(Physical Chemistry) THERMODYNAMICS - 02

EXERCISE # (O-I)
Carnot cycle and 2nd law of thermodynamics
1. The maximum efficiency of a heat engine operating between 100°C and 25°C is :-
(A) 20.11% (B) 22.2% (C) 25.17% (D) 30%
2. A heat engine operating between 227°C and 27°C absorbs 2 Kcal of heat from the 227°C
reservoir reversibly per cycle. The amount of work done in one cycle is :-
(A) 0.4 Kcal (B) 0.8 Kcal (C) 4 Kcal (D) 8 Kcal
3. A reversible heat engine A (based on carnot cycle) absorbs heat from a reservoir at 1000 K and
rejects heat to a reservoir at T2. A second reversible engine B absorbs, the same amount of heat
as rejected by the engine A, from the reservoir at T2 and rejects energy to a reservoir at 360K. If
the efficiencies of engines A and B are the same then the temperature T2 is :-
(A) 680 K (B) 640 K (C) 600 K (D) 800 K
Entropy calculation and S
4. Considering entropy (S) as a thermodynamic parameter, the criterion for the spontaneity of any
process is :-
(A) Ssystem – Ssurroundings > 0 (B) Ssystem > 0 only
(C) Ssurroundings > 0 only (D) Ssystem + Ssurroundings > 0
5. 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) :-
(A) 92.1 (B) 0 (C) 4 (D) 9.2
6. The entropy changes when two moles of ideal monoatomic gas are heated from 200 to 300° C
reversibly and isochorically :-
3  300  5  573   573  3  573 
(A) R ln   (B) R ln   (C) 3R ln   (D) R ln  
2  200  2  273   473  2  473 
7. When one mole of an ideal gas is compressed to half to its initial volume & simultaneously
heated to twice its initial temperature. The change in entropy (S) of gas is :
(A) Cvln2 (B) Cpln2 (C) Rln2 (D) (Cv –R) ln2
8. The change in entropy of 2 moles of an ideal gas upon isothermal expansion at 243.6 K from 20
litre until the pressure becomes 1 atm, is :-
(A) 1.385 cal/K (B) – 1.2 cal/K (C) 1.2 cal/K (D) 2.77 cal/K

9. Pressure of 10 moles of an ideal gas is changed from 2 atm to 1 atm against constant external
pressure without change in temperature. If surrounding temperature (300 K) and pressure
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(1 atm) always remains constant then calculate total entropy change (Ssystem + Ssurrounding) for
given process.
(A) 56 J/K (B) 14 J/K (C) 16 J/K (D) 20 J/K
10. An isobaric process having one mole of ideal gas has entropy change 23.03 J/K for the
temperature range 27°C to 327°C. What would be the molar specific heat capacity (CV) ?
10 10
(A) J/K mol (B) – 8.3 J/ K mol
log 2 log 2
(C) 10 x log2 J/K mol (D) 10 log2 + 8.3 J/K mol
11. When two equal sized pieces of the same metal at different temperatures Th (hot piece) and Tc
(cold piece) are brought into thermal contact and isolated from it's surrounding. The total
change in entropy of system is given by ?
Tc + Th T2 ( Tc + Th )
2
( Tc + Th )
2

(A) C ln (B)C ln (C) C ln (D) C ln

2Tc T1 2Th .Tc 4Th .Tc

Entropy change for phase change

12. If Hvaporisation of substance X() (molar mass : 30 g/mol) is 300 J/g at it's boiling point 300 K,

then molar entropy change for reversible condensation process is :-

(A) 30 J/mol.K (B) –300 J/mol.K (C) –30 J/mol.K (D) 300 J/mol.K
13. For the liquid A whose normal boiling point is 300K, Suniv for the reaction at one atm and
300K is-
A(l) ⎯⎯⎯
1atm
300K
→ A(g) ;

Vaporisation = 60kJ / mol at 1atm & 300K

(A) zero
(B) –2 J/mol-K
(C) 200 J/mol-K
(D) –200 J/mol-K
Physical significance of entropy, disorder
14. When two gases are mixed the entropy :–
(A) Remains constant (B) Decreases (C) Increases (D) Becomes zero
15. For the process, CO2(s) ⎯→ CO2(g) :
(A) Both H and S are +ve (B) H is negative and S is +ve
(C) H is +ve and S is –ve (D) Both H and S are –ve
16. S for the reaction ; MgCO3(s) ⎯→ MgO(s) + CO2(g) will be :
(A) 0 (B) –ve (C) +Ve (D) 

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17. Change in entropy is negative for :-
(A) Bromine ( ) ⎯→ Bromine (g)

(B) C(s) + H2O(g) ⎯→ CO(g) + H2(g)

(C) (C) N2(g, 10 atm, 298 K) ⎯→ N2 (g, 1 atm, 298K)
(D) Fe(at 400 K) ⎯→ Fe(at 300 K)
18. For which reaction from the following, S will be maximum ?
(A) Ca(s) + ½O2(g) ⎯→ CaO(s) (B) CaCO3(s) ⎯→ CaO(s) + CO2(g)
(C) C(s) + O2(g) ⎯→ CO2 (g) (D) N2(g) + O2(g) ⎯→ 2NO(g)
19. For conversion C(graphite) → C(Diamond), the S is :-
(A) Zero (B) Positive (C) Negative (D) Can not be predicted
S for chemical reaction
20. If S0 for H2, Cl2 and HCl are 0.13, 0.22 and 0.19 KJ K–1 mol–1 respectively. The total change in
standard entropy for the reaction, H2 + Cl2 ⎯→ 2HCl is :
(A) 30 JK–1 mol–1 (B) 40 JK–1 mol–1 (C) 60 JK–1 mol–1 (D) 20 JK–1 mol–1
21. Given rSº = –266 and the listed [Sºm values].
Calculate Sº for Fe3O4(s) :
4Fe3O4 (s) [..............] + O2 (g) [205] ⎯⎯
→ 6Fe2O3 (s) [87]
(A) +111.1 (B) +122.4 (C) 145.75 (D) 248.25

Kirchoff's equation : Variation of S and H with Temperature

22. In Haber's process of manufacturing of ammonia :
0
→ 2NH3(g) ;  H 25C = –92.2 kJ
N2(g) + 3H2(g) ⎯⎯

Molecule N2(g) H2(g) NH3(g)

CP JK-1 mol–1 29.1 28.8 35.1

If CP is independent of temperature, then reaction at 100°C as compared to that of 25°C will be :
(A) More endothermic (B) Less endothermic
(C) More exothermic (D) Less exothermic
23. Predict the standard enthalpy of the reaction 2 NO2(g) → N2O4(g) at 100°C. If standard
enthalpy of this reaction is –57.2 kJmol–1 at 25°C ? (Given Cp(NO2) = 37.2 Jmol–1 K–1, Cp(N2O4) =
77.28 J. mol–1 k–1)
(A) – 56.98 Jmole–1 (B) – 76.27 Jmole–1 (C) – 54.23 Jmole–1 (D) – 120 Jmole–1
24. Entropy change for H2O (l) → H2O (s) at 1 atm and – 10°C, is

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[Given : Hfusion (0ºC) = 6000 J/ mol,
 273 
Cp,m (H2O, s) = 36 J/K-mol, Cp,m (H2O, l) = 75 J/K-mol, ln   = 0.04
 263 
(A) –23.47 J/K-mol
(B) –20.41 J/K-mol
(C) 21 J/K-mol
(D) 20.47 J/K-mol
Change in Gibb's free energy (G)
25. Identify the correct statement for change of Gibbs energy for a system (Gsystem) at constant
temperature and pressure.
(A) If Gsystem > 0, the process is spontaneous.
(B) If Gsystem = 0, the system has attained equilibrium.
(C) If Gsystem = 0, the system is still moving in a particular direction.
(D) If Gsystem < 0, the process is not spontaneous.
26. A process must be spontaneous (feasible) if
(A) Entropy of system increases
(B) Energy of system decreases
(C) Gibbs free energy decreases
(D) Entropy of universe increases
27. Heat liberated for an ideal gas undergoing reversible isothermal process is 1200 cal at 300 K.
What will be Gibb’s free energy change for the process
(A) 1200 cal (B) –1200 cal (C) 400 cal (D) –400 cal
28. Which of the following extensive variable will increase during isothermal compression of an
ideal gas-
(A) U (B) S (C) H (D) G
G for chemical reaction
29. Which of the following pairs of a chemical reaction is certain to result in a spontaneous
reaction.?
(A) endothermic and decreasing disorder (B) exothermic and increasing disorder
(C) endothermic and increasing disorder (D) exothermic and decreasing disorder
30. For the reaction at 25°C, X2O4 (l) ⎯⎯
→ 2XO2 (g)

H = 2.1 Kcal and S = 20 cal K–1. The reaction would be

(A) spontaneous (B) non-spontaneous (C) at equilibrium (D) unpredictable

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31. For the reaction at 298 K, 2A + B ⎯⎯
→C
H = 100 kcal and S = 0.050 kcal K–1. If H and S are assumed to be constant over the
temperature range, above what temperature will the reaction become spontaneous ?
(A) 1000 K (B) 1500 K (C) 2000 K (D) 2500 K
32. For the reaction at 300 K
A(g) + B (g) ⎯→ C (g)
U = –3.0 kcal ; S = –10.0 cal/K
value of G is ?
(A) –600 cal (B) –6600 cal (C) –6000 cal (D) –6 cal
33. What can be concluded about the values of H and S from this graph?

