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THERMODYNAMICS
JAM-2010
(1) The molar internal energy of a gas at temperature T is 𝑈𝑚 (𝑇). The molar internal energy
At T=0 is 𝑈𝑚 (0). The correct expression that relates these two with appropriate
contribution is ---
(A) 𝑈𝑚 (𝑇) = 𝑈𝑚 (0) + 3𝑅𝑇 [ 𝐿𝑖𝑛𝑒𝑎𝑟 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒, 𝑡𝑟𝑎𝑛𝑠𝑙𝑎𝑡𝑖𝑜𝑛 𝑜𝑛𝑙𝑦]
7
(B) 𝑈𝑚 (𝑇) = 𝑈𝑚 (0) + 𝑅𝑇 [ 𝐿𝑖𝑛𝑒𝑎𝑟 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒, 𝑡𝑟𝑎𝑛𝑠𝑙𝑎𝑡𝑖𝑜𝑛 𝑎𝑛𝑑 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛 𝑜𝑛𝑙𝑦]
2
3
(B) 𝑈𝑚 (𝑇) = 𝑈𝑚 (0) + 𝑅𝑇 [ 𝑛𝑜𝑛 𝑙𝑖𝑛𝑒𝑎𝑟 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒, 𝑡𝑟𝑎𝑛𝑠𝑙𝑎𝑡𝑖𝑜𝑛 𝑎𝑛𝑑 𝑟𝑜𝑡𝑎𝑡𝑖𝑜𝑛 𝑜𝑛𝑙𝑦]
2
For each rotational D.O.F Energy = 𝑁𝑘𝑇 so, total rotational Energy = 2𝑁𝑘𝑇
7 7
So total translational and rotational contribution is = 𝑁𝑘𝑇 = 𝑅𝑇
2 2
(2) The work done during the free expansion of one mole of an ideal gas at 27℃ to twice its
original volume is (given : 2494 J mol−1 , in2 =0.7 ,log2=0.3)
(A) 1746 J mol−1 (B) -1746 J mol−1 (C) Zero (D) 748.2 J mol−1
Ans: For free expansion work done by the system is zero
So option (C) is the correct answer
Assuming that at 273 K the molar enthalpy of fusion of ice is 6006 J mol−1 ,the heat capacity
𝐶𝑝,𝑚 (s) of ice is 38 𝐽𝐾 −1 𝑚𝑜𝑙𝑒 −1 and the heat capacity 𝐶𝑝,𝑚 (l) of liquid water is 76
𝐽𝐾 −1 𝑚𝑜𝑙𝑒 −1 . Consider the heat capacity to be constants. (given ln263=5.57 and ln273=5.61)
0
We know from Kirchoff’s law ∆𝐻𝑚 = ∆𝐻𝑚 + ∆𝐶𝑝 (𝑇2 − 𝑇1 )
= 6986 J mol−1
∆𝐻𝑚 6986 J/mole
∆𝑆𝑚 = = = 404.20 𝐽𝐾 −1 𝑚𝑜𝑙𝑒 −1
𝑇𝑓 273𝐾
JAM-2011
(1) Based on the principle of equipartition of energy, the molar heat capacity of CO 2 at
constant volume Cv,m is
(A) 3.5R (B) 6R (C) 6.5R (D) 9R
Ans: Total degree of freedom for CO2 molecule is = 9 Out of which three translational and
two rotational mode and rest four are vibrational mode
1
So internal energy of this molecule is U = 3 × 𝑘𝑇 + 2 × 𝑘𝑇 + 4 × 𝑘𝑇 = 7.5 𝑘𝑇
2
So Cv,m = 7.5R
(2) One mole of a van der Waals gas undergoes reversible isothermal transformation from an
initial volume 𝑉1 to a final volume 𝑉2 . The expression for the work done is ---
𝑉2 𝑉2 −𝑏 1 1
(A) 𝑅𝑇 ln + 𝑎(𝑉2 − 𝑉1 ) (B) −𝑅𝑇 ln +𝑎( − )
𝑉1 𝑉 −𝑏1 𝑉 𝑉 1 2
𝑃2 𝑉2 −𝑏 1 1
(C) 𝑅𝑇 ln (D) 𝑅𝑇 ln −𝑎( − )
𝑃1 𝑉 −𝑏
1 𝑉1𝑉 2
(i) reversibly and (ii) irreversibly against a constant external pressure of 2 atm until the
final pressure becomes equal to the external pressure.
