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31. The reversible expansion of an ideal gas under adiabatic and

isothermal conditions is shown in the figure. Which of the following
statement(s) is(are) correct? (2012)
(A) T1  T 2

(B) T 3  T1

(C) w isothermal  w adiabatic

(D) U isothermal  Uadiabatic

Paragraph for Question No. 32 – 33 (2013)

A fixed mass ‘m’ of a gas is subjected to transformation of states
from K to L to M to N and back to K as shown in the figure.

32. The succeeding operations that enable this transformation of states are :
(A) heating, cooling, heating, cooling (B) cooling, heating, cooling, heating
(C) heating, cooling, cooling, heating (D) cooling, heating, heating, cooling

33. The pair of isochoric processes among the transformation of states is :

(A) K to L and L to M (B) L to M and N to K
(C) L to M and M to N (D) M to N and N to K

34. An ideal gas in a thermally insulated vessel at

internal pressure  P1, volume  V1 and absolute

temperature  T1 expands irreversibly against zero

external pressure, as shown in the diagram. The final

internal pressure, volume and absolute temperature
of the gas are P 2 , V2 and T 2 , respectively. For this

expansion, (2014)
(A) q 0 (B) T 2  T1

(C) P 2 V2  P1V1 (D) P 2 V2  P1 V1

35. 
For the process, H2O ℓ  H2O g   at T = 100C and 1 atmosphere pressure, the correct choice is:

(A) Ssystem  0 and Ssurrounding  0 (2014)

(B) Ssystem  0 and Ssurrounding  0

(C) Ssystem  0 and Ssurrounding  0

(D) Ssystem  0 and Ssurrounding  0

VMC | Thermodynamics 71 DTS-3 | JEE Advanced (Archive)

Paragraph for Question No. 36 - 37 (2016)
Thermal decomposition of gaseous X2 to gaseous X at 298 K takes place according to the following equation:

X2(g) ↽ ⇀ 2X(g)
The standard reaction Gibbs energy,  r 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)

36. The equilibrium constant KP for this reaction at 298 K, in terms of equilibrium , is :

82
equilibrium 82
equilibrium
(A) (B)
2  equilibrium 4  2
equilibrium

42
equilibrium 42
equilibrium
(C) (D)
2 4  2
equilibrium equilibrium

37. 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 spontaneously
(C) equilibrium  0.7
(D) Kc  1

38. The standard state Gibbs free energies of formation of C(graphite) and C(diamond) as T = 298 K are :

 f G [C(graphite)]  0 kJ mol 1 ;  f G [C(diamond)]  2.9 kJ mol 1. (2017)

The standard state means that the pressure should be 1 bar, and substance should be pure at a given
temperature. The conversion of graphite [C(graphite)] to diamond [C(diamond)] reduces its volume by

2  10 6 m 3mol 1. If C(graphite) 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: 1 J  1kg m 2s 2 ;

1 Pa  1kg m 1 s2 ; 1 bar  105 Pa]

(A) 14501 bar (B) 29001 bar

(C) 1450 bar (D) 58001 bar

*39. 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 : (2017)
(A) With increase in temperature, the value of K for exothermic reaction decreases because the
entropy change of the system is positive
(B) With increase in temperature, the value of K for endothermic reaction increases because
unfavourable change in entropy of the surroundings decreases
(C) With increase in temperature, the value of K for endothermic reaction increases because the
entropy change of the system is negative
(D) With increase in temperature, the value of K for exothermic reaction decreases because
favourable change in entropy of the surroundings decreases

VMC | Thermodynamics 72 DTS-3 | JEE Advanced (Archive)

40. An ideal gas is expanded from (p1, V1, T1) to (p2, V2, T2) under different conditions. The correct
statement(s) among the following is (are) (2017)
(A) The work done on the gas is maximum when it is compressed irreversibly from (p2, V2) to (p1, V1)
against constant pressure p1
(B) The change in internal energy of the gas is (i) zero, if it is expanded reversibly with T1 = T2, and
(ii) positive, if it is expanded reversibly under adiabatic conditions with T1  T2 .

(C) If the expansion is carried out freely, it is simultaneously both isothermal as well as adiabatic.
(D) The work done by the gas is less when it is expanded reversibly from V1 to V2 under adiabatic
conditions as compared to that when expanded reversibly from V1 to V2 under isothermal
conditions.

41. Which of the following lines correctly show the temperature dependence of
equilibrium constant, K, for an exothermic reaction? (2018)

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

42. An ideal gas undergoes a cyclic process as shown in figure. (2018)

1 1
U BC   5 kJ mol , q AB  2 kJ mol ;

WAB   5 kJ mol 1, WCA  3 kJ mol 1

Heat absorbed by the system during process CA is :

(A)  5 kJ mol 1 (B) 5 kJ mol 1

(C) 18 kJ mol 1 (D) 18 kJ mol 1

*43. A reversible cyclic process for an ideal gas is shown below. Here, P, V, and T are pressure, volume and
temperature, respectively. The thermodynamic parameters q, w, H and U are heat, work, enthalpy and
internal energy, respectively . The correct option(s) is (are) : (2018)

(A) 
q AC  UBC and w AB  P2 V2  V1 
(B)  
w BC  P2 V2  V1 and q BC  H AC

(C) HCA  UCA and q AC  UBC

(D) q BC  U AC and HCA  UCA

VMC | Thermodynamics 73 DTS-3 | JEE Advanced (Archive)

*44. For a reaction, A ⇌ P, the plots of [A] and [P] with time at temperatures T1 and T2 are given below.

If T 2  T1, the correct statement(s) is (are) : (2018)

(Assume HΘ and SΘ are independent of temperature and ratio of ln K at T1 to ln K at T 2 is greater

T2
than . Here H, S, G and K are enthalpy, entropy, Gibbs energy and equilibrium constant,
T1

respectively)
(A) HΘ  0, SΘ  0 (B) G Θ  0, HΘ  0

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

VMC | Thermodynamics 74 DTS-3 | JEE Advanced (Archive)