THERMODYNAMICS AND THERMOCHEMISTRY 1

EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

Introduction of Thermodynamics 8. Which of the following changes would definitely increase
1. Which of the following is not a state function ? the internal energy of a system?
(a) Heat (b) Internal energy (a) The system gains heat and performs work.
(c) Enthalpy (d) Entropy (b) The system gains heat and has work performed on it.
Ans. (a) (c) The system loses heat and performs work.
Sol. Heat depends on the path taken. (d) The system loses heat and has work performed on it.
Ans. (b)
2. Which of the following quantities is not a state function ? Sol. DU= Q +W, heat given to system and work done on the
(a) Temperature (b) Entropy system are both positive.
(c) Enthalpy (d) Work
Ans. (d) 9. What is the change in internal energy when a gas contracts
Sol. Work done depends on the path taken. from 377 mL to 177 mL under a constant pressure of 1520
3. Which of the following is not an intensive property ? torr, while at the same time being cooled by removing 124
(a) Entropy (b) Pressure J heat?
(c) Temperature (d) Molar volume (a) 40.52 J (b) –83.48 J
Ans. (a) (c) –248 J (d) None of these
Sol. Intensive property is the property which doesn’t depend Ans. (b)
on the amount of matter. Sol. DH = -124J(Q the heat is removed)
4. Which of the following is a state function and also an
extensive property? V1 = 377mL
(a) Internal energy (b) Pressure V2 = 177mL
(c) Molar heat capacity (d) Temperature
Ans. (a) \ DV = V2 - V1 = 177 - 377 = -200mL = -0.2L
Sol. State functions are dependent of path taken while 1520
extensive properties are dependent of amount. P = 1520 torr = = 2atm
760
5. Warming ammonium chloride with sodium hydroxide in a
test tube is an example of : P.DV = 2 ´ (-0.2) = -0.4 L atm
(a) Closed system (b) Isolated system As we know that,
(c) Open system (d) None of these 1 L atm = 101.3 J
Ans. (c) \ P.DV = -0.4Latm = (-0.4 ´ 101.3)J = -40.52J
Sol. NH 4 Cl + NaOH ® NH3 + H 2 O + NaCl As we know that,
Open system, as both energy and matter can exchange DU = q - PDV
with surrounding
DU = -124 - (-40.52)
6. A tightly closed thermoflask contains some ice cubes. This Þ DU = -124 + 40.52 = -83.48J
constitutes 10. A given mass of gas expands from the state A to the state
(a) closed system (b) open system B by three paths 1, 2 and 3 as shown in the figure. If w1, w2
(c) isolated system and w3 respectively be the magnitudes work done by the
(d) Non-thermodynamic system gas along three paths then :
Ans. (c)
Sol. Isolated as neither energy nor matter can exchange with
surrounding.

Internal Energy, Concept of Heat and Work

7. A sample of gas changes from P1, V1 and T1 to P2, V2 and T2
by one path and then back to P1, V1 and T1, DU for the
process is :
(a) Infinite (b) > 0
(c) < 0 (d) equal to 0 (a) w1 > w2 > w3 (b) w1 < w2 < w3
Ans. (d) (c) w1 = w2 = w3 (d) w2 < w3 < w1
Sol. DU=0 for a cyclic process. Ans. (b)
Sol. Work done is area under P-V graph, so w1 < w2 < w3.
dw = PDV
 2 THERMODYNAMICS AND THERMOCHEMISTRY

11. An ideal gas is taken around the cycle ABCA as shown in Ans. (b)
P-V diagram Sol. At constant volume, w=0
The net work done by the gas during the cycle is equal to : DU=10 kJ
15. As per the First Law of thermodynamics, which of the
following statement would be appropriate :
(a) Energy of the system remains constant
(b) Energy of the surroundings remains constant
(c) Entropy of the universe remains constant
(d) Energy of the universe remains constant
Ans. (d)
Sol. The first law of thermodynamics is a version of the law of
conservation of energy, adapted for thermodynamic
system. The law of conservation of energy states that the
total energy of an isolated system is constant; energy can
(a) 12 P1V1 (b) 6P1V1 be transformed from one form to another, but cannot be
(c) 5P1V1 (d) P1V1 created or destroyed.
Ans. (c) 16. A sample of liquid in a thermally insulated container (a
Sol. Work done= Area under P-V graph, calorimeter) is stirred for 2 hr. by a mechanical linkage to a
motor in the surrounding, for this process;
1 1 (a) w < 0; q = 0; DU = 0 (b) w > 0; q > 0; DU > 0
w= AC× BC = 3V1 - V1 6P1 - P1
2 2 (c) w < 0; q > 0; DU = 0 (d) w > 0; q = 0; DU > 0
1 Ans. (d)
= × 2V1 × 5P1 = 5P1 V1 Sol. It is stirred. Since energy is provided, positive work is
2 done on the system. Since its isolated, q=0.
12. An ideal gas is taken through the cycle A ® B ® C ® A
By 1st law, DU =w>0.
as shown in fig. If the net heat supplied to the gas in cycle
is 5 J, the work done by the gas in the process C ® A.
17. For a particular process q = –10 kJ and w=25 kJ. Which of
the following statements is true?
(a) Heat flows from the surroundings to the system.
(b) The system does work on the surroundings.
(c) DE= –35 kJ
(d) None of the above is true
Ans. (d)
Sol. DU = -10 + 25 = 15
Heat flows from system to surroundings
Work is done on the system, DE= +15 kJ
(a) –5 J (b) –10 J So none of the above is true.
(c) –15 J (d) –20 J
Ans. (a) Reversible and Irreversible Work
Sol. Work done by gas is negative, and DU=0 in a cyclic 18. In an isothermal expansion of an ideal gas
process. Therefore, w = -5 J. (a) q = 0 (b) DV = 0
13. In a system where DE = –51.0 kJ, a piston expanded against (c) DU = 0 (d) w = 0
a pext of 1.2 atm giving a change in volume of 32.0 L. What Ans. (c)
was the change in heat of this system? Sol. Isothermal means temp. constant. Hence, DU = 0.
(a) –36 kJ (b) –13 kJ 19. Two moles of Helium gas undergo a reversible cyclic
(c) –47 kJ (d) 24 kJ process as shown in figure. Assuming gas to be ideal.
Ans. (c) What is the work for the process C to D ?
Sol. W = -1.2 ´ 32 ´ 101.3 = -3.89kJ
DE = q + w
-51 = q - 3.89
q = -47kJ

First Law of Thermodynamics

14. A system absorb 10 kJ of heat at constant volume and its (a) –800 Rln2 (b) zero
temperature rises from 27°C to 37°C. The value of DU is (c) +200 Rln2 (d) –600 Rln2
(a) 100 kJ (b) 10 kJ Ans. (a)
(c) 0 (d) 1 kJ
THERMODYNAMICS AND THERMOCHEMISTRY 3
Sol. C to D is isothermal process
Work Done= Ans. (b)

