 Topic: Section 16.8 Standard Free-Energy Changes for Reactions

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9) Standard free energies of formation, G, in kJ/mol, are given below each reactant and product in the reaction shown below. The standard free energy of reaction, G, for this reaction is ________ kJ. CH4(g) + 2 O2(g) CO2(g) + 2 H2O(l) 50.8 0 394.4 237.2 Answer: 818.0 Topic: Section 16.9 Standard Free Energies of Formation 10) The standard free energy for a reaction is G = 33.0 kJ. At 25C the equilibrium constant for this reaction , Kp = ________. Answer: 6.09 105 Topic: Section 16.11 Free Energy and Chemical Equilibrium

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