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PHYSICAL CHEMISTRY By: Shailendra Kumar 1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 4 2. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna Page No.: 1 1. For a process at 451 K and constant pressure, S surr is -326 J K –1 . Calculate the quantity of heat (in kJ) absorbed by the system. 2. Which of the following produces an INCREASE in entropy of the system? a. H 2 O (l) –––H 2 O (s) b. 2 O 2 (g) + 2 SO (g) –––2 SO 3 (g) c. 2 CH 3 OH (g) + 3 O 2 (g) –––2 CO 2 (g) + 4 H 2 O (l) d. I 2 (s) –––I 2 (l) e. None of the above. 3. The gas-phase reaction between H 2 and Cl 2 can be initiated by ultraviolet light at 25°C, H 2 (g) + Cl 2 (g) –––2 HCl (g) Using the thermodynamic data provided below, calculate the standard free energy change (in kJ) at 25°C for this reaction. compound f , kJ mol –1 S°, J mol –1 K –1 H 2 0 130.57 Cl 2 0 222.96 HCl -92.307 186.80 4. In lecture, you observed the following reaction, 2 H 2 (g) + O 2 (g) –––2 H 2 O (g) For this reaction, H° = -241.8 kJ and S° = -88.8 JK –1 Assumeing that H° = H and S° = S at all temperatures, calculate the temperature (in K) at which this reaction would become non-spontaneous. 5. For a particular chemical reaction at 400°C, G = -67 kJ. Calculate the time (in seconds) it will take for the reaction to reach completion. 6. For a particular chemical reaction, H° is positive and S° is negative. Which of the following statements about the spontaneity of the reaction under standard is conditions TRUE? a. The reaction will be spontaneous only if the magnitude of H° is large enough to overcome the unfavorable entropy change PHYSICAL CHEMISTRY SCIENCE TUTORIALS; Opp. Khuda Baksh Library, Ashok Rajpath, Patna PIN POINT STUDY CIRCLE; House No. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna Topic: Thermodynamics Classes at: - by: SHAILENDRA KR. Meq. Approach

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Page 1: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 1

1. For a process at 451 K and constant pressure, ∆Ssurr is -326 J K–1. Calculate the quantity of heat

(in kJ) absorbed by the system.

2. Which of the following produces an INCREASE in entropy of the system?

a. H2O (l) –––→ H2O (s)

b. 2 O2 (g) + 2 SO (g) –––→ 2 SO3 (g)

c. 2 CH3OH (g) + 3 O2 (g) –––→ 2 CO2 (g) + 4 H2O (l)

d. I2 (s) –––→ I2 (l)

e. None of the above.

3. The gas-phase reaction between H2 and Cl

2 can be initiated by ultraviolet light at 25°C,

H2 (g) + Cl

2 (g) –––→ 2 HCl (g)

Using the thermodynamic data provided below, calculate the standard free energy change(in kJ) at 25°C for this reaction.

compound ∆H°f, kJ mol–1 S°, J mol–1 K–1

H2 0 130.57 Cl2 0 222.96 HCl -92.307 186.80

4. In lecture, you observed the following reaction,

2 H2 (g) + O2 (g) –––→ 2 H2O (g)

For this reaction, ∆H° = -241.8 kJ and ∆S° = -88.8 JK–1 Assumeing that H° = ∆H and ∆S° = ∆S atall temperatures, calculate the temperature (in K) at which this reaction would becomenon-spontaneous.

5. For a particular chemical reaction at 400°C, ∆G = -67 kJ. Calculate the time (in seconds) it willtake for the reaction to reach completion.

6. For a particular chemical reaction, ∆H° is positive and ∆S° is negative. Which of the followingstatements about the spontaneity of the reaction under standard is conditions TRUE?

a. The reaction will be spontaneous only if the magnitude of ∆H° is large enough toovercome the unfavorable entropy change

PHYSICAL CHEMISTRY

SCIENCE TUTORIALS; Opp. Khuda Baksh Library, Ashok Rajpath, PatnaPIN POINT STUDY CIRCLE; House No. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Topic: Thermodynamics

Classes at: -

by: SHAILENDRA KR.Meq. Approach

Page 2: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 2

b. The reaction will be spontaneous only if the magnitude of ∆S° is large enough toovercome the unfavorable enthalpy change.

c. The reaction will be spontaneous regardless of the magnitudes of ∆H° and ∆S°.

d. The reaction cannot be spontaneous.

e. The reaction will be spontaneous only of ∆G° is positive.

7. Which of the following is TRUE for an operating voltaic cell?

a. ∆G > 0 ; E = 0 b. ∆G < 0 ; E < 0

c. ∆G = 0 ; E > 0 d. ∆G = 0 ; E = 0

e. ∆G < 0 ; E > 0

8. Which of the following produces a DECREASE in entropy of the system?

Hint :- the system is shown in bold

a. Dissolving sugar in a cup a coffee.

b. Condensation of water on the surface of a glass of iced tea on a hot summer day.

c. Boiling water in a pot on the stove to make spaghetti.

d. Allowing the liquid propane in a gas grill to escape from the tank.

e. Producing CO2 gas from baking soda (NaHCO3) when baking a cake.

9. Consider the following reaction and thermodynamic data,

2 H2O2 (aq) º 2 H2O (l) + O2 (g)

substance ∆H°f, kJ mol–1 S°, J mol–1 K–1

H2O2 (aq) -191.17 143.9

H2O (l) -285.83 69.91

O2 (g) 0 205.14

Calculate the value (in kJ) of ∆G° at 25°C.

10. For particular chemical reaction, both ∆H° and ∆S° are negative. Which of the following statementsabout the spontaneity of the reaction under standard conditions is TRUE?

a. The reaction will be spontaneous only if the magnitude of ∆H° is large enough toovercome the unfavorable entropy change.

b. The reaction will be spontaneous only if the magnitude of ∆S° is large enough toovercome the unfavorable entropy change.

c. The reaction will be spontaneous regardless of the magnitudes of ∆H° and ∆S°.

d. The reaction cannot e spontaneous.

e. The reaction will be spontaneous only of ∆G° is positive.

Page 3: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 3

11. The boiling point of a substance is the temperature at which equilibrium is established betweenthe liquid and the vapor.

CH3CH

2OH (l) º CH

3CH

2OH (g)

Calculate the boiling point (in K) of ethanol, CH3CH

2OH, if ∆H = 42.6 kJ and ∆S = 122 J/K for this

process.

12. What is the significance of the Third Law of Thermodynamics? Choose the best answer.

a. The absolute entropy of a substance decreases with increasing temperature.

b. The change in entropy of the universe must be positive for a spontaneous process.

c. The absolute value of entropy can be measured for some very pure substances.

d. The change in entropy of the universe equals the sum of the change in entropy of thesystem plus the change in entropy of the surroundings.

e. The entropy of the universe is constant.

