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Thermodynamics
Solutions
SECTION - A
Objective Type Questions
(Thermodynamic process and parameters, Internal energy and enthalpy)
1. Tea placed in thermos flask is an example of
(1) Open system (2) Close system
(3) Isolated system (4) It can't act as system
Sol. Answer (3)
A thermos flask does not allow exchange of energy and matter. Hence, it is an isolated system.
2. Gaseous system is placed with pressure P1, volume V1 and temperature T1, it has undergone thermodynamic
changes where temperature is remaining constant, it is
(1) Adiabatic process (2) Isothermal process (3) Isobaric process (4) Isochoric process
Sol. Answer (2)
A system which undergoes change such that temperature remains constant. Such a change is called isothermal
process.
3. A thermally isolated, gaseous system can exchange energy with the surroundings. The mode of energy may
be
(1) Heat (2) Work (3) Heat and radiation (4) Internal energy
Sol. Answer (2)
Since the system is thermally isolated, energy can only be transferred through a non-thermal mode i.e. work.
5. If ‘r’ is the work done on the system and ‘s’ is heat evolved by the system then,
(1) E = r + s (2) E = r – s (3) E = r (4) E = s
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134 Thermodynamics Solutions of Assignment (Set-2)
6. A system absorbs 10 kJ of heat and does 4 kJ of work. The internal energy of the system
(1) Decreases by 6 kJ (2) Increases by 6 kJ
(3) Decreases by 14 kJ (4) Increases by 14 kJ
Sol. Answer (2)
As per Ist law,
U = q + w
q = +10 kJ (heat is absorbed by the system)
w = –4 kJ (work is done by the system)
U = q + w = 10 – 4 kJ = +6 kJ
7. Regarding the internal energy of the molecule, which of the following statement is correct?
(1) Its absolute value can be successfully calculated
(2) Its absolute value cannot be determined
(3) It is the sum of vibrational and rotational energies
(4) Both (1) & (3)
Sol. Answer (2)
The absolute value of internal energy cannot be determined since it is the sum total of all the energies at a
molecular level. These energies cannot be determined and hence the absolute value of U cannot be determined.
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Solutions of Assignment (Set-2) Thermodynamics 135
10. For stretched rubber, Entropy
(1) Increases (2) First increases then decreases
(3) Decreases (4) First decreases then increases
Sol. Answer (3)
For stretched rubber, entropy decreases.
∵ Upon releasing , it regains its original shape
Spontaneous process, S = positive
So, for the reverse process (stretching),
S must have been negative.
13. The standard entropies of N2 (g), H2 (g) and NH3 (g) are 191.5, 130.5, 192.6 JK–1 mol–1. The value of Sº of
formation of ammonia is
(1) –98.9 JK–1 mol–1 (2) Zero (3) +129.4 JK–1 mol–1 (4) –29.4 JK–1 mol–1
Sol. Answer (1)
1 3
N2 H2 NH3
2 2
S° = SNH SH SN
3 2 2
⎛3 1 191.5 ⎞
= (192.6 JK–1 mol–1 × 1 mol) – ⎜ 130.5 JK JK 1 ⎟
⎝ 2 2 ⎠
= 192.6 JK–1 – 195.75 JK–1 – 95.75 JK–1
= – 98.9 JK–1 for 1 mole of NH3
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136 Thermodynamics Solutions of Assignment (Set-2)
14. What is the increase in entropy when 11.2 L of O2 are mixed with 11.2 L of H2 at STP?
(1) 0.576 J/K (2) 5.76 J/K (3) 7.56 J/K (4) 2.76 J/K
Sol. Answer (2)
Smix = – n R × 2.303 xH2 log H2 xO2 log O2
Total moles = (0.5 + 0.5) moles = 1 mole
1
xH2 xO2
2
11.2
∵ moles of O2 = = 0.5
22.4
11.2
moles of H2 = = 0.5
22.4
S = – 1 mol × 8.314 JK–1 (0.5 log 0.5 + 0.5 log 0.5)
= – 8.314 JK–1 (– log 2) = + 5.76 JK–1
15. Given S C 2H6 = 225 J mol-1K–1,
SC2H4 = 220 J mol–1K–1, SHo = 130 J mol–1K–1. Then S° for the process
2
C2H4 + H2 C2H6 is
(1) +25 J (2) –125 J (3) 135 J (4) 315 J
Sol. Answer (2)
For the reaction,
16. For the melting of NaCl heat required is 7.26 kcal mol–1 and S increases by 6.73 cal mol–1k–1. The melting
point of the salt is
(1) 805.75°C (2) 500 K (3) 1.77 K (4) 1.77°C
Sol. Answer (1)
Let melting temperature = T
Hfusion
Sfusion =
T
Hfusion
T = S
fusion
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Solutions of Assignment (Set-2) Thermodynamics 137
17. The S for the reaction
o
2H2(g) + O2(g) 2H2O(l) at 300 K when SHo 2 (g) = 126.6, SO2 (g) = 201.20,
(1) –318.4JK–1mol–1 (2) 318.4JK–1mol–1 (3) 31.84 JK–1mol–1 (4) 3.184 JK–1mol–1
Sol. Answer (1)
Always Always
positive positive
G is always positive.
19. Entropy of vaporisation of water at 100°C, if molar heat of vaporisation is 9710 cal mol–1 will be
(1) 20 cal mol–1 K–1 (2) 26.0 cal mol–1 K–1 (3) 24 cal mol–1 K–1 (4) 28.0 cal mol–1 K–1
Sol. Answer (2)
Molar entropy of vaporisation of water,
20. A particular reaction at 27°C for which H > 0 and S > 0 is found to be non-spontaneous. The reaction may
proceed spontaneously if
(1) The temperature is decreased (2) The temperature is increased
(3) The temperature is kept constant (4) It is carried in open vessel at 27°C
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138 Thermodynamics Solutions of Assignment (Set-2)
G =
H
TS
Positive Negative
So, G < 0 only when
H < TS
So, the reaction would proceed only when temperature is high.
22. The standard free energy change G° is related to K (equilibrium constant) as
(1) G° = –2.303 RT logK (2) G° = 2.303 RT logK
(3) G° = RT logK (4) G° = –RT logK
Sol. Answer (1)
We know,
G = G° + RT ln Q ; Q = Reaction quotient.
At equilibrium, G = 0 ; Q = K
0 = G° + RT ln K
or, G° = – RT ln K = – 2.303 RT log K
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Solutions of Assignment (Set-2) Thermodynamics 139
25. At 27°C the reaction,
C6H6(l) + 15/2 O2(g) 6CO2(g) + 3H2O(l)
proceeds spontaneously because the magnitude of
(1) H = TS (2) H > TS (3) H < TS (4) H > 0 and TS < 0
Sol. Answer (2)
For the given reaction,
S = negative (∵ Lesser number of gaseous products are formed)
–TS = positive
But H = –ve
Since, it is a combustion reaction and hence exothermic.
