CHEMICAL THERMODYNAMICS & THERMOCHEMISTRY

1. Objective Questions 5 moles of an ideal gas at 27C expands isothermally and reversibly from a volume of 6 L to 60 L. The work done in kJ is: (a) 14.7 (b) 28.72 (c) +28.72 (d) 56.72 10 moles of an ideal gas confined to a volume of 10 L is released into atmosphere at 300 K where the pressure is 1 bar. The work done by the gas is: (R = 0.083 L bar K1 mol1) (a) 249 L bar (b) 259 L bar (c) 239 L bar (d) 220 L bar 1 litre-atm work is approximately equal to: (a) 101.3 J (b) 8.314 J (c) 931 J (d) 19.2 J A system absorbs 20 kJ heat and also does 10 kJ of work. The net internal energy of the system: (a) increases by 10 kJ (b) decreases by 10 kJ (c) increases by 30 kJ (d) decreases by 30 kJ One mole of a gas is heated at constant pressure to raise its temperature by 1C. The work done in joules is: (a) 4.3 (b) 8.314 (c) 16.62 (d) unpredictable In open system: (a) there will be exchange of both matter and energy (b) there will be no exchange of matter and energy (c) there will be exchange of energy only (d) there will be exchange of matter only H 298 K of methanol is given by the chemical f equation:
1 O2(g) CH3OH(g) 2 1 (b) C (graphite) + O2 (g) + 2H2 (g) CH3OH(l) 2 1 (c) C (diamond) + O2 (g) + 2H2 (g) CH3OH(l) 2 (d) CO(g) + 2H2 (g) CH3OH(l) The standard molar heat of formation of ethane, CO2 and H2O (l) are respectively 21.1, 94.1 and 68.3

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kcal. The standard molar heat of combustion of ethane will be: (a) 372 kcal (b) 240 kcal (c) 162 kcal (d) 183.5 kcal When ethyne is passed through a red hot tube, then formation of benzene takes place: H f H f
( C 2H 2 )(g ) = ( C 6 H 6 )( g )

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230 kJ mol1

= 85 kJ mol1

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Calculate the standard heat of trimetisation of ethyne to benzene. 3C2H2 (g) C6H6 (g) (a) 205 kJ mol1 (b) 605 kJ mol1 (c) 605 kJ mol1 (d) 205 kJ mol1 F2 (g) + 2HCl(g) 2HF(g) + Cl2 (g); H = 352.18 kJ H f
( HF ) =

268.3 kJ

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(a) CH4 (g) +

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The heat of formation of HCl will be: (a) 22 kJ mol1 (b) 88 kJ mol1 1 (c) 92.21 kJ mol (d) 183.8 kJ mol1 The enthalpy of combustion at 25C of H2, cyclohexane (C6H12) and cyclohexene (C6H10) are 241, 3920 and 3800 kJ/mol respectively. The heat of hydrogenation of cyclohexene is: (a) 121 kJ/mol (b) +121 kJ/mol (c) 242 kJ/mol (d) +242 kJ/mol The enthalpy change H for the neutralization of 1 M HCl by caustic potash in dilute solution at 298 K is: (a) 68 kJ (b) 65 kJ (c) 57.3 kJ (d) 50 kJ Enthalpy of neutralization of the reaction between CH3COOH (aq.) and NaOH (aq.) is 13.2 kcal eq1 and that of the reaction between H2SO4 (aq.) and KOH (aq.) is 13.7 kcal eq1. The enthalpy of dissociation of CH3COOH (aq.) is: (a) 0.5 kcal eq-1 (b) +0.5 kcal eq-1 -1 (c) 26.9 kcal eq (d) +13.45 kcal eq-1 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 H neutralization of a strong acid and a strong base is 140 kcal mol1.

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(a) 14 kcal (b) 35 cal (c) 10 cal (d) 7.5 cal Equal volumes of 1 M HCl and 1 M H2SO4 are neutralized by 1 M NaOH solution and x and y kJ/equivalent of heat are liberated respectively. Which of the following relation is correct? (a) x = 2y (b) x = 3y (c) x = 4y (d) x = 1/2y Which of the following acid will release maximum amount of heat when completely neutralized by strong base NaOH? (a) 1 M HCl (b) 1 M HNO3 (c) 1 M HClO4 (d) 1 M H2SO4 Heat of combustion of diamond and graphite are 94.5 kcal and 94 kcal/mol respectively. What will be the heat of transition from diamond to graphite? (a) 0.5 kcal (b) +0.5 kcal (c) 1 kcal (d) 1 kcal The bond energies of C C and C C at 298 K are 590 and 331 kJ mol1 respectively. The enthalpy of polymerisation per mole of ethylene is: (a) 70 kJ (b) 72 kJ (c) 72 kJ (d) 68 kJ For the reaction, 2H2 (g) + O2(g) 2H2O(g); H = 571 kJ bond energy of (H H) = 435 kJ; of (O O) = 498 kJ; then calculate the average bond energy of (O H) bond using the above data. (a) 484 kJ (b) 484 kJ (c) 271 kJ (d) 271 kJ Heat of formation of 2 moles of NH3 (g) is 90 kJ; bond energies of H H and N H bonds are 435 kJ and 390 kJ mol1 respectively. The value of the bond energy of N N will be: (a) 472.5 kJ (b) 945 kJ (c) 472.5 kJ (d) 945 kJ mol1 If value of H of ICl(g), Cl(g) and I(g) are f respectively 17.57, 121.34, 106.96 J mol1. The value of ICl (bond energy) in J mol1 is: (a) 17.57 (b) 210.73 (c) 35.15 (d) 106.96 For a liquid, enthalpy of fusion is 1.435 kcal mol1 and molar entropy change is 5.26 cal mol1 K1. The melting point of the liquid is: (a) 0C (b) 273C (c) 173 K (d) 100C Latent heat of vaporization of water is 540 cal g1 at 100C. Calculate the entropy change when 1000 g water is converted to steam at 100C. (a) 1447 cal