13. The Ksp for the sparingly soluble salt barium chromate (BaCrO4) at 25°C is equal to 2.0 x 10–10.Calculate ∆G° (in kJ) for the following reaction.

BaCrO4 (s) º Ba2+ (aq) + CrO42– (aq)

14. A student of chemistry determined the value of Ksp

for a saturated solution of borax at severaldifferent temperatures. The value for ∆S° for the dissolution of borax in water can be determinedfrom:

a. the slope of the line resulting from a plot of ln KSP

versus (1/T).

b. the y-intercept of the line resulting from a plot of ln KSP

versus T.

c. the slope of the line resulting from a plot of KSP

versus (1/T)

d. the y-intercept of the line resulting from a plot of KSP versus (1/T)

e. the slope of the curve at 25°C from a plot of ln KSP versus T.

15. Consider the following gas-phase reaction

2NO2 (g) º 2NO (g) + O2 (g), ∆G° = + 70.5 kJ

If 1.00 mole of NO2 (g) is placed in a 1.00-L flask (no NO (g) or O2 (g) initially) at 25°, Which of thefollowing statements is TRUE ?

a. The reaction will occur spontaneously from left to right

b. The reaction will occur spontaneously from right to left

c. The reaction is not spontaneous in either direction.

d. The reaction is spontaneous in both directions.

e. At equilibrium, the concentrations of NO (g) and O2 (g) will be much larger than theconcentration of NO2 (g).

Page 4: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 4

16. For which one of the following reactions does the entropy of the system INCREASE?

a. NH3 (g) +HCl (g) –––→ NH

4Cl (s) b. Ag+ (aq) + Cl– (aq) –––→ AgCl (s)

c. 2 H2 (g) + O

2 (g) –––→ 2 H

2O (g) d. NH

3 (g) + H

2O (l) –––→ NH

4+ (aq) + OH– (aq)

e. 2 H2O

2 (l) –––→ 2 H

2O (l) + O

2 (g)

17. Consider the following characteristics of chemical reactions,

I. spontaneity II. maximum amount of work that can be done III. speed

The value of ∆G for a chemical reaction under a given set of conditions provides informationabout:

a. I only b. II only

c. III only d. I and II

e. I, II and III

18. Consider the following standard reduction potentials,

Half-reaction E°,V

I3

– (aq) 2e– –––→ 3 I– (aq) 0.53

Cr3+ (aq) + e– –––→ Cr2+ (aq) -0.41

Calculate ∆G° (in kJ) for the following reaction at 25°C.

Cr2+ (aq) I3– (aq) –––→ Cr3+ (aq) + I– (aq)

19. Consider the following reaction,

2 SO2 (g) + O2 (g) º 2 SO3 (g)

and the following thermochemical data,

Substance ∆Gf°, kJ/mol

SO2 (g) -300.194

O2 (g) 0.0

SO3 (g) -371.06

Calculate the value of the equilibrium constant for this reaction at 25°C.

20. For the dissociation of acetic acid in water at 25°C,

CH3COOH (l) + H2O º H3O+ (aq) + CH3COO– (aq)

∆H°=284.3kJ and ∆S°= -143.1 J K–1. Calculate the value of ∆G° (in kJ) for this reaction at equilibrium.

21. Consider the carbonylation (i.e., addition of CO) of methanol, CH3OH, to produce acetic acid,CH3COOH, in a closed system at constant temperature and pressure,

CH3OH (g) CO (g) º CH3COOH (g)

and the following data :

Page 5: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 5

substance ∆Hf°, kJ mol–1 S°, J mol–1 K–1

CH3OH (g) -201 240

CO (g) -110 198

CH3COOH (g) -432 283

If the initial concentration of CH3OH (g) is 1.5 M and the initial concentration of CO (g) is 2.0 M,what is the concentration (in M) of CH3OH (g) at equilibrium, at 298 K?

22. For which of the following process does the entropy of the system DECREASE?

a. Melting of ice b. Dissolving table salt in water.

c. Decomposition of liquid hydrogen peroxide to produce liquid water and oxygen gas.

d. Precipitation of silver chloride from a solution containing silver ions and chloride ions.

e. The entropy of the system increases in all of the above processes.

23. For a particular chemical reaction, the values for ∆H and ∆S are both positive. Which of thefollowing statements is TRUE about this reaction?

a. The reaction is spontaneous at any temperature.

b. The reaction is not spontaneous at any temperature.

c. The reaction is spontaneous when the temperature is high enough to overcome ∆H.

d. The reaction is spontaneous when the temperature is low enough to overcome ∆H.

e. The reaction is spontaneous when the temperature is low enough to overcome ∆S.

24. For the boiling of methanol,

CH3OH (l) –––→ CH

3OH (g)

∆H° = +38.0 kJ, and ∆S° = +113.0 J/K. Assume that methanol boils at a temperature at which thevalue of ∆G is equal to zero. Using the values of ∆H° and ∆S°, calculate the temperature (in K) atwhich methanol boils.

25. Which of the following reactions is unfavorable at low temperatures but becomes favorable asthe temperature increases?

a. 2 CO(g) + O2(g) –––→ CO

2(g); ∆H° = -566 kJ; ∆S° = -173 J/K

b. 2 H2O(g) –––→ 2 H

2(g) + O

2(g); ∆H° = 484 kJ; ∆S° = 90.0 J/K

c. 2 N2O(g) –––→ 2 N2(g) + O2(g); ∆H° = -164 kJ; ∆S° = 149 J/K

d. PbCl2(s) –––→ Pb2+(aq) + O2(g); ∆H° = 23.4 kJ; ∆S° = -12.5 J/K

26. The following reaction is spontaneous as written:

Zn (s) + Cu2+ (aq) –––→ Zn2+ (aq) + Cu (s)

Which of the following statement is TRUE :

a. Keq > 1 and ∆G° = 0 b. Keq > 1 and ∆G° < 0

c. Keq < 1 and ∆G° < 0 d. Keq > 1 and ∆G° > 0

e. Keq < 1 and ∆G° = 0

Page 6: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 6

27. A spontaneous reaction ALWAYS occurs when:

a. ∆H° < 0 and ∆S° < 0 b. ∆H° > 0 and ∆S° < 0

c. ∆H° < 0 and ∆S° > 0 d. ∆H° > 0 and ∆S° = 0

e. ∆H° > 0 and ∆S° > 0

28. When a reaction is at equilibrium, which of the following statements is TRUE?

a. ∆G = ∆G° b. ln Keq

= 0

c. ∆G° = 0 d. Q = 0

e. ∆G = 0

29. For mercury the molar entropy of vaporization is 92.92 J K–1 mol–1 and the molar enthalpy ofvaporization is 58.51 kJ mol–1. Therefore, the normal boiling point of mercury in °C is :

a. 273°C b. 357°C

c. 516°C d. 670°C

e. unable to determine unless ∆G of vaporization is known.

