Thermodynamics - THT

PHYSICAL CHEMISTRY
PHYSICAL CHEMISTRY
by:
By: Shailendra Kumar
SHAILENDRA KR.
Meq. Approach
Classes at: 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
1. 2. For a process at 451 K and constant pressure, Ssurr is -326 J K1. Calculate the quantity of heat (in kJ) absorbed by the system. 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 Cl2 can be initiated by ultraviolet light at 25C, H2 (g) + Cl2 (g) 2 HCl (g) Using the thermodynamic data provided below, calculate the standard free energy change (in kJ) at 25C for this reaction. compound H2 Cl2 HCl 4. Hf, kJ mol1 0 0 -92.307 S, J mol1 K1 130.57 222.96 186.80
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 JK1 Assumeing that H = H and S = S at all temperatures, calculate the temperature (in K) at which this reaction would become non-spontaneous.
5. 6.
For a particular chemical reaction at 400C, G = -67 kJ. Calculate the time (in seconds) it will take for the reaction to reach completion. 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
1. 2.
Opp. Khuda Baksh Library, Ashok Rajpath, Patna - 4 House no. 5A/65, Opp. Mahual Kothi, Alpana Market, Patna
Page No.: 1
PHYSICAL CHEMISTRY
b. The reaction will be spontaneous only if the magnitude of S is large enough to overcome 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 c. 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) substance H2O2 (aq) H2O (l) O2 (g) 10. Hf, kJ mol1 -191.17 -285.83 0 b. G < 0 ; E < 0 d. G = 0 ; E = 0
2 H2O (l) + O2 (g) S, J mol1 K1 143.9 69.91 205.14
Calculate the value (in kJ) of G at 25C. For particular chemical reaction, both H and S are negative. Which of the following statements about 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 to overcome the unfavorable entropy change. b. The reaction will be spontaneous only if the magnitude of S is large enough to overcome 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.
1. 2.
Page No.: 2
PHYSICAL CHEMISTRY
11.
The boiling point of a substance is the temperature at which equilibrium is established between the liquid and the vapor. CH3CH2OH (l) CH3CH2OH (g) Calculate the boiling point (in K) of ethanol, CH3CH2OH, 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 the system plus the change in entropy of the surroundings. e. The entropy of the universe is constant. The Ksp for the sparingly soluble salt barium chromate (BaCrO4) at 25C is equal to 2.0 x 1010. Calculate G (in kJ) for the following reaction. BaCrO4 (s)
13.
Ba
2+
(aq) + CrO42 (aq)
14.
A student of chemistry determined the value of Ksp for a saturated solution of borax at several different temperatures. The value for S for the dissolution of borax in water can be determined from: 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 25C from a plot of ln KSP versus T.
15.
Consider the following gas-phase reaction 2NO2 (g) 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 the following 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 the concentration of NO2 (g).
1. 2.
Page No.: 3
PHYSICAL CHEMISTRY
16. a. NH3 (g) +HCl (g) NH4Cl (s) c. 2 H2 (g) + O2 (g) 2 H2O (g) e. 2 H2O2 (l) 2 H2O (l) + O2 (g) 17. Consider the following characteristics of chemical reactions, I. spontaneity b. d.

Ag+ (aq) + Cl (aq) AgCl (s) NH3 (g) + H2O (l) NH4+ (aq) + OH (aq)
For which one of the following reactions does the entropy of the system INCREASE?
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 information about: a. I only c. III only e. I, II and III 18. Consider the following standard reduction potentials, Half-reaction I3 (aq) 2e 3 I (aq)

b. d.
II only I and II
E,V 0.53 -0.41
Cr3+ (aq) + e Cr2+ (aq)
Calculate G (in kJ) for the following reaction at 25C. Cr2+ (aq) I3 (aq) Cr3+ (aq) + I (aq) 19. Consider the following reaction, 2 SO2 (g) + O2 (g) and the following thermochemical data, Substance SO2 (g) O2 (g) SO3 (g) 20. Gf, kJ/mol -300.194 0.0 -371.06
2 SO
(g)
Calculate the value of the equilibrium constant for this reaction at 25C. For the dissociation of acetic acid in water at 25C, CH3COOH (l) + H2O 21.
HO
3
(aq) + CH3COO (aq)
H=284.3kJ and S= -143.1 J K1. Calculate the value of G (in kJ) for this reaction at equilibrium. 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) CH3COOH (g) and the following data :
1. 2.
Page No.: 4
PHYSICAL CHEMISTRY
substance CH3OH (g) CO (g) CH3COOH (g) Hf, kJ mol1 -201 -110 -432 240 198 283