Calculate ∆Ssystem for (i) and (ii). For (ii), express the final answer in terms of R.
Given: Molar heat capacity at constant volume Cv,m = 3R/2
Answer :
(i) For adiabatic reversible process TdS=dQ = 0 So, the entropy change is zero
(ii) Initial pressure 𝑃1 = 10 𝑎𝑡𝑚 Final pressure 𝑃2 = 𝑃𝑒𝑥𝑡 = 2 𝑎𝑡𝑚
In contrast to the reversible expansion, an irreversible expansion is not performed
continuously at equilibrium by means of infinitesimal changes in pressure. In the limiting
case, the value of the pressure P abruptly changes from 𝑃1 and 𝑃2 . The following expansion
proceeds in one step against a constant pressure 𝑃2 . Hence,
𝑑𝑊 = −𝑃𝑑𝑉
And thus 𝐶𝑣 𝑑𝑇 = −𝑃2 𝑑𝑉
𝑇2 𝑉2
∫ 𝐶𝑣 𝑑𝑇 = ∫ 𝑃2 𝑑𝑉
𝑇1 𝑉1
0
(2) The standard enthalpy of formation ∆𝑓 𝐻300 at 1 bar and 300 K for the formation of
𝐶𝐹2 𝐶𝑙𝐶𝐹2 𝐶𝑙 (g) from its constituent elements in the standard state is −900 kJ mol −1. Given
R = 8.3 J K−1 mol−1, the standard internal energy of formation ∆𝑓 𝑈3000
at the same pressure
and temperature is-
(A) −905 kJ mol−1 (B) −895 kJ mol−1 (C) 895 kJ mol−1 (D) 905 kJ mol−1
𝜕𝑈 𝜕𝑃
( ) = 𝑇( ) −𝑃
𝜕𝑉 𝑇 𝜕𝑇 𝑉
𝑎𝑛2
For van der Waals gas (𝑃 +
𝑉2
) (𝑉 − 𝑛𝑏) = 𝑛𝑅𝑇
𝑛𝑅𝑇 𝑎𝑛2
𝑃= −
(𝑉 − 𝑛𝑏) 𝑉 2
𝜕𝑃 𝑛𝑅
( ) =
𝜕𝑇 𝑉 (𝑉 − 𝑛𝑏)
So,
𝜕𝑈 𝑛𝑅
( ) =𝑇 −𝑃
𝜕𝑉 𝑇 (𝑉 − 𝑛𝑏)
𝜕𝑈 𝑎𝑛2 𝑎𝑛2
( 𝜕𝑉 ) = 𝑃 + 𝑉2
−𝑃 =
𝑉2
𝑇
(5) Can a gas that obeys the equation of state p (V- nb)= nRT be liquefied?
Ans : Since the gas equation does not contain any attractive term (a) so there is no
interaction force acting on the gas molecule. Hence this gas can’t be liquefied.
(6) Consider ideal mixing of 2 moles of toluene and 2 moles of benzene at 1 atm and
300 K. Calculate the values of ΔmixV, ΔmixU, ΔmixH, ΔmixG, and ΔmixS for the process.
(ln2 = 0.69)
Ans : Entropy of mixing between two substances (Toluene and Benzene) can be calculate by
2
JAM-2013
(1) The following reaction is carried out at 1 atm and 300 K
2𝐻2 (𝑔) + 𝑂2 (𝑔) → 2𝐻2 𝑂(𝑙)
∆𝑈 for the above reaction is 550 KJ, Assuming ideal gas behavior for 𝐻2 and 𝑂2 ,calculate
the value of ∆𝐻
Ans: We know ∆𝐻 = ∆𝑈 + ∆𝑛𝑅𝑇
So ∆𝐻 = 550000 𝐽 𝑚𝑜𝑙𝑒 −1 + (−3 × 8.314 𝐽𝐾 −1 𝑚𝑜𝑙𝑒 −1 × 300 𝐾)
∆𝐻 = 542.517 𝐽 𝑚𝑜𝑙𝑒 −1
JAM-2014
(1) The following graph represents the dependence of certain properties I to V (given below)
as a function of temperature
Property
I. The enthalpy change of a gas phase reaction in which the sum of number of moles of
products is greater than the sum of the number of moles of reactants.