30. Which statement is TRUE for an operating electrolytic cell?

a. ∆G > 0 and ECell < 0 b. ∆G = 0 and ECell > 0

c. ∆G < 0 and ECell = 0 d. ∆G = 0 and ECell = 0

e. ∆G > 0 and ECell > 0

31. For which ONE of the following reactions does the entropy of the system DECREASE?

a. NH4NO

3(s) –––→ NH

4+(aq) + NO

3–(aq)

b. 2 H2O

2(l) –––→ 2 H

2O(l) + O

2(g)

c. Ba(OH)2.8 H

2O(s) + 2 NH

4SCN(s) –––→ Ba(SCN)

2(aq) + 2 NH

3(aq) + 10 H

2O(l)

d. NO(g) + NO2(g) –––→ N

2O

3 (g)

e. CO2(s) –––→ CO2(g)

32. For a particular chemical reaction at 25°C, ∆H = -432 kJ. Which of the following statement isTRUE?

a. The reaction will be spontaneous, at any temperature, if ∆S is positive.

b. The reaction will be spontaneous, at any temperature, if ∆S is Negative.

c. The reaction will be spontaneous only if ∆G is positive.

d. The reaction can never be spontaneous, at any temperature.

e. There is insufficient information provided to answer this question.

33. For a particular chemical reaction, ∆H° = +60.0 kJ and ∆S° = +121 J/K. At what temperature(in K) would this reaction become spontaneous?

34. Consider the gas-phase hydrogenation of ethylene, C2H

2, to produce ethane, C

2H

6,

C2H

2(g) + 2 H

2(g) –––→ C

2H

6(g)

Page 7: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 7

and the following thermodynamic data:

substance ∆Hf°, kJ mol–1 S°, J mol–1 K–1

C2H2(g) 227.0 201.0

H2(g) 0 131.0

C2H6(g) -84.70 229.5

Under standard conditions, which of the following statements is TRUE?

a. The reaction is spontaneous; ∆H° is favorable while ∆S° is not.

b. The reaction is spontaneous; ∆S° is favorable while ∆H° is not.

c. The reaction is not spontaneous; ∆S° is favorable while ∆H° is not.

d. The reaction is not spontaneous; ∆H° is favorable while ∆S° is not.

e. The reaction is not spontaneous; neither ∆H° nor ∆S° are favorable.

35. Consider the gas-phase reaction of hydrogen, H2,and oxygen, O2, to produce water,

2 H2(g) + O2(g) –––→ 2 H2O(g)

and the following thermodynamic data:

substance ∆Gf°, kJ/mol

H2(g) 0

O2(g) 0

H2O(g) -228.6

Calculate the value of the equilibrium constant for this reaction under standard conditions.

36. Consider the gas-phase reaction of hydrogen, H2, with carbon monoxide, CO, to from

formaldehyde, H2CO, in a closed system at constant pressure,

H2(g) + CO(g) –––→ H

2CO(g)

and the following thermodynamic data,

substance ∆Hf°, kJ mol–1 S°, J mol–1 K–1

H2(g) 0 131

CO(g) -110 198

H2CO(g) -116 219

If the initial concentration of CO(g) is 1.5 M and the initial concentration of H2(g) is 2.3 M, calculatethe concentration (in M) of H2CO(g) at equilibrium, at 298 K.

37. For a certain process, ∆S(system) >0 and ∆S(surroundings) > 0. The process:

a. is spontaneous b. is exothermic.

c. decreases the entropy of the universe. d. is endothermic.

e. is at equilibrium.

Page 8: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 8

38. In which case does the spontaneity of a reaction depend on the temperature?

a. ∆H = 0 and ∆S < 0 b. ∆H > 0 and ∆S > 0

c. ∆H < 0 and ∆S = 0 d. ∆H > 0 and ∆S = 0

e. ∆H < 0 and ∆S > 0

39. Consider the following reaction:

H2O(g) + Cl

2O(g) º 2 HOCl(g)

For this reaction, Keq

= 0.090 at 25°C. Calculate the value (in kJ/mol) of ∆G° for this reaction.

40. For a particular process at 500 K, ∆G = -3.0 kJ and ∆H = -23.0 kJ. If the process is carried outreversibly, Calculate the amount (in kJ) of useful work that can be performed.

41. Which of the following statements concerning the change in ∆G° and ∆G during a chemicalreaction is most correct?

a. ∆G° remains constant while ∆G changes and becomes equal to ∆G° at equilibrium.

b. Both ∆G° and ∆G remain constant during a chemical reaction.

c. Initially both ∆G and ∆G° are equal to zero. The value of ∆G° changes to a valuedetermined by the equilibrium constant; the value of ∆G peaks and then decrease tozero at equilibrium.

d. ∆G° remains constant if the reaction is carried out under standard conditions; ∆Gremains constant if the reaction is carried out under non-standard conditions.

e. ∆G° remains constant while ∆G changes and becomes equal to zero at equilibrium.

42. The enthalpy of vaporization of ethanol is 38.7 kJ/mol at its boiling point of 78°C. Calculate thechange in entropy (in J/mol) of the surroundings when 1.00 mole of ethanol is vaporized at 78°Cand 1.00 atm of pressure.

43. A certain chemical reaction carried out at constant temperature and pressure has ∆S > 0. Whatcan you conclude about the spontaneity of this reaction?

a. The reaction is not spontaneous if it is endothermic and the temperature is sufficientlyhigh.

b. The reaction is not spontaneous at any temperature.

c. The reaction is not spontaneous if it is exothermic and the temperature is sufficientlylow

d. The reaction is only spontaneous at high temperatures.

e. The reaction is spontaneous if it is exothermic and the temperature is sufficiently high.

44. Consider the following reaction:

2 C(graphite) + H2(g) –––→ C2H2(g)

∆G° = 209.2 kJ at 25°C, P(H2) = 100 atm, P(C2H2) = 0.10 atm

Calculate the value (in kJ) of ∆G for reaction.