S, J mol1 K1
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 the following 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) CH3OH (g) H = +38.0 kJ, and S = +113.0 J/K. Assume that methanol boils at a temperature at which the value of G is equal to zero. Using the values of H and S, calculate the temperature (in K) at which methanol boils. 25. Which of the following reactions is unfavorable at low temperatures but becomes favorable as the temperature increases? a. 2 CO(g) + O2(g) CO2(g); H = -566 kJ; S = -173 J/K b. 2 H2O(g) 2 H2(g) + O2(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 c. Keq < 1 and G < 0 e. Keq < 1 and G = 0 b. d. Keq > 1 and G < 0 Keq > 1 and G > 0
1. 2.
Page No.: 5
PHYSICAL CHEMISTRY
27. A spontaneous reaction ALWAYS occurs when: a. H < 0 and S < 0 c. H < 0 and S > 0 e. H > 0 and S > 0 28. b. d.

H > 0 and S < 0 H > 0 and S = 0
When a reaction is at equilibrium, which of the following statements is TRUE? a. G = G c. G = 0 e. G = 0 b. d. ln Keq = 0 Q=0
29.
For mercury the molar entropy of vaporization is 92.92 J K1 mol1 and the molar enthalpy of vaporization is 58.51 kJ mol1. Therefore, the normal boiling point of mercury in C is : a. 273C c. 516C b. d. 357C 670C
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 c. 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. NH4NO3(s) NH4+(aq) + NO3(aq) b. 2 H2O2(l) 2 H2O(l) + O2(g) c. Ba(OH)2.8 H2O(s) + 2 NH4SCN(s) Ba(SCN)2(aq) + 2 NH3(aq) + 10 H2O(l) d. NO(g) + NO2(g) N2O3 (g) e. CO2(s) CO2(g) 32. For a particular chemical reaction at 25C, H = -432 kJ. Which of the following statement is TRUE? 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. 34. For a particular chemical reaction, H = +60.0 kJ and S = +121 J/K. At what temperature (in K) would this reaction become spontaneous? Consider the gas-phase hydrogenation of ethylene, C2H2, to produce ethane, C2H6, C2H2(g) + 2 H2(g) C2H6(g) b. d. G = 0 and ECell > 0 G = 0 and ECell = 0
1. 2.
Page No.: 6
PHYSICAL CHEMISTRY
and the following thermodynamic data: substance C2H2(g) H2(g) C2H6(g) Hf, kJ mol1 227.0 0 -84.70

S, J mol1 K1 201.0 131.0 229.5
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 H2(g) O2(g) H2O(g) 36. Gf, kJ/mol 0 0 -228.6
Calculate the value of the equilibrium constant for this reaction under standard conditions. Consider the gas-phase reaction of hydrogen, H 2, with carbon monoxide, CO, to from formaldehyde, H2CO, in a closed system at constant pressure, H2(g) + CO(g) H2CO(g) and the following thermodynamic data, substance H2(g) CO(g) H2CO(g) Hf, kJ mol1 0 -110 -116 S, J mol1 K1 131 198 219
If the initial concentration of CO(g) is 1.5 M and the initial concentration of H2(g) is 2.3 M, calculate the 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 c. decreases the entropy of the universe. e. is at equilibrium. b. d. is exothermic. is endothermic.
1. 2.
Page No.: 7
PHYSICAL CHEMISTRY
38. a. H = 0 and S < 0 c. H < 0 and S = 0 e. H < 0 and S > 0 39. Consider the following reaction: H2O(g) + Cl2O(g) 40. 41. b. d.