II. The osmotic pressure of an ideal solution at a given concentration.
III. The standard Gibb’s free energy of formation of metal oxide.
IV. The molar heat capacity at constant volume for an ideal gas, as predicted by the
equipartition of energy.
V. The rate constant of a reaction with 𝐸𝑎 = 100 𝑘𝐽𝑚𝑜𝑙 −1
The lines/curves A,B,C,D,E corresponding to the appropriate property are
Property Line/Curve
I E
II B
III C
IV D
V A
JAM-2015
(1) For an isothermal free expansion of an ideal gas into vacuum, which one of the following
set of values is correct?
(A) ΔU = 0, q > 0, w < 0 (B) ΔU > 0, q > 0, w = 0
(C) ΔU = 0, q = 0, w = 0 (D) ΔU < 0, q = 0, w < 0
Ans: Since it is isothermal process so ∆𝑇 = 0 ,again ∆𝑈 = 𝐶𝑣 ∆𝑇 = 0
For free expansion work done by the system is zero so w = 0
Again from First law of thermodynamics ∆𝑈 = 𝑄 + 𝑊 ,since both w and ∆𝑈 is zero so
Q=0
So correct option is (C)
(2) Which of the following thermodynamic relation(s) is/are correct?
𝜕𝑇 𝜕𝑃 𝜕𝑇 𝜕𝑉
(A) (𝜕𝑉) = ( 𝜕𝑆 ) (B) (𝜕𝑃) = ( 𝜕𝑆 )
𝑆 𝑉 𝑆 𝑃
𝜕𝑆 𝜕𝑃 𝜕𝑆 𝜕𝑉
(C) ( ) = ( ) (D) ( ) = ( )
𝜕𝑉 𝜕𝑇 𝑇 𝑉 𝜕𝑃 𝜕𝑇𝑇 𝑃
𝜕𝑇 𝜕𝑉
Ans : From Maxwell’s relation we know ( ) = ( ) So correct option is (B)
𝜕𝑃 𝜕𝑆 𝑆 𝑃
(3) For the reaction, 2 𝑆𝑂2 + 𝑂2 ⇋2 𝑆𝑂3 , the equilibrium constant 𝐾𝑃 = 5.0 at 207 ℃. If the
partial pressures of 𝑆𝑂2 , 𝑂2 and 𝑆𝑂3 are 1.0 × 10−3, 0.20 and 1.0 × 10−4, respectively, then
the Gibbs free energy of the reaction ( ΔrG) in 𝑘𝐽𝑚𝑜𝑙𝑒 −1 at 207 ℃ is _______ [Given: R =
8.314 𝐽𝐾 −1 𝑚𝑜𝑙𝑒 −1 ]
2 2
𝑃𝑆𝑂3 𝑃𝑆𝑂3
Ans : For this given reaction ∆𝐺 = ∆𝐺 0 + 𝑅𝑇 ln 2 ×𝑃 = −𝑅𝑇 ln 𝐾𝑃 + 𝑅𝑇 ln 2 ×𝑃
𝑃𝑆𝑂2 𝑂2 𝑃𝑆𝑂2 𝑂2
−1 −1
0.0012
= −8.314 𝐽𝐾 𝑚𝑜𝑙𝑒 × 480 𝐾 × (ln 5.0 − ln ) = −11.95 𝑘𝐽𝑚𝑜𝑙𝑒 −1
0.202 × 0.0001
(4) Two moles of an ideal gas is expanded isothermally and reversibly from 5 to 1 bar at 298
K. The change in the entropy (in J K−1) of the system is _______
Ans : Here given that the number of mole (n) = 2 mole
Initial pressure (𝑃1 ) = 5 𝑏𝑎𝑟 , Final pressure (𝑃2 ) = 1 𝑏𝑎𝑟
Temperature (T) = 298 K
We know Change of Entropy for isothermal reversible process
𝑃𝑖𝑛𝑖𝑡𝑖𝑎𝑙 5 𝑏𝑎𝑟
∆𝑆 = n𝑅 ln = 2 𝑚𝑜𝑙𝑒 × 8.314 𝐽𝐾 −1 𝑚𝑜𝑙𝑒 −1 × ln = 26.76 𝐽𝐾 −1
𝑃𝑓𝑖𝑛𝑎𝑙 1 𝑏𝑎𝑟
JAM-2016
1