∵ G = H – TS ; So for G to be negative, |H| > |TS|
(Thermochemistry, Enthalpy of reaction)
aA(s) + bB(g)
dD(s) + cC(g). Then
(1) H – E = (b – d) RT (2) H – E = (c – b) RT
(3) H – E = (a + b) – (c + d) RT (4) H – E = (a – d) RT
Sol. Answer (2)
For the reaction,
ng = (c – b) [∵ rest are solid substances]
We know,
H = U + ng RT
or, H = U + (c – b) RT
or, H – U = (c – b) RT
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140 Thermodynamics Solutions of Assignment (Set-2)
31. The heats of combustion of yellow P and red P are –9.91kJ and –8.78kJ respectively. The heat of transition
of yellow to red phosphorus is
(1) –18.69 kJ (2) +1.13 kJ (3) +18.69 kJ (4) –1.13 kJ
Sol. Answer (4)
5 1
P yellow O2 g P2O5 s ; H1 9.91kJ
2 2
5 1
Pred O2 g P2O5 s ; H2 8.78 kJ
2 2
Rearranging, we get
5
P yellow O2 g P2O5 g ; H 9.91kJ
2
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Solutions of Assignment (Set-2) Thermodynamics 141
5
P2O5 Pred O2 g ; H 8.78 kJ
2
Adding these two equations, we get
Also,
N2 O2 2NO g ; H y
Adding, we get
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142 Thermodynamics Solutions of Assignment (Set-2)
ng = 12 – 15 = – 3 mol
H = U + ng RT
or, H – U = – 3 × 8.314 Jk–1 mol–1 × 298 K × mol = –7.432 kJ
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Solutions of Assignment (Set-2) Thermodynamics 143
37. If S + O2 SO2; H = –298.2 kJ
SO2 + 1/2O2 SO3; H = –98.7 kJ
SO3 + H2O H2SO4; H = –130.2 kJ
H2 + 1/2O2 H2O; H = –287.3 kJ
then the enthalpy of formation of H2SO4 at 298 K is
(1) –814.4 kJ (2) –650.3 kJ (3) –320.5 kJ (4) –433.5 kJ
Sol. Answer (1)
Given:
1
SO2 O2 SO3 ; H = – 98.7 kJ
2
SO3 H2O H2SO4 ; H = – 130.2 kJ
1
H2 O2 H2O ; H = – 287.3 kJ
2
Additing all these, we get
38. The volume of a gas expands by 0.25 m3 at a constant pressure of 103N m–2. The work done is equal to
(1) 2.5 erg (2) 250 J (3) 250 watt (4) 250 newton
Sol. Answer (2)
We know, work done, w = – Pex + V.
Given, pressure is 103 N m–2
and, V = 0.25 m3
w = – 103 Nm–2 × 0.25 m3 = – 250 J
So, work done by the gas is 250 J.
39. When 1 g of anhydrous oxalic acid is burnt at 25°C, the amount of heat liberated is 2.835 kJ. H combustion
is (oxalic acid : C2H2O4)
(1) –255.15 kJ (2) –445.65 kJ (3) –295.24 kJ (4) –155.16 kJ
Sol. Answer (1)
1
H2C2O4 s O2 g 2CO2 g H2O l
oxalic acid 2
We know,
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144 Thermodynamics Solutions of Assignment (Set-2)
Hcombustion = Amount of heat liberated when 1 mole of substance reacts with oxygen.
Mol. wt. of oxalic acid = 90 g mol–1
1 g oxalic acid liberates 2.835 kJ
90 g (1 mole) oxalic acid liberates 2.835 × 90 kJ mol–1 = 255.15 kJ
Heat involved = – 255.15 kJ
40. The heat of neutralization of LiOH and HCl at 25°C is 34.868 kJ mol–1. The heat of ionisation of LiOH will be
(1) 44.674 kJ (2) 22.232 kJ (3) 32.684 kJ (4) 96.464 kJ
Sol. Answer (2)
Let heat of ionization be a of LiOH.
x H
LiOH Li OH HCl
neut. LiCl H2O
H = – 34.868 kJ
x – 57.1 kJ mol–1 = – 34.868 kJ mol–1
or, x = (57.1 – 34.868) kJ mol–1 = 22.232 kJ
41. Which compound will absorb the maximum amount of heat when dissolved in the same amount of water?
(Integral heats of solution at 25°C in kcal/mol of each solute are given in brackets)
(1) HCl (H = –17.74) (2) HNO3 (H = –7.85)
(3) NH4NO3 (H = +16.08) (4) NaCl (H = +1.02)
Sol. Answer (3)
Maximum heat is absorbed by NH4NO3
H = + 16.08 (maximum positive value)
42. HA + OH–H2O + A– + q1 kJ
H+ + OH– H2O + q2 kJ
The enthalpy of ionisation of HA is
(1) (q1 + q2) (2) (q1 – q2) (3) (q2 – q1) (4) –(q1 + q2)
Sol. Answer (3)
HA H A ; H
Given:
Adding, we get
HA H A ; H q2 – q1 kJ
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Solutions of Assignment (Set-2) Thermodynamics 145
43. An athlete takes 100 g of glucose of energy equivalent to 1560 kJ. How much amount of energy is uptaken
by 1 g molecule of glucose?
(1) 15.6 kJ (2) 2808 kJ (3) 1560 kJ (4) 28.08 kJ
Sol. Answer (2)
100 g 1560 kJ
1560
180 g 180 kJ
100
∵ wt. of 1 gram molecule
1560 180
= 180 g which gives kJ = 2808 kJ
100
45. For strong acid strong base neutralisation energy for 1 mole H2O formation is –57.1 kJ. If 0.25 mole of strong
monoprotic acid is reacted with 0.5 mole of strong base then enthalpy of neutralisation is
(1) –(0.25 × 57.1) (2) 0.5 × 57.1 (3) 57.1 (4) –(0.5 × 57.1)
Sol. Answer (1)
1 mole of strong monoprotic acid reacts with 1 mole of strong base to give – 57.1 kJ
0.25 mol of strong acid will react with only 0.25 mol of strong base (and not 0.5 mol)
Energy involved = – 57.1 kJ × 0.25
46. The heat of combustion of solid benzoic acid at constant volume is –321.3 kJ at 27°C. The heat of combustion
at constant pressure is
(1) –321.3 – 300R (2) –321.30 + 300R (3) –321.3 – 150R (4) –321.3 + 900R
Sol. Answer (3)
COOH
15
O2 g 7CO2 g 3H2O
2
15 1
ng = 7 – =–
2 2
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146 Thermodynamics Solutions of Assignment (Set-2)
We know,
H = U + ng RT
H = qP
U = qV
qP = qV + ng RT
⎛ 1 ⎞
= – 321.3 + ⎜ 300 K R ⎟
⎝ 2 ⎠
= – 321.3 – 150 R
1
47. H2 (g) O2 (g)
H2O( )
2
H2O(l) H2O(g); H = x4
Given, EH–H = x1
EO=O = x2
EO–H = x3
HF of H2O vapour is
x2 x2 x2 x2
(1) x1 x3 x4 (2) 2 x 3 x1 x4 (3) x1 2x 3 x 4 (4) x1 2x 3 x 4
2 2 2 2
Sol. Answer (4)
1 Hf
H2 g O2 g H2O g
2
H
H2O ()
x4
1
Now, for H2 g O2 g H2O ; H
2
1
H = (B.D.E)reactants – (B.D.E)products = x1 x 2 2x3
2
1
Hf = H + x4 = x1 x2 2x3 x 4
2
48. A cylinder contains either ethylene or propylene. 12 ml of gas required 54 ml of oxygen for complete
combustion. The gas is
(1) Ethylene (2) Propylene
(3) 1 : 1 mixture of two gases (4) 1 : 2 mixture
Sol. Answer (2)
12 ml of gas requires 54 ml of O2
9
or, 1 mole of gas requires mole of O2
2
If the gas is C2H4
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Solutions of Assignment (Set-2) Thermodynamics 147
49. The specific heat of a gas is found to be 0.075 calories at constant volume and its formula wt is 40. The
atomicity of the gas would be
(1) One (2) Two (3) Three (4) Four
Sol. Answer (1)
Specific heat = 0.075 calories
Molar specific heat capacity, CV = 0.075 × 40 = 3 cal mol–1 k–1
CP = CV + R = 3 cal mol–1 k–1 + 2 cal mol–1 k–1 = 5 cal mol–1 k–1
CP 5
1.66
CV 3
Monoatomic gas.
