1. General gas equation is (a) PV = RT (b) PV= mRT (c) PV = Constant (d) = constant ANSWER: (a) 2.

An isolated system is one, which (a) Permits the passage of energy and matter across the boundaries (b) Permits the passage of energy only (c) Does not permit the passage of energy and matter across it (d) Permits the passage of matter only ANSWER: (b) 3. In an isolated system, boundary of the system is crossed by (a) Heat (b) Work (c) Mass (d) Both (a) and (b) above ANSWER: (d) 4. The characteristic of a control volume is/are (a) The volume, shape and position with respect to an observer are fixed (b) Material flow across the boundary (c) Both (a) and (b) above (d) None of the above ANSWER: (c) 5. Specific heat is the amount of heat required to raise the temperature (a) By unit degree of a substance (b) By unit degree of a unit mass (c) Of a unit mass by 10 (d) None of the above ANSWER: (b) 6. Internal energy of a perfect gas depends upon (a) Temperature only (b) Temperature and pressure (c) Temperature, pressure and specific heats (a) None of the above ANSWER: (a) 7. With rise of temperature, the specific heat of water

(a) Increases (b) Decreases (c) First decreases to minimum then increases (d) Remains constant ANSWER: (c) 8. For a closed system, difference between the heat added to the system and work done by the gas, is equal to the change in (a) Enthalpy (b) Entropy (c) Internal energy (d) Temperature ANSWER: (c) 9. Specific heat of water is (a) 1 (b) 0.1 (c) 0.97 (d) None of the above ANSWER: (a) 10. Properties of the system, whose value for the entire system is equal to the sum of their values for individual parts ofthe system, are known as (a) Thermodynamic properties (b) Extensive properties (c) Intensive properties (d) None of the above ANSWER: (b) 1. The extensive property of a thermodynamic system is (a) Viscosity (b) Surface tension (c) Refractive index (d) Heat capacity ANSWER: (d) 12. Thermal equilibrium between two or more bodies exists, when they are brought together; there is no change in (a) Density (b) Pressure (c) Temperature (d) All of the above ANSWER: (c)

13. When two bodies are in thermal equilibrium with a third body, they are also in thermal equilibrium with each other This statement is (a) Zero the law of thermodynamics (b) First law of thermodynamics (c) Second law of thermodynamics (d) None of the above ANSWER: (a) 14. First law of thermodynamics deals with conservation of (a) Mass (b) Heat (c) Momentum (d) Energy ANSWER: (d) 15. According to first law of thermodynamics (a) total energy of a system remains constant (b) total energy of a system during a process remains constant (c) enthalpy entropy and total energy remains constant (d) none of the above ANSWER: (a) 16. For the measurement of thermodynamic property known as temperature, is based on (a) Zeroth law of thermodynamics (b) First law of thermodynamics (c) Second law of thermodynamics (b) Third law of thermodynamics ANSWER: (a) 17. Energy can neither be created nor destroyed but only converted from one form to another. This statement is (a) Zeroth law of thermodynamics (b) First law of thermodynamics (c) Second law of thermodynamics (d) None of the above ANSWER: (b) 18. Kelvin-Planks law deals with (a) Conversion of work into heat (b) Conversion of heat into work (c) Conservation of work (d) Conservation of heat ANSWER: (b)

19. A perpetual motion machine of the first kind is a machine which produces power without consuming any energy is, (a) Possible according to first law of thermodynamics (b) Impossible according to first law of thermodynamics (c) Impossible according to second law of thermodynamics (d) Possible according to second law of thermodynamics ANSWER: (b) 20. Heat flows from cold substance to hot substance with the aid of external work This statement is given by (a) Kelvin (b) Joule (c) Gay Lussac (d) Clausius ANSWER: (d) 21. The fastest moving gas molecules are of (a) Oxygen (b) Hydrogen (c) Chlorine (d) Nitrogen ANSWER: (b) 22. In actual gases, the molecular collisions are (a) Elastic (b) Plastic (c) Inplastic (d) Ineclastic ANSWER: (d) 23. If a perfect gas, undergoing any change in the variable, which control physical properties, its behaviour is governed by (a) Boyles law (b) Charless law (c) Gay Lussac law (d) All of the above ANSWER: (d) 24. According of Boyles law at constant temperature PV= C. In this relation value of C depends upon (a) Atmospheric pressure (b) Quantity Of the gas (c) Molecular weight of the gas (d) All of the above ANSWER: (b)