+100
( G kJ mol )
–1

+50
0
–50

–100

100 200 300 400 500

Temperature, K

(A) H > 0, S > 0 (B) H > 0, S < 0 (C) H < 0, S > 0 (D) H < 0, S < 0
34. What is the free energy change (G) when 1.0 mole of water at 100°C and 1 atm pressure is
converted into steam at 100°C and 1 atm pressure ?
(A) 80 cal (B) 540 cal (C) 620 cal (D) zero
35. What is the free energy change (G) when 1.0 mole of water at 100°C and 1 atm pressure is
converted into steam at 100°C and 2 atm pressure ?
(A) Zero cal (B) 540 cal (C) 517.13 cal (D) 510 cal
36. G for the conversion of 2 mol of C6H6(l) at 80°C (normal boiling point) to vapour at the same
temperature and a pressure of 0.2 atm is
(A) –9.44 Kcal/mol (B) –2.27 Kcal/mol
(C) –1.135 Kcal/mol (D) zero

H2O(s) ⎯⎯⎯⎯⎯⎯→ H2O(l)

2atm,273.15K
37.
The correct set of sign of G, H and S respectively for the above given process is :
(A) +, +, + (B) +, –, + (C) –, +, + (D) –, –, +

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38. For hypothetical reversible reaction, ½ A2(g) + 3/2 B2 (g) ⎯→ AB3(g) ; H = –20 KJ
if standard entropies of A2, B2 and AB3 are 60, 40 and 50 JK–1 mole–1 respectively. The above
reaction will be in equilibrium at the temperature :-
(A) 400 K (B) 500 K (C) 250 K (D) 200 K
39. Standard entropy of X2, Y2 and XY3 are 60, 40 and 50 JK–1mol–1, respectively. for the reaction,
1 3
X 2 + Y2 → XY3, H = –30 kJ to be at equilibrium, the temperature will be :-
2 2
(A) 1250 K (B) 500 K (C) 750 K (D) 1000 K

40. Following reaction is in equilibrium at 477ºC, 1 N2 (g) + 3 H2 (g) ⎯⎯→ NH3 (g) ; H = – 30 kJ.
2 2
If standard entropy of N2 (g) and NH3 (g) are 60 and 50 J mole–1 K–1 respectively then what is
the standard entropy of H2(g) at same temperature ?
(A) 40 Jmole–1K–1 (B) 60 Jmole–1K–1 (C) 80 Jmole–1K–1 (D) 120 Jmole–1K–1
Variation of G with temperature
41. At 298 K, H°combustion (sucrose) = –5737 KJ/mol & G°combustion (sucrose) = –6333 KJ/mol.
Estimate additional non-PV work that is obtained by raising temperature to 310 K. Assume
rCP = 0 for this temperature change
(A) 0 (B) 2 kJ/mol (C) 24 kJ/mol (D) 23.07 kJ/mol

42. For the hypothetical reaction, A2(g) + B2(g) 2AB(g)

rG and rS are 20 kJ/mole and –20 JK–1 mol–1 respectively at 200 K.
If rCp is 20 JK–1 mol–1 then rH at 400 K is :-
(A) 20 kJ/mole (B) 7.98 kJ/mole (C) 28 kJ/mole (D) None of these
G and non PV work
43. Combustion of sucrose is used by aerobic organisms for providing energy for the life sustaining
processes. If all the “capturing” of energy from the reaction is done through electrical process
(non– PV work) then calculate maximum available energy which can be captured by combustion
of 3.42 gm of sucrose.
Given : Hcombustion (sucrose) = – 6000 kJ mol–1
Scombustion = 180 J/Kmol & Body temperature is 300 K.
(A) 60 kJ (B) 59.46 kJ (C) 0.54 kJ (D) 60.54 kJ
Thermodynamic and equilibrium constant
44. The correct relationship between free energy change in a reaction and the corresponding
equilibrium constant K is :-
(A) – G° = RT ln K (B) G = RT ln K (C) – G = RT ln K (D) G° = RT ln K
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45. The value of G° for a reaction in aqueous phase having Kc= 1, would be:
(A) –RT (B) –1 (C) 0 (D) + RT
46. If G° > 0 for a reaction then :
(A) KP > 1
(B) KP < 1
(C) The products predominate in the equilibrium mixture
(D) KP = 1

47. For the reaction takes place at certain temperature NH4HS(s) NH3(g) + H2S(g), if

equilibrium pressure is X bar, then rG° would be :-

(A) – 2 RT ln X (B) – RT ln (X – ln2)
(C) – 2 RT (ln X–ln 2) (D) None of these

48. For a reaction A(g) B(g) at equilibrium, the partial pressure of B is found to be one fourth

of the partial pressure of A. The value of G° of the reaction A(g) B(g) is

(A) RT n 4 (B) – RT n 4 (C) RT log 4 (D) – RT log 4

49. What is rG(KJ/mole) for synthesis of ammonia at 298 K at following sets of partial pressure :

N2(g) + 3H2(g) 2NH3(g) ; rG° = – 33 kJ/mole.

[Take R = 8.3 J/K mole, log 2 = 0.3 ; log 3 = 0.48]

Gas N2 H2 NH3
Pressure (atm) 1 3 0.02
(A) + 6.5 (B) – 6.5 (C) + 60.5 (D) – 60.5
TS diagram
50. Efficiency of reversible cycle show will be

(A) 33.33% (B) 56% (C) 66.6% (D) 16.7%

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EXERCISE # (S-I)
Carnot cycle and 2nd law of thermodynamics
1. A Carnot cycle has an efficiency of 40%. Its low temperature reservoir is at 70C. What is the
temperature of source ?
2. A heat engine absorbs 760 kJ heat from a source at 380K. It rejects (i) 650 kJ, (ii) 560 kJ,
(iii) 504 kJ of heat to sink at 280K. State which of these represent a reversible, an irreversible
and an impossible cycle.
3. The efficiency of a cannot cycle is 1/6. On decreasing the temperature of the sink by 65°C, the
efficiency increases to 1/3. Calculate the temperature of source and sink.
Entropy and S Calculations
4. Find the change in entropy of 1 mole of O2 gas (CV = 5/2 R), when it is
(a) heated from 300 K to 400 K isobarically
(b) heated from 300 K to 400 K isochorically (Given : ln 3 = 1.1)
5. 5 moles of an ideal gas is expended isothermally from 10 bar to 2 bar at 27°C against a constant
external pressure of 2 bar. Calculate Ssys, Ssurr and Suniv.
6. One mole of an ideal monoatomic gas (initial temperature = 127°C) is expended adiabatically
and reversibly from 5 m3 to 20 m3 . Calculate Ssys, Ssurr and Suniv.
7. One mole of an ideal monoatomic gas (initial temperature = 127°C) is expended adiabatically
from 20 bar to 1 bar against a constant external pressure of 1 bar. Calculate Ssys, Ssurr and
Suniv.
8. 2 moles of an ideal monoatomic gas undergo a reversible process for which P2V = constant. The
gas sample is made to expand from initial volume of 1L to final volume of 4L starting from
initial temperature of 300K. Find the value of Ssys for the above process. Report your answer
as 'X' where Ssys = XRln2.
9. Consider two moles of an ideal monoatomic gas initially at 27°C and 1 atm pressure,
undergoing the following reversible cycle :
(a) Isothermal compression to 2 atm.
(b) Isobaric temperature increase to 127°C.
(c) Return to the initial stage by the different path.
Calculate S for each step.
10. Oxygen is heated from 300 to 600 K at a constant pressure of 1 bar. What is the increases in
molar entropy ? The molar heat capacity in JK–1 mol–1 for the O2 is (Given ln2 = 0.7)
CP = 10 + 10–2T