H g O g O – H g ; H
H = (B.D.E)reactants – (B.D.E)Products
= O – Bond energy of O – H
H = – Bond energy of O – H
51. Energy required to dissociate 4 g of gaseous H2 into free gaseous atoms is 872 kJ at 25°C. The bond energy
of H-H bond will be
(1) 8.72 kJ (2) 4.36 kJ (3) 436 kJ (4) 43.6 kJ
Sol. Answer (3)
H2 g 2H g ; H
1mole (2g)
H = (B.D.E)reactants – (B.D.E)Products = Bond energy of H2
Given that 4 g of H2 requires 872 kJ to dissociate
2 g of H2 requires 436 kJ
1 mole of H2 require 436 kJ
H = +436 kJ = Bond energy of H2
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148 Thermodynamics Solutions of Assignment (Set-2)
52. The dissociation energy of CH4 (g) is 360 kcal mol–1 and that of C2H6 (g) is 620 kcal mol–1. The C – C bond energy
(1) 260 kcal mol–1 (2) 180 kcal mol–1 (3) 130 kcal mol–1 (4) 80 kcal mol–1
Sol. Answer (4)
H
C C(g) + 4 H (g) ; H7
H H
H
H H
H C–C–H 2 C(g) + 6 H (g) ; H2
H H
Given: H1 = 360 kcal mol–1 ; H2 = 620 kcal mol–1
Also, H1 = 4 × Bond energy of C – H = 360 kcal mol–1
Bond energy of C – H = 90 kcal mol–1
Now, H2 = 6 × Bond energy of C – H + Bond energy of C – C
H2 = 6 × 90 kcal mol–1 + Bond energy of C – C
∵ H2 = 620 kcal mol–1
620 kcal mol–1 = 540 kcal mol–1 + Bond energy of C – C or, Bond energy of C – C = 80 kcal mol–1
= 2 ECH ECH 2 ECC 5 EOO – 4 ECO ECO 2 EOH EOH
= 4ECH 2 ECC 5 EOO 8ECO 4EOH
= 4p + 2q + 5r – (8s + 4t)
5C(s) + 4H2(g) H 2C = C – CH = CH 2
CH3
Given C–H, H–H, C–C, C = C and C(s) C(g) respectively as 98.8 kcal, 104 kcal, 83 kcal,
147 kcal, 171 kcal
(1) – 21 kcal (2) 21 kcal (3) 40 kcal (4) 50 kcal
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Solutions of Assignment (Set-2) Thermodynamics 149
Sol. Answer (2)
Given
H
H H
Hf
5 C(s) + 4 H2(g) C=C–C=C
H H
5x C
H H
H H
C(g) + 4 H2(g)
H = (B.D.E)reactants – (B.D.E)products
= 4 EH – H – (2 EC = C + 8 EC – H + EC – C)
Hf = 5x + H (∵ H is a state function)
x = 171 kcal
Hf = 5 × 171 kcal + [4 × 104 kcal – (2 × 147) – 8 × 98.8 kcal] – 2 × 83 kcal
= 855 kcal + (416 kcal – 294 kcal – 790.4 kcal – 166 kcal)
= 20.6 kcal 21 kcal
55. In a flask colourless N2O4 is in equilibrium with brown coloured NO2. At equilibrium when the flask is heated
at 100°, the brown colour deepens and on cooling it becomes less coloured. The change in enthalpy, H for
formation of NO2 is
(1) Negative (2) Positive (3) Zero (4) Undefined
Sol. Answer (2)
N2O4 2NO2
Upon heating, brown colour deepens, i.e. NO2 is formed.
The reaction is as follows
N2O4 H
2NO2
The reaction is, hence, endothermic.
SECTION - B
Objective Type Questions
(Thermodynamic processes and parameter, Internal energy and enthalpy)
1. When an ideal gas is compressed adiabatically and reversibly, the final temperature is
(1) Higher than the initial temperature (2) Lower than the initial temperature
(3) The same as the initial temperature (4) Dependent on the rate of compression
Sol. Answer (1)
When an ideal gas is compressed adiabatically and reversibly,
Then q = 0
According to 1st law:
U = q + w = w
∵ Gas is compressed work done is positive i.e. w is positive in magnitude
U is positive
T is positive as well.
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150 Thermodynamics Solutions of Assignment (Set-2)
2. A closed flask contains a substance in all its three states, solids, liquids and vapour at its triple point. In this
situation the average KE of the water molecule will be
(1) Maximum in vapour state (2) Maximum in solid state
(3) Greater in the liquid than in vapour state (4) Same in all the three states
Sol. Answer (4)
The triple point for water exists at a particular temperature.
∵ Temperature is same K.E. of water is also same.
4. 16 kg oxygen gas expands at STP (1 atm) isobarically to occupy double of its original volume. The work done
during the process is nearly
(1) 260 kcal (2) 180 kcal (3) 130 kcal (4) 271 kcal
Sol. Answer (4)
We know, work done,
w = – Pex + V
= – P V (∵ pressure is constant)
= – P(2V – V) ; where V is initial volume
= – PV
= – nRT (Considering ideal behaviour)
16000 g
n= 500 mol
32 g mol1
R = 2 cal mol–1 K–1
T = 273 K
w = – 500 mol × 2 × 273 cal mol–1 K–1 × K = – 273 cal
work done by oxygen gas is 271 cal.
5. One mole of a non ideal gas undergoes a change of state (2.0 atm, 3.0 L, 95 K) (4.0 atm, 5.0 L, 245 K)
with a change in internal energy U = 30.0 L atm. The change in enthalpy of the process in L atm is
(1) 40.0 (2) 42.3 (3) 44.0 (4) 56.0
Sol. Answer (3)
Enthalpy is given as,
H = U + pV
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Solutions of Assignment (Set-2) Thermodynamics 151
This can be rewritten as
H = U + (pV)
= U + (p2V2 – p1V1)
= 30.0 L atm + (4.0 atm × 5.0 L – 2.0 atm × 2.0 L)
= (30.0 + 14.0) L atm = 44.0 L atm
7. In an insulated container water is stirred with a rod to increase the temperature. Which of the following is true?
(1) U = W 0, q = 0 (2) U = W = q 0
(3) U = 0, W = q 0 (4) W = 0, U = q 0
Sol. Answer (1)
∵ Container is isolated
q=0
According to first law,
U = q + W
or U = W
U and W are both same in magnitude
∵ T increases
U is positive
U + W = 2 U = positive and hence non-zero.