25. Change of internal energy is proportional to the change of temperature. This is (a) Boyles law (b) Charless law (c) Joules law (d) Gay Lussac law ANSWER: (c)

Thermodynamics-Entropy and free energy

Multiple Choice Identify the choice that best completes the statement or answers the question. 1. If the reaction A + B C has an equilibrium constant greater than one, which of the following statements is correct? a. The reaction is not spontaneous. b. The forward rate of reaction is fast. c. The backward rate of reaction is slow. d. The reaction is product favored. e. All of the above statements are correct. 2. If a chemical reaction has a positive change in entropy, S, then a. the disorder of the system increases. b. the reaction is exothermic. c. heat goes from the system into the surroundings. d. the Gibbs free energy is negative. e. the reaction is spontaneous. 3. Thermodynamics can be used to determine all of the following EXCEPT a. the direction in which a reaction is spontaneous. b. the extent to which a reaction occurs. c. the rate of reaction. d. the temperature at which a reaction is spontaneous. e. the enthalpy change of a reaction. 4. Which of the following involves a decrease in entropy? a. the sublimation of carbon dioxide b. the dissolution of NaCl in water c. the decomposition of N2O4(g) to NO2(g) d. the evaporation of ethanol e. the freezing of liquid water into ice 5. Which of the following substances is likely to have the highest standard entropy in the liquid state? a. CH2Cl2 b. CCl4 c. CH3OH d. C5H12 e. C8H18 6. A statement of the second law of thermodynamics is that a. spontaneous reactions are always exothermic. b. energy is conserved in a chemical reaction. c. the entropy of the universe is continually increasing. d. the enthalpy of reaction is the difference between product and reactant enthalpies. e. the Gibbs free energy is a function of both enthalpy and entropy. 7. Of the following product-favored processes, which are endothermic? 1. the combustion of methane to produce water and carbon dioxide

2. the expansion of an ideal gas 3. the melting of ice at temperatures greater than 0C. a. 1 only b. 2 only c. 3 only d. 1 and 2 e. 2 and 3 8. All of the following statements concerning entropy are true EXCEPT a. entropy is zero for elements under standard conditions. b. entropy is a state function. c. a positive change in entropy denotes a change toward greater disorder. d. entropy values are greater than or equal to zero. e. the entropy a substance in the gas phase is greater than the solid phase. 9. All of the following processes lead to an increase in entropy EXCEPT a. increasing the temperature of a gas. b. freezing a liquid. c. evaporating a liquid. d. forming mixtures from pure substances. e. chemical reactions that increase the number of moles of gas. 10. Which reaction is likely to have a negative change in entropy? a. 2 NH3 N2(g) + 3 H2(g) b. CaO(s) + CO2(g) CaCO3(g) c. NaCl(s) Na+(aq) + Cl-(aq) d. N2O4(g) 2 NO2(g) e. 2 C(s) + O2(g) 2 CO(g) 11. Calculate the standard molar entropy change for the combustion of methane. CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g) Species S (J/Kmol) CH4(g) 186.3 O2(g) 205.1 CO2(g) 213.7 H2O(g) 188.8 a. -5.2 J/K b. -1.0 J/K c. +1.0 J/K d. +5.2 J/K e. +11.1 J/K 12. Calculate the standard entropy change for the following reaction, 2 Ag2O(s) 4 Ag(s) + O2(g) given S[Ag2O] = 121.3 J/Kmol, S[Ag(s)] = 42.6 J/Kmol, and S[O2(g)] = 205.1 J/Kmol. a. -205.1 J/K b. -126.4 J/K c. +126.4 J/K d. +132.9 J/K e. +205.1 J/K 13. The standard entropy of formation of CCl4(_) is 235.48 J/Kmol. Calculate the standard molar entropy of CCl4(_) given S[C(s)] = 5.74 J/Kmol and S[Cl2(g)] = 223.07 J/Kmol. a. 687.36 J/K b. +6.67 J/K c. +216.40 J/K