H > 0 and S > 0 H > 0 and S = 0
In which case does the spontaneity of a reaction depend on the temperature?
2 HOCl(g)
For this reaction, Keq = 0.090 at 25C. Calculate the value (in kJ/mol) of G for this reaction. For a particular process at 500 K, G = -3.0 kJ and H = -23.0 kJ. If the process is carried out reversibly, Calculate the amount (in kJ) of useful work that can be performed. Which of the following statements concerning the change in G and G during a chemical reaction 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 value determined by the equilibrium constant; the value of G peaks and then decrease to zero at equilibrium. d. G remains constant if the reaction is carried out under standard conditions; G remains 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 78C. Calculate the change in entropy (in J/mol) of the surroundings when 1.00 mole of ethanol is vaporized at 78C and 1.00 atm of pressure. A certain chemical reaction carried out at constant temperature and pressure has S > 0. What can you conclude about the spontaneity of this reaction? a. The reaction is not spontaneous if it is endothermic and the temperature is sufficiently high. b. The reaction is not spontaneous at any temperature. c. The reaction is not spontaneous if it is exothermic and the temperature is sufficiently low 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 25C, P(H2) = 100 atm, P(C2H2) = 0.10 atm Calculate the value (in kJ) of G for reaction.
43.
1. 2.
Page No.: 8
PHYSICAL CHEMISTRY
45.
We observed that when two white crystalline substances were mixed the beaker froze to the wooden board it was sitting on. The reaction is as follows: Ba(OH)2 .8 H2O(s) + 2 NH4NO3(s) Ba(NO3)2(aq) + 2 NH3(g) + 10 H2O(l) For this reaction , H = 170.44 kJ and S = 657.4 J/K. Which of the following statements must be 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 must be 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 these reactions does the entropy of the system INCREASE? a. NH3(g) + HCl(g) NH4Cl(s) c. 2 H2(g) + O2(g) 2 H2O(g) b. d. 2 H2O2(l) 2 H2O(l) + O2(g) 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 c. G e. G 49. Consider the hydrogenation of acetylene, C2H2, to produce ethane, C2H6, C2H2(g) + 2 H2(g) C2H6(g) and the following data: substance C2H2 Hf, kJ mol1 227.0 S, J mol1 K1 201.0 b. d. H S
1. 2.
Page No.: 9
PHYSICAL CHEMISTRY
H2 C2H6 0 -84.70 131.0 229.5
At 25C and 1 atm pressure, which of the following statements is TRUE about the spontaneity of this 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 -5C and 1 atm. Which of the following statements is most likely TRUE? a. Liquid water freezes at -5C because the increase in entropy overcomes the endothermicity. b. Liquid water freezes at -5C because the exothermicity overcomes the decrease in entropy. c. Liquid water freezes at -5C because the exothermicity overcomes the increase in entropy. d. Liquid water freezes at -5C because the endothermicity overcomes the decrease in entropy. e. None of these statements is TRUE? 51. Solid ammonium nitrate, NH4NO3 (s) dissolves spontaneously in water at 25C, NH4NO3(s) NH4+(aq) + NO3(aq) If this process is endothermic, which of the following is most likely TRUE? a. G > 0 c. S < 0 e. S = 0 52. Consider the following reaction for the dissociation of lactic acid, HC3H5O3 (a weak acid): HC3H5O3 (l) + H2O(l) 53. b. d. G = 0 S > 0
H O (aq) + C H O
3 3 5
(aq)
If Ka for lactic acid 1.4 x 104, calculate the value of G (in J) for this reaction at 25C. In lecture, you observed the following reaction, Ba(OH)2 : 8 H2O(s) + 2 NH4SCN(s) Ba(SCN)2(aq) + 2 NH3(aq) + 10 H2O(l) H for this reaction is : 102.0 kJ, and S is : 495 J/K. Calculate the TEMPERATURE (in K) at which this reaction will become non-spontaneous. 54. Early in the development of thermodynamics, it was believed that exothermic reactions would be spontaneous. This is often true, but there are some exothermic reactions that are NOT spontaneous. In the absence of any kinetic barriers, which of the following factors must also be
1. 2.
Page No.: 10
PHYSICAL CHEMISTRY
considered (in addition to the enthalpy change) to determine whether or not a reaction will be spontaneous? a. activation energy c. Ssys 55. b. d. rate constant Concentrations of reactants
Which of the following statements best describes the spontaneity of a reaction at 25C for which Ssys is negative and Hsurr is positive? a. The reaction cannot be spontaneous at 25C. 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 is positive.
56.
Which of the following processes will result in a DECREASE in the entropy of the system? All systems are closed systems. a. CH4(l) CH4(g) c. Cl2(g) (298 K) Cl2(g) (450 K) b. d. Zn2+(aq) + 4 NH3(aq) Zn(NH3)42+(aq) ZnS(s) Zn2+(aq) + S2(aq)
e. NH3(g) (3 atm, 298 K) NH3(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 are spontaneous 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, and iodine, 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 this reaction. compound HI (g) H2 (g) I2 (g) 59. Hf, kJ mol1 25.9 0 62.4 S, J mol1 K1 206.3 131.0 260.6
Methylene chloride, CH2Cl2, is common organic solvent. Using the thermodynamic data below, calculate the boiling point (in C) for CH2Cl2.
1. 2.
Page No.: 11
PHYSICAL CHEMISTRY
compound CH2Cl2 (l) CH2Cl2(g) 60. Hf, kJ mol -121.5 -92.5
1 1