8. Two atoms of hydrogen combine to form a molecule of hydrogen gas the energy of the H2 molecule is
(1) Greater than that of separate atoms (2) Equal to that of separate atoms
(3) Lower than that of separate atoms (4) Sometimes lower and sometimes higher
Sol. Answer (3)
2 atoms of hydrogen forms bond to form H2 molecule. Bond is formed Attractive forces Energy is
released during the process.
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152 Thermodynamics Solutions of Assignment (Set-2)
10. If x mole of ideal gas at 27°C expands isothermally and reversibly from a volume of y to 10y, then the work done is
y
(1) w = x R 300 ln y (2) w = – 300x R ln 10 y
1
(3) w = – 300x R ln 10 (4) w = 100x R ln y
10 y
= – x × R × 300 ln y
= – x × R × 300 ln 10
= – 300x R ln 10
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Solutions of Assignment (Set-2) Thermodynamics 153
Sol. Answer (2)
Viscosity, refractive index, and specific heat do not depend upon mass and hence are intensive properties.
14. For the expansion occurring from initial to final stage in finite time, which is incorrect?
(1) Equilibrium exist in initial and final stage
(2) Work obtained is maximum
(3) Driving force is much greater than the opposing force
(4) Both (1) & (2)
Sol. Answer (2)
Work obtained is maximum in case of reversible process (i.e. process occurring in infinite time)
Hence, work done infinite time is not maximum.
(Heat Capacity)
15. For one mole of an ideal gas (Cp and Cv are molar heat capacities at constant pressure and constant volume
respectively)
R
(1) Cp – Cv = R (2) Cp – Cv = (3) Cp – Cv = –2R (4) Cp – Cv = 0
2
Sol. Answer (1)
For one mole of an ideal gas,
Cp – Cv = R ; where Cp is molar heat capacity at const. pressure while Cv is molar heat capacity at constant.
volume.
16. The molar heat capacity of water at constant pressure P is 75 J K–1 mol–1. When 1.0 kJ of heat is supplied
to 1000 g of water, which is free to expand, the increase in temperature of water is
(1) 1.2 K (2) 2.4 K (3) 4.8 K (4) 0.24 K
Sol. Answer (4)
Molar heat capacity of water is 75 J K–1 mol–1
To raise temperature by 1°C (or 1 K), heat required is 75 J for 1 mole of water
i.e. 75 J for 18 g of H2O.
75
So for 1 g of H2O, heat required is J
18
75
Specific heat capacity = J g–1 K–1
18
q = mCT
q 1000 J
or, T =
mC 75
1000 g J K 1 g1
18
18
= K = 0.24 K
75
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154 Thermodynamics Solutions of Assignment (Set-2)
⎛ dU ⎞ dU
⎜ dV ⎟ i.e., at constant volume is 0.
⎝ ⎠T dV
20. The enthalpy and entropy change for a chemical reaction are –2.5 × 103 cal and 7.4 cal K–1 respectively.
Predict the nature of reaction at 298 K is
(1) Spontaneous (2) Reversible (3) Irreversible (4) Non-spontaneous
Sol. Answer (1)
H = – 2.5 × 103 cal
S = + 7.4 cal K–1
∵ H < 0 and S > 0
G < 0 Process is spontaneous
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Sol. Answer (1)
At equilibrium, G = 0
H = TS (at equilibrium)
H 30.5 k J mol1
T= 462.12 K
S 0.066 k J mol1 K 1
22. The temperature of 15 ml of a strong acid increases by 2°C when 15 ml of a strong base is added to it. If
5 ml of each are mixed, temperature should increase by
(1) 0.6°C (2) 0.3°C (3) 2°C (4) 6°C
Sol. Answer (3)
Heat of neutralization, H depends upon number of gram equivalents of strong acid and strong base.
Number of g equivalents depends upon volume of acid/base taken.
H g equivalents of acid and base
H volume of acid and base
Also, H = qp = mCPT
H
or, T =
mCp
Cp is intensive variable
m
and = d m = dV
V
H 1
T =
V Cp d
We know, H V
H = KV (where K is proportionality constant)
K
T = Change in temperature remains constant when all these conditions are same.
Cp d
23. The standard heat of formation of NO2(g) and N2O4(g) are 8.0 and 4.0 kcal mol–1 respectively. The heat of
dimerisation of NO2 in kcal is
(1) –12 kcal (2) 12 kcal (3) 4 kcal (4) 16 kcal
Sol. Answer (1)
1
N2 g O2 g NO2 g ; H 8.0 kcal mol1
2
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Adding, we get
1 1
24. If X O(s) X(s) + O2(g); H = 90 kJ. Then heat change during reaction of metal X with one mole of O2
2 2 4
to form oxide to maximum extent is
(1) 360 kJ (2) –360 kJ (3) –180 kJ (4) +180 kJ
Sol. Answer (2)
1 1
Given, X2O s X s O2 g ; H 90 kJ
2 4
1 1
X s O2 g X2O s ; H 90 kJ
4 2
Multiplying with 4, we get
Given: A g 3B g 3C g 3D g
ng = 6 – 4 = 2
We know,
H = U + pV
Considering ideal behaviour, we have
H = U + ngRT
= 17 kcal + 2 × 2 cal K–1 × 298 K
= (17000 + 4 × 298) cal
= 18192 kcal = 18.2 kcal
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Sol. Answer (3)
27. Bond dissociation energy of XY, X2 and Y2 (all diatomic molecules) are in the ratio of 1 : 1 : 0.5 and Hf of
XY is –200 kJ mol–1. The bond dissociation energy of X2 will be
(1) 800 kJ mol–1 (2) 200 kJ mol–1 (3) 300 kJ mol–1 (4) 400 kJ mol–1
Sol. Answer (1)
B.D.E of XY, X2 and Y2 are in the ratio 1 : 1 : 0.5
Let B.D.E. of XY be x, X2 be x and Y2 be 0.5 x.
H = – 2 × (B.D.E)XY + B.D.E X2
B.D.E. Y
2
= – 2x + (x + 0.5 x) = – 0.5x
Also, Hf of XY is – 200 kJ mol–1
1 1
i.e. X2 g Y2 g XY g ; Hf
2 2
H = 2 × Hf = 2 × – 200 kJ mol–1 = – 400 kJ
So, 0.5x = + 400 kJ
x = 800 kJ
28. Enthalpy of formation of NH3 is – X kJ and HH–H, HN–H are respectively Y kJ mol–1 andZ kJ mol–1. The value of
HN N is
X
(1) Y – 6Z + (2) – 3Y + 6Z – 2X (3) 3Y + 6Z + X (4) Y + 6X + Z
3
Sol. Answer (2)
1 3
N2 g H2 g NH3 g ; Hf – x kJ
2 2
Hf = H = (B.D.E)reactants – (B.D.E)products
1 3
= HN2 HH2 3NH
2 2
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158 Thermodynamics Solutions of Assignment (Set-2)
HNN 3
= XY 3XZ
2 2
We have,
HNN 3Y
–X= 3 Z
2 2
⎛ 3Y ⎞
or, HNN = ⎜ 3Z X ⎟ 2 = 6Z – 3Y – 2X
⎝ 2 ⎠
29. The heat of neutralisation for strong acid and strong base forming 2 moles of water is
(1) – 2 × 57.1 kJ
(2) – 57.1 kJ
57.1
(3) kJ
2
(4) Strong acid and strong base will not undergo neutralisation
Sol. Answer (1)
When 1 mole of water is formed upon neutralization, – 57.1 kJ is released when 2 moles of water are formed,
– 57.1 × 2 kJ of energy is released.