Page 9: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 9

45. We observed that when two white crystalline substances were mixed the beaker froze to thewooden board it was sitting on. The reaction is as follows:

Ba(OH)2 .8 H

2O(s) + 2 NH

4NO

3(s) –––→ Ba(NO

3)

2(aq) + 2 NH

3(g) + 10 H

2O(l)

For this reaction , ∆H° = 170.44 kJ and ∆S° = 657.4 J/K. Which of the following statements mustbe TRUE about the process?

a. Enthalpy is favorable and entropy is unfavorable.

b. Neither entropy nor entropy are favorable.

c. Both enthalpy and entropy are favorable.

d. Enthalpy is unfavorable and entropy is favorable.

e. The process is not spontaneous because it had to be stirred.

46. In the thermite reaction we observed that after glycerin was added a vigorous reaction proceeded.The reaction is as follows:

Fe2O3(s) + 2 Al(s) –––→ 2 Fe + Al2O3(s)

For this reaction , ∆H° = -851.5 kJ and ∆S° = -38.58 J/K. Which of the following statements mustbe TRUE about the process?

a. Enthalpy is favorable and entropy is unfavorable.

b. Neither entropy nor entropy are favorable.

c. Both enthalpy and entropy are favorable.

d. Enthalpy is unfavorable and entropy is favorable.

e. The process is not spontaneous because glycerin had to be added.

47. You have observed all of the following chemical reactions in lecture. For which one of thesereactions does the entropy of the system INCREASE?

a. NH3(g) + HCl(g) –––→ NH4Cl(s) b. 2 H2O2(l) –––→ 2 H2O(l) + O2(g)

c. 2 H2(g) + O2(g) –––→ 2 H2O(g) d. NH3(g) + H2O(l) –––→ NH4+(aq) + OH–(aq)

e. Na+(aq) + CH3COO–(aq) –––→ CH3COONa(s)

48. Which of the following thermodynamic properties CANNOT be experimentally determined?

a. ∆S° b. ∆H°

c. G° d. S°

e. ∆G°

49. Consider the hydrogenation of acetylene, C2H

2, to produce ethane, C

2H

6,

C2H

2(g) + 2 H

2(g) –––→ C

2H

6(g)

and the following data:

substance ∆Hf°, kJ mol–1 S°, J mol–1 K–1

C2H2 227.0 201.0

Page 10: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 10

H2 0 131.0

C2H6 -84.70 229.5

At 25°C and 1 atm pressure, which of the following statements is TRUE about the spontaneity ofthis reaction?

a. Both ∆H° and ∆S° favor spontaneity.

b. ∆H° favors spontaneity but ∆S° opposes it.

c. ∆H° opposes spontaneity but ∆S° favors it.

d. Both ∆H° and ∆S° opposes spontaneity.

e. There is insufficient information to answer this question.

50. Consider the following information:

i. Ice has a more ordered structure than liquid water.

ii. Liquid water freezes spontaneously at -5°C and 1 atm.

Which of the following statements is most likely TRUE?

a. Liquid water freezes at -5°C because the increase in entropy overcomes the endothermicity.

b. Liquid water freezes at -5°C because the exothermicity overcomes the decrease in entropy.

c. Liquid water freezes at -5°C because the exothermicity overcomes the increase in entropy.

d. Liquid water freezes at -5°C because the endothermicity overcomes the decrease in entropy.

e. None of these statements is TRUE?

51. Solid ammonium nitrate, NH4NO

3 (s) dissolves spontaneously in water at 25°C,

NH4NO

3(s) –––→ NH

4+(aq) + NO

3–(aq)

If this process is endothermic, which of the following is most likely TRUE?

a. ∆G > 0 b. ∆G = 0

c. ∆S < 0 d. ∆S > 0

e. ∆S = 0

52. Consider the following reaction for the dissociation of lactic acid, HC3H5O3 (a weak acid):

HC3H5O3 (l) + H2O(l) º H3O+(aq) + C3H5O3

–(aq)

If Ka for lactic acid 1.4 x 10–4, calculate the value of ∆G° (in J) for this reaction at 25°C.

53. In lecture, you observed the following reaction,

Ba(OH)2 : 8 H

2O(s) + 2 NH

4SCN(s) –––→ Ba(SCN)

2(aq) + 2 NH

3(aq) + 10 H

2O(l)

∆H° for this reaction is : 102.0 kJ, and ∆S° is : 495 J/K. Calculate the TEMPERATURE (in K) atwhich this reaction will become non-spontaneous.

54. Early in the development of thermodynamics, it was believed that exothermic reactions would bespontaneous. This is often true, but there are some exothermic reactions that are NOTspontaneous. In the absence of any kinetic barriers, which of the following factors must also be

Page 11: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 11

considered (in addition to the enthalpy change) to determine whether or not a reaction will bespontaneous?

a. activation energy b. rate constant

c. ∆Ssys d. Concentrations of reactants

55. Which of the following statements best describes the spontaneity of a reaction at 25°C for which∆Ssys is negative and ∆Hsurr is positive?

a. The reaction cannot be spontaneous at 25°C.

b. The reaction will be spontaneous at all temperatures.

c. The reaction will be spontaneous only if ∆Ssys is greater in magnitude than ∆Ssurr.

d. The reaction will be spontaneous only if ∆Ssurr is greater in magnitude than ∆Ssys.

e. The reaction will only be spontaneous if the change in free energy for the system ispositive.

56. Which of the following processes will result in a DECREASE in the entropy of the system? Allsystems are closed systems.

a. CH4(l) –––→ CH4(g) b. Zn2+(aq) + 4 NH3(aq) –––→ Zn(NH3)42+(aq)

c. Cl2(g) (298 K) –––→ Cl

2(g) (450 K) d. ZnS(s) –––→ Zn2+(aq) + S2–(aq)

e. NH3(g) (3 atm, 298 K) –––→ NH

3(g) (1 atm, 298 K)

57. Which of the following statements is TRUE?

a. Endothermic reactions are never spontaneous, at any temperature.

b. Exothermic reactions are always spontaneous, at any temperature.

c. Exothermic reactions in which the entropy change for the system is negative arespontaneous at any temperature.

d. Reactions in which the entropy change for the system is negative are never spontaneous,at any temperature.

e. None of the above statements is TRUE.

58. At elevated temperatures, hydrogen iodide, HI, decomposes to produce hydrogen, H2, andiodine, I2, as shown in the equation below:

2 HI (g) –––→ H2 (g) + I2 (g)

Using the thermodynamic data below, calculate the standard free energy change (in KJ) for thisreaction.

compound ∆Hf°, kJ mol–1 S°, J mol–1 K–1

HI (g) 25.9 206.3

H2 (g) 0 131.0

I2 (g) 62.4 260.6

59. Methylene chloride, CH2Cl

2, is common organic solvent. Using the thermodynamic data below,

calculate the boiling point (in °C) for CH2Cl

2.