S, J mol K1 178.0 270.1
Consider the gas-phase reaction of chlorine, Cl2, with fluorine, F2, to produce chlorine trifluoride, ClF3, in a closed system at constant temperature and pressure, Cl2(g) + 3 F2(g) 2 ClF3(g) and the following data : compound Cl2(g) F2(g) ClF3(g) Hf, kJ mol1 0 0 -163 S, J mol1 K1 223.0 202.7 281.5
If the initial concentration of Cl2 (g) is 2.4 M and the initial concentration of F2 (g) is 5.7 M, what is the 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 be positive 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) H2O (l) 62. 63. Exothermicity greatly favors the spontaneity of a chemical process or reaction. Briefly explain, in thermodynamic terms, why this is true. For a certain process S(system) > 0 and S(surroundings) >0. The process a. is spontaneous c. decreases the entropy of the universe e. is at equilibrium 64. Arrange the following compounds in order of increasing standard molar entropy at 25C. a. ZnS (s) < H2O (l) < C3H8 (g) < C2H4 (g) c. ZnS (s) < C3H8 (g) < C2H4 (g) < H2O (g) 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 is 21.16 kJ/mol . Therefore, the normal boiling point of HI is: a. -273C c. 23.8 K b. d. -35.4C 42C b. d. C2H4 (g) < H2O (l) < C3H8 (g) < NaCl (aq) C3H8 (g) < C2H4 (g) < H2O (l) < ZnS (s) b. d. is exothermic is endothermic
e. Unable to determine unless G of vaporization is known.
1. 2.
Page No.: 12
PHYSICAL CHEMISTRY
66. H2O2 (l) H2O (l) + 1/2O2 (g)
Hydrogen peroxide decomposes according to the following reaction: For this reaction H = -98.2 kJ and S = 70.1 J/K. Which is the approximate value of Kp for this reaction at 25C ? a. -1 x 1013 c. 5 x 102 e. 9 x 1045 b. d. -3 x 102 7 x 1020
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. For a particular process at 300 K, G = -23.0 kJ and H = -3.0 kJ. If the process is carried out reversibly, the amount of useful work that can be performed is: a. -23.0 kJ c. -3.0 kJ d. 0.00 kJ b. d. -10.0 kJ -7.0 kJ
68.
69.
The reaction rates for many spontaneous reactions are actually very slow. Which of the following is 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 The normal freezing point of NH3 is -78C at one atmosphere. Predict the signs of H, S, and G for NH3 when NH3 supercools and then freezes at -80C and one atmosphere. a. H < 0, S < 0, G = 0 c. H > 0, S < 0, G > 0 e. H < 0, S < 0, G < 0 b. d. H < 0, S > 0, G < 0 H > 0, S > 0, G = 0
70.
71.
We observed a demonstration of the reaction : H2O2 H2O + 1/2O2 to which I was added. A large foaming mass of bubbles was formed. The following mechanism has been proposed for this reaction: H2O2 + I H2O + IO Slow fast
Page No.: 13
H2O + IO H2O + 1/2O2 + I
1. 2.
PHYSICAL CHEMISTRY
The function of the I in this reaction is to: a. Raise the H of the products c. Increase the concentration of products e. Raise the S of the reactants. 72. b. d.