(1) x + 4y – z – 2r (2) r + z + 4y – x
(3) 2r + z + 4y + x (4) x + 4y + z – 2r
Sol. Answer (4)
For the reaction,
H° = HfCCl4 HfSO2 2 HfN2 2 HfCS2 (l) HNOCl 4
= z + 2(–r) + 2(0) – (– x) – (– y)
= x – 2r + x + y
Hf of N2(g) is o since if is in its reference state.
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Solutions of Assignment (Set-2) Thermodynamics 159
31. The heat liberated on complete combustion of 1 mole of CH4 gas to CO2(g) and H2O(l) is 890 kJ. Calculate the heat
evolved by 2.4 L of CH4 on complete combustion.
32. The work done in an open vessel at 300 K, when 112 g iron reacts with dil HCl to give FeCl2, is nearly
(1) 1.1 kcal (2) 0.6 kcal (3) 0.3 kcal (4) 0.2 kcal
Sol. Answer (1)
1
33. A schematic representation of enthalpy changes for the C( graphite ) O (g) CO (g) reaction, is given below.
2 2
The missing value is
Cgraphite + O2(g)
??
CO(g) + ½O(g)
– 393.5 kJ
– 283.0 kJ
CO2(g)
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160 Thermodynamics Solutions of Assignment (Set-2)
34. Which of the following equations represent standard heat of formation of CH4?
(1) C(diamond) + 2H2(g) CH4(g) (2) C(graphite) + 2H2(g) CH4(g)
(3) C(diamond) + 4H(g) CH4(g) (4) C(graphite) + 4H(g) CH4(g)
Sol. Answer (2)
Standard heat of formation is enthalpy change when 1 mole of substance is formed from its constituents
elements in their reference states.
75.6 kcal
1 g yields –
60 g
745.6 4.2
1 g yields kJ g1 –52.2 kJ g1
60
Hence, calorific value of ethane is – 52.2 kJ g–1
SECTION - C
Previous Years Questions
1. A gas is allowed to expand in a well insulated container against a constant external pressure of 2.5 atm from
an initial volume of 2.50 L to a final volume of 4.50 L. The change in internal energy U of the gas in joules
will be [NEET-2017]
(1) 1136.25 J (2) –500 J (3) –505 J (4) +505 J
Sol. Answer (3)
U = q + w
For adiabatic process, q = 0
U = w
= – P·V
= –2.5 atm × (4.5 – 2.5) L
= –2.5 × 2 L-atm
= –5 × 101.3 J
= –506.5 J
–505 J
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Solutions of Assignment (Set-2) Thermodynamics 161
2. For a given reaction, H = 35.5 kJ mol–1 and S = 83.6 JK–1 mol–1. The reaction is spontaneous at : (Assume
that H and S do not vary with temperature) [NEET-2017]
(1) T < 425 K (2) T > 425 K (3) All temperatures (4) T > 298 K
Sol. Answer (2)
∵ G = H – TS
For a reaction to be spontaneous, G = –ve
i.e., H < TS
H 35.5 103 J
T i.e., T > 425 K
S 83.6 JK –1
3. For a sample of perfect gas when its pressure is changed isothermally from pi to pf, the entropy change is
given by [NEET (Phase-2) 2016]
⎛p ⎞ ⎛p ⎞
(1) S nRln ⎜ f ⎟ (2) S nRln ⎜ i ⎟
⎝ pi ⎠ ⎝ pf ⎠
⎛p ⎞ ⎛p ⎞
(3) S nRTln ⎜ f ⎟ (4) S RT ln ⎜ i ⎟
⎝ pi ⎠ ⎝ pf ⎠
Sol. Answer (2)
⎛p ⎞
S nRln ⎜ i ⎟
⎝ pf ⎠
4. The correct thermodynamic conditions for the spontaneous reaction at all temperatures is [NEET-2016]
(1) H < 0 and S < 0 (2) H < 0 and S = 0
(3) H > 0 and S < 0 (4) H < 0 and S > 0
Sol. Answer (2 & 4)
∵ G = H – TS
For reaction to be spontaneous, G should be negative.
Note : G can be negative in option (2) also.
5. The heat of combustion of carbon to CO2 is –393.5 kJ/mol. The heat released upon formation of 35.2 g of CO2
from carbon and oxygen gas is [Re-AIPMT-2015]
(1) –630 kJ (2) –3.15 kJ (3) –315 kJ (4) +315 kJ
Sol. Answer (3)
For 44 g CO2 heat released = –393.5 kJ
For 35.2 g CO2 heat released
393.5
– 35.2
44
= –314.8 kJ
–315 kJ
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162 Thermodynamics Solutions of Assignment (Set-2)
7. In which of the following reactions, standard reaction entropy change (S°) is positive and standard Gibb's
energy change (G°) decreases sharply with increasing temperature ? [AIPMT (Prelims)-2012]
1 1 1 1
(1) Mg(s)+ O (g)MgO(s) (2) C graphite + O2(g) CO2(g)
2 2 2 2 2
1 1
(3) C graphite + O (g)CO(g) (4) CO(g)+ O (g)CO2(g)
2 2 2 2
Sol. Answer (3)
For the reaction
1
C graphite O2 g CO g
2
1 1
ng = 1
2 2
S is positive
and hence G decreases with increase in temperature
∵ G = H – TS
8. Standard enthalpy of vapourisation vapH(0) for water at 100C is 40.66 kJmol–1.The internal energy of vapourisation
of water at 100C (in kJmol–1) is [AIPMT (Prelims)-2012]
(1) +43.76 (2) +40.66 (3) +37.56 (4) –43.76
Sol. Answer (3)
We know,
H = U + ngRT
or, U = H – ngRT
The reaction is
ng = +1
U = 40.66 kJ mol–1 – 1 mol × 8.314 J mol–1 K–1 × 373 K
= 40.66 – 3101 J
= +37.56 J
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Solutions of Assignment (Set-2) Thermodynamics 163
9. The enthalpy of fusion of water is 1.435 kcal/mol. The molar entropy change for the melting of ice at 0C is
[AIPMT (Prelims)-2012]
(1) 5.260 cal/(mol K) (2) 0.526 cal/(mol K) (3) 10.52 cal/(mol K) (4) 21.04 cal/(mol K)
Sol. Answer (1)
Hfus
Sfus
T
1.435 103 cal mol1
= 5.26 cal mol–1 K–1
273 K
10. Equal volumes of two monoatomic gases, A and B, at same temperature and pressure are mixed. The ratio
of specific heats (Cp/Cv) of the mixture will be [AIPMT (Mains)-2012]
(1) 0.83 (2) 1.50 (3) 3.3 (4) 1.67
Sol. Answer (4)