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11. 100 kJ heat is transferred from a larger heat reservoir at 400 K to another large heat reservoir
at 300 K. Suppose there is no change in temperature due to exchange of heat :

400K 400K

Source Sink

Find (a)Ssource, (b) Ssink and (c) Stotal. Comment on spontaneity of process.]
12. A thermostat was maintained at 370K. For one hour 4.2 kJ of heat leaked out through
thermostat insulation into a room where temperature of air was 300K. If the entropy change of
the air in room is

Entropy Change for phase change

13. One mole of NaCl(s) on melting absorbed 30 KJ of heat and its entropy is increased by 30 JK–1.
What is the melting point of sodium chloride ?
S for Chemical Reaction
14. Calculate the entropy of a substance at 600 K using the following data.
(i) Heat capacity of solid from 0K to normal melting point 200 K
CP,m(s) = 0.035 T JK–1mol–1.
(ii) Enthalpy of fusion = 7.5 kJ mol–1,
(iii) Enthalpy of vaporisation = 30 kJ mol–1,
(iv) Heat capacity of liquid from 200K to normal boiling point 300K
CP,m(l) = 60 + 0.016T JK–1mol–1.
(v) Heat capacity of gas from 300K to 600K at 1atm
CP,m(g) = 50.0 JK–1mol–1.
15. Calculate Sr° at 298K of ;
1
(i) Na(s) + Cl2(g) ⎯→ NaCl(s),
2
1 1
(ii) N2(g) + 2H2(g) + Cl2(g) ⎯→ NH4Cl(s)
2 2

(iii) C(graphite) ⎯→ C(diamond).

The values of S° (JK–1 mol–1 )of Na, Cl2, NaCl, NH4Cl, N2, H2 diamond & graphite are 51, 223, 72,
95, 192, 131, 2.43 & 5.69 JK–1 mol–1 respectively.
16. Find (S)universe (in Joule/mole/K) for a chemical reaction at 300 K given Hº300 K = 75 kJ/mol ;
Sº300 K = 300 J/K

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Kirchoff's equation : Variation of S and H with Temperature
17. The standard enthalpy for the reaction H2(g) + 1/2 O2(g) ⎯→ H2O(l) is –285 kJ at 298K.
Calculate the value of H at 373K. The molar heat capacities at constant pressure (CP) in the
given temperature range of H2(g), O2(g) and H2O(l) are respectively 40, 30 and 75 JK–1 mol–1.
18. Predict the standard reaction enthalpy of 2 NO2(g) → N2O4(g) at 100°C. H° at 25°C is –57.2 kJ.
mol–1 Cp(NO2) = 37.2 J mol–1 K–1 Cp(N2O4) = 77.28 J mol–1 k–1.
Change in Gibb's Free energy (G)
19. Calculate G (in bar-L) when a definite mass of a monoatomic ideal gas at 1 bar & 27ºC is
expanded adiabatically against vacuum from 10 L to 20 L (ln2 = 0.7)
G for Chemical Reaction
20. 5 mole H2O(l) at 373K and 1 atm is converted into H2O(g) at 373K and 5 atm. Calculate G for
this process. [Given : R = 2Cal/K-mol]
21. Calculate the free energy change at 300 K for the reaction;
Br2(l) + Cl2(g) ⎯→ 2BrCl(g). For the reaction H° = 29.3 kJ & the entropies of Br2(l), Cl2(g) &
BrCl(g) at the 300 K are 150, 220, 240 J mol–1K–1 respectively.
22. The entropies of H2(g) and H(g) are 130 and 115 J mol–1K–1 respectively at 298K. Using the data
given below calculate the bond energy of H2(in kJ/mol) :–
H2(g) ⎯→ 2H(g) ; G° = 406 kJ/mol
Variation of G with temperature
23. A liquid freeze into a solid (H = –1000 J/mole) at 200 K and 1 atm, at its normal melting point.
(a) What is the value of G at 200 K?
(b) What is the S value at 200 K?
(c) Will the freezing be spontaneous at 150 K and 1 atm?
(d) What is the sign of G at 250 K and 1 atm?
Assume rCP = 0 for this temperature change
G and non PV work
24. Animals operate under conditions of constant pressure and most of the processes that
maintain life are electrical (in a broad sense). How much energy is available for sustaining this
type of muscular and nervous activity from the combustion of 1 mol of glucose molecules
under standard conditions at 37°C (blood temperature) ? The entropy change is + 182.4 JK–1 for
the reaction as stated.
Hcombustion [glucose] = –2808 kJ

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G and equilibrium constant
25. -D Glucose undergoes mutarotation to -D-Glucose in aqueous solution. If at 298K there is
60% conversion. Calculate G° of the reaction.
-D-Glucose -D-Glucose
26. For the reaction at 298 K
A(g) + B(g) . C(g) + D(g)
H° = –29.8kcal; S° = –0.1 kcal/K
Calculate G° and K.
27. 2A(s) ⎯→ B(g) +2C(g) + 3D(g)
Total pressure developed in closed container by decomposition of A at equilibrium is 12 atm at
727ºC. Calculate |Gº| (in kcal), of the reaction at 727ºC (R = 2cal/mole-K, ln 2 = 0.7, ln3 = 1.1)
Fill your answer as sum of digits (excluding decimal places) till you get the single digit
answer.

28. The equilibrium constant of the reaction 2C3H6(g) C2H4(g) + C4H8(g) is found to fit the

expression
ln K =–1.04 – 1080/T
Calculate the standard reaction enthalpy and entropy at 400 K.
29. Find G of the reaction in calorie at 300 K
A(g) 2B (g) ; K 0p = 10 at 300 K

when partial pressures of A(g) & B(g) are 100 kPa & 1000 kPa respectively
Given : ln 10 = 2.3 ; R = 2 cal/mol-K
30. For the reaction SO2(g) + 1/2 O2(g) SO3(g) H°298 = –98.32 kJ/mole, S°298 = –95.0
J/K/mole. Find the Kp for this reaction at 298 K.

31. Calculate the magnitude of standard entropy change for reaction X Y if Hº = 25 KJ and

Keq is 10–7 at 300 K.

TS Diagram
32. From the given T-S diagram of a reversible Carnot engine, find

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(i) work delivered by engine in one cycle
(ii) heat taken from the source in each cycle.
(iii) Ssink in each cycle.

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EXERCISE # (O-II)
ONLY ONE OPTION IS CORRECT :
1. A heat engine that converts heat into mechanical work involving ideal monoatomic gas
performing following cycle

Calculate the efficiency of the cycle (Use : ln2 = 0.7)

(A) 50 % (B) 23.5 % (C) 32.5 % (D) 52.3%
2. Starting with same initial conditions, an ideal gas expands from volume V1 to volume V2 in three
different paths AB, AC & AD as shown. Compare the entropy change during these expansions

(A) SAB > SAC > SAD

(B) SAB > SAD > SAC
(C) SAC > SAD > SAB
(D) SAD > SAC > SAB
3. An ideal gas with the adiabatic exponent  goes through a process P = Po – V, where Po and  are
positive constants and V is the volume. At what volume will the gas entropy have the maximum
value?
.Po .Po .Po .Po
(A) (B) (C) (D)
(  − 1) (  + 1)  +1  −1
4. Identify the correct statement regarding entropy.
(A) At absolute zero temperature, the entropy of perfectly crystalline substance is +ve.
(B) At absolute zero temp. entropy of perfectly crystalline substance is taken to be zero.
(C) At 0 °C the entropy of a perfectly crystalline substance is taken to be zero.
(D) At absolute zero temperature, the entropy of all crystalline substances is taken to be zero.
5. The value of G°f of gaseous mercury is 31 KJ/mole. At what total external pressure mercury start
1boiling at 25°C. [R = 8.3 J/K mole]
(A) 10–5.44 (B) 10–12.5 (C) 10–6.52 (D) 10–3.12