d. +465.02 J/K e. +687.36 J/K 14. For the following reaction at 25C, N2(g) + O2(g) 2 NO(g) Calculate S given S = 24.8 J/K and H = 181.8 kJ. a. -585 J/K b. +24.2 J/K c. +157 J/K d. +174 J/K e. +634 J/K 15. Use the following thermodynamic data Species H (kJ/mol) S (J/Kmol) H2O2(_) -187.78 109.6 H2O(_) -285.83 69.91 O2(g) 0 205.14 to calculate for S the decomposition of hydrogen peroxide at 25C. 2 H2O2(_) 2 H2O(_) + O2(g) a. 657.9 J/K b. 532.3 J/K c. +125.7 J/K d. +435.8 J/K e. +783.8 J/K 16. Predict the signs of H and S for the evaporation of water at 35C. 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. Not enough information is provided to answer this question. 17. Predict the signs of H, S, and G for the combustion of hydrogen gas at 25C. 2 H2(g) + O2(g) 2 H2O(_) 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 18. Predict the signs of H, S, and G for the melting of ice at 50C. 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 19. If G < 0 for a reaction at all temperatures, then S is ________ and H is ________. a. positive, positive b. positive, negative c. zero, positive d. negative, positive e. negative, zero 20. The dissolution of ammonium nitrate occurs spontaneously in water. As NH4NO3 dissolves, the temperature of the water decreases. What are the signs of H, S, and G for this process?

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 21. Diluting concentrated sulfuric acid with water can be dangerous. The temperature of the solution can increase rapidly. What are the signs of H, S, and G for this process? 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 22. All of the following relationships are true EXCEPT a. G = H - TS b. G = - RT 1n(K) c. S = S + S d. H = H + RT 1n(K) e. G - TS 23. Above what temperature would you expect a reaction to become spontaneous if H = +322 kJ and S = +531 J/K? a. 171 K b. 209 K c. 606 K d. The reaction will be spontaneous at any temperature. e. The reaction will NOT be spontaneous at any temperature. 24. At what temperature would you expect a reaction to become spontaneous if H = +67.0 kJ and S = 131 J/K? a. T < -511 K b. T > 238 K c. T > 511 K d. The reaction will be spontaneous at any temperature. e. The reaction will NOT be spontaneous at any temperature. 25. For a reaction, H = +265 kJ and S = +271.3 J/K. At what temperature will G = 0.00? a. 6.30 K b. 102 K c. 359 K d. 719 K e. 977 K 26. If a process is endothermic and spontaneous, which of the following must be true? a. G > 0 and H < 0 b. G < 0 and H < 0 c. G < 0 and S > 0 d. H < 0 and S > 0 e. H > 0 and S < 0 27. Calculate G for the reaction below at 25.0C 2 H2S(g) + O2(g) 2 H2O(g) + S(s) given H = -442.4 kJ, and S = -175.4 J/K. a. -438.0 kJ b. -390.1 kJ c. -321.9 kJ