Lower the G between reactants and products Lower the activation energy
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 of the following is the most reasonable explanation of that observation? a. The reaction is exothermic c. The process is not spontaneous b. d. The activation energy is high 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 will always be spontaneous
75.
Which of the following processes will result in a INCREASE in the entropy of the system? All systems are closed systems. a. H2O (g) H2O (l) c. O2 (g) (373 K) O2 (g) (298 K) b. d. Zn2+(aq)+4 NH3 (aq) Zn(NH3)42+ (aq) Zn2+ (aq) + S2- (aq) ZnS (s)
e. NH3 (g) (3 atm, 298 K) NH3 (g) (1 atm,298 K) 76. Methylene chloride, CH2Cl2, is a common organic solvent. Consider the following process at 25C, in a closed system: CH2Cl2 (l) CH2Cl2 (g) This process is endothermic (H = +29.0 kJ). Which of the following statements is most likely TRUE regarding the spontaneity of this process at 25C?
1. 2.
Page No.: 14
PHYSICAL CHEMISTRY
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 25C d. The process will be spontaneous if the freezing point of CH2Cl2 is greater than 25C e. The process will be spontaneous if the boiling point of CH2Cl2 is greater than 25C 77. Acetic acid, CH3COOH, has an enthalpy of vaporization equal to 52.25 kJ an entropy of vaporization equal to 122 J/K at its boiling point. Calculate the boiling point of acetic acid. a. 0.43 K c. 100 K d. 563 K 78. Suppose we place 1.0 mole of the brown gas, NO2 in a large glass tube at 25C and 1 atm pressure. We then seal the tube, and wait for equilibrium to be established between a NO2 and the colorless species, N2O4, 2 NO2 (g) N2O4 (g) After equilibrium has been established at 25C, we observe that the inside of the tube is light brown in color. Next, we cool the tube in liquid nitrogen (-196C) and again wait until equilibrium has been established. Which of the following statements most likely describes what we would observe at -196C (for this reaction, H = -57.2 kJ and S = -175.8 J/K)? a. The value of the equilibrium constant at -196C is much larger than at 25C so the brown color should disappear b. The value of the equilibrium constant at -196C is much smaller than at 25C so the brown color should become darker c. The equilibrium constant does not depend on temperature so we would not observe any change d. The value of the equilibrium constant at 25C much larger than at -196C so the brown color should 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 or negative. Explain your reasoning. a. H2O (g) H2O (l) c. NaCl (s) Na+ (aq) + Cl (aq)
b. d.
2.3 K 428 K
b. NH3 (g) 1/2N2 (g) + 3/2H2 (g) d. Cu2+(aq) + 4 NH3(aq) Cu(NH3)42+(aq)
e. Precipitation of the Group I ions in the qualitative analysis scheme as AgCl, Hg2Cl2 and PbCl2. 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 is 9.65 J/mol K, calculate the melting point (in K) of tungsten.
1. 2.
Page No.: 15
PHYSICAL CHEMISTRY
81. a. 2 Au(s) + 3 Fe2+(aq) 2 Au3+(aq) + 3 Fe(s) c. Br2(l) + Co(s)