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compound ∆Hf°, kJ mol–1 S°, J mol–1 K–1

CH2Cl2 (l) -121.5 178.0

CH2Cl

2(g) -92.5 270.1

60. Consider the gas-phase reaction of chlorine, Cl2, with fluorine, F

2, to produce chlorine trifluoride,

ClF3, in a closed system at constant temperature and pressure,

Cl2(g) + 3 F

2(g) –––→ 2 ClF

3(g)

and the following data :

compound ∆Hf°, kJ mol–1 S°, J mol–1 K–1

Cl2(g) 0 223.0

F2(g) 0 202.7

ClF3(g) -163 281.5

If the initial concentration of Cl2 (g) is 2.4 M and the initial concentration of F2 (g) is 5.7 M, what isthe molar concentration of F2 (g) at equilibrium, at 298 K?

61. For each of the following processes, predict whether the change in entropy for the system will bepositive or negative. Briefly explain your reasoning.

a. 2 C8H18 (g) + 25 O2 (g) –––→ 16 CO2 (g) +18 H2O (g)

b. AgCl (s) + 2 NH3 (aq) –––→ Ag(NH3)+ (aq) + Cl– (aq)

c. H2O (g) –––→ H

2O (l)

62. Exothermicity greatly favors the spontaneity of a chemical process or reaction. Briefly explain, inthermodynamic terms, why this is true.

63. For a certain process ∆S(system) > 0 and ∆S(surroundings) >0. The process

a. is spontaneous b. is exothermic

c. decreases the entropy of the universe d. is endothermic

e. is at equilibrium

64. Arrange the following compounds in order of increasing standard molar entropy at 25°C.

a. ZnS (s) < H2O (l) < C3H8 (g) < C2H4 (g) b. C2H4 (g) < H2O (l) < C3H8 (g) < NaCl (aq)

c. ZnS (s) < C3H8 (g) < C2H4 (g) < H2O (g) d. C3H8 (g) < C2H4 (g) < H2O (l) < ZnS (s)

e. ZnS (s) < H2O (l) < C2H4 (g) < C3H8 (g)

65. For HI the molar entropy of vaporization is 89.0 J/K mol and the molar enthalpy of vaporization is21.16 kJ/mol . Therefore, the normal boiling point of HI is:

a. -273°C b. -35.4°C

c. 23.8 K d. 42°C

e. Unable to determine unless ∆G of vaporization is known.

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66. Hydrogen peroxide decomposes according to the following reaction:

H2O

2 (l) –––→ H

2O (l) + 1/2O

2 (g)

For this reaction ∆H = -98.2 kJ and ∆S = 70.1 J/K. Which is the approximate value of Kp for this

reaction at 25°C ?

a. -1 x 1013 b. -3 x 102

c. 5 x 10–2 d. 7 x 1020

e. 9 x 1045

67. The significance of the Second Law of Thermodynamics is that for spontaneous processes the:

a. entropy of the universe is increasing

b. entropy of the surrounding must decrease

c. entropy is the driving force of all chemical reactions

d. entropy of an ideal solid does not change

e. absolute value for entropy can be calculated.

68. For a particular process at 300 K, ∆G = -23.0 kJ and ∆H = -3.0 kJ. If the process is carried outreversibly, the amount of useful work that can be performed is:

a. -23.0 kJ b. -10.0 kJ

c. -3.0 kJ d. -7.0 kJ

d. 0.00 kJ

69. The reaction rates for many spontaneous reactions are actually very slow. Which of the followingis the best explanation for this observation?

a. Kp for the reaction = 0

b. The activation energy is high

c. The standard free energy change for the reaction is > 0

d. These reactions are endothermic

e. The standard entropy change is < 0

70. The normal freezing point of NH3 is -78°C at one atmosphere. Predict the signs of ∆H, ∆S, and∆G for NH3 when NH3 supercools and then freezes at -80°C and one atmosphere.

a. ∆H < 0, ∆S < 0, ∆G = 0 b. ∆H < 0, ∆S > 0, ∆G < 0

c. ∆H > 0, ∆S < 0, ∆G > 0 d. ∆H > 0, ∆S > 0, ∆G = 0

e. ∆H < 0, ∆S < 0, ∆G < 0

71. We observed a demonstration of the reaction : H2O

2 –––→ H

2O + 1/2O

2 to which I– was added. A

large foaming mass of bubbles was formed. The following mechanism has been proposed forthis reaction:

H2O

2 + I– –––→ H

2O + IO– Slow

H2O + IO– –––→ H2O + 1/2O2 + I– fast

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The function of the I– in this reaction is to:

a. Raise the ∆H of the products b. Lower the ∆G between reactants and products

c. Increase the concentration of products d. Lower the activation energy

e. Raise the ∆S of the reactants.

72. In the thermite reaction, we observed that after glycerin was added a vigorous reaction proceeded.The reaction is as follows:

Fe2O3 (s) + 2 Al (s) –––→ 2 Fe (l) + Al2O3 (s)

For this reaction, the standard enthalpy change is = -851.5 kJ and the standard entropy change is= -38.58 J/K. Which of the following statements must be TRUE about the process?

a. Enthalpy is favorable and entropy is unfavorable

b. Neither entropy or entropy are favorable

c. Both enthalpy and entropy are favorable

d. Enthalpy is unfavorable and entropy is favorable

e. The process is not spontaneous because glycerin had to be added

73. In the thermite reaction we observed that glycerin was necessary to start the reaction. Which ofthe following is the most reasonable explanation of that observation?

a. The reaction is exothermic b. The activation energy is high

c. The process is not spontaneous d. Glycerin is a powerful explosive

74. Which of the following statements is TRUE?

a. An exothermic process will always be spontaneous

b. A process in which the entropy of the system increases will always be spontaneous

c. An endothermic process can never be spontaneous

d. A process in which the entropy of the surroundings increases will always be spontaneous

e. An exothermic process that is accompanied by an increase in the entropy of the system willalways be spontaneous

75. Which of the following processes will result in a INCREASE in the entropy of the system? Allsystems are closed systems.

a. H2O (g) –––→ H2O (l) b. Zn2+(aq)+4 NH3 (aq) –––→ Zn(NH3)42+ (aq)

c. O2 (g) (373 K) –––→ O

2 (g) (298 K) d. Zn2+ (aq) + S2- (aq) –––→ ZnS (s)

e. NH3 (g) (3 atm, 298 K) –––→ NH

3 (g) (1 atm,298 K)

76. Methylene chloride, CH2Cl

2, is a common organic solvent. Consider the following process at

25°C, in a closed system:

CH2Cl

2 (l) –––→ CH

2Cl

2 (g)

This process is endothermic (∆H° = +29.0 kJ). Which of the following statements is most likelyTRUE regarding the spontaneity of this process at 25°C?