APNI KAKSHA 13
(Physical Chemistry) THERMODYNAMICS - 02
6. Statement-1 : Net heat absorbed in a cyclic process must always equal to net work done by the
system in the cyclic process.
Statement-2 : Internal energy of system is a function of state.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-
1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
7. Statement-1 : Entropy change in reversible adiabatic expansion of an ideal gas is zero. Because
Statement-2 : The increase in entropy due to volume increase just compensate the decrease in
entropy due to fall in temperature.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-
1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
MORE THAN ONE MAY BE CORRECT :
8. Which of the following statements is correct:
(A) Reversible adiabatic process is iso-entropic process
(B) Ssystem for irreversible adiabatic compression is greater than zero
(C) Ssystem for adiabatic free expansion in zero
(D) Ssurrounding for irreversible isothermal compression is greater than zero
9. Select incorrect statements -
dq
(A) T is always independent of path followed between two points

(B) Entropy of universe is conserved

(C) For a process in isolated system entropy either increases or remain constant
(D) Entropy decreases with increase in temperature at constant V

APNI KAKSHA 14
(Physical Chemistry) THERMODYNAMICS - 02
10. For the cyclic process given below, which of the following relations are CORRECT?
Reversible
1 2
Irreversible

q rev qirr
2 1
(A) S1→2 = S2 − S1 =  (B) S2→1 = S1 − S2 = 
1
T 2
T
2
q rev
1
q  2 q 1
q 
(C) Scycle =  +  irr = 0 (D) Scycle = 0    rev +  irr 
T T  T T 
1 2 1 2

11. The normal boiling point of a liquid ‘A’ is 350 K. Hvap at normal boiling point is 35 kJ/mole.
Pick out the correct statement(s). (Assume Hvap to be independent of pressure).
(A) Svaporisation > 100 J/K mole at 350 K and 0.5 atm
(B) Svaporisation < 100 J/K mole at 350 K and 0.5 atm
(C) Svaporisation < 100 J/K mole at 350 K and 2 atm
(D) Svaporisation = 100 J/K mole at 350 K and 2 atm
12. In isothermal ideal gas compression :
(A) w is + ve (B) H is zero (C) Sgas is + ve (D) G is + ve
13. The normal boiling point of a liquid `X` is 400 K. Which of the following statement is true about
the process
X (l) ⎯⎯
→ X(g)?

(A) at 400 K and 1 atm pressure G = 0 (B) at 400 K and 2 atm pressure G = + ve
(C) at 400 K and 0.1 atm pressure G = – ve (D) at 410 K and 1 atm pressure G = + ve
14. Which of the following statement (s) is/are false :
(A) When (Gsystem) T,P < 0; the reaction must be exothermic
(B) Gsystem is always zero for a reversible process in a closed system
(C) G° for an ideal gas is a function of temperature and pressure
(D) dG = VdP – SdT is applicable for any chemical and phase change

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(Physical Chemistry) THERMODYNAMICS - 02
15. Choose the correct statement (s)
(A) Entropy of system increases when an ideal gas expanded isothermally
(B) All adiabatic processes are iso-entropic (or isentropic) processes
(C) No cyclic process is possible in which the sole result is absorption of heat from a hot
reservoir and its complete conversion into work
(D) Two solid blocks of same material and same mass having different temperature kept in an
isolated system then entropy of system must increase.
16. Choose the correct statement (s)
(A) For phase transformation of liquid water at 1 atm, 373K to water vapour at 1atm, 373K, G
will be zero
1
(B) rS for N2(g) ⎯→ N(g) is positive
2
(C) rH & rS both are +ve for the decomposition of MgCO3(s).
(D) If –76.9° C is the transition temperature for the conversion of P4 (s,) → P4 (s,) and this
phase transition is spontaneous at T < –76.9°C if rS<0
17. Which of the following statement(s) is/are correct :
(A) The entropy of isolated system with P–V work only is always maximized at equilibrium
(B) It is possible for the entropy of close system to decrease substantially in an irreversible
process.
(C) Entropy can be created but not destroyed.
(D) Ssystem is always zero for reversible process in an isolated system

18. The 3rd law of thermodynamics states that entropy of pure and perfect crystalline substances is
0 at 0 K. Which of the following is not true ?
(A) Standard molar entropy of any pure element / compound is greater than 0 at T > 0 K.
(B) Standard molar entropy of all ions in aqueous phase is greater than 0 at T > 0 K (as per
thermodynamic data).
(C) Standard molar entropy of ions are always greater than that of H+ (aq) at any T > 0 K.
(D) Standard molar entropy of ions may be negative (as per thermodynamic data).
19. Select the correct statement(s) -
(A) Hvap at equilibrium pressure & temperature is zero
(B) Gvap at equilibrium pressure & temperature is zero
(C) (Ssys)vap at equilibrium pressure & temperature is zero
(D) (Suniv)vap at equilibrium pressure & temperature is zero

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(Physical Chemistry) THERMODYNAMICS - 02
Paragraph for Question 20 to 21
The reactions whose G° are positive can not take place under standard state conditions.
However, another reaction whose G° is negative can be coupled with the former type of
reaction to give overall spontaneous process.
Consider the given reactions whose G° at 300 K are provided to answer following questions.
A(g) + 3B(g) ⎯→ 2C(g) : G° = +24 kJ/mol ; H° = –24 kJ/mol
3C(g) ⎯→ 2D(g) : G° = –60 kJ/mol ; H° = –84 kJ/mol
All data at 300 K temperature.
20. What is S° at 300 K of reaction (in J/K/mole) :
3A(g) + 9B(g) ⎯→ 4D (g)
(A) –640 (B) –480 (C) +640 (D) –240
21. Assuming H° and S° do not vary with temperature - at what temperature reaction
A(g) + 3B(g) ⎯→ 2C(g) become spontaneous-
(A) 6250 K (B) 625 K (C) 150 K (D) 1000 K
Paragraph for 22 to 23
Thermodynamics stability is often used in chemical reactions to predict extent of reactions or to
predict the preferred product in some reaction. Thermodynamically a more stable substance will
be the one which has lower Gibb’s free energy. In various cases it might be decided on the basis of
enthalpy, however that may not always be true. The thermodynamic data therefore can be used
for predicting stability among isotopes & to decide the possible transformation. Based on this
information & the data given below, answer the questions that follow.
Data:  H f of Sn(white) = 0  H f of Sn(gray) = –2.1 kJ/mole

Sº of Sn(white) = 52 J/K-mole Sº of Sn(gray) = 44 J/K-mole

All above data at 300 K.
Density of Sn(w) = 7.36 g/ml
Density of Sn(g) = 5.769 gm/ml
One such transformation is ‘tin pest’ an allotropic transformation of the element white tin to gray
results in brittleness of tin objects at low temperatures.

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(Physical Chemistry) THERMODYNAMICS - 02
22. Which of the following graph is correct for the allotropic transition Sn(white) → Sn(gray) at 1 bar &
300 K.

(A) (B)

(C) (D)

23. Choose correct option -

(A) both forms exist at all temperature
(B) There will be a contraction in volume as temperature is reduced.
(C) At 200 K, only gray tin exists.
(D) At 300 K, only white tin exists.
MATCH THE COLUMN :
24. Column–I Column-II
(A) Reversible adiabatic compression (P) Ssystem > 0
(B) Reversible vaporisation (Q) Ssystem < 0
(C) Adiabatic free expansion of ideal gas in vacuum (R) Ssurroundig < 0
(D) Dissociation of CaCO3(s) ⎯→ CaO(s) + CO2(g) (S) Ssurrounding = 0
25. Column-I Column-II
(Related to process) (Related to system)
(A) Fusion at melting point (P) G = 0
(B) Vapourisation at boiling point (Q) G < 0
(C) Condensation at triple point (R) S > 0
(D) Melting at normal boiling point (S) H  U

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(Physical Chemistry) THERMODYNAMICS - 02
26. Match the column :
Column-I Column-II
P2
(P) – (G)T,P (1) nRT ln
P1
(Q) Work done in irreversible isothermal ideal gas (2) non-PV work done by system
expansion
P2
(R) G for reversible isothermal expansion of (3) –nR ln
P1
an ideal gas.
 nRT nRT 
(S) Sgas for isothermal expansion of an ideal gas. (4) – Pext  − 
 P2 P1 