(1) The ∆𝐻0 for the reaction C𝑂(𝑔)+ 𝑂2(𝑔) → 𝐶𝑂2(𝑔) at 400 K in 𝑘𝐽𝑚𝑜𝑙𝑒 −1 is ---------
2
= −284 𝑘𝐽𝑚𝑜𝑙𝑒 −1
JAM-2017
(1) The intensive variable (s) is/are
(A) Temperature (B) Volume (C) Pressure (D) Density
Ans : Density ,Pressure, Temperature
(2) At 298K and 1 atm, the molar enthalpies of combustion of cyclopropane and propane are
-2091 𝑘𝐽𝑚𝑜𝑙𝑒 −1 and -2058 𝑘𝐽𝑚𝑜𝑙𝑒 −1 , respectively. The enthalpy change (𝑘𝐽𝑚𝑜𝑙𝑒 −1 ) for
the conversion of one mole of propane to one mole of cyclopropane is ---------
Ans : Propane → Cyclopropane
∆𝐻𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = 𝐻𝐶𝑦𝑐𝑙𝑜𝑝𝑟𝑜𝑝𝑎𝑛𝑒 − 𝐻𝑃𝑟𝑜𝑝𝑎𝑛𝑒
∆𝐻𝑐𝑜𝑚𝑏𝑢𝑠𝑡𝑖𝑜𝑛 = (−2091 − (−2058))𝑘𝐽𝑚𝑜𝑙𝑒 −1 = 33 𝑘𝐽𝑚𝑜𝑙𝑒 −1
(3) Consider an isothermal reversible compression of one mole of an ideal gas in which the
pressure of the system is increased from 5 atm to 30 atm at 300 K. The entropy change of the
surroundings (in kJ/mole) is ---------------
Ans : Here given that the number of mole (n) = 1 mole
Initial pressure (𝑃1 ) = 5 𝑎𝑡𝑚 , Final pressure (𝑃2 ) = 30 𝑎𝑡𝑚
Temperature (T) = 300 K
For Isothermal process the change of entropy
𝑃𝑖𝑛𝑖𝑡𝑖𝑎𝑙 5 𝑎𝑡𝑚
∆𝑆 = 𝑅 ln = 1 𝑚𝑜𝑙𝑒 × 8.314 𝐽𝐾 −1 𝑚𝑜𝑙𝑒 −1 × ln = −14.89 𝐽𝐾 −1
𝑃𝑓𝑖𝑛𝑎𝑙 30 𝑎𝑡𝑚
JAM-2018
(1) The CORRECT expression that corresponds to reversible and adiabatic expansion of an
ideal gas is
(A) ∆𝑈 = 0 (B) ∆𝐻 = 0 (C) ∆𝑆 = 0 (D) ∆𝐺 = 0
Ans: For reversible process ∆Q=T ∆𝑆
For adiabatic process ∆Q=0 ; So ∆𝑆=0
Ans : At high enough temperature and low enough pressure, most of the gases behave
ideally. In this cases, room temp and pressure is good enough. As the temp is lowered, the
intermolecular forces will become more important and as the pressure is raised (gas volume
gets smaller) the size of the molecules becomes important. So the gas that behaves ideally
the longest as you lower temp and raise pressure is the smallest one and the one with the
smallest intermolecular forces.
So answer will be (C)
(3) The CORRECT expression(s) for isothermal expansion of 1 mol of an ideal gas is(are)
𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙
(A) ∆𝐴 = 𝑅𝑇 ln (B) ∆𝐺 = 𝑅𝑇 ln
𝑉𝑓𝑖𝑛𝑎𝑙 𝑉𝑓𝑖𝑛𝑎𝑙
𝑉𝑓𝑖𝑛𝑎𝑙 𝑉𝑓𝑖𝑛𝑎𝑙
(C) ∆𝐻 = 𝑅𝑇 ln (D) ∆𝑆 = 