æP ö æ V2 ö
nRTln ç 1 ÷ = -2R(400)ln(2) = -800Rln2 Sol. W = - 2.303RT log ç ÷n
è V1 ø
è P2 ø
20. A heat engine carries one mole of an ideal mono-atomic æ 40 ö
= -2.303 2 2 300 log ç ÷ = -11.488kJ
gas around the cycle as shown in figure, the amount of è 4 ø
heat added in the process AB and heat removed in the 24. 5 mole of an ideal gas expand isothermally and irreversibly
process CA are: from a pressure of 10 atm to 1 atm against a constant
external pressure of 1 atm. wirr at 300 K is:
(a) –15.921kJ (b) –11.224 kJ
(c) –110.83 kJ (d) None of these
Ans. (b)
Sol. ò dw = - ò Pext dV
é nRT nRT ù é 1ù
Wirr = - Pext ê - ú = -[5 ´ 8.314 ´ 300] ê1 - ú
ë P2 P1 û ë 10 û
Wirr = -11.224 kJ
(a) qAB = 450 R and qCA = –450 R
(b) qAB = 450 R and qCA = –225 R
25. 10 mole of ideal gas expand isothermally and reversibly
(c) qAB = 450 R and qCA = –375 R
from a pressure of 10 atm to 1 atm at 300 K. What is the
(d) qAB = 375 R and qCA = –450 R
largest mass which can lifted through a height of 100 meter?
Ans. (c)
(a) 31842 kg (b) 58.55 kg
Sol. AB is isochoric. Work done is zero
(c) 342.58 kg (d) None of these
æ 3R ö Ans. (b)
\ q = V = nCV RT = 1ç ÷ (300) = 450R
è 2 ø Sol. Work done is isothermal and reversible.
AC is isobaric æP ö
\ w = 2.303nRT log ç 1 ÷ = mgh
æ 5R ö è P2 ø
\ q = - nCp DT = -1ç ÷ (150) = -375R
è 2 ø \ 2.303 × 10 × 8.3 × 300 = m × 9.8 × 100
21. An ideal gas receives 10 J of heat in a reversible isothermal
Þ m = 58.55kg
expansion. Then the magnitude of work done by the gas :
(a) would be more than 10 J 26. Which of the following statement is true?
(b) 10 J (a) A thermodynamic process is defined by initial and
(c) would be less than 10 J final states.
(d) cannot be determined (b) DE=0 for a reversible phase change at constant T and
Ans. (b) P.
Sol. Change in internal energy 0, and th process reversible. (c) q must be zero for an isothermal process.
Hence, Work done heat supplied q = w = 10J (d) A reversible adiabatic process is also isoentropic.
Ans. (d)
22. The maximum work obtained by an isothermal reversible
Sol. In an isoentropic process, entropy change is 0.
expansion of 1 mole of an ideal gas at 27°C from 2.24 to
22.4 L is (R = 2 cal)
27. In the thermodynamic sense of the word, an irreversible
(a) – 1381.8 cal (b) – 600 cal
process
(c) –138.18 cal (d) – 690.9 cal
(a) does the same work (but of opposite sign) as a
Ans. (a)
reversible process
Sol. Work done in reversible isothermal
(b) violates the 1st law of thermodynamics, unlike a
æV ö reversible process
= - 2.303RT log ç 2 ÷ (c) involves non-ideal gases (as opposed to ideal gases
è V1 ø
in a reversible process)
æ 2 2 .4 ö (d) exchanges the same amount of heat (but of opposite
= - 2 .3 0 3 2 3 0 0 lo g ç ÷ = - 1 3 8 1 .8c al
è 2 .2 4 ø sign) as a reversible process.
o
23. 2 mole of an ideal gas at 27 C expands isothermally and Ans. (c)
reversibly from a volume of 4 litres to 40 litre. The work Sol. In the thermodynamic sense of the word, an irreversible
done (in kJ) is: process involves non-ideal gases (as opposed to ideal
(a) w = –28.72 kJ (b) w = –11.488 kJ gases in a reversible process)
(c) w = –5.736 kJ (d) w = –4.988 kJ
 4 THERMODYNAMICS AND THERMOCHEMISTRY
Heat Capacity of a System, Adiabatic Process and decreases.
Poisson’s Ratio 34. One mole of an ideal gas expands reversibly and
28. Molar heat capacity of water in equilibrium with ice at adiabatically from a temperature of 27oC. If the work done
constant pressure is during the process is 3 kJ, then final temperature of the
gas is:(CV = 20 J/K )
(a) zero (b) ¥
(a) 100 K (b) 150 K
(c) 40.45 kJ K–1 mol–1 (d) 75.48 J K–1 mol–1 (c) 195 K (d) 255 K
Ans. (b) Ans. (b)
Sol. As it is in equilibrium with ice, it is an isothermal process. Sol. In adiabatic process q=0
\ CP = ¥ DU = w = nCV dt
29. Ice–Water mass ratio is maintained as 1 : 1 in a given \ -3 ´ 103 = 20(dT)
system containing water in equilibrium with ice at constant
–1 –1
pressure. If CP (ice) = CP (water) = 4.18 J mol K molar \ dT = -150
heat capacity of such a system is Tf - 300 = -150
(a) Zero (b) Infinity Tf = 150
–1 –1 –1 –1
(c) 4.182 JK mol (d) 75.48 JK mol
Ans. (b)
Enthalpy of a system
Sol. In isothermal process, heat capacity is infinity. 35. For a chemical reaction at constant P and V, DH is equal to
30. In an adiabatic expansion of an ideal gas (a) DU (b) zero
(a) DT = 0 (b) w = 0 (c) DU + PDV (d) p/T
(c) q = 0 (d) DU = 0 Ans. (a)
Ans. (c) Sol. DH=DU + PDV but as volume is constant,
Sol. In an adiabatic expansion of an ideal gas, q = 0 DH=DU.
31. The temperature of the system decreases in an 36. For an endothermic reaction, DS is positive. The reaction
is :
(a) Isothermal compression (b) Isothermal expansion (a) feasible when TDS > DH
(c) Adiabatic compression (d) Adiabtic expansion (b) feasible when DH > TDS
Ans. (d) (c) feasible at all temperatures
Sol. Temperature remains constant in isothermal process. (d) not feasible at all
In adiabatic process, q=0; DU=w. Ans. (a)
Expansion will do negative work. DU<0. Sol. DH > 0; DG < 0; DG = DH – TDS
Hence there is a decrease in temperature. \ TD S > DH
32. 1 mole of NH3 gas at 27°C is expanded in reversible adiabatic 37. Which of the following conditions is not favourable for