Code:
P Q R S
(A) 2 4 1 3
(B) 4 2 3 1
(C) 3 1 2 4
(D) 2 3 1 4
27. Match the Column :
Column-I Column-II
(P) H2O (l, 1 atm, 363 K) → H2O (g, 1 atm, 363 K) (1) rS > 0
(Q) H2O (s, 1 atm, 373 K) → H2O (g, 1 atm, 373 K) (2) rG > 0
(R) H2O (l, 1 atm, 273 K) → H2O (s, 1 atm, 273 K) (3) rH < 0
(S) H2O (s, 1 atm, 353 K) → H2O (l, 1 atm, 353 K) (4) rU > 0
Code:
P Q R S
(A) 2 4 1 3
(B) 4 2 3 1
(C) 2 1 3 4
(D) 4 3 1 2

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(Physical Chemistry) THERMODYNAMICS - 02
EXERCISE # (S-II)
INTEGER
1. A reversible cyclic process involves 6 steps. In step-1, 3 system absorb 500 J, 800 J of heat from a
heat reservoir at temperature 250K & 200K respectively. Step 2, 4, 6, are adiabatic such that the
temperature of one reservoir changes to that of next. Total work done by the system in whole
cycle is 700 J. Find the temperature during step 5 if it exchange heat from a reservoir at
temperature T5
2. 1 mole of ideal monoatomic gas in heated by supplying 5 kJ heat from a reservoir maintained at
400 K from 300 K to 400 K. In the process volume of gas increased from 1 L to 10 L. Find Stotal
(in J/K -mol) in the process
4
Use : ln   = 0.3, ln 10 = 2.3, R = 8.3 J/K-mol and ln x = 2.3 log x
3
3. One mole of ideal monoatomic gas was taken through reversible isochoric heating from 100 K to
1000 K. Calculate Ssystem, Ssurr, and Stotal in
(i) when the process carried out reversibly
(ii) when the process carried out irreversibly (one step)
4. Heat capacity of a solid A(s), given be aT3 in vicinity at absolute zero. Taking heat capacity to be a
T3 from 0 K to 10 K, b from 10 K, 10 K to normal M.P. at 150 K and c from 150 K to 200 K, find the
absolute entropy of A (l) at 200 K.
Given; a = 0.5 × 10–3 J (K mole)
b = 15 J/(K mole)
c = 20 J/(K mole)
Hfusion = + 30 KJ/ mole
5. Fixed amount of an ideal mono atomic gas contained in a sealed rigid vessel (V = 24.6 litre) at 1.0

bar is heated reversibly form 27oC to 127oC. Determine change in Gibb's energy (in Joule) if

entropy of gas S = 10 + 10–2 T (J/K)

6. The enthalpy change for vapourisation of liquid 'A' at 200 K and 1 atm is 22 kJ/mol. Find out
Svaporisation for liquid 'A' at 200 K? The normal Boiling point of liquid 'A' is 300 K ?
A (l) [200 K 1 atm] → A (g) [200 K 1 atm] Svap = ?
Given: Cp,m (A(g)) = 30J /mol K
Cp,m (A(l)) = 40J / mol K
Use : ln(3/2) = 0.405

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(Physical Chemistry) THERMODYNAMICS - 02
7. At 300 K, H°combustion (sucrose) = – 5000 KJ/mol & G°combustion(sucrose) = –6000 KJ/mol.
Estimate additional non-PV work that is obtained by raising temperature to 309 K. Assume rCP =
0 for this temperature change.
8. The KP for reaction A + B C + D is 1.34 at 60°C and 6.64 at 100°C. Determine the standard
free energy change of this reaction at each temperature and H° for the reaction over this range
of temperature ?
9. Calculate the equilibrium pressure (in Pascal) for the conversion of graphite to diamond at 25°C. The
densities of graphite and diamond may be taken to be 2.20 and 3.40 g/cc respectively independent of
pressure.
Given : G° (C (graphite) → C(diamond) = 2900 J/mol.
10. Select the conditions which represent the criteria for spontaneity of a process in a closed system,
from the following given conditions.
Serial Number conditions
1. (dG) P,T  0

2. (S) universe  0

3. (dU)S,V  0

4. (dH)S.P  0

5. (dS) U,V  0

6. (dS) H,P  0

(Answer by adding the serial numbers of the correct conditions.)

APNI KAKSHA 21
(Physical Chemistry) THERMODYNAMICS - 02
EXERCISE (JEE-MAIN)
1. The standard entropy change for the reaction 4Fe(s) + 3O2 ( g) → 2Fe2 O3 ( s) is −550JK −1

at 298 K. [JEE Main, 2022]

[Given : The standard enthalpy change for the reaction is −165 kJ mol−1. The temperature in K
at which the reaction attains equilibrium is . (Nearest Integer)

2. Given below are two statements: One is labelled as [JEE Main, 2022]
Assertion 𝐀 and the other is labelled as Reason 𝐑
Assertion A : The reduction of a metal oxide is easier if the metal formed is in liquid state than
solid state.

Reason 𝑅 : The value of Δ𝐺 Θ becomes more on negative side as entropy is higher in liquid state
than solid state.

In the light of the above statements. Choose the most appropriate answer from the options
given below
(A) Both A and R are correct and R is the correct explanation of A
(B) Both A and R are correct but R is NOT the correct explanation of A
(C) A is correct but R is not correct
(D) A is not correct but R is correct

3. Which of the following relation is not correct? [JEE Main, 2022]

(A) H = U – PV (B) U = q + W
(C) Ssys + Ssurr  0 (D) G = H – TS
4. For combustion of one mole of magnesium in an open container at 300 K and 1 bar pressure,
CHΘ = –601.70 kJ mol–1, the magnitude of change in internal energy for the reaction is _____ kJ.
(Nearest integer)
(Given : R = 8.3 J K–1 mol–1) [JEE Main, 2022]
5. For the reaction 2NO2 ( g) ⇌ N2 O4 ( g), when ΔS = −176.0JK −1 and ΔH = −57.8 kJ mol−1, the
magnitude of ΔG at 298 K for the reaction is kJmol−1. (Nearest integer) [JEE Main, 2021]

6. For a chemical reaction 𝐴 + 𝐵 ⇌ 𝐶 + 𝐷(Δ𝑟 H ⊖ = 80 kJ mol−1 ) the entropy change Δ𝑟 S ⊖

depends on the temperature T (in K) as Δ𝑟 𝑆 ⊖ = 2𝑇(𝐽 K −1 mol−1 )
Minimum temperature at which it will become spontaneous is K. [JEE Main, 2021]

7. For water vap H = 41 kJ mol–1 at 373 K and 1 bar pressure. Assuming that water vapour is an
ideal gas that occupies a much larger volume than liquid water, the internal energy change
during evaporation of water is_____kJ mol–1 S[Use : R = 8.3 J mol–1 K–1]
[JEE Main, August 2021]
8. Select the correct option :
(1) Entropy is function of temperature and also entropy change is function of temperature.
(2) Entropy is a function of temperature & entropy change is not a function of temperature.
APNI KAKSHA 22
(Physical Chemistry) THERMODYNAMICS - 02
(3) Entropy is not a function of temperature & entropy change is a function of temperature.
(4) Both entropy & entropy change are not a function of temperature. [Jee Main, 2020]

9. For a dimerization reaction, [Jee Main, 2020]

2 A( g) → A2 ( g)

at 298 K, ΔU ∘ = −20kJmol−1 , ΔS ∘ = −30

JK −1 mol−1, then the ΔG∘ will be J.