b. Sn (s) + Zn2+ (aq) Sn2+ (aq) + Zn (s) d. 2 Ag+ (aq) + Pt (s) 2 Ag (s) + Pt2+ (aq)
Which of the following reactions IS spontaneous under standard conditions?
2 Br (aq) + Co
2+
(aq)
e. 2 Cu2+ (aq) + 4 OH (aq) 2 Cu (s) + O2 (g) + 2 H2O (l) 82. Consider the gas-phase reaction of hydrogen (H 2) with carbon monoxide (CO) to from formaldehyde (H2CO), H2 (g) + CO (g) H2CO (g) and the following thermodynamic data, substance H2 (g) CO (g) H2CO (g) Hf, kJ mol1 0 -110 -116 S, J mol1 K1 131 198 219
Which of the following best explains why this reaction is NOT spontaneous under standard conditions? 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 25C 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
1. 2.
Page No.: 16
PHYSICAL CHEMISTRY
85.
The Kf for the complex ion, [Zn(NH3)4]2+, at 25C is equal to 2.9 x 109. Calculate G (in kJ) for the following reaction. Zn2+ (aq) + 4 NH3 (aq) [Zn(NH3)4]2+ (aq)
86.
For which one of the following processes does the entropy of the system DECREASE? a. Melting of ice c. Dissolving NaCl in water e. None of these b. d. Boiling of liquid water Precipitating silver chloride
87.
Consider the gas-phase reaction of hydrogen, H2, and chloride, Cl2, to produce hydrogen chloride, and the following themodynamic data? H2 (g) + Cl2 (g) 2 HCl (g) substance H2 (g) Cl2 (g) HCl (g) Gf, kJ/mol 0 0 -95.30
Calculate the value of H (in kJ) for this reaction at 25C if the standard state entropy change is equal to 20.0 J/K. 88. Consider the gas-phase reaction of hydrogen, H2, and iodine, I2, to produce hydrogen iodide, H2 (g) +I2 (g) 2 HI (g) and the following thermodynamic data substance H2 (g) I2 (g) HI (g) Gf, kJ/mol 0 0 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 Thermite Reaction becomes non-spontaneous. substance Fe2O3 (s) Al (s) Fe (s) Al2O3 (s) Hf, kJ mol1 -822.2 0 0 -1669.8 S, J mol1 K1 90.0 28.3 27.2 51.0
1. 2.
Page No.: 17
PHYSICAL CHEMISTRY
90.
For the Thermite Reaction described in the preceding question, which of the following statements is 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 reaction more 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 transferred to 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 c. -64.0 J/K e. 0.00 J/K b. d. -213 J/K 213 J/K
93.
The following reaction has a standard free energy change value of 42.6 kJ/mol at 25C : HB (aq) + H2O (l) H3O+ (aq) + B (aq) The Ka of the acid HB is : a. 1.63 c. 3.41 x 10
8
b. d.
-17.19 4.26 x 104
e. 2.92 x 107 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 needles formed on the copper wire. Which of the following statements must be TRUE about this process? a. G > 0 and Ecell < 0 c. G < 0 and Ecell = 0 e. G < 0 and Ecell > 0 b. d. G = 0 and Ecell > 0 G = 0 and Ecell = 0
1. 2.
Page No.: 18
PHYSICAL CHEMISTRY
95. a. G < 0 and Ecell = 0 c. G > 0 and Ecell = 0 e. G = 0 and Ecell = 0 96. b. d.