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a. The process will be spontaneous because ∆Ssys

is negative

b. The process will be spontaneous because ∆Ssurr is positive

c. The process will be spontaneous if the boiling point of CH2Cl2 is less than 25°C

d. The process will be spontaneous if the freezing point of CH2Cl2 is greater than 25°C

e. The process will be spontaneous if the boiling point of CH2Cl2 is greater than 25°C

77. Acetic acid, CH3COOH, has an enthalpy of vaporization equal to 52.25 kJ an entropy of vaporizationequal to 122 J/K at its boiling point. Calculate the boiling point of acetic acid.

a. 0.43 K b. 2.3 K

c. 100 K d. 428 K

d. 563 K

78. Suppose we place 1.0 mole of the brown gas, NO2 in a large glass tube at 25°C and 1 atm

pressure. We then seal the tube, and wait for equilibrium to be established between a NO2 and

the colorless species, N2O

4,

2 NO2 (g) º N

2O

4 (g)

After equilibrium has been established at 25°C, we observe that the inside of the tube is lightbrown in color. Next, we cool the tube in liquid nitrogen (-196°C) and again wait until equilibriumhas been established. Which of the following statements most likely describes what we wouldobserve at -196°C (for this reaction, ∆H° = -57.2 kJ and ∆S° = -175.8 J/K)?

a. The value of the equilibrium constant at -196°C is much larger than at 25°C so the browncolor should disappear

b. The value of the equilibrium constant at -196°C is much smaller than at 25°C so the browncolor should become darker

c. The equilibrium constant does not depend on temperature so we would not observe anychange

d. The value of the equilibrium constant at 25°C much larger than at -196°C so the brown colorshould become darker

e. It is impossible to predict what will happen from the data provided here

79. For each of the following processes, determine whether the change in entropy will be positive ornegative. Explain your reasoning.

a. H2O (g) –––→ H2O (l) b. NH3 (g) –––→ 1/2N2 (g) + 3/2H2 (g)

c. NaCl (s) –––→ Na+ (aq) + Cl– (aq) d. Cu2+(aq) + 4 NH3(aq) ––→ Cu(NH

3)

42+(aq)

e. Precipitation of the Group I ions in the qualitative analysis scheme as AgCl, Hg2Cl

2 and PbCl

2.

80. The melting point of tungsten (used in some light bulbs) is the second highest among the elements(only that of carbon is higher). If the enthalpy of fusion is 35.23 kJ/mol and the entropy of fusion is9.65 J/mol K, calculate the melting point (in K) of tungsten.

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81. Which of the following reactions IS spontaneous under standard conditions?

a. 2 Au(s) + 3 Fe2+(aq) º 2 Au3+(aq) + 3 Fe(s) b. Sn (s) + Zn2+ (aq) º Sn2+ (aq) + Zn (s)

c. Br2(l) + Co(s) º 2 Br–(aq) + Co2+(aq) d. 2 Ag+ (aq) + Pt (s) º 2 Ag (s) + Pt2+ (aq)

e. 2 Cu2+ (aq) + 4 OH– (aq) º 2 Cu (s) + O2 (g) + 2 H

2O (l)

82. Consider the gas-phase reaction of hydrogen (H2) with carbon monoxide (CO) to from

formaldehyde (H2CO),

H2 (g) + CO (g) º H

2CO (g)

and the following thermodynamic data,

substance ∆Hf°, kJ mol–1 S°, J mol–1 K–1

H2 (g) 0 131

CO (g) -110 198

H2CO (g) -116 219

Which of the following best explains why this reaction is NOT spontaneous under standardconditions?

a. Both ∆H° and ∆S° oppose spontaneity

b. Both ∆H° and ∆S° favor spontaneity

c. ∆H° favors spontaneity but ∆S° opposes spontaneity

d. ∆H° opposes spontaneity but ∆S° favors spontaneity

e. There is insufficient information provided to answer the question.

83. The change in Gibbs free energy, ∆G, for a chemical reaction provides information about:

a. the balance between enthalpy and entropy changes for the reaction

b. the maximum amount of work that can be harnessed from the reaction

c. the amount of available energy that can potentially be harnessed to do useful work

d. Both (b) and (c) are true

e. All of the above are true

84. Solid ammonium nitrate, NH4NO3, dissolves in water at 25°C according to the following equation,

NH4NO3 (s) –––→ NH4+ (aq) + NO3

– (aq)

For this process, ∆H = +28.1 kJ and ∆S = +108 J/K. Which of the following statements is TRUE?

a. The reaction is spontaneous ; ∆H is favorable while ∆S is not

b. The reaction is spontaneous; ∆S is favorable while ∆H is not

c. The reaction is spontaneous; both ∆H and ∆S are favorable

d. The reaction is not spontaneous; ∆S is favorable while ∆H is not

e. The reaction is not spontaneous; neither ∆H nor ∆S is favorable

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85. The Kf for the complex ion, [Zn(NH3)4]2+, at 25°C is equal to 2.9 x 109. Calculate ∆G° (in kJ) for the

following reaction.

Zn2+ (aq) + 4 NH3 (aq) º [Zn(NH3)4]2+ (aq)

86. For which one of the following processes does the entropy of the system DECREASE?

a. Melting of ice b. Boiling of liquid water

c. Dissolving NaCl in water d. Precipitating silver chloride

e. None of these

87. Consider the gas-phase reaction of hydrogen, H2, and chloride, Cl

2, to produce hydrogen chloride,

and the following themodynamic data?

H2 (g) + Cl2 (g) –––→ 2 HCl (g)

substance ∆Gf°, kJ/mol

H2 (g) 0

Cl2 (g) 0

HCl (g) -95.30

Calculate the value of ∆H° (in kJ) for this reaction at 25°C if the standard state entropy change isequal to 20.0 J/K.

88. Consider the gas-phase reaction of hydrogen, H2, and iodine, I2, to produce hydrogen iodide,

H2 (g) +I

2 (g) –––→ 2 HI (g)

and the following thermodynamic data

substance ∆Gf°, kJ/mol

H2 (g) 0

I2 (g) 0

HI (g) 1.37

Calculate the value of the equilibrium constant for this reaction under standard conditions.