10. For the reaction; A(l) → 2B(g) U = 2.1 kcal, S = 20 cal K–1 at 300 K.
Hence G in kcal is___________: [Jee Main, 2020]
11. For one mole of an ideal gas, which of these statements must be true? [Jee Main, 2020]

(A) U and H each depends only on temperature

(B) Compressibility factor z is not equal to 1

(C) CP, m – CV, m = R

(D) dU = CVdT for any process

(1) (A) and (C) (2) (B), (C) and (D)

(3) (A), (C) and (D) (4) (C) and (D)

12. A process will be spontaneous at all temperatures if: [JEE-MAIN 2019 (April)]
(1) H < 0 and S > 0 (2) H > 0 and S < 0
(3) H > 0 and S > 0 (4) H < 0 and S < 0
13. Enthalpy of sublimation of iodine is 24 cal g–1 at 200ºC. If specific heat of I2(s) and I2(vap) are
0.055 and 0.031 cal g–1 K–1 respectively, then enthalpy of sublimation of iodine at 250ºC in cal
g–1 is: [JEE-MAIN 2019 (April)]
(1) 2.85 (2) 22.8 (3) 11.4 (4) 5.7
14. The INCORRECT match in the following is: [JEE-MAIN 2019 (April)]
(1) G0 > 0, K < 1 (2) G0  0, K < 1 (3) G0 < 0, K > 1 (4) G0 = 0, K = 1
15. The entropy change associated with the conversion of 1 kg of ice at 273 K to water vapours at
383 K is : (Specific heat of water liquid and water vapour are 4.2 kJ K–1kg–1 and 2.0 kJ K–1kg–1;
heat of liquid fusion and vapourisation of water are 334 kJ kg–1 and 2491 kJ kg–1; respectively).
(log 273 = 2.436, log 373 = 2.572, log 383 = 2.583) [JEE-MAIN 2019 (Jan)]
(1) 7.90 kJ kg–1 K–1 (2) 8.49 kJ kg–1 K–1 (3) 9.26 kJ kg–1 K–1 (4) 2.64 kJ kg–1 K–1

APNI KAKSHA 23
(Physical Chemistry) THERMODYNAMICS - 02
16. A process has H = 200 Jmol–1 and S = 40 JK–1mol–1. Out of the values given below, choose
the minimum temperature above which the process will be spontaneous:
[JEE-MAIN 2019 (Jan)]
(1) 12K (2) 20K (3) 4K (4) 5K
17. The process with negative entropy change is: [JEE-MAIN 2019 (Jan)]
(1) Dissolution of iodine in water
(2) Synthesis of ammonia from N2 and H2
(3) Sublimation of dry ice
(4) Dissolution of CaSO4(s) to CaO(s) and SO3(g)
18. Two blocks of the same metal having same mass and at temperature T1 and T2, respectively, are
brought in contact with each other and allowed to attain thermal equilibrium at constant
pressure. The change in entropy, S, for this process is : [JEE-MAIN 2019 (Jan)]
 1

 (T + T ) 2
  (T + T )2 
(1) 2Cp In 1 2
(2) Cp In  1 2 
 T1T2   4T1T2 
 

T +T  T + T 
(3) 2Cp in  1 2  (4) 2Cp In  1 2 
 4T1T2   2T1T2 

19. For the chemical reaction X Y , the standard reaction Gibbs energy depends on
3
temperature T (in K) as : rG° (in kJ mol–1) = 120 – T
8
The major component of the reaction mixture at T is : [JEE-MAIN 2019 (Jan)]
(1) Y if T = 280 K (2) X if T = 315 K (3) Y if T = 300 K (4) X if T = 350 K
20. The reaction,
MgO(s) + C(s) → Mg(S) + CO(g), for which
rH° = + 491.1 kJ mol–1 and rSº = 198.0 JK–1 mol–1, is not feasible at 298 K. Temperature
above which reaction will be feasible is :- [JEE-MAIN 2019 (Jan)]
(1) 2040.5 K (2) 1890.0 K (3) 2480.3 K (4) 2380.5 K

21. For the equilibrium, 2H2O H3O+ + OH–, the value of Gº at 298 K is approximately :

[JEE-MAIN 2019 (Jan)]

(1) –80 kJ mol–1 (2) –100 kJ mol–1 (3) 80 kJ mol–1 (4) 100 kJ mol–1
22. The standard reaction Gibbs energy for a chemical reaction at an absolute temperature T is
given by rGº = A – Bt [JEE-MAIN 2019 (Jan)]

APNI KAKSHA 24
(Physical Chemistry) THERMODYNAMICS - 02
Where A and B are non-zero constants. Which of the following is TRUE about this reaction ?
(1) Exothermic if B < 0 (2) Endothermic if A > 0
(3) Exothermic if A > 0 and B < 0 (4) Endothermic if A < 0 and B > 0
23. Which of the following lines correctly show the temperature dependence of equilibrium
constant, K, for an exothermic reaction ? (JEE MAIN - 2018)

(1) A and D (2) A and B (3) B and C (4) C and D

24. The following reaction is performed at 298 K. (JEE MAIN - 2015)

2NO(g) + O2(g 2NO2(g)

The standard free energy of formation of NO(g) is 86.6 kJ/mol at 298 K. What is the standard
free energy of formation of NO2 (g) at 298 K? (K P = 1.6 × 1012)
ln (1.6 1012 )
(1) 86600 + R(298) ln(1.6×1012) (2) 86600 −
R(298)
(3) 0.5[2×86,600 – R(298) ln (1.6×1012)] (4) R(298)ln (1.6×1012) – 86600
25. The molar heat capacity (Cp) of CD2O is 10 cals at 1000 K. The change in entropy associated
with cooling of 32 g of CD2O vapour from 1000 K to 100 K at constant pressure will be
(D = deuterium, at. mass = 2u) (JEE MAIN -(online) 2014)
(1)– 23.03 cal deg–1 (2) 2.303 cal deg–1 (3) 23.03 cal deg–1 (4) – 2.303 cal deg–1
26. The entropy (Sº) of the following substances are : (JEE MAIN -(online) 2014)
CH4 (g) 186.2 J K–1 mol–1
O2 (g) 205.0 J K–1 mol–1
CO2 (g) 213.6 J K–1 mol–1
H2O (l) 69.9 J K–1 mol–1
The entropy change (Sº) for the reaction
CH4(g) + 2O2(g) → CO2(g) + 2H2O () is:-

(1)–312.5 JK–1 mol–1 (2) – 37.6 JK–1 mol–1

(3) – 108.1 JK–1 mol–1 (4) – 242.8 JK–1 mol–1

APNI KAKSHA 25
(Physical Chemistry) THERMODYNAMICS - 02
27. The incorrect expression among the following is :- (AIEEE - 2012)

(1) K = e–G°/RT
G system
(2) = –T
Stotal
Vf
(3) In isothermal process, Wreversible = – nRT ln
Vi

G system
(4) lnK =
Stotal
28. The entropy change involved in the isothermal reversible expansion of 2 moles of an ideal gas
from a volume of 10 dm3 to a volume of 100 dm3 at 27°C is :- (AIEEE - 2011)
(1) 32.3 J mol–1 K–1 (2) 42.3 J mol–1 K–1 (3) 38.3 J mol–1 K–1 (4) 35.8 J mol–1 K–1

29. For a particular reversible reaction at temperature T, H and S were found to be both +ve. If Te
is the temperature at equilibrium, then reaction would be spontaneous when:– (AIEEE - 2010)
(1) T = Te (2) Te > T (3) T > Te (4) Te is 5 times T
30. In conversion of lime-stone to lime, CaCO3(s) ⎯→ CaO(s) + CO2(g)
The values of H° and S° are +179.1 kJ mol–1 and 160.2 J/K respectively at 298 K and 1 bar.
Assuming that H° and S° do not change with temperature, temperature above which
conversion of limestone to lime will be spontaneous is :– (AIEEE - 2007)
(1) 1008 K (2) 1200 K (3) 845 K (4) 1118 K
31. Identify the correct statement regarding a sponateous process :– (AIEEE - 2007)
(1) For a spontaneous process in an isolated system, the change in entropy is positive
(2) Endothermic processes are never spontaneous
(3) Exothermic processes are always spontaneous
(4) Lowering of energy in the reaction process is the only criterion for spontaneity
32. In a irreversible process taking place at constant T and P and in which only pressure-volume
work is being done the change in Gibbs free energy (dG) and change in entropy (dS) satisfy the
criteria:- (AIEEE - 2003)
(1) (dS)V, E = 0, (dG)T, P = 0 (2) (dS)V, E = 0, (dG)T, P > 0
(3) (dS)V, E < 0, (dG)T, P < 0 (4) (dS)V, E > 0, (dG)T, P < 0
33. The correct relationship between free energy change in a reaction and the corresponding
equilibrium constant KC is :- (AIEEE - 2003)
(1) G° = RT lnKC (2) –G° = RT lnKC
(3) G = RT lnKC (4) –G = RT lnKC
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(Physical Chemistry) THERMODYNAMICS - 02
EXERCISE # (JEE-ADVANCED)
1. One mole of an ideal gas at 900 K, undergoes two reversible processes, I followed by II, as
v
shown below. If the work done by the gas in the two processes are the same, the value of In⁡ v3
2

is ______ . [JEE Adv. 2021]