d. +3943 kJ e. +5182 kJ 28. Calculate G for the reaction below at 25.0C Mg(s) + O2(g) 2 MgO given H = -1203.4 kJ, and S = -216.6 J/K. a. -2076 kJ b. -1421 kJ c. -1139 kJ d. +2888 kJ e. +63390 kJ 29. Calculate for the reaction below at 25.0C 2 H2O2(_) 2 H2O(_) + O2(g) given G [H2O2(_)] = -120.35 kJ/mol, G [H2O(_)] = -237.13 kJ/mol, G [O2(g)] = 0 kJ/mol. a. 714.96 kJ b. 543.91 kJ c. -438.23 kJ d. -233.56 kJ e. -67.03 kJ 30. The for the following reaction is -70.9 kJ. SO2(g) + 1/2 O2(g) SO3(g) Given G [ SO2(g)] = -300.2 kJ/mol, calculate G [SO3(g)]. a. -371.1 kJ b. -229.3 kJ c. -158.4 kJ d. + 88.2 kJ e. +229.3 kJ 31. Calculate for the reaction below at 25.0C. 4 Fe(s) + 3 O2(g) 2 Fe2O3(s) Species H (kJ/mol) S (J/Kmol) Fe(s) 0 27.78 O2(g) 0 205.14 Fe2O3(s) -824.2 87.40 a. -1629 kJ b. -1484 kJ c. -780.8 kJ d. -659.7 kJ e. +1629 kJ 32. Calculate for the reaction below at 25.0C. PCl3(g) + Cl2(g) PCl5(g) Species H (kJ/mol) S (J/Kmol) PCl3(g) -287.0 311.8 Cl2(g) 0 223.1 PCl5(g) -374.9 364.5 a. -1432.6 kJ b. -930.1 kJ c. -879.0 kJ d. -50.8 kJ e. -37.1 kJ 33. Calculate G for the reaction below at 25.0C. C2H5OH_) + 3 O2(g) 2 CO2(g) + 3 H2O(_)

Species H (kJ/mol) S (J/Kmol) C2H5OH(_) -277.7 160.7 O2(g) 0 205.1 CO2(g) -393.5 213.7 H2O(_) -285.8 69.1 a. 1325 kJ b. 365.1 kJ c. 141.3 kJ d. +1038 kJ e. +2435 kJ 34. If G< 0, then a. K >1 b. K = 0 c. K < 1 d. K = 1 e. K < 0 35. All of the following substances have a free energy of zero EXCEPT a. He(g). b. O(g). c. S8(s). d. Cu(s). e. Cl2(g). 36. For a chemical system, G and G are equal when a. the equilibrium constant, K, equals 1. b. the equilibrium constant, K, equals 0. c. a system is at equilibrium. d. the reactants and products are in standard state concentrations. e. the reactant and products are in the gas phase. 37. The free energy change for a given reaction is +15.0 kJ. What is the equilibrium constant for the reaction at 75C? (R = 8.314 J/Kmol) a. 5.60 10-3 b. 6.82 10-1 c. 1.01 d. 5.18 e. 178 38. The free energy change for the formation of the complex ion AlF6 3- is -140. kJ at 25C. What is the equilibrium constant for the reaction? a. 2.9 10-25 b. 5.65 101 c. 3.5 1024 d. 5.2 1029 e. 2.3 1056 39. What is the equilibrium constant for formation of carbon dioxide at 25C? (R = 8.314 J/Kmol) C(s) + O2(g) CO2(g) G = 3.90 102 kJ/mol a. 5.7 101 b. 5.4 1013 c. 2.9 1024 d. 4.9 1042 e. 2.3 1068