G > 0 and Ecell < 0 G = 0 and Ecell < 0
Which of the following is most likely TRUE for a dead battery ?
Which of the following does NOT influence the spontaneity of a chemical reaction? a. The temperature c. S sys e. The activation energy. b. d. H sys S surr
97. 98.
Calculate the boiling point (in K) of titanium tetrachloride,TiCl4, if the standard enthalpy of vaporization is: 41.0 kJ mol1 and the standard entropy of vaporization is: 102.5 J mol1 K1. Which of the following statements best describes the spontaneity of a reaction at 25C for which Ssys is negative and Ssurr is positive? a. The reaction will only be spontaneous if the change in free energy for the system is positive 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 25C.
99.
The equilibrium constant for a chemical reaction will be equal to one (1) under which one of the following conditions? a. H < 0 and S = 0 c. H < 0 and S > 0 e. H > 0 and S = 0 b. d. H = 0 and S = 0 H > 0 and S < 0
100. Benzene, C6H6, is an extremely toxic organic solvent. Consider the following process at 25C in a closed system: C6H6 (l) C6H6 (s) This process is exothermic (standard enthalpy change = -9.95 kJ). Which of the following statements is most likely TRUE regarding the spontaneity of this process at 25C? 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 25C d. The process will be spontaneous if the freezing point C6H6 is greater than 25C e. The process will be spontaneous if the freezing point C6H6 is less than 25C 101. Calculate the value of Ka for hydrofluoric acid (HF) at 25C if the standard free energy change for the following reaction is equal to +17.9 kJ/mol:
1. 2.
Page No.: 19
PHYSICAL CHEMISTRY
a. 4.0 x 1038 c. 9.2 x 101 e. 1.4 x 103 b. d. 7.3 x 104 9.9 x 101
HF (g) + H2O (l) H3O+ (aq) + F (aq)
102. If a reaction is spontaneous at 25C 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 c. Standard entropy change = 100 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 is 89.0 J/K mol. Therefore , the normal boiling point of HI is : a. -273C c. 4C b. d. -35C 24C b. d. Standard entropy change = 40 J/mol K Standard entropy change = 250 J/mol K
e. The normal boiling point cannot be determined unless the free energy of vaporization is known. 104. The normal freezing point of water is 0C. predict the signs of H, S and G when H2O is supercooled and freezes at -10C and one atmosphere. a. H < 0, S < 0, G < 0 c. 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 formation equilibrium constant, Kf, is equal to 2.1 x 1013. Cu2+ (aq) + 4 NH3 (aq) Cu(NH3)42+ (aq) a. -150 kJ c. -6.4 kJ e. 43 kJ 106. Calculate the standard enthalpy change for a cell reaction which has a standard cell potential of 1.50 V. The cell reaction involves the transfer of 2 moles of electrons and the standard entropy change is 110J/K. a. -287 kJ c. -144 kJ e. 344 kJ 107. Consider the following gas-phase reaction and average bond enthalpies, 2 NOCl (g) 2 NO (g) + Cl2 (g) b. d. -257 kJ 123 kJ b. d. -76 kJ 19 kJ b. d. H < 0, S > 0, G = 0 H < 0, S > 0, G < 0
1. 2.
Page No.: 20
PHYSICAL CHEMISTRY
bond N Cl N=O Cl Cl 201 716 243

average bond enthalpy, kJ mol1
Which of the following statements about the spontaneity of this reaction is TRUE at 25C? a. The reaction will be spontaneous only if the magnitude of H is large enough to overcome the unfavorable entropy change b. The reaction will be spontaneous only if the magnitude of S is large enough to overcome 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 is most likely to be non-spontaneous at ALL temperatures? a. COCl2 (g) CO (g) + Cl2 (g) c. N2O4 (g) 2 NO2 (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 for the formation of the solution (Gsoln) must be negative. Which of the following thermodynamic properties is primarily responsible for determining whether or not a solution will form? a. S soln c. W soln e. B soln 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 the motions of particles e. Entropy is a measure of the tendency of energy to become less concentrated. b. d. Hsoln E soln b. d. 2 SO3 (g) 2 SO2 (g) + O2 (g) CH3OH (g) CO (g) + 2 H2 (g)
1. 2.
Page No.: 21
PHYSICAL CHEMISTRY
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 25C and 1 atm pressure. Which of the following is responsible for the fact these reactions are very slow under these conditions? a. entropy c. internal 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 to 450 K at constant value. Microscopic shapshots. For the He (g) are shown below. b. d. enthalpy activation energy
He (g), 298 K
He (g), 450 K
using positional entropy arguments, Ssys for this process is: a. positive c. equal to zero b. d. negative It is impossible to tell
114. The normal freezing point of water is 0C. Predict the signs of Ssys, Ssurr and Suni v when H2O is supercooled and freezes at -10C and 1 atm. a. Ssys < 0; Ssurr< 0; Suni v < 0 c. Ssys = 0; Ssurr< 0; Suni v > 0 e. Ssys > 0; Ssurr= 0; Suni v < 0 115. At 25C, formic acid (HCO2H, Ka = 1.8 x 104) dissolves in water and reacts according to the following equation, HCO2H (aq) + H2O (l) H3O+ (aq) + HCO2 (aq) S for this reaction is -71.1 JK1. Under standard conditions at 25C, the reaction of formic acid with water is: a. exothermic c. neither exothermic nor endothermic b. d. endothermic both exothermic and endothermic b. Ssys > 0; Ssurr< 0; Suni v = 0 d. Ssys < 0; Ssurr> 0; Suni v > 0
1. 2.
Page No.: 22
PHYSICAL CHEMISTRY
A N S W E R S
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 1.5 x 102 D -1.9 x 102 2.7 x 103 D E B -2.1 x 102 A 3.5 x 102 C 55 D A E D -1.8 x 102 7.0 x 10
24
32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57. 58. 59. 60.
A 496 A 1.4 x 1080 7.0 x 105 A B 6.0 -3.0 E -110 E 192 D A B C B B D 2.2 x 104 206 C D B E 16.9 42 1.3 x 1014
There is insufficient information provided to answer the question
3.3 x 102 2.3 x 10 D C 336 B B C E B A D