11. Which of the following is correct option for free expansion of an ideal gas under adiabatic condition?
[AIPMT (Prelims)-2011]
(1) q = 0, T < 0, w 0 (2) q = 0, T 0, w = 0
(3) q 0, T = 0, w = 0 (4) q = 0, T 0, w = 0
Sol. Answer (4)
Free expansion Pext = 0
w=0
U = w + q = q (∵ w = 0)
∵ Expansion is adiabatic
q=0
Hence U = 0
T = 0 (∵ U is proportional to temperature)
12. If the enthalpy change for the transition of liquid water to steam is 30 kJ mol–1 at 27°C, the entropy change
for the process would be [AIPMT (Prelims)-2011]
(1) 100 J mol –1 K–1 (2) 10 J mol –1 K–1
(3) 1.0 J mol –1 K–1 (4) 0.1 J mol –1 K–1
Sol. Answer (1)
Hvap 30000 J mol1
S vap 100 J mol1 K 1
T 300 K
13. Enthalpy change for the reaction, 4 H(g) 2H2 (g) is –869.6 kJ. The dissociation energy of H – H bond is
[AIPMT (Prelims)-2011]
(1) + 217.4 kJ (2) – 434.8 kJ
(3) – 869.6 kJ (4) + 434.8 kJ
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164 Thermodynamics Solutions of Assignment (Set-2)
4 H g 2 H2 g
H = B.D.E. of reactants – B.D.E. of products
= 0 – 2 × HH–H = – 2HH–H
This is equal to – 869.6 kJ
– 2HH–H = – 869.6 kJ
HH–H = + 434.8 kJ
B D E 2C ; H = – 175 kJ
1 3
15. Standard entropies of X2, Y2 and XY3 are 60, 40 and 50 JK–1 mol–1 respectively. For the reaction X2 Y2
2 2
XY3;H = –30kJ to be at equilibrium, the temperature should be [AIPMT (Prelims)-2010]
(1) 750 K (2) 1000 K (3) 1250 K (4) 500 K
Sol. Answer (1)
For the reaction to be at equilibrium,
G = 0
H = TS
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Solutions of Assignment (Set-2) Thermodynamics 165
⎛1 3 ⎞
Now, S = ⎜ S X 2 S Y2 ⎟ S XY3
⎝ 2 2 ⎠
⎛ 60 3 ⎞
= ⎜ 50 40 ⎟ J K 1
⎝ 2 2 ⎠
= – 40 J K–1
H 30000 J
T= 750 K
S 40
16. Match List-I (Equations) with List-II (Type of process) and select the correct option [AIPMT (Mains)-2010]
List-I List-II
(Equations) (Type of process)
a. Kp > Q (i) Non-spontaneous
b. G< RT ln Q (ii) Equilibrium
17. Three moles of an ideal gas expanded spontaneously into vacuum. The work done will be
[AIPMT (Mains)-2010]
(1) Infinite (2) 3 Joules (3) 9 Joules (4) Zero
Sol. Answer (4)
For a spontaneous process,
G = H– TS < 0
or, H < TS
H
or, T
S
For a non-spontaneous process,
G > 0
or, G° + RT ln Q > 0 [∵ G = G° + RT ln Q]
∵ RT ln Q > 0
So, G° has to be greater in magnitude than RT ln Q for the reaction to be spontaneous.
∵ G° < RT ln Q Non spontaneous
kp = Q G = 0
i.e. process is at equilibrium.
When kp > Q.
Reaction will move in forward direction
Spontaneous.
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166 Thermodynamics Solutions of Assignment (Set-2)
18. For vaporization of water at 1 atmospheric pressure, the values of H and S are 40.63 kJ mol–1 and 108.8
JK–1 mol–1 respectively. The temperature when Gibbs energy change (G) for this transformation will be zero,
is [AIPMT (Mains)-2010]
(1) 273.4 K (2) 393.4 K (3) 373.4 K (4) 293.4 K
Sol. Answer (3)
∵ Pext = 0
w=0
20. The values of H and S for the reaction, C(graphite) + CO2(g) 2CO(g) are 170 kJ and 170 JK–1 respectively.
This reaction will be spontaneous at [AIPMT (Prelims)-2009]
(1) 910 K (2) 1110 K (3) 510 K (4) 710 K
Sol. Answer (2)
Reaction will be spontaneous at higher temperature when G < 0
At 1110 K
H – TS
G = (17000 J – 1110 × 170 J) = – 171.7 kJ i.e., G = – ve
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Solutions of Assignment (Set-2) Thermodynamics 167
C – H bond energy : 410.50 kJ mol–1
Enthalpy for the reaction,
H H H H
C=C+H–H H–C–C–H
H H H H
will be [AIPMT (Prelims)-2009]
(1) –243.6 kJ mol–1 (2) –120.0 kJ mol–1 (3) 553.0 kJ mol–1 (4) 1523.6 kJ mol–1
Sol. Answer (2)
Given reaction :
H H H H
C=C +H–H H C C H ; Hr
H H H H
Hr = (B.D.E)reactants – (B.D.E)products
= HC = C + 4 HC – H + HH – H – Hc – C – (HC – H) × 6
= (606.10 + 4 × 410.5 + 431.37 – 336.49 – 6 × 410.5) kJ mol–1
= – 120.0 kJ mol–1
22. Bond dissociaton enthalpy of H2, Cl2 and HCl are 434, 242 and 431 kJ mol–1 respectively. Enthalpy of formation
of HCl is [AIPMT (Prelims)-2008]
(1) 245 kJ mol–1 (2) 93 kJ mol–1 (3) –245 kJ mol–1 (4) –93 kJ mol–1
Sol. Answer (4)
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168 Thermodynamics Solutions of Assignment (Set-2)
26. Given that bond energies of H–H and Cl – Cl are 430 kJ/mol and 240 kJ/mol respectively and fH of HCl is –90
kJ/mol. Bond enthalpy of HCl is [AIPMT (Prelims)-2007]
(1) 245 kJ mol–1 (2) 2909 kJ mol–1
(3) 380 kJ mol–1 (4) 425 kJ mol–1
Sol. Answer (4)
27. Identify the correct statement for change of Gibbs energy for a system (Gsystem) at constant temperature and
pressure [AIPMT (Prelims)-2006]
(1) If Gsystem > 0, the process is spontaneous
(2) If Gsystem = 0, the system has attained equilibrium
(3) If Gsystem = 0, the system is still moving in a particular direction
(4) If Gsystem < 0, the process is not spontaneous
Sol. Answer (2)
28. Assume each reaction is carried out in an open container. For which reaction will H = E?
[AIPMT (Prelims)-2006]
(1) H2(g) + Br2(g) 2HBr(g) (2) C(s) + 2H2O(g) 2H2(g) + CO2(g)
(3) PCl5(g) PCl3(g) + Cl2(g) (4) 2CO(g) + O2(g) 2CO2(g)
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Solutions of Assignment (Set-2) Thermodynamics 169
Sol. Answer (1)
H 30000 J mol1
or, T = = 285.7 K
S 105 J K 1 mo1
30. The enthalpy of combustion of H2, cyclohexene (C6H10) and cyclohexane (C6H12) are – 241, –3800 and –3920
kJ per mol respectively. Heat of hydrogenation of cyclohexene is [AIPMT (Prelims)-2006]
(1) – 121 kJ per mol (2) + 121 kJ per mol (3) + 242 kJ per mol (4) – 242 kJ per mol
Sol. Answer (1)
32. Which of the following pairs of a chemical reaction is certain to result in a spontaneous reaction ?
3AIPMT (Prelims)-2005]
(1) Exothermic and decreasing disorder (2) Endothermic and increasing disorder
(3) Exothermic and increasing disorder (4) Endothermic and decreasing disorder
Sol. Answer (3)
A chemical reaction is certainly spontaneous
if H < 0 and S > 0
for which G < 0 at all temperature.