condition to make volume 8 times (g = 1.33). Final the feasibility of a process ?
temperature and work done by the gas respectively are : (a) DH = –ve, TDS = –ve and TDS < DH
(a) 151 K, –900 cal (b) 151 K, –400 cal (b) DH = +ve, TDS = +ve and TDS > DH
(c) 250 K, 1000 cal (d) 200 K, –800 cal (c) DH = –ve, TDS = +ve and DH > TDS
Ans. (a) (d) DH = +ve, TDS = +ve and DH > TDS
Ans. (d)
Sol. T1V1g -1 = T2 V2 g-1 Sol. For feasibility DG < 0; DG = DH – TDS .
4
T1 -1 For (d), DG will be positive angle.
= (8) 3 38. In which of the following cases, the reaction is
T2
spontaneous at all temperatures ?
i.e., T1 = 2T2 (a) DH > 0, DS > 0 (b) DH < 0, DS > 0
(c) DH < 0, DS < 0 (d) DH > 0, DS < 0
300
T2 = = 150K Ans. (b)
2
Sol. DG = DH – T DS
nRDT 2 ´ 150
w= = = 900cal \ DG < 0;
g -1 1/ 3
DH < 0, DS > 0
33. During the adiabatic expansion of an ideal gas against
atmospheric pressure, the internal energy will 39. Which of the following is true for the reaction ?
(a) Increase (b) decrease ˆˆ† H2O(g) at 100°C and 1 atm pressure
H2O(l) ‡ˆˆ
(c) stay the same (d) Impossible to say
(a) DS = 0 (b) DH = TDS
Ans. (b)
(c) DH = DU (d) DH = 0
Sol. In adiabatic process, q = 0. Hence, in expansion process,
temperature decreases and hence internal enegry also
THERMODYNAMICS AND THERMOCHEMISTRY 5
Ans. (b) –7.43 ´ 103 kJ
Sol. At Equilibrium 45. For the reaction :
\ DG = 0 = DH – TDS
C 2 H 4 g + 3O 2 g ¾¾ ® 2CO 2 g + 2H 2 O l
\ TDS = DH at 298 K, DU = – 1415 kJ.
40. For the reaction : –1
If R = 0.0084 kJ K , then DH is equal to
C s + O2 g ¾¾ ® CO2 g (a) –1400 kJ (b) –1410 kJ
(a) DH < DU (b) DH > DU (c) –1420 kJ (d) –1430 kJ
(c) DH = DU (d) DH = 0 Ans. (c)
Ans. (c) Sol. Dn = 2 – 4 = –2
Sol. DH = DU + DnRT
\ DH = DU + DnRT
\ DH = DU
= –1415 – 5 = –1420
Dn = 0
41. For which of the following reactions, DH is greater than
DU ? 46. The difference between DH and DE on a molar basis for
the combustion of methane gas at 300K (kelvin) would be :
(a) N2(g) + 3H2(g) ¾¾® 2NH3(g)
(a) zero (b) –RT
(b) CH4(g) + 2O2(g) ¾¾ ® CO (g) + 2H O(l)
2 2 (c) –2RT (d) –3RT
(c) PCl5(g) ¾¾ Ans. (c)
® PCl3(g) + Cl2(g)
Sol. Combustion of methane:
(d) HCl(aq) + NaOH(aq) ¾¾ ® NaCl(aq) + H2O(aq) CH 4 g + 2O 2 g ® CO 2 g + 2H 2 O i
Ans. (c)
Sol. DH = DU + DnRT DH – DU = DnRT = (1 - 3)RTDn = –2RT
\ for DH = DU 47. Consider the reaction at 300 K
\ Dn > 0 H2(g) + Cl2 (g) ¾¾ ® 2HCl(g); DHº = –185 kJ
42. For the reaction, If 2 mole of H2 completely react with 2 mole of Cl2 to form
PCl5 g ¾¾ ® PCl3 g + Cl 2 g HCl. What is DU° for this reaction ?
(a) 0 (b) –185 kJ
(a) DH = DU (b) DH > DU (c) 370 kJ (d) –370 kJ
(c) DH < DU (d) None of these Ans. (d)
Ans. (b) Sol.
Sol. DH = DU+DnRT, since Dn is positive, DH > DU
43. (DU – DH) for the following equation is N2 + 3H2 ® 2NH3. H 2 + Cl2 ® 2HCl
(a) RT (b) 2 RT \ Dn = 0; DH = –185 ´ 2
1 \ DH = DU + DnRT = DU
(c) -2 RT (d) RT
T
2 \ DH = DU = –185 ´ 2KJ = –370KJ
Ans. (b)
Sol. N 2 + 3H 2 ƒ 2NH 3 48. In an endothermic reaction
(a) DH is negative
Dn = 2 – 4 = –2 (b) Heat is given to the surroundings
\ DH = DU + DnRT (c) Enthalpy of the reactants is less than that of the
products
\ DU – DH = – DnRT = -2RT
(d) DE is negative
44. The difference between heats of reaction at constant Ans. (c)
pressure and constant volume for the reaction.
Sol. In endothermic reaction, DH > 0
2C2H6(l) + 15O2(g) ¾¾ ® 12CO2(g) + 6H2O(l) at 25°C is DH = DHp – DHr > 0. \DHp > DHr
(a) –7.43 kJ (b) +3.72 kJ
(c) –3.72 kJ (d) 7.43 kJ 49 For the process : CO2(s) ¾¾ ® CO2(g)
Ans. (a) (a) Both DH and DS are +ve
Sol. Heat of rxn at constant pressure = DH (b) DH is –ve, DS is +ve
(c) DH is +ve, DS is –ve
Heat of rxn at constant volume = DU
(d) Both DH and DS are –ve.
DH = DU + DnRT; Dn = 12 – 15 = –3 Ans. (a)
\ DH – DU = DnRT = –3 ´ 8.3 ´ 298 Sol. Energy is required \ DH > 0
Entropy of is higher than solid
 6 THERMODYNAMICS AND THERMOCHEMISTRY
\ DS > 0 Ans. (b)
Second Law of Thermodynamics q(rev)
50. The statement “A heat engine always loses some of its Sol. For a reversible process at equilibrium, DS =
T
heat energy to the surroundings.” is an example of which 56. Entropy is a measure of
of the following laws? (a) disorder
(a) The Law of Corresponding States (b) internal energy
(b) The Zeroth Law of Thermodynamics (c) efficiency
(c) The First Law of Thermodynamics (d) useful work done by the system
(d) The Second Law of Thermodynamics Ans. (a)
Ans. (d) Sol. Entropy is a measure of disorder and randomness
Sol. The Second Law of Thermodynamics 57. When a solid is converted directly into gaseous state, the
51. The entropy of the universe process is called sublimation. The entropy change during
(a) tends towards a maximum the process is :
(b) tends towards a minimum (a) zero (b) negative
(c) tends to be zero (d) remains constant (c) positive (d) may be negative or zero
Ans. (a) Ans. (c)
Sol. Always increases Sol. Entropy of gas is always more. DS>0.
52. Heat cannot by self flow from a body at lower temperature 58. The enthalpy of vaporisation of a substance is
to a body at higher temperature a statement of –1
8400 J mol and its boiling point is –173ºC. The entropy
consequence of: change for vaporisation is :
(a) 1st law of thermodynamics –1
(a) 84 J mol K
–1 –1
(b) 21 J mol K
–1