13
1. 2.
Page No.: 23
PHYSICAL CHEMISTRY
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 must increase for a spontaneous process. The "universe" is composed of the "system" and the "surroundings". Exothermicity favors spontaneity because exothermic processes always have positive entropy changes in the surroundings. A E B D A A B E D A B E E C D A (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 1 mole of product. Therefore, negative. (e) Group I ions existed as aquated ions in solution. We are precipitating these as SOLIDS and we are combining two aqueous ions to produce a single product. Therefore, negative.
63. 64. 65. 66. 67. 68. 69. 70. 71. 72. 73. 74. 75. 76. 77. 78. 79.
1. 2.
Page No.: 24
PHYSICAL CHEMISTRY
80. 81. 82. 83. 84. 85. 86. 87. 88. 89. 90. 91. 92. 93. 94. 95. 96. 97. 98. 99. 100. 101. 102. 103. 104. 105. 106. 107. 108. 109. 110. 3650 C C E B -54 x 10 D -1.85 x 102 0.33 2.1 x 104 D E D C E E E 400 D B D B E B A B B B E D B
1

111. 112. 113. 114. 115. B D C D B
1. 2.
Page No.: 25

Thermodynamics - THT

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Thermodynamics - THT

Uploaded by

Copyright:

Available Formats

PHYSICAL CHEMISTRY

By: Shailendra Kumar

By: Shailendra Kumar

2 H2O (l) + O2 (g) S, J mol1 K1 143.9 69.91 205.14

By: Shailendra Kumar

(aq) + CrO42 (aq)

By: Shailendra Kumar

II. maximum amount of work that can be done

E,V 0.53 -0.41

Cr3+ (aq) + e Cr2+ (aq)

(aq) + CH3COO (aq)

By: Shailendra Kumar

By: Shailendra Kumar

By: Shailendra Kumar

By: Shailendra Kumar

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

By: Shailendra Kumar

By: Shailendra Kumar

By: Shailendra Kumar

By: Shailendra Kumar

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

By: Shailendra Kumar

H2O + IO H2O + 1/2O2 + I

By: Shailendra Kumar

By: Shailendra Kumar

b. NH3 (g) 1/2N2 (g) + 3/2H2 (g) d. Cu2+(aq) + 4 NH3(aq) Cu(NH3)42+(aq)

By: Shailendra Kumar

Which of the following reactions IS spontaneous under standard conditions?

By: Shailendra Kumar

By: Shailendra Kumar

-17.19 4.26 x 104

By: Shailendra Kumar

Which of the following is most likely TRUE for a dead battery ?

By: Shailendra Kumar

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

By: Shailendra Kumar

By: Shailendra Kumar

By: Shailendra Kumar

There is insufficient information provided to answer the question

3.3 x 102 2.3 x 10 D C 336 B B C E B A D

By: Shailendra Kumar

By: Shailendra Kumar

You might also like