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170 Thermodynamics Solutions of Assignment (Set-2)
34. Which reaction, with the following values of H, S, at 400 K is spontaneous and endothermic?
(1) H = –48 kJ; S = + 135 J/K (2) H = –48 kJ; S = – 135 J/K
(3) H = +48 kJ; S = + 135 J/K (4) H = +48 kJ; S = – 135 J/K
Sol. Answer (3)
∵ G = H – TS
= + 48 kJ – 400 × 135 J K–1 (∵ Reaction has to be endothermic)
= (+ 48000 – 54000) J = – 6000 J
G < 0
1
(ii) C(graphite) + O (g) CO(g); rH° = y kJ mol–1
2 2
1
(iii) CO (g) + O (g) CO2(g); rH° = z kJ mol–1
2 2
Based on the above equations, find out which of the relationship given below is correct:
(1) x = y – z (2) z=x+y (3) x=y+z (4) y = 2z – x
Sol. Answer (3)
Subtracting equation (ii) from (i), we get
1
CO O2 CO2 ; H x y kJ
2
Also, H = z kJ mol–1
x–y=z
or, x = (y + z)
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Solutions of Assignment (Set-2) Thermodynamics 171
36. Following reaction occurring in an automobile 2C8H18(g) + 25O2(g) 16CO2(g) + 18H2O (g). The sign of H,
S and G would be
(1) –, +, + (2) +, +, – (3) +, –, + (4) –, +, –
Sol. Answer (4)
For the reaction, ng = 18 + 16 – 25 – 2 = + 7
S = positive
It is a combustion reaction, H = negative
G is negative, H is negative and S is positive.
37. When 5 litres of a gas mixture of methane and propane is perfectly combusted at 0°C and 1 atmosphere, 16
litre of oxygen at the same temperature and pressure is consumed. The amount of heat released from this
combustion in kJ (Hcomb (CH4) = 890 kJ mol–1, Hcomb (C3H8) = 2220 kJ mol–1) is
(1) 32 (2) 38 (3) 317 (4) 477
Sol. Answer (3)
Let volume of methane be x L
volume of propane be (5 – x) L
For methane,
2
Moles of propane combusted = mol
22.4
2
Energy due to propane combusted = 2220 kJ
22.4
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172 Thermodynamics Solutions of Assignment (Set-2)
⎛ 3 2 ⎞
= ⎜ 890 2220 ⎟ kJ
⎝ 22.4 22.4 ⎠
1
= 3 890 4440 kJ
22.4
1
= 2670 4440 kJ = 317.41 kJ
22.4
38. If enthalpies of formation for C2H4(g), CO2(g) and H2O(l) at 25°C and 1 atm pressure are 52, –394 and –286
kJ/mol respectively, then enthalpy of combustion of C2H4(g) will be
(1) + 14.2 kJ/mol (2) + 1412 kJ/mol
(3) – 141.2 kJ/mol (4) – 1412 kJ/mol
Sol. Answer (4)
2 C s O2 g CO2 g ; H2 …(1)
⎛ 1 ⎞
2 ⎜ H2 O2 g H2O g ; H3 ⎟ …(2)
⎝ 2 ⎠
Also, we have,
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Solutions of Assignment (Set-2) Thermodynamics 173
40. Given that C + O2 CO2, H° = –x kJ
2CO + O2 2CO2, H° = –y kJ
What is heat of formation of CO?
y 2x 2x y
(1) (2) 2x – y (3) y – 2x (4)
2 2
Sol. Answer (1)
1
C s O2 CO ; Hr
2
C O2 CO2 ; H x kJ
1 y
CO2 CO O2 ; H kJ
2 2
Adding, we get
1 y y 2x
C O2 CO : Hr x
2 2 2
42. One mole of an ideal gas at 300 K is expanded isothermally from an initial volume of 1 litre to 10 litres. The E for
this process is (R = 2 cal. Mol–1K–1)
(1) 1381.1 cal (2) Zero (3) 163.7 cal (4) 9 L atm
Sol. Answer (2)
The process is isothermal, T = 0 and, U T
U = 0
43. In the reaction : S + 3/2 O2 SO3 + 2x kcal and SO2 + 1/2 O2 SO3 + y kcal, the heat of formation of
SO2 is
(1) (2x + y) (2) (x – y) (3) (x + y) (4) (y – 2x)
Sol. Answer (4)
S O2 SO2 : H
3
Given : S O2 SO3 : H1 2x kcal
2
1
and, SO3 SO2 O2 : H2 y kcal
2
Adding, S O2 SO2 : H H1 H2 y 2x kcal
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174 Thermodynamics Solutions of Assignment (Set-2)
44. At 27°C latent heat of fusion of a compound is 2930 J/mol. Entropy change is
(1) 9.77 J/mol·K (2) 10.77 J/mol·K (3) 9.07 J/mol·K (4) 0.977 J/mol·K
Sol. Answer (1)
46. Change in enthalpy for reaction, 2H2O2 (l ) 2H2O (l ) +O2 (g) if heat of formation of H2O2(l ) and H2O(l ) are –188 and
–286 kJ/mol respectively, is
(1) –196 kJ/mol (2) +196 kJ/mol (3) +948 kJ/mol (4) –948 kJ/mol
Sol. Answer (1)
2 H2O2 H2 O2 ; – H1 188 kJ mol1
⎛ 1 ⎞
and 2 ⎜ H2 O2 H2O ; H2 – 286 kJ mol1 ⎟
⎝ 2 ⎠
Adding, we get
2H2O2 2H2O O2 ; Hr 2 2 2 – 1
= [– 286 × 2 + 2(188)] kJ
= (– 572 + 376) kJ = – 196 kJ
47. When 1 mol of gas is heated at constant volume temperature is raised from 298 to 308 K. Heat supplied to
the gas is 500 J. Then which statement is correct?
(1) q = U = –500 J, w = 0 (2) q = U = 500 J, w = 0
(3) q = w = 500 J, U = 0 (4) U = 0, q = w = –500 J
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Solutions of Assignment (Set-2) Thermodynamics 175
Sol. Answer (2)
∵ Volume is constant
V = 0
– pex + V = 0
w=0
As per 1st law of thermodynamics,
U = q + w = q = +500 J
1
48. Enthalpy of CH4 + O CH3OH is negative. If enthalpy of combustion of CH4 and CH3OH are x and y
2 2
respectively. Then which relation is correct?