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(b) 2447 cal (c) 3447 cal (d) 4447 cal Enthalpy of fusion of water is 6.01 kJ mol1. The entropy change of 1 mole of ice at its melting point will be: (a) 22 kJ mol1 (b) 109 kJ mol1 (c) 44 kJ mol1 (d) 11 kJ mol1 For spontaneous process: (a) Stotal = 0 (b) Stotal > 0 (c) Stotal < 0 (d) none of these Melting point of a solid is x K and its latent heat of fusion is 600 cal mol1. The entropy change for fusion of 1 mol solid is 2 cal mol1 K1. The value of x will be: (a) 100 K (b) 200 K (c) 300 K (d) 400 K The entropy change involved in the conversion of 1 mole of liquid water at 373 K to vapour at the same temperature will be: Hvap = 2.257 kJ/g (a) 0.119 kJ (b) 0.109 kJ (c) 0.129 kJ (d) 0.120 kJ The free energy for a reaction having H = 31400 cal, S = 32 cal K1 mol1 at 1000C is: (a) 9336 cal (b) 7386 cal (c) 1936 cal (d) +9336 cal For the equilibrium reaction, the value of Gibbs free energy change is: (a) > 0 (b) < 0 (c) = 0 (d) 0 For the homogeneous reactions: xA + yB lY + mZ H = 30 kJ mol1, S = 100 J K1 mol1. At what temperature the reaction is at equilibrium? (a) 50C (b) 250C (c) 100 K (d) 27C (e) 500 K 1 For the reaction CO(g) + O2(g) CO2(g), H 2 and S are 283 kJ and 87 J K1 mol1 respectively. It was intended to carry out this reaction at 1000, 1500, 3000 and 3500 K. At which of these temperatures would this reaction be thermodynamically spontaneous? (a) 1500 and 3500 K (b) 3000 and 3500 K (c) 1000, 1500 and 3000 K (d) 1500, 3000 and 3500 K

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For a reaction, H = + 29 kJ mol1; S = 35 JK1 mol1 at what temperature, the reaction will be spontaneous? (a) 828 7C (b) 828.7 K (c) Spontaneous at all temperature (d) Not possible What is the sign of G and the value of K for an electrochemical cell for which E cell = 0.80 volt? G K (a) >1 (b) + >1 (c) + <1 (d) <1 The free energy of formation of NO is 78 kJ mol1 at the temperature of an automobile engine (1000 K). What is the equilibrium constant for this reaction at 1000 K? 1 1 N2 (g) + O2 (g) NO (g) 2 2 (a) 8.4 105 (b) 7.1 109 10 (c) 4.2 10 (d) 1.7 1019 Equilibrium constant for the reaction: H2 (g) + I2 (g) 2HI (g) is Kc = 50 at 25C. The standard Gibbs free energy change for the reaction will be: (a) 6.964 kJ (b) 9.694 kJ (c) 4.964 kJ (d) 6.496 kJ Standard Gibbs free energy change G for a reaction is zero. The value of the equilibrium constant will be: (a) 10 (b) 1 (c) 100 (d) The standard free energy change of a reaction is G = 115 kJ at 298 K. Calculate the equilibrium constant Kp in log Kp. (R = 8.314 JK1 mol1) (a) 20.16 (b) 2.303 (c) 2.016 (d) 13.83 If an endothermic reaction occurs spontaneously at constant temperature T and pressure P, then which of the following is true? (a) G > 0 (b) H < 0 (c) S > 0 (d) S < 0 Which is the correct expression that relates changes of entropy with the change of pressure for an ideal gas at constant temperature, among the following? P (a) S = nRT ln 2 P1 (b) S = T (P2 P1)

P (c) S = nR ln 1 P 2 P (d) S = 2.303 nRT ln 1 P 2

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Given two processes: 1 P4 (s) + 3Cl2 (g) 2PCl3 (l): 2 kJ PCl3 (l) + Cl2 (g) PCl5 (s); kJ The value of Hf of PCl5 is: (a) 454.5 kJ mol1 (b) 454.5 kJ (c) 772 kJ mol1 (d) 498 kJ mol1 ANSWERS

H = 635

H = 137

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1. (b) 7. (b) 13. (b) 19. (a) 25. (b) 31. (c) 37. (a)

2. (c) 8. (a) 14. (b) 20. (d) 26. (c) 32. (d) 38. (c)

3. (a) 9. (c) 15. (d) 21. (b) 27. (b) 33. (a) 39. (c)

4. (a) 10. (c) 16. (d) 22. (a) 28. (a) 34. (a) 40. (b)

5. (b) 11. (a) 17. (b) 23. (a) 29. (c) 35. (b)

6. (a) 12. (c) 18. (b) 24. (a) 30. (d) 36. (b)

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