40. The equilibrium constant for a reaction at 298 K is 9.3 10-12. What is G? (R = 8.314 J/Kmol) a. 2.54 kJ b. +2.54 kJ c. +5.28 kJ d. +62.9 kJ e. +87.1 kJ 41. Calculate G for the following reaction at 298 K, N2O4(g) 2 NO2(g) given K = 0.15. (R = 8.314 J/K mol) a. +1.15 kJ b. +4.70 kJ c. +8.13 kJ d. +38.1 kJ e. +87.0 kJ 42. Given that C(s) + O2(g) CO2(g) G = -394.4 kJ CO(g) + O2(g) CO2(g) G = -257.2 kJ calculate G for the following reaction. C(s) + O2(g) CO(g) a. 651.6 kJ b. 137.2 kJ c. +1.53 kJ d. +45.3 kJ e. +651.6 kJ 43. Calculate for CaCO3 given the following information. C(s) + O2(g) CO2(g) G = -394.4 kJ CaO(g) + CO2(g) CaCO 3(s) G = -130.4 kJ Ca(s) + O2(g) CaO(s) G = -604.0 kJ a. 1128.8 kJ b. 340.0 kJ c. 130.4 kJ d. +868.0 kJ e. +1128.8 kJ Completion Complete each statement. 44. The total energy of the universe is constant. This is a statement of the ________ law of thermodynamics. 45. A chemical reaction with an equilibrium constant greater than one is said to be ________-favored. 46. The change in entropy for any process is not dependent upon the pathway by which the process occurs. In other words, the change in entropy for any process is a ________ function. 47. For any process, the change in entropy of the universe equals the sum of the entropy changes to the system and the ________. 48. The entropy of a pure crystal at 0 K is ________ J/K. Essay 49. Does the formation of complex molecules such as proteins and nucleic acids from more simple molecules break the second law of thermodynamics? 50. At the boiling point, liquid and gas phases exist at equilibrium. In addition, for a system at equilibrium G = 0.

Calculate the enthalpy of vaporization of water at its normal boiling point if S [H2O(_)] = 69.9 J/K mol and S [H2O(g)] = 188.8 J/K mol.

Thermodynamics-Entropy and free energy Answer Section

MULTIPLE CHOICE 1. D 2. A 3. C 4. E 5. E 6. C 7. E 8. A 9. B 10. B 11. A 12. D 13. C 14. A 15. E 16. A 17. A 18. E 19. B 20. D 21. B 22. D 23. C 24. E 25. E 26. C 27. B 28. C 29. D 30. A 31. B 32. E 33. A 34. A 35. B 36. D 37. A 38. C 39. E 40. D 41. B 42. B 43. A COMPLETION

44. first 45. product 46. state 47. surroundings 48. 0 ESSAY 49. No. The formation of complex molecules involves a decrease in entropy locally. This local decrease is offset by an increase in entropy to the universe. 50. 44.3 kJ/mol

Objective Questions of Thermodynamics

Prob 1. A system is taken from state A to state B along two different paths 1 and 2. The heat absorbed and work done by the system along these paths are Q1 and Q2 and W1 and W2respectively. Then (A) Q1 = Q2 (C) W1 = W2 Sol. (D) (B) W1 + Q1 = Q2 + W2 (D) Q1 - W1 = Q2 - W2

Prob 2. In which of the following process does the entropy decrease? (A) dissolving of NaCl in water (C) conversion of CO2(g) into dry ice Sol. (C) (B) evaporation of water (D) none

Prob 3. Calculate the enthalpy change when 50 ml of 0.01 M Ca(OH)2 reacts with 25 ml of 0.01 M HCl. Given that H0neut of a strong acid and strong base is 140 cal/ equivalent (A) 14.0 cal (C) 10.0 cal Sol. (B) (B) 35 cal (D) 7.5 cal

Prob 4 In a reversible adiabatic change S is (A) infinity (C) equal to CvdT (B) zero (D) equal to nRln V2/V1

Sol.

(B)

Prob 5 At constant temperature and pressure which one of the following statements is correct for the reaction? CO(g) + 1/2O2(g) > CO2(g) (A) H = E (B) H < E (C) H > E (D) H is independent physical state of reactant Sol. (B)

Prob 6 For the reaction, C7H8(l) + 9O2(g) > 7CO2(g) + 4H2O(l), the calculated heat of reaction is 232 kJ/mol and observed heat of reaction is 50.4 kJ/mol, then the resonance energy is (A) 182.2 kJ / mol (C) 172 kJ/ mol Sol. (A) As we know that, Resonance energy = H (observed) DH (calculated) = (50.4 232.6) kJ / mol = 182.2 kJ mol1 Fill in the Blanks Prob 7 An isolated system is one which neither shows exchange of .. nor . with surroundings. Sol. Prob 8 Sol. Prob 9 (heat, mass) During fusion, the entropy of the system . (increases) N2 + O2 > 2 NO, shows an .. of heat. (B) + 182.2 kJ / mol (D) None

Sol. Prob 10 Sol.