(b) 2nd law of thermodynamics –1

(c) 49 J mol K
–1 –1
(d) 12 J mol K
–1

(c) conservation of momentum Ans. (a)

(d) conservation of mass
Ans. (b) q rev 8400
Sol. DS = = = 84Jmol-1K -1
Sol. From Kelvin Plank statement and Claussius's statement T 100
we can say that heat can not be flow from lower temperature 59. The enthalpy of vaporisation of a compound AB at its
–1
to higher temperature until and unless we are adding any boiling point (127°C) is 6.4 kJ mol . Its entropy of
external source like heat pump, which justifies Second Law vaporisation is :
–1 –1
of Thermodynamics. (a) 2.56 kJ mol (b) 16 J mol
–3 –1 3 –1
53. When steam condenses to water at 90oC, the entropy of (c) 16 × 10 J mol (d) 1.6 × 10 kJ mol
the system decreases. What must be true if the second Ans. (b)
law of thermodynamics is to be satisfied?
(a) Entropy of the universe also decreases. q rev 64000
Sol. DS = = = 16Jmol -1
(b) Entropy of the surroundings also decreases. T 400
(c) Entropy of the surroundings increases to same extent 60. The entropy change for the conversion of 1 mol of a–tin
to which entropy of the system decreases. (at 13°C, 1 atm) to 1 mol of b–tin (13°C, 1 atm), if enthalpy
–1
(d) Increase in entropy in the surroundings is greater than of transition is 2.095 kJ mol is :
–1 –1 –1 –1
decrease in entropy of the system. (a) 7.32 J mol K (b) 14.62 J K mol
–1 –1
Ans. (d) (c) 56.3 J mol K (d) 0
Sol. All spontaneous processes are thermodynamically Ans. (a)
irreverisble and entropy of the system increases in all
spontaneous process. DH 2.095 ´103
Sol. DS = = = 7.32Jmol-1K -1
Here, the condensation of water is not a spontaneous T 286
process, so the entropy of system deceases and the 61. The following data is known about the melting of a
entropy of surroundings increases. –1 –1 –1
compound AB. DH = 9.2 kJ mol . DS = 0.008 kJ K mol . Its
Entropy and spontaneity melting point is :
54. Which of the following has highest entropy ? (a) 736 K (b) 1050 K
(a) Mercury (b) Hydrogen (c) 1150 K (d) 1150°C
(c) Water (d) Graphite Ans. (c)
Ans. (b)
Sol. Gas has highest entropy. DH
Sol. DS =
55. For a reversible process at equilibrium, the change in T
entropy may be expressed as : DH 9.2 9200
\T = = = = 1150K
q rev DS 0.008 8
(a) DS = Tqrev (b) DS =
T 62. When potassium chloride is dissolved in water
DH (a) Entropy increases
(c) DS = - (d) DS = DG (b) Entropy decreases
T (c) Entropy increases and then decreases
THERMODYNAMICS AND THERMOCHEMISTRY 7
(d) Free energy increases
Ans. (a) æT ö æ3ö æ 573 ö
DS = nC V ln ç 2 ÷ = 2 ç ÷ R ln ç ÷
Sol. Entropy is the measure of randomness.As KCl dissociates è T1 ø è2ø è 473 ø
+ -
it forms total 2 ions K and Cl . So, randomness
increases.As Randomness increases, the Entropy of the æ 573 ö
= 3R ln ç ÷
system also increases.So, When potassium chloride is è 473 ø
dissolved in water its Entropy Increases.
63. Which of the following processes is not accompanied by æ 5 ö
67. If one mole of an ideal gas ç Cp.m. = R ÷ is expanded
increase of entropy ? è 2 ø
(a) dissolution of NH4Cl in water isothermally at 300 K until it’s volume is tripled, then
(b) burning of rocket fuel change in entropy of gas is :
(c) sublimation of dry ice (a) zero (b) infinity
(d) condensing steam
Ans. (d) 5
(c) R ln 3 (d) R ln 3
Sol. By condensing steam we go from gaseous state to liquid 2
state. While going from gaseous state to liquid state Ans. (d)
entropy decreases as randomness decreases. Sol. For isothermal process
æ 5 ö æV ö
64. When two mole of an ideal gas ç Cp,m. = R ÷ heated from DS = nR ln ç 2 ÷ = 1R ln 3 = R ln 3
è 2 ø è V1 ø
300 K to 600 K constant pressure. The change in entropy 68. When one mole of an ideal gas is compressed to half of its
of gas (DS) is : initial volume and simultaneously heated to twice its initial
3 3 temperature, the change in entropy of gas (DS) is :
(a) R ln 2 (b) - R ln 2 (a) Cp,m ln2 (b) Cv,m ln2
2 2
(c) R ln2 (d) (Cv,m –R) ln2
5 Ans. (d)
(c) 5 R ln 2 (d) R ln 2
2
Ans. (c) æT ö æ v2 ö
Sol. DS = nC v,m ln ç 2÷ + nRln ç ÷
Sol. For isobaric process, è T1
ø è v1 ø
æT ö æ5ö æ 600 ö æ1ö
DS = nC P ln ç 2 ÷ = 2 ç ÷ R ln ç ÷ = 5R ln 2 = C v,m ln 2 + Rln ç ÷ = C v,m – R ln2
T
è 1ø 2
è ø è 300 ø è2ø
65. In the above question calculate DSgas if process is carried 69. Two mole of a monoatomic ideal gas is expanded
out at constant volume : irreversibly and isothermally at T Kelvin until its volume
is doubled and q joules of heat is absorbed from
3
(a) 5 R ln 2 (b) R ln 2 surrounding. DStotal (J/K) (system + surrounding) is :
2 (a) zero (b) 2 Rln2–q/T
(c) 3 R ln 2 (d) – 3 R ln 2 (c) 3Rln2–q/T (d) –2 Rln2 + q/T
Ans. (c) Ans. (b)
Sol. For isochoric process, Sol. For isothermal process,
æT ö æ 3ö æ 600 ö æV ö
DS = nC V ln ç 2 ÷ = 2 ç ÷ R ln ç ÷ = 3R ln 2 nRln2 ç 2 ÷ = 2 Rln2
è T1 ø è 2ø è 300 ø è V1 ø
66. The entropy change when two moles of ideal monoatomic
gas is heated from 200°C to 300°C reversibly and –q
Since heat is absorbed =
isochorically ? T
3 æ 300 ö 5 æ 573 ö From surroundings
(a) R ln ç ÷ (b) R ln ç ÷
2 è 200 ø 2 è 273 ø q
Total = 2Rln2 -
T
æ 573 ö 3 æ 573 ö
(c) 3R ln ç ÷ (d) R ln ç ÷ 70. One mole of an ideal diatomic gas (Cv = 5 cal) was
è 473 ø 2 è 473 ø transformed from initial 25°C and 1 L to the state when
Ans. (c) temperature is 100°C and volume 10 L. The entropy change
Sol. For isochoric process of the process can be expressed as (R = 2 calories/mol/K)
298 373
(a) 3ln + 2 ln10 (b) 5ln + 2 ln10
373 298
 8 THERMODYNAMICS AND THERMOCHEMISTRY