(U: internal energy, S: entropy, p: pressure, V: volume, R: gas constant)

(Given: molar heat capacity at constant volume, C of the gas is 5/2R )

2. An ideal gas undergoes a reversible isothermal expansion from the state I to state II followed by
a reversible adiabatic expansion from state II to state III. The correct plot(s) representing the
changes from the state I to state III is(are) (p: pressure, V: volume, T: temperature, H: enthalpy,
S: entropy) [JEE Adv. 2021]

(A) (B)

(C) (D)

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(Physical Chemistry) THERMODYNAMICS - 02

Question stem for Question Nos. 3 and 4

pz 104
For the reaction X(s)  Y(s) + Z(g), the plot of ln versus is given below (in solid line),
p T

where pz is the pressure (in bar) of the gas Z at temperature T and P = 1 bar. [JEE Adv. 2021]

d(ln K) H  p
(Given, =− , where the equilibrium constant, K = z and the gas constant, R =
1 R p
d 
T
8.314 J K–1 mol–1)

3. The value of standard enthalpy, H  (in kJ mol–1) for the reaction is_____ .
4. The value of S (in J K–1 mol–1) for the given reaction, at 1000 K is_________ .
5. For a reaction, A P, the plots of [A] and [P] with time at temperatures T1 and T2 are given

below. [JEE ADV. 2018]

If T2 > T1, the correct statement(s) is (are)

(Assume H and S are independent of temperature and ratio of lnK at T1 to lnK at T2 is
T2
greater than. Here H, S, G and K are enthalpy, entropy, Gibbs energy and equilibrium
T1
constant, respectively.)

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(Physical Chemistry) THERMODYNAMICS - 02

(A) H  0, S  0 (B) G  0, H  0

(C) G  0, S  0 (D) G  0, S  0

6. The surface of copper gets tarnished by the formation of copper oxide. N2 gas was passed to
prevent the oxide formation during heating of copper at 1250 K. However, the N2 gas contains 1
mole % of water vapour as impurity. The water vapour oxidises copper as per the reaction
given below: [JEE ADV. 2018]
2Cu(s) + H2O(g) ⎯→ Cu2O(s) + H2(g)

p H2 is the minimum partial pressure of H2 (in bar) needed to prevent the oxidation at 1250 K.

The value of ln p H 2 is ____.

(Given: total pressure = 1 bar, R (universal gas constant) = 8 J K–1 mol–1, ln(10) = 2.3. Cu(s)
and Cu2O(s) are mutually immiscible.

At 1250 K: 2Cu(s) + 1 O2(g) ⎯→ Cu2O(s); G = –78,000 J mol–1

2
1
H2(g) + O2(g) ⎯→ H2O(g); G = –1,78,000 J mol–1; G is the Gibbs energy)
2
7. Consider the following reversible reaction,

A(g) + B(g) AB(g)

The activation energy of the backward reaction exceeds that of the forward reaction by 2RT.
(in J mol–1). If the pre-exponential factor of the forward reaction is 4 times that of the reverse
reaction, the absolute value of G (in J mol-1) for the reaction at 300 K is ____.
(Given; ln(2) = 0.7, RT = 2500 J mol–1 at 300 K and G is the Gibbs energy) (JEE ADV. 2018)
8. The standard state Gibbs fee energies of formation of C(graphite) and C(diamond) at T = 298 are
ƒGº [C(graphite)] = 0 kJ mol–1
ƒGº [C(diamond)] = 2.9 kJ mol–1.
The standard state means that the pressure should be 1 bar, and substance should be pure at a
given temperature. The conversion of graphic [C(graphite)] to diamond [C(diamond)] reduces
its volume by 2 ×10–6 m3 mol–1. If C(graphic) is converted to C(diamond) isothermally at
T = 298 K , the pressure at which C(graphite) is in equilibrium with C(diamond), is
[Useful information : 1J = 1 kg m2 s–2 ; 1 Pa = 1 kg m–1 s–2 ; 1 bar = 105 Pa] [JEE ADV. 2017]
(A) 29001 bar (B) 58001 bar (C) 14501 bar (D) 1450 bar
9. For a reaction taking place in a container in equilibrium with its surroundings, the effect of
temperature on its equilibrium constant K in terms of change in entropy is described by

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(Physical Chemistry) THERMODYNAMICS - 02
[JEE ADV. 2017]
(A) with increase in temperature, the value of K for exothermic reaction decreases because the
favourable change in entropy of the surroundings decreases
(B) With increases in temperature, the value of K for endothermic reaction increases because
the entropy change of the system is negative
(C) With increase in temperature, the value of K for endothermic reaction increases because
unfavourable change in entropy of the surrounding decreases
(D) With increase in temperature, the value of K for exothermic reaction decreases because the
entropy change of the system is positive
Paragraph-10-11
Thermal decomposition of gaseous X2 to gaseous X at 298 K takes place according to the
following equation: [JEE(Advanced) 2016]
X2(g)  2X (g)

The standard reaction Gibbs energy, G°, of this reaction is positive. At the start of the reaction,
there is one mole of X2 and no X. As the reaction proceeds the number of moles of X formed is
given by . Thus, equilibrium is the number of moles of X formed at equilibrium. The reaction is
carried out at a constant total pressure of 2 bar. Consider the gases to behave ideally.
(Given: R = 0.083 L bar K–1 mol–1)
10. The equilibrium constant Kp for this reaction at 298 K, in terms of equilibrium, is

8equilibrium
2
8equilibrium
2
4equilibrium
2
4equilibrium
2

(A) (B) (C) (D)

2 − equilibrium 4 − equilibrium
2
2 − equilibrium 4 − equilibrium
2

11. The INCORRECT statement among the following, for this reaction, is
(A) Decrease in the total pressure will result in formation of more moles of gaseous X
(B) At the start of the reaction, dissociation of gaseous X2 takes place spontaneoulsy

(C) equilibrium = 0.7

(D) Kc < 1
12. One mole of an ideal gas at 300 K in thermal contact with surroundings expands isothermally
from 1.0 L to 2.0 L against a constant pressure of 3.0 atm. In this process, the change in entropy
of surroundings (Ssurr) in J K–1 is [JEE(Advanced) 2016]
(1 L atm = 101.3 J)
(A) 5.763 (B) 1.013 (C) –1.013 (D) –5.763

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(Physical Chemistry) THERMODYNAMICS - 02
13. Match the thermodynamic processes given under Column I with the expressions given under
Column II. [JEE(Advanced) 2015]
Column I Column II
(A) Freezing of water at 273 K and 1 atm (P) q=0
(B) Expansion of 1 mol of an ideal gas into a (Q) w=0
vacuum under isolated conditions
(C) Mixing of equal volumes of two ideal gases at (R) Ssys < 0
constant temperature and pressure in an
isolated container
(D) Reversible heating of H2(g) at 1 atm from (S) U = 0
300 K to 600 K, followed by reversible cooling
to 300 K at 1 atm (T) G = 0
14. For the process, H2O(l) ⎯→ H2O(g)

at T = 100 C and 1 atmosphere pressure, the correct choice is: [JEE(Advanced) 2014]
(A) Ssystem > 0 and Ssurroundings > 0 (B) Ssystem > 0 and Ssurroundings < 0
(C) Ssystem < 0 and Ssurroundings > 0 (D) Ssystem < 0 and Ssurroundings < 0

15. For an ideal gas, consider only P-V work in going from an initial state X to the final state Z. The final
state Z can be reached by either of the two paths shown in the figure. Which of the following
choice(s) is (are) correct ? [Take S as change in entropy and w as work done] [JEE 2012]
P(atmosphere)

X Y

Z
V(L)
(A) Sx→z = Sx→y + Sy→z (B) Wx→z = Wx→y + Wy→z

(C) Wx→y→z = Wx→y (D) Sx→y→z = Sx→y

16. Match the transformations in Column-I with appropriate option in Column-II [JEE 2011]
Column-I Column-II
(A) CO2(s) → CO2(g) (P) phase transition
(B) CaCO3(s) → CaO(s) + CO2(g) (Q) allotropic change
(C) 2H• → H2(g) (R) H is positive