(absorption) For spontaneous reaction G is (negative)

Prob 11 Bomb calorimeter used for determining change in internal energy at constant Sol. Volume

True and False Prob 12. Specific heat is an intensive property. Sol. True

Prob 13. A thermodynamic equilibrium represents the state when all the three equilibrium (i.e. chemical, thermal and mechanical equilibrium) are attained at a time. Sol. True

Prob 14. The process is isothermal if temperature of the system remains constant throughout the course of studies. Sol. True

Prob 15. Rivers flowing from mountain to field shows decrease in entropy. Sol. False

Prob 16. Enthalpy of combustion at a given temperature is defined as the enthalpy change for the compete combustion of 1 gm of substance. Sol. False

Level 2 Objective Problems of Thermodynamics

Level 2
1. Evaporation of water is a spontaneous process although it (A) Is an exothermic reaction (B) is an endothermic reaction

(C) Is a photo chemical reaction (D) proceed without heat loss or heat gain 2. For the two reactions given below H2(g) + 1/2 O2(g) > H2O(g) + X1KJ H2(g) + 1/2 O2(g) > H2O(l) + X2KJ Select the correct answer (A) X1 > X2 (C) X1 = X2 3. Which of the following is wrong? (A) change in internal energy of an ideal gas on isothermal expansion is zero (B) in a cyclic process w Q (C) for an ideal gas [H/P]T = 0 (D) all 4. The heats of neutralization of four acids a, b c and d when neutralized against a common base are 13.7, 9.4, 11.2 and 12.4 Kcal respectively. The weakest among these acids is (A) c (C) a (B) b (D) d (B) X1 < X2 (D) X1 + X2 = 0

5. The bond energies of C = C, C H, H H and C = C are 198, 98, 103, 145 Kcal respectively. The enthalpy change of the reaction CH = CH + H2 > CH2 = CH2 is (A) -152 Kcal (C) 48 Kcal (B) 96 Kcal (D) -40 Kcal

6. Which plot represents for an exothermic reaction?

7. The molar heat capacity of water in equilibrium with ice at constant pressure is (A) negative (C) infinity (B) zero (D) 40.45 KJK-1mol-1

8. Enthalpy of CH4 + 1/2 O2 > CH3OH is negative. If enthalpy of combustion of CH4 and CH3OH are x and y respectively. Then which relation is correct? (A) x > y (C) x = y (B) x < y (D) x < y

9. When 10 ml of a strong acid are added to 10 ml of an alkali, the temperature rises 5C. If 100 ml of each liquids are mixed, the temperature rise would be (A) 0.5C (C) 7.5C 10. X is a metal that forms an oxide X2O 1/2 X2O > X + 1/4 O2, H = 120 Kcal When a sample of metal X reacts with one mole of oxygen, what will be the DH in that case? (A) 480 kcal (C) -480 kcal (B) -240 kcal (D) 240 kcal (B) 10C (D) same

11. AB, A2 and B2 are diatomic molecules. If the bond enthalpies of A2, AB & B2 are in the ratio 1:1:0.5 and enthalpy of formation of AB from A2 and B2 100 kJ/mol1. What is the bond enthalpy of A2? (A) 400 kJ/mol (C) 100 kJ/mol (B) 200 kJ/mol (D) 300 kJ/mol

12. Which of the following corresponds to the definition of enthalpy of formation at 298 K? (A) C(graphite) + 2H2(g) + 1/2 O2(l) CH3OH(g) (B) C(diamond) + 2H2(g) + 1/2 O2(g) CH3OH (l) (C) 2C(graphite) + 4H2(g) + O2(g) 2CH3OH (l) (D) C(graphite) + 2H2(g) + 1/2 O2(g) CH3OH(l) 13. The heat of neutralisation of HCl by NaOH is 12.1kJ/mole, the energy of dissociation of HCl is (A) 43.8 kJ (C) 68 kJ (B) 43.8 kJ (D) 68 kJ