373 1 373 1 temperature gas increases entropy. The gas expands in

(c) 7ln + 2 ln (d) 5ln + 2 ln particular temperature as there is increase in entropy.
298 10 298 10 therefore DG = -T DS
Ans. (b) 76. For the reaction at 300 K
æT ö æ v2 ö A(g) + B(g) ¾¾ ® C(g)
Sol. DS = nCv ln ç 2 ÷ + nRln ç ÷
è T1 ø è v1 ø DU = –3.0 kcal DS = –10.0 cal/K
–1 –1
(R » 2 cal mol K )
æ 373 ö æ 373 ö DG is :
= 5ln ç ÷ + 2ln 10 = 5ln ç ÷ + 2ln10. (a) –600 cal (b) –3600 cal
è 298 ø è 298 ø
(c) 2400 cal (d) 3000 cal
71. A reaction has DH = – 33 kJ and DS = +58 J/K. This reaction
Ans. (a)
would be :
(a) spontaneous below a certain temperature Sol. DH = DU + DnRT
(b) non-spontaneous at all temperature
(c) spontaneous above a certain temperature \ n = –1
(d) spontaneous at all temperature –3
Ans. (d) \ DH = –3 – 1 2 300 ´ 10 = –3.6Kcal
Sol. DH < 0; DS > 0 \ DG = DH – TDS
\ spontaneous at all temperature.
72. Calculate the entropy change (J/mol K) of the given = –3600 – 300 –10 = –600kcal
reaction. The molar entropies [J/K–mol] are given in 77. The enthalpies of elements in their standard states are
brackets after each substance. taken as zero. Hence the enthalpy of formation of a
2 Pb S(s) [91.2] + 3O2(g)[205.1] ¾¾ ® compound
2PbO(s) [66.5] + 2SO2(g)[248.2] (a) should always be negative
(a) –113.5 (b) –168.3 (b) should always be positive
(c) +72.5 (d) –149.2 (c) will be equal to twice the energy of combination
Ans. (b) (d) may be positive or negative
Sol. DS = 2DS(PbO) + 2DS(SO2) – 2DS(PbS) – 3DS(O2) Ans. (d)
= 2(66.5) + 2(248.2) – 2(91.2) + 3(205.1) Sol. Depends on whether the reaction is endothermic or
= –168.3 J/mol.K exothermic.
o o 78. Which of the following pairs has heat of neutralisation
73. Given DrS = –266 and listed [ Som values] calculate S for equal to –57.1 kJ ?
Fe3O4(s) : (a) HNO3,KOH (b)HCl, NH4OH
4Fe3 O 4 (s)[.......] + O 2 (g)[205] ® 6Fe 2 O3 (S)[87] (c) H2SO4,NH4OH (d) CH3COOH,NaOH
(a) +111.1 (b) +122.4 Ans. (a)
(c) +145.75 (d) 248.25 Sol. Strong acid+ strong base will have heat of neutralisation -
Ans. (c) 57.1 kJ.
79. Which of the following neutralisation reactions is most
Sol. D r S = 6DS Fe2 O3 – 4DS Fe3 O 4 – DS O2 exothermic ?
(a) HCl and NaOH
\ –266 = 6 87 – 4DS Fe3O 4 – 205 (b) HCN and NaOH
\ –266 + 205 – 6 87 = –4DS Fe3O 4 (c) HCl and NH4OH
(d) CH3COOH and NH4OH
\ DS Fe 3 O 4 = 145.75 Ans. (a)
Sol. Strong acid + strong base is most exothermic.
Gibb’s Energy, Enthalpy of reactions/processes 80. The enthalpy change for the reaction,
74. For a reaction to be spontaneous at all temperatures H 2 O s ¾¾ ® H 2 O l is called
(a) DG and DH should be negative
(a) Enthalpy of formation
(b) DH = DG = 0
(b) Enthalpy of fusion
(c) DG and DH should be positive
(c) Enthalpy of vaporisation
(d) DH < DG
(d) Enthalpy of transition
Ans. (a)
Ans. (b)
Sol. DG < 0; for spontaneous reaction Sol. Factual
75. For isothermal expansion in case of an ideal gas : 81. The enthalpies of formation of N2O and NO at 298 K are 82
(a) DG = DS (b) DG = DH –1
and 90 kJ mol . The enthalpy of the reaction :
(c) DG = – T.DS (d) None of these
Ans. (c) N 2O g + ½O 2 g ¾¾
® 2NO g
Sol. Isothermal expansions of a ideal gas is defined as increase (a) –8 kJ (b) 98 kJ
in the volume of gas at particular temperature. At particular
THERMODYNAMICS AND THERMOCHEMISTRY 9