89. In lecture, you observed the Thermite Reaction:

Fe2O3 (s) + 2 Al (s) –––→ 2 Fe (s) + Al2O3 (s)

Using the following thermodynamic data, calculate the temperature (in K) at which the ThermiteReaction becomes non-spontaneous.

substance ∆Hf°, kJ mol–1 S°, J mol–1 K–1

Fe2O

3 (s) -822.2 90.0

Al (s) 0 28.3

Fe (s) 0 27.2

Al2O

3 (s) -1669.8 51.0

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90. For the Thermite Reaction described in the preceding question, which of the following statementsis TRUE under STANDARD CONDITIONS?

a. The reaction is non-spontaneous; neither ∆H° nor ∆S° are favorable

b. The reaction is non-spontaneous; ∆H° is favorable while ∆S° is not

c. The reaction is spontaneous; ∆S° is favorable while ∆H° is not

d. The reaction is spontaneous; ∆H° is favorable while ∆S° is not

e. The reaction is spontaneous; both ∆S° and ∆H° are favorable

91. A mixture of hydrogen and chlorine gas remains unreacted UNTIL exposed to ultraviolet light.Then the following reaction occurs very rapidly:

H2 (g) + Cl2 (g) –––→ 2 HCl (g)

∆G = -45.54 kJ ∆H = -44.12 kJ ∆S = -4.76 J/K

Select the statements below which BEST explains this behavior.

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 reactionmore favorable

d. The negative value for ∆S slows down the reaction.

e. The reaction is thermodynamically spontaneous, but the reactants are kinetically stable.

92. A change of state occurs within a system and produces 64.0 kJ of heat. This heat is transferredto the surroundings at a constant pressure and a constant temperature of 300 K. For this process,∆S of the surroundings is :

a. 64.0 J/K b. -213 J/K

c. -64.0 J/K d. 213 J/K

e. 0.00 J/K

93. The following reaction has a standard free energy change value of 42.6 kJ/mol at 25°C :

HB (aq) + H2O (l) º H3O+ (aq) + B– (aq)

The Ka of the acid HB is :

a. 1.63 b. -17.19

c. 3.41 x 10–8 d. 4.26 x 104

e. 2.92 x 10–7

94. In the lecture you saw a copper wire placed in a solution of silver nitrate (AgNO3). Over a period

of time, you observed a spontaneous reaction in which the solution turned blue and silvery needlesformed on the copper wire. Which of the following statements must be TRUE about this process?

a. ∆G > 0 and Ecell

< 0 b. ∆G = 0 and Ecell

> 0

c. ∆G < 0 and Ecell = 0 d. ∆G = 0 and Ecell = 0

e. ∆G < 0 and Ecell > 0

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95. Which of the following is most likely TRUE for a “dead battery ”?

a. ∆G < 0 and Ecell = 0 b. ∆G > 0 and Ecell < 0

c. ∆G > 0 and Ecell = 0 d. ∆G = 0 and Ecell < 0

e. ∆G = 0 and Ecell = 0

96. Which of the following does NOT influence the spontaneity of a chemical reaction?

a. The temperature b. ∆Hsys

c. ∆Ssys d. ∆Ssurr

e. The activation energy.

97. Calculate the boiling point (in K) of titanium tetrachloride,TiCl4, if the standard enthalpy of

vaporization is: 41.0 kJ mol–1 and the standard entropy of vaporization is: 102.5 J mol–1 K–1.

98. Which of the following statements best describes the spontaneity of a reaction at 25°C for which∆S

sys is negative and ∆S

surr is positive?

a. The reaction will only be spontaneous if the change in free energy for the system ispositive

b. The reaction will be spontaneous at all temperatures

c. The reaction will be spontaneous only if ∆Ssys

is greater in magnitude than ∆Ssurr

.

d. The reaction will be spontaneous only if ∆Ssurr is greater in magnitude than ∆Ssys.

e. The reaction cannot be spontaneous at 25°C.

99. The equilibrium constant for a chemical reaction will be equal to one (1) under which one of thefollowing conditions?

a. ∆H° < 0 and ∆S° = 0 b. ∆H° = 0 and ∆S° = 0

c. ∆H° < 0 and ∆S° > 0 d. ∆H° > 0 and ∆S° < 0

e. ∆H° > 0 and ∆S° = 0

100. Benzene, C6H

6, is an extremely toxic organic solvent. Consider the following process at 25°C in

a closed system:

C6H

6 (l) –––→ C

6H

6 (s)

This process is exothermic (standard enthalpy change = -9.95 kJ). Which of the followingstatements is most likely TRUE regarding the spontaneity of this process at 25°C?

a. The process will be spontaneous because ∆Ssys

is positive

b. The process will be spontaneous because ∆Ssurr

is positive

c. The process will be spontaneous if the boiling point C6H6 is less than 25°C

d. The process will be spontaneous if the freezing point C6H6 is greater than 25°C

e. The process will be spontaneous if the freezing point C6H6 is less than 25°C

101. Calculate the value of Ka for hydrofluoric acid (HF) at 25°C if the standard free energy change forthe following reaction is equal to +17.9 kJ/mol:

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HF (g) + H2O (l) º H3O+ (aq) + F– (aq)

a. 4.0 x 10–38 b. 7.3 x 10–4

c. 9.2 x 10–1 d. 9.9 x 10–1

e. 1.4 x 103

102. If a reaction is spontaneous at 25°C and has a standard enthalpy change equal to +100 kJ/mol,which of the following must be TRUE about the standard entropy of reaction?

a. Standard entropy change < 0 J/mol K b. Standard entropy change = 40 J/mol K

c. Standard entropy change = 100 J/mol K d. Standard entropy change = 250 J/mol K

e. Standard entropy change > 335 J/mol K

103. For HI the molar enthalpy of vaporization is 21.16 kJ/mol and the molar entropy of vaporization is89.0 J/K mol. Therefore , the normal boiling point of HI is :

a. -273°C b. -35°C

c. 4°C d. 24°C

e. The normal boiling point cannot be determined unless the free energy of vaporizationis known.

104. The normal freezing point of water is 0°C. predict the signs of ∆H, ∆S and ∆G when H2O issupercooled and freezes at -10°C and one atmosphere.

a. ∆H < 0, ∆S < 0, ∆G < 0 b. ∆H < 0, ∆S > 0, ∆G = 0

c. ∆H > 0, ∆S > 0, ∆G > 0 d. ∆H < 0, ∆S > 0, ∆G < 0

e. ∆H > 0, ∆S > 0, ∆G = 0

105. Calculate the standard free energy change for the following reaction if the complex ion formationequilibrium constant, K

f, is equal to 2.1 x 1013.