(1) x > y (2) x < y
(3) x = y (4) x y
Sol. Answer (1)
1
CH4 O2 CH3 OH ; H 0
2
Given:
3
CH3 OH O2 CO2 2 H2O ; Hr y
2
3
CO2 2H2O CH 3 OH O2 ; H' y …(2)
2
Adding (1) and (2), we get
1
CH4 O2 CH3 OH ; H x y
2
We know, H < 0
x–y<0
∵ |x|>|y|
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176 Thermodynamics Solutions of Assignment (Set-2)
50. In a closed insulated container a liquid is stirred with a paddle to increase the temperature which of the following
is true?
(1) E = W 0, q = 0 (2) E = W = q 0
(3) E = 0, W = q 0 (4) W = 0, E = q 0
Sol. Answer (1)
Since container is insulated,
q=0
According to 1st Law,
U = q + W = W 0 [work is done]
51. 2 mole of ideal gas at 27°C temperature is expanded reversibly from 2 lit. to 20 lit. Find entropy change
(R = 2 cal/mol K)
(1) 92.1 (2) 0 (3) 4 (4) 9.2
Sol. Answer (4)
We know,
V2
S = 2.303 nR log
V1
Given: V2 = 20 L ; V1 = 2 L
n = 2 mol., R = 2 cal mol–1 K–1
20
S = 2.303 × 2 mol × 2 cal mol–1 K–1 × log = 9.2 cal K–1
2
52. Heat of combustion for C(s), H 2 (g) and CH 4 (g) are –94, –68 and –213 kcal/mol, then H for
C(s) + 2H2(g) CH4(g) is
(1) –17 kcal (2) –111 kcal (3) –170 kcal (4) –85 kcal
Sol. Answer (1)
⎛ 1 ⎞
2 ⎜ H2 O2 H2O ; H2 ⎟ …(2)
⎝ 2 ⎠
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Solutions of Assignment (Set-2) Thermodynamics 177
53. For the reaction, C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l) at constant temperature, H – E is
(1) + RT (2) – 3RT (3) + 3RT (4) – RT
Sol. Answer (2)
For the reaction,
ng = 3 – (5 + 1) = – 3
H = U + ngRT
H – U = –3RT
54. What is the entropy change (in JK–1 mol–1) when one mole of ice is converted into water at 0°C? (The enthalpy
change for the conversion of ice to liquid water is 6.0 kJ mol–1 at 0°C)
(1) 20.13 (2) 2.013 (3) 2.198 (4) 21.98
Sol. Answer (4)
55. For which one of the following equations is Hreact equal to Hf for the product?
56. Standard enthalpy and standard entropy changes for the oxidation of ammonia at 298 K are
–382.64 kJ mol–1 and –145.6 J mol–1, respectively. Standard Gibb’s energy change for the same reaction at
298 K is
(1) –221.1 kJ mol–1 (2) –339.3 kJ mol–1 (3) –439.3 kJ mol–1 (4) –523.2 kJ mol–1
Sol. Answer (2)
G = H – TS
⎡ ⎛ 145.6 ⎞ ⎤
= ⎢ 382.64 298 K ⎜ 1000 ⎟ ⎥ kJ mol–1
⎣ ⎝ ⎠⎦
= – 339.3 kJ mol–1
57. Considering entropy (S) as a thermodynamic parameter, the criterion for the spontaneity of any process is
(1) Ssystem + Ssurroundings > 0 (2) Ssystem – Ssurroundings > 0
(3) Ssystem > 0 only (4) Ssurroundings > 0 only
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178 Thermodynamics Solutions of Assignment (Set-2)
58. The work done during the expansion of a gas from a volume of 4 dm3 to 6 dm3 against a constant external
pressure of 3 atm is (1 L atm = 101.32 J)
(1) –6 J (2) –608 J
(3) +304 J (4) –304 J
Sol. Answer (2)
We know,
w = – pext V
= – 3 atm (6 L – 4 L )
= – 3 × 2 L atm
= – 6 × 101.32 J
= – 607.92 J
59. The enthalpy of hydrogenation of cyclohexene is –119.5 kJ mol–1. If resonance energy of benzene is –150.4
kJ mol–1, its enthalpy of hydrogenation would be
(1) –358.5 kJ mol–1 (2) –508.9 kJ mol–1
(3) –208.1 kJ mol–1 (4) –269.9 kJ mol–1
Sol. Answer (3)
Enthalpy of hydrogenation of cyclohexene = – 119.5 kJ mol–1
Expected enthalpy of hydrogenation of benzene = (– 119.5 × 3) kJ mol–1
non-resonated benzene
Eres
resonated benzene
Energy
E
cyclohexane
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Solutions of Assignment (Set-2) Thermodynamics 179
G° for the following reaction
2ZnS + 3O2 2ZnO + 2SO2 is
(1) –1462 J (2) –1317 J
(3) –501 J (4) –731 J
Sol. Answer (4)
Given:
2 Zn O2 ZnO ; G – 616 J
2 ZnS 2 Zn S2 ; G 293 J
S2 2 O2 2 SO2 ; G 408 J
Adding, we get
SECTION - D
Assertion - Reason Type Questions
1. A : Cdiamond Cgraphite
H and U are same for this reaction.
R : Entropy increases during the conversion of diamond to graphite.
Sol. Answer (2)
For the reaction, ng = 0
H = U
Also, graphite is more disordered because of sp2 hybridization and electrons.
S is +ve
q
Specific heat C = m T
q Extensive
Intensive
m Extensive
q
Heat capacity, S =
T
∵ q is extensive
S is also extensive
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180 Thermodynamics Solutions of Assignment (Set-2)
4. A : Enthalpy of neutralisation of 1 equivalent each of HCl and H2SO4 with NaOH is same.
R : Enthalpy of neutralisation is always the heat evolved when 1 mole acid is neutralised by a base.
Sol. Answer (3)
1 eq of strong acid and strong base gives out – 57.1 kJ g eq–1
Enthalpy of neutralisation is heat evolved when 1 g equivalent of acid reacts with 1 g equivalent of base.
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Solutions of Assignment (Set-2) Thermodynamics 181
9. A : Total enthalpy change of a multistep process is sum of H1 + H2 + H3 + .....
R : When heat is absorbed by the system, the sign of q is taken to be negative.
Sol. Answer (3)
∵ H is a state function, So for multistep process,
H = H1 + H2 + H3 + ……
Also, when heat is absorbed by the system, q is +ve.
1
H2 O2 H2O ; Hf
2
Hf = (B.E.)reactants – (B.E.)products
Hf = – (Hf)reactants + (Hf)products
Comparing, (Hf) = – B.E.
12. A : The energy of the universe is constant, whereas the entropy of the universe is continuously increasing.
R : For spontaneous process S > 0.
Sol. Answer (2)
For universe, energy is constant while
S > 0
Also, for a spontaneous process,
Suniverse > 0
13. A : A non-spontaneous process becomes spontaneous when coupled with a suitable spontaneous reaction.
R : The overall free energy of coupled spontaneous reaction is negative.
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182 Thermodynamics Solutions of Assignment (Set-2)
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