(c) –74 kJ (d) 8 kJ (c) y – x (d) x – y/2

Ans. (b) Ans. (c)
Sol. N 2 O + 1 / 2O 2 ® 2NO Sol. CH 3 COOH + OH – ® CH 3 COO – + H 2 O; DH = –xkJ
\ DH = 2DH g NO – DH g N 2 O H + + OH – ® H 2 O; DH = – y kJ
= 2 ´ 90 – 82 = 180 – 82 = 98KJ \ CH 3COOH ® CH 3 COO – + H + ® DH = –x – (– y)
As DH (oxygen gas)=0. 86. Which of the following reactions represents enthalpy of
82. The enthalpies of solution of anhydrous CuSO4 and formation of AgCl ?
–1
CuSO4.5H2O are –15.89 and 2.80 k cal mol respectively.
The enthalpy of hydration of CuSO4 to CuSO4.5H2O is : (a) Ag + aq + Cl - aq ¾¾
® AgCl s
(a) –18.69 kcal (b) 13.09 kcal 1
(c) –13.09 kcal (d) 18.69 kcal (b) AgCl s ¾¾
® Ag s + Cl 2 g
2
Ans. (a)
(c) Ag s + AuCl s ¾¾
® AgCl s + Au s
Sol. CuSO 4 + 5H 2 O ® CuSO 4 .5H 2 O
1
DH = DH s CuSO4.5H 2 O (d) Ag s + Cl2 g ¾¾ ® AgCl s .
2
– DH s CuSO 4 – 5 éë DH H 2 O ùû Ans. (d)
= –2.80 – 15.89 = –18.69Kcal Sol. For the enthalpy of formation, all the reactants should be
in their Standard states.
83. Calculate the heat required to make 6.4 Kg CaC2 from CaO(s) 1
\ Ag s + Cl 2 g ® AgCl s
and C(s) from the reaction : 2
87. Which of the following equations represents standard heat
CaO(s) + 3 C(s) ¾¾
® CaC2(s) + CO(g) given that of formation of methane ?
D f H º CaO = –151.6 kcal, D f H º CaC 2 = –14.2kcal. (a) C (diamond) + 2H2(g) ¾¾ ® CH4(g)
D f H º CO = –26.4 kcal. (b) C (graphite) + 2H2(g) ¾¾
® CH4(g)
(a) 5624 kcal
4
(b) 1.11 × 10 kcal (c) C (diamond) + 4H(g) ¾¾ ® CH4(g)
3
(c) 86.24 × 10 (d) 1100 kcal (d) C (graphite) + 4H(g) ¾¾ ® CH4(g)
Ans. (b) Ans. (b)
Sol. Sol. For the enthalpy of formation, all the reactants should be
in their standard states. C(graphite) and H2(g) are standard
mass 6.4 ´ 103 states of carbon and hydrogen
n= = = 100
M.W 64 88. For the reaction,
For1mole of CaC 2 2H 2 O g ¾¾
® 2H 2 g + O 2 g DH = 571.6 KJ
DH = DH f CaC2 + DH f CO – DH f CaO
Df Hq of water is :
= –14.2 – 26.4 + 151.6 = 111.1Kcal (a) 285.8 kJ (b) –285.8 kJ
For100 moles, DH = 1.11´10 4 Kcal (c) 1143.2 kJ (d) –1143.2 kJ
Ans. (b)
84. Given : Sol. Formation of water:
H2(g) + ½O2(g) ® H2O(g) + q1
1
H2(g) + ½O2(g) ® H2O (l) + q2 H 2 + O2 ® H 2O
2
The enthalpy of vaporisation of water is equal to
(a) q1 + q2 (b) q1 – q2 -DH -571.6
\ DH f = = = -285.8kJ
(c) q2 – q1 (d) q1q2 2 2
Ans. (c) 89. DH for the reaction,
Sol. Vaporisation: H 2 O l ® H 2 O g ;q 2 – q1 1 ˆˆ† SO3 g
SO 2 g + O 2 g ‡ˆˆ DH = –98.3 kJ
– 2
85. If CH3COOH + OH ¾¾® CH COO– + H O + x kJ
3 2 If the enthalpy of formation of SO3(g) is –395.4 kJ then the
+ –
H + OH ¾¾ ® H2O + y kJ enthalpy of formation of SO2(g) is :
The enthalpy change for the reaction : (a) –297.1 kJ (b) 493.7 kJ
® CH COO– + H+ is (c) –493.7 kJ (d) 297.1 kJ
CH3COOH ¾¾ 3 Ans. (a)
(a) x + y (b) x – y
 10 THERMODYNAMICS AND THERMOCHEMISTRY

1 is –1583.2 kJ. Standard enthalpy of formation of sulphur

Sol. DH = DH g (SO 3 ) - DH g (SO 2 ) - DH g (O 2 ) ´
2 trioxide is :
But DHg(O2) = 0 (a) –3166.4 kJ (b) 3166.4 kJ
(c) –395.8 kJ (d) 395.8 kJ
-98.3 = -395.4 - DH g (SO2 )
Ans. (c)
\ DH g (SO2 ) = -297.1kJ
DH o –1583.2
90.
–2
The standard heat of formation at 101.3 kNm and 298 K is Sol. DH f = = = –395.8KJ
4 4
arbitrarily taken to be zero for : 95. Calculate the heat of formation of PCl5(s) from the following
(a) gaseous bromine atoms data :
(b) gaseous bromine molecules
(c) liquid bromine 2P(s) + 3Cl2(g) ¾¾ ® 2PCl (l)
3
DH = –151.8 kcal
(d) solid bromine. PCl3(l) + Cl2(g) ¾¾ ® PCl5(s) DH = –32.8 kcal
Ans. (c) (a) –108.7 kcal (b) 108.7 kcal
Sol. The standard molar enthalpy of formation of the element (c) –184.6 kcal (d) 184.6 kcal
in its standard state is taken as zero. Since the standard Ans. (a)
state of bromine is liquid.therefore D H formation = 0 5
91. The enthalpy of formation of two compounds A and B are Sol. P s + Cl 2 ® PCl5 s
2
–84 kJ and –156 kJ respectively. Which one of the following
statements is correct ? 3 –151.8
\ P s + Cl 2 ® PCl3 l ® DH = = 75.6
(a) A and B are endothermic compounds 2 2
(b) A is more stable than B
PCl3 l + Cl2 g ® PCl5 ® DH = –32.8
(c) A is less stable than B
(d) Both A and B are unstable \ Adding, –75.6 – 32.8 = –108.7Kcal.
Ans. (c)
Sol. More the energy released during formation, higher stability, 96. If S + O2 ¾¾
® SO2 DH = –298.2 kJ
Hence A is less stable. 1
92. When 0.5 g of sulphur is burnt to SO2 4.6 kJ of heat is SO 2 + O 2 ¾¾
® SO3 DH = –98.2 kJ
liberated. What is the enthalpy of formation of sulphur 2
dioxide ? ® H 2SO 4 DH = –130.2 kJ
SO3 + H 2 O ¾¾
(a) –147.2 kJ (b) +147.2 kJ
(c) +294.4 kJ (d) –294.4 kJ 1
H 2 + O 2 ¾¾ ® H2O DH = –287.3 kJ
Ans. (d) 2
Sol. S + O 2 g ® SO 2 g the enthalpy of formation of H2SO4 at 298 K will be
(a) –433.7 kJ (b) –650.3 kJ
Mass 0.5 (c) +320.5 kJ (d) –813.9 kJ
n= = Ans. (d)
M.W. 32
Sol. Let the rxn be number (i),(ii),(iii),(iv) respectively
0.5
\ For moles, ΔH = –4.6kJ \ H 2 + S + 2O 2 ® H 2SO 4.
32
We get the abo ve rxn by i + ii + iii + iv
- 4.6 ´ 32 \ DH g = –298.2 – 98.2 – 130.2 – 287.3
\ For 1 mole, ΔH = = -294.4 kJ
0.5 = –813.97kJ
–1
93. The heat of formation of Fe2O3(s) is –824.2 kJ mol . DH for
the reaction. 97. The enthalpies of combustion of carbon and carbon
–1
monoxide are –393.5 and –283.0 kJ mol respectively. The
2Fe 2 O3 s ¾¾ ® 4Fe s + 3O2 g is : enthalpy of formation of carbon monoxide is :
(a) –412.1 kJ (b) –1648.4 kJ (a) –676.5 kJ (b) 110.5 kJ
(c) –3296.8 kJ (d) 1648.4 kJ (c) –110.5 kJ (d) 676.5 kJ
Ans. (d) Ans. (c)