Cu2+ (aq) + 4 NH3 (aq) º Cu(NH3)42+ (aq)

a. -150 kJ b. -76 kJ

c. -6.4 kJ d. 19 kJ

e. 43 kJ

106. Calculate the standard enthalpy change for a cell reaction which has a standard cell potential of1.50 V. The cell reaction involves the transfer of 2 moles of electrons and the standard entropychange is 110J/K.

a. -287 kJ b. -257 kJ

c. -144 kJ d. 123 kJ

e. 344 kJ

107. Consider the following gas-phase reaction and average bond enthalpies,

2 NOCl (g) –––→ 2 NO (g) + Cl2 (g)

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bond average bond enthalpy, kJ mol–1

N – Cl 201

N = O 716

Cl – Cl 243

Which of the following statements about the spontaneity of this reaction is TRUE at 25°C?

a. The reaction will be spontaneous only if the magnitude of ∆H is large enough toovercome the unfavorable entropy change

b. The reaction will be spontaneous only if the magnitude of ∆S is large enough toovercome the unfavorable enthalpy change

c. The reaction will be spontaneous regardless of the magnitudes of ∆H and ∆S.

d. The reaction cannot be spontaneous

e. The reaction will be spontaneous only of ∆G is positive.

108. All of the gas-phase reactions listed below are endothermic. Which one of these reactions ismost likely to be non-spontaneous at ALL temperatures?

a. COCl2 (g) –––→ CO (g) + Cl2 (g) b. 2 SO3 (g) –––→ 2 SO2 (g) + O2 (g)

c. N2O4 (g) –––→ 2 NO2 (g) d. CH3OH (g) –––→ CO (g) + 2 H2 (g)

e. 4 NO(g) + 6 H2O(g) –→ 4NH3(g) + 5O2(g)

109. A change in which of the following will also change the value of ∆G for a chemical reaction?

a. partial pressure of a gaseous reactant b. temperature

c. concentration of a product in aqueous solution

d. Changes in (a), (b) or (c) will change the value of ∆G.

e. A change in neither (a), (b) nor (c) will change the value of ∆G.

110. In order for a solution to form spontaneously at a given temperature, the change in free energy forthe formation of the solution (∆Gsoln) must be negative. Which of the following thermodynamicproperties is primarily responsible for determining whether or not a solution will form?

a. ∆Ssoln b. ∆Hsoln

c. Wsoln d. ∆Esoln

e. ∆Bsoln

111. Which of the following statements is FLASE?

a. Entropy is a measure of the driving force behind chemical reactions

b. Entropy is a measure of disorder or randomness

c. Entropy can be created and destroyed

d. Entropy is a measure of the number of ways energy can be distributed among themotions of particles

e. Entropy is a measure of the tendency of energy to become less concentrated.

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112. Chemical thermodynamics predicts (correctly) that materials made of wood, metal, paper, plastic,leather and rubber react with oxygen in the atmosphere and decompose at 25°C and 1 atmpressure. Which of the following is responsible for the fact these reactions are very slow underthese conditions?

a. entropy b. enthalpy

c. internal energy d. activation energy

e. potential energy

113. A sample of He (g) is placed in a 1.0 - L flask at 298 K. The sample of He (g) is then heated to450 K at constant value. Microscopic “shapshots”. For the He (g) are shown below.

He (g), 298 K He (g), 450 K

using “positional entropy ’’ arguments, ∆Ssys

for this process is:

a. positive b. negative

c. equal to zero d. It is impossible to tell

114. The normal freezing point of water is 0°C. Predict the signs of ∆Ssys, ∆Ssurr and ∆Suni v when H2Ois supercooled and freezes at -10°C and 1 atm.

a. ∆Ssys < 0; ∆Ssurr< 0; ∆Suni v < 0 b. ∆Ssys > 0; ∆Ssurr< 0; ∆Suni v = 0

c. ∆Ssys = 0; ∆Ssurr< 0; ∆Suni v > 0 d. ∆Ssys < 0; ∆Ssurr> 0; ∆Suni v > 0

e. ∆Ssys > 0; ∆Ssurr= 0; ∆Suni v < 0

115. At 25°C, formic acid (HCO2H, Ka = 1.8 x 10–4) dissolves in water and reacts according to thefollowing equation,

HCO2H (aq) + H

2O (l) º H3O

+ (aq) + HCO2– (aq)

∆S° for this reaction is -71.1 JK–1. Under standard conditions at 25°C, the reaction of formic acidwith water is:

a. exothermic b. endothermic

c. neither exothermic nor endothermic d. both exothermic and endothermic

Page 23: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 23

A N S W E R S

1. 1.5 x 102 32. A

2. D 33. 496

3. -1.9 x 102 34. A

4. 2.7 x 103 35. 1.4 x 1080

5. There is insufficient information provided to answer the question

6. D 36. 7.0 x 10–5

7. E 37. A

8. B 38. B

9. -2.1 x 102 39. 6.0

10. A 40. -3.0

11. 3.5 x 102 41. E

12. C 42. -110

13. 55 43. E

14. D 44. 192

15. A 45. D

16. E 46. A

17. D 47. B

18. -1.8 x 102 48. C

19. 7.0 x 1024 49. B

20. 3.3 x 102 50. B

21. 2.3 x 10–13 51. D

22. D 52. 2.2 x 104

23. C 53. 206

24. 336 54. C

25. B 55. D

26. B 56. B

27. C 57. E

28. E 58. 16.9

29. B 59. 42

30. A 60. 1.3 x 10–14

31. D

Page 24: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 24

61. (a) Positive. All substances are gases but 27 moles of reactants produces 34 moles of products.

(b) Positive. Losing a solid, and forming aqueous solutions of ions.

(c) Negative. Gases have much more entropy than liquids.

62. The Second Law of Thermodynamics states that the entropy of the universe mustincrease for a spontaneous process. The "universe" is composed of the "system" andthe "surroundings". Exothermicity favors spontaneity because exothermic processesalways have positive entropy changes in the surroundings.

63. A

64. E

65. B

66. D

67. A

68. A

69. B

70. E

71. D

72. A

73. B

74. E

75. E

76. C

77. D

78. A

79. (a) The entropy of a liquid is much lower than the entropy of a gas. Therefore,negative.

(b) All components are gases, but 1 mole of reactants produces 2 moles of products.Therefore, positive.

(c) The entropy of aquated ions is much higher than the entropy in a crystal.Therefore, positive.

(d) All components are aqueous species; however, 5 moles of reactants produces 1mole of product. Therefore, negative.

(e) Group I ions existed as aquated ions in solution. We are precipitating these asSOLIDS and we are combining two aqueous ions to produce a single product. Therefore,negative.

Page 25: Thermodynamics - THT

PHYSICAL CHEMISTRY By: Shailendra Kumar

1. Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 42. House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna

Page No.: 25

80. 3650 111. B

81. C 112. D

82. C 113. C

83. E 114. D

84. B 115. B

85. -54 x 101

86. D

87. -1.85 x 102

88. 0.33

89. 2.1 x 10–4

90. D

91. E

92. D

93. C

94. E

95. E

96. E

97. 400

98. D

99. B

100. D

101. B

102. E

103. B

104. A

105. B

106. B

107. B

108. E

109. D

110. B