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(Physical Chemistry) THERMODYNAMICS - 02
(D) P(white, solid) → P(red,solid) (S) S is positive
(T) S is negative
17. Statement-1 : For every chemical reaction at equilibrium, standard Gibbs energy of reaction is
zero.
Statement-2 : At constant temperature and pressure, chemical reactions are spontaneous in the
direction of decreasing Gibbs energy. [JEE 2008]
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for
statement-1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
18. Statement-1 : There is a natural asymmetry between converting work to heat and converting
heat to work. [JEE 2008]
Statement-2 : No process is possible in which the sole result is the absorption of heat from a
reservoir and its complete conversion into work.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-
1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.
19. For the process H2O (l) (1 bar, 373 K) ⎯→ H2O(g) (1 bar, 373 K), the correct set of
thermodynamic parameters is :- [JEE 2007]
(A) G = 0, S = + ve (B) G = 0, S = – ve
(C) G = + ve, S = 0 (D) G = – ve, S = +ve
20. A process A ⎯→ B is difficult to occur directly instead it takes place in three successive steps.
C D

A B S (A ⎯→ C) = 50 e.u.
S (C ⎯→ D) = 30 e.u.
S (B ⎯→ D) = 20 e.u.
Where e.u. is entropy unit.
Then the entropy change for the process S (A ⎯→ B) is :- [JEE 2006]

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(Physical Chemistry) THERMODYNAMICS - 02
(A) + 100 e.u. (B) – 60 e.u. (C) – 100 e.u. (D) + 60 e.u.
21. The enthalpy of vapourization of a liquid is 30 kJ mol–1 and entropy of vapourization is 75 J
mol–1 K–1. The boiling point of the liquid at 1 atm is :- [JEE 2004]
(A) 250 K (B) 400 K (C) 450 K (D) 600 K

22. N2O4(g) 2NO2(g) [JEE 2004]

This reaction is carried out at 298 K and 20 bar. 5 mol each of N2O4 and NO2 are taken initially.
Given : ( G 0f ) = 100 kJ mol–1 ; ( G 0f ) = 50kJ mol–1
N O
2 4 2 NO

(i) Find G for reaction at 298 K under given condition.

(ii) Find the direction in which the reaction proceeds to achieve equilibrium.
23. Show that the reaction CO(g) + ½ O2(g) ⎯→ CO2(g) at 300 K is spontaneous and exothermic,
when the standard entropy is – 0.094 kJ mol–1 K–1. The standard Gibbs free energies of
formation for CO2 and CO are –394.4 and –137.2 kJ mol–1, respectively. [JEE 2001]
24. When 1-pentyne (A) is treated with 4N alcoholic KOH at 175°C, it is converted slowly into an
equilibrium mixture of 1.3% 1-pentyne (A), 95.2% 2-pentyne(B) & 3.5% of 1, 2-pentadiene (C).
[JEE 2001]
The equilibrium was maintained at 175°C. Calculate DG° for the following equilibria.

B A G10 = ?

B C G 02 = ?

From the calculated value of G1° & G2° indicate the order of stability of A, B & C. Write a
reasonable reaction mechanism sharing all intermediate leading to A, B & C.

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(Physical Chemistry) THERMODYNAMICS - 02
ANKSWER KEY
EXERCISE # (O-I)
1. (A) 2. (B) 3. (C) 4. (D) 5. (D) 6. (C) 7. (D)
8. (D) 9. (C) 10. (B) 11. (D) 12. (C) 13. (A) 14. (C)
15. (A) 16. (C) 17. (D) 18. (B) 19. (C) 20. (A) 21. (C)
22. (C) 23. (A) 24. (B) 25. (B) 26. (D) 27. (A) 28. (D)
29. (B) 30. (A) 31. (C) 32. (A) 33. (A) 34. (D) 35. (C)
36. (B) 37. (C) 38. (B) 39. (C) 40. (A) 41. (C) 42. (A)
43. (D) 44. (A) 45. (C) 46. (B) 47. (C) 48. (A) 49. (D)
50. (A)
EXERCISE # (S-I)
1. (193.670C) 2. ((i) irreversible, (ii) reversible, (iii) impossible)
7 5
3. (117°C, 52°C) 4. ((a) R (0.286) ; (b) R (0.286))
2 2
5. (Ssys =  J/K, Ssurr = –33.256 J/K and Suniv = 33.66 J/K)
6. (Ssys , Ssurr and Suniv = 0)
7. (Ssys =  J/K, Ssurr = 0 and Suniv = 15.63 J/K)
8. (7) 9. ((a) –11.52 J/K, (b) 11.96 J/K, (c) – 0.44 J/K)
10. (10 J/K)
11. ((a) –250 J/K (b) 333.33 J/K (c) +83.33 J/K process is spontaneous.)
12. (14) 13. (1000K) 14. (205.08 JK–1mol–1)
15. ((i) –90.5 (ii) –374.5 (iii) –3.26)
16. ((50)) 17. (–283.5 kJ) 18. (– 56.98 kJ mol–1)
19. (7) 20. (3730 ln5 Cal) 21. (– 3.7 kJ)
22. (436 kJ) 23. ((a) 0, (b) – 5 J/mole.K, (c) Yes, (d) positive)
24. (– 2864.5 KJ) 25. (–1.005 kJ/mol) 26. (G° = 0; K = 1)
27. ((17.8) OMR ANS (8)) 28. (H° = 9.04 kJ/mol; S° = –8.64 J/mol–1 K–1)
29. (1380) 30. (Kp = 1.862 × 1012 atm–1/2)
31. (– 51 J/K) 32. (100J/K)

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(Physical Chemistry) THERMODYNAMICS - 02
EXERCISE # (O-II)
1. (C) 2. (A) 3. (B) 4. (B) 5. (A)
6. (A) 7. (A) 8. (A,B,D) 9. (A,B,D) 10. (A,D)
11. (A,C) 12. (A,B,D) 13. (A,B,C) 14. (A,B,C,D)
15. (A,C,D) 16. (A,B,C,D) 17. (A,B,C,D) 18. (B,C)
19. (B,D) 20. (A) 21. (C) 22. (C) 23. (A)
24. ((A)→S; (B)→P,R; (C)→P,S; (D)→P,R)
25. ((A)→P,S,R; (B)→P,R; (C)→P; (D)→Q,R,S)
26. (A) 27. (C)

EXERCISE # (S-II)
1. (100) 2. (10.352)
3 3
3. (i) Rev. Process Ssyst = R ln 10; Ssurr = – R ln 10
2 2

3 3 3
(ii) Irr Process Ssys = R ln 10; Ssurr = R (0, 9) ; Stotal = R (1.403)
2 2 2
4. (ST = 246.586 J / (mole. K)) 5. (–530 J) 6. (74.05 J/K)
7. (30 kJ/mole)
8. (–810 J/mol; –5872 J/mol and 41.3 kJ/mol) 9. (𝑷𝟐 = 𝟏. 𝟓𝟎 × 𝟏𝟎𝟗 𝑷𝒂)
10. (12)
EXERCISE # (JEE-MAIN)
1. 300 2. A 3. A 4. (600) 5. (5) 6. (200)
7. (38 kJ/mol) 8. (A) 9. (-13537.57) 10. (2.70 Kcal/mol)
11. (C) 12. (A) 13. (B) 14. (B) 15. (C) 16. (D) 17. (B)
18. (B) 19. (B) 20. (C) 21. (C) 22. (C) 23. (B) 24. (C)
25. (A) 26. (D) 27. (D) 28. (C) 29. (C) 30. (D) 31. (A)
32. (D) 33. (B)

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(Physical Chemistry) THERMODYNAMICS - 02

EXERCISE (JEE-ADVANCED)
1. (10) 2. (A,B,D) 3. (166.28) 4. (141.34)
5. (A,C) 6. (14.6) 7. (8500) 8. (C) 9. (A,C)
10. (B) 11. (C) 12. (C)
13. (((A)→R,T (B)→P,Q,S (C)→P,Q,S (D)→P,Q,S,T))
14. (B) 15. (AC) 16. ((A)→P,R,S ; (B)→R,S ; (C)→T ; (D)→P,Q,T)
17. (D) 18. (A) 19. (A) 20. (D) 21. (B)
22. (i) 5.705 × 103 J mol–1
(ii) Since initial gibbs free energy change of the reaction is positive, so the reverse
reaction will take place
23. (H° = –285.4 kJ/mol, G° = –257.2 kJ/mol)
24. (15991 K,mol–1, 12304 J mol–1; B > C > A)

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