Sol. DH = 2 ´ DH 0f Sol. C s + O 2 ® CO 2 . . . .DH1 = –393.5

æ kJ ö CO +12 O 2 ® CO 2 . . . .DH 2 = –283.0
= 2 ç -824.2 ÷
è mole -1 ø C(s) +12 O 2 ® CO. . . .DH = DH1 - DH 2
= -1648.4 KJ = –393.5 + 283 = –110.5KJ
q
94. The DH for the reaction, 98. On combustion, carbon forms two oxides CO and CO2.
4S(s) + 6O2 (g) ¾¾
® 4 SO3(g) Heat of formation of CO2 is –393.5 kJ and that of CO is –
THERMODYNAMICS AND THERMOCHEMISTRY 11
110.5 kJ. Heat of combustion of CO is : DH 57.3
(a) –393.5 kJ (b) –504.0 kJ \ = = 28.65kJ
(c) –283.0 kJ (d) 2830.0 kJ 2 2
Ans. (c) 104. The heat of neutralisation of strong base and strong acid
is 57.0 kJ. The heat released when 0.5 mol of HNO3 is
Sol. C + O 2 ® CO2 . . .DH1 = –393.5KJ added to 0.2 mol of NaOH solution is :
1 (a) 57.0 kJ (b) 11.40 kJ
C + O 2 ® CO. . .DH 2 = –110.5KJ (c) 28.5 kJ (d) 34.9 kJ
2
Ans. (b)
The heat of combustion is equal to the heat of formation Sol. 0.2 moles of NaOH will neutralise 0.2 moles of HNO3
as carbon and oxygen are in their standard states.
\ DH(n) = 57 ´ 0.2 = 11.4kJ
1 105. In which of the following neutralisation reaction, the heat
CO + O 2 ® CO 2 . . .DH 3 = DH1 – DH 2
2 of neutralisation will be highest ?
= –393.5 + 110.5 = –283KJ (a) NH4OH and H2SO4 (b) HCl and NaOH
99. Which of the following compounds will absorb maximum (c) CH3COOH and KOH (d) CH3COOH and NH4OH
quantity of heat when dissolved in the same amount of Ans. (b)
water. The enthalpies of solution of these compounds at Sol. Strong acid + strong base is most exothermic.
25°C in kJ/mole are given in brackets ? 106. The enthalpies of neutralization of a weak base AOH and
–1 –1
(a) P (DH = –32.6 kJ mol ) (b) Q (DH = –17.3 kJ mol ) a strong base BOH by HCl are –12250 cal/mol and –13000
–1 –1
(c) R (DH = +2.56 kJ mol ) (d) S (DH = +25.6 kJ mol ) cal/mol respectively. When one mole of HCl is added to a
Ans. (d) solution containing 1 mole of AOH and 1 mole of BOH,
Sol. More the positive value of DH, the more the heat absorbed. the enthalpy change was –12500 cal/mol. In what ratio is
100. Which of the following salts will have maximum cooling the acid distribution between AOH and BOH?
effect when 0.5 mole of the salt is dissolved in same amount (a) 2:1 (b) 2:3
of water. Integral heat of solution at 298 K is given for (c) 1:2 (d) None of these
each salt ?
–1 Ans. (a)
(a) KNO3 (DH = 35.4 kJ mol )
(b) NaCl (DH = 5.35 kJ mol )
–1 Sol. Let the mole fraction of AOH be x
(c) HBr (DH = –83.3 kJ mol )
–1
\ BOH mole fraction is 1-x.
–1
(d) KOH (DH = –55.6 kJ mol ) \ 12250(x) - 13000 (1-x) = –12500
Ans. (a) \ 1225x + 1300 – 1300x = 1250
Sol. More the heat absorbed, more will be the cooling effect. \ 50 = 75x
Hence, more the positive value of DH , more the
cooling effect. 2
\x=
101. The enthalpy of neutralisation of HCl by NaOH is –57.1 kJ 3
–1
and that of HCN by NaOH is –12.1 kJ mol . The enthalpy
2 1
of ionization of HCN is : AOH ® ;BOH ®
(a) –69.2 kJ (b) –45.0 kJ 3 3
(c) 69.2 kJ (d) 45.0 kJ \ Ratio – 2 : 1
Ans. (d) 107. In what proportion 1 M NaOH and 0.5M H2SO4 are mixed
Sol. The difference in the energy of neutralisation is the so as to release maximum amount of energy and to form
enthalpy of ionisation as that is the amount of energy 100 mL solution ?
required to ionise it. (a) 33 and 67 (b) 67 and 33
\ DH (HCN) + = –12.1 + 57.1 = 45KJ (c) 40 and 60 (d) 50 and 50
102. The enthalpy of neutralisation of NH4OH and HCl is : Ans. (d)
–1 –1
(a) 57.1 kJ mol (b) < 57.1 kJ mol Sol.
–1
(c) > 57.1 kJ mol (d) zero
Ans. (b) 2NaOH + H 2SO 4 ® Na 2SO 4
Sol. NH4OH is a weak base, hence enthalpy of neutralisation 2x x
–1
< 57.1 kJ mol H 2SO 4 = 2 ´ molarity = 2 ´ 0.5 = N1
–1
103. The heat of neutralisation of NaOH and HCl is 57.3 kJ mol .
The amount of heat liberated when 0.25 mol of H2SO4 reacts N1V1 = N 2 V2 \ V1 = 50ml
with 1 mole of NaOH is 108. The enthalpies of combustion of rhombic sulphur and
(a) 57.3 kJ (b) 14.325 kJ monoclinic sulphur are –295.1 and –296.4 kJ mol
–1

(c) 28.65 kJ (d) 114.6 kJ respectively. The enthalpy of allotropic transformation of