14. The dissociation energy of CH4 and C2H6 are respectively 360 & 620 k. cal/mole. The bond energy of CC is (A) 260 kcal/mole (C) 130 kcal/mole (B) 180 kcal/mole (D) 80 kcal/mole

15. Identify the intensive property from the following: (A) Enthalpy (C) Volume (B) Temperature (D) Refractive index

16. Which of the following expression is not correct?

17. For a reaction A(g) > B(g) at equilibrium, the partial pressure of B is found to be one fourth of the partial pressure of A. The value of G0 of the reaction A > B is (A) RT ln4 (C) RT log4 (B) -RT ln4 (D) -RT log4

18. For an irreversible isothermal expansion of an ideal gas (A) Ssys = Ssurr (C) |Ssys| > |Ssurr| 19. H2(g) > 2H(g) (A) H atom has higher entropy (C) both have same entropy (B) hydrogen molecule has entropy (D) none (B) Ssys = Ssurr (D) |Ssys| < |Ssurr|

20. An endothermic reaction is spontaneous only if (A) the entropy of the surrounding increases (C) total entropy decreases (B) entropy of the system increases (D) none

Level II
1. 4. 7. 10. 13. 16. B B C C C C 2. 5. 8. 11. 14. 17. A D B A D A 3. 6. 9. 12. 15. 18. B A D d B&D C

19.

20.

ANSWERS TO ASSIGNMENT PROBLEMS

Subjective: Level - O 1. Since sublimation involves the process Hs Solid > Vapour .. (1) Hf Hv

or Solid > Liquid > Vapour ...... (2) By (1) and (2), Hs > Hs + Hv 2. At all temperature conditions, H < 0 and S > 0, so that HG < 0. 3. It is so because only H+ and OH react in every case and it is the enthalpy of formation of water. 4. (i) When number of molecules of products are more than number of molecules in the reactants. (ii) When solid state changes to liquid state. (iii) When liquid state changes to gaseous state. (iv) When solid changes to gaseous state. 5. Solute molecules also set free to move in solution and thus disorder increases. 6. The system: ice water at m. pt., is in equilibrium and thus G = 0. 7. G = H TS; since the reaction proceeds to completion that is irreversible or spontaneous and thus G = ve. Therefore, since H = +ve... H TS = ve orS. should be +ve. 8. The standard state chosen for carbon is graphite and not diamond.

9. No, because it is the sum of different types of energies and some of which can not be determined? 10. Heat evolved will be different. This is because they have different crystal structure. 11. Because all chemical reactions are accompanied by bond rearrangements. The total bond energy of reactants is not equal to the total bond energy of products hence heat is either evolved or absorbed. 12. Sublimation is a process which is assumed to take place in two step: First a solid converts into liquid and second a liquid converts into vapours hence the sum of enthalpy of fusion and enthalpy of vapourisation is equal to enthalpy of sublimation. 13. In an ideal gas, there are no intermolecular forces of attraction. Hence no energy is required to overcome these forces. Moreover, when a gas expands against vacuum, work done is zero (because Pext = 0). Hence internal energy of the system does not change i.e. there is no absorption or evolution of heat. 14.-212.76 kcal 15.-29.00 kcal 16.Chemical energy 18. Zero 19. 2.4 102 20. At equilibrium products are much more in abundance than the reactants (k > > 1). Objective: Level I 1. 4. 7. 10. 13. 16. D D B C C D 2. 5. 8. 11. 14. 17. C A C d D D 3. 6. 9. 12. 15. 18. A D B D d D

19. 22. 25. Level II 1. 4. 7. 10. 13. 16. 19.

B D A

20. 23.

C B

21. 24.

B C

B B C C C C A

2. 5. 8. 11. 14. 17. 20.

A D B A D A B

3. 6. 9. 12. 15. 18.

B A D d B&D C