Ans. (c) monoclinic to rhombic sulphur is :
Sol. H2SO4 is a strong acid, but its valency factor is 2. (a) 1.3 kJ (b) –1.3 kJ
0.25 moles will be required to neutralise 0.5 moles of NaOH.
(c) –591.5 kJ (d) 0
 12 THERMODYNAMICS AND THERMOCHEMISTRY
Ans. (b) (kJ/mol) (kJ/mol)
Sol. P +780 –920
Q +1012 –812
Sm ® Sr R +828 –878
\ Sr + O 2 ® SO 2 . . .DH1 = –295.1 S +632 –600
The pair of compounds which is soluble in water is
Sm + O 2 ® SO 2 . . .DH 2 = –296.4 (a) P and Q (b) Q and R
\ Sm > Sr; DH 2 – DH1 = –296.4 + 295.1 (c) R and S (d) P and R
–1.3kJ Ans. (d)
Sol. If the absolute value of hydration energy>lattice,
109. Which of the following enthalpies is always negative ? compound is soluble.
(a) Enthalpy of solution Bond Dissociation Enthalpy
(b) Enthalpy of combustion 113. The standard enthalpies of formation of HCl(g), H(g) and
–1
(c) Enthalpy of sublimation Cl(g) are –92.2, 217.7 and 121.4 kJ mol respectively. The
(d) Enthalpy of formation bond dissociation energy of HCl is :
Ans. (b) (a) +431.3 kJ (b) 236.9 kJ
Sol. The Enthalpy of combustion is always negative (c) –431.3 kJ (d) 339.1 kJ
i.e., DH < 0 Ans. (a)
110. In the reaction : 1 1
Sol. H 2 + Cl2 ® HCl. . .DH = –92.2
CO 2 g + H 2 g ¾¾ ® CO g + H 2 O g 2 2
DH = 2.8 kJ \ DH = B.E(H) + B.E)(Cl) – B.E (HCl)
then DH represents \ –92.2 = (217 . 7) + (121.4) – B.E(HCl)
(a) heat of formation (b) heat of reaction B.E(HCl) = 217.7 + 121.4 + 92.2 = 431.3 kJ
(c) heat of solution (c) heat of combustion 114. The enthalpy changes at 25°C in successive breaking of
Ans. (b) O–H bonds of water are :
Sol. As we know, H2O(g) ¾¾ ® H(g) + OH(g) DH = 498 kJ mol–1
Heat of reaction, the amount of heat that must be added or OH(g) ¾¾ ® H(g) + O(g) DH = 428 kJ mol–1
removed during a chemical reaction in order to keep all of the bond enthalpy of the O–H bond is :
–1 –1
the substances present at the same temperature. If the (a) 498 kJ mol (b) 463 kJ mol
–1 –1
pressure in the vessel containing the reacting system is (c) 428 kJ mol (d) 70 kJ mol
kept at a constant value, the measured heat of reaction Ans. (b)
also represents the change in the thermodynamic quantity Sol. Bond enthalpy of O – H bond is average of the two.
called enthalpy, or heat content, accompanying the
process—i.e., the difference between the enthalpy of the 498 + 428
\ DH = = 463KJmol –1
substances present at the end of the reaction and the 2
enthalpy of the substances present at the start of the 115. Calculate the heat of the reaction
reaction. Thus, the heat of reaction determined at constant CH2 = CH2(g) + H2(g) ¾¾ ® CH3CH3(g)
pressure is also designated the enthalpy of reaction, given that bond energy of C – C, C = C, C – H and H – H is
represented by the symbol DH . 80, 145, 98 and 103 kcal.
–1 –1
So, here DH represents heat of reaction. (a) –28 kcal mol (b) –5.6 kcal mol
–1 –1
111. Using the following energy values, determine the lattice (c) –2.8 kcal mol (d) –56 kcal mol
energy of KF(s): Ans. (a)
–1
Property Energy (kJ mol ) Sol. DH = 4(C - H) + (C = C) + (H - H)
DHatomization of K(s) 90
DHatomization of F2(g) 158 -6(C - H) - (C - C)
DHf of KF(s) –567 = -2 98 + 145 + 103 - (80)
IE of K(g) 419
EA of F(g) 328 = -28kcal / mol
(a) 51 kJ (b) + 827 kJ 116. The enthalpy change for the following reaction is 368 kJ.
(c) + 1145 kJ (d) + 1483 kJ Calculate the average O–F bond energy.
Ans. (b) OF2 (g) ® O(g) + 2F(g)
Sol. All the above steps are required in the formation of KF, (a) 184 kJ/mol (b) 368 kJ/mol
therefore addition of the enthalpies will give the lattice (c) 536 kJ/mol (d) 736 kJ/mol
energy. 90+158/2-567+419+328=827 kJ Ans. (a)
112. The lattice enthalpy and hydration enthalpy of four
compounds are given below: Sol. In OF2 (g) ® O(g) + 2F(g) ,
Compound Lattice enthalpy Hydration enthalpy Two O-F bonds are broken.
Thus O-F bond energy is 368/2= 184 kJ/mol
THERMODYNAMICS AND THERMOCHEMISTRY 13
(N2H4) = 941 + 436 × 2 – 4(398) – 159 = 62 kJ / mol
117. The enthalpy change for the reaction, 119. The dissociation energy of CH4 and C2H6 are respectively
C2H6(g) ® 2C(g) + 6H(g) is X kJ. The bond energy of C–H 360 and 620 kcal/mole. The bond energy of C–C is
bond is: (a) 260 k cal/mole (b) 180 k cal/mole
X (c) 130 k cal/mole (d) 80 k cal/mole
X
(a) (b) Ans. (d)
2 3
360
X Sol. The B.E of C – H = = 90
(c) (d) data insufficient 4
6 For C2H6 ® 620 = 6(C – H) + C – C
Ans. (d) 620 = 540 + C – C
Sol. No information given about C-C bond. C – C = 80 kcal / mol
o
118. Based on the values of B.E. given, DfH of N2H4(g) is: 120. An imaginary reaction X ® Y takes place in three steps
–1 –1
Given: N–N = 159 kJ mol ; H–H = 436 kJ mol X ® A, DH = –q1; B ® A, DH = –q2, B ® Y,, DH = –q3
–1 –1
N º N = 941 kJ mol , N–H = 398 kJ mol If Hess’ law is applicable, then the heat of the reaction
–1 –1
(a) 711 kJ mol (b) 62 kJ mol (X ® Y) is:
–1 –1
(c) –98 kJ mol (d) –711 kJ mol (a) q1–q2+q3 (b) q2–q3–q1
Ans. (b) (c) q1–q2–q3 (d) q3–q2–q1
Sol. DHf = (N º N) + (H – H) × 2 Ans. (b)
–(N – H) – (N – N) Sol. X ® A ; DH = –q1
B ® Y ; DH = –q3
B ® A ; DH = –q2
\ DH = –q1 + q2 - q3
= q2 – q 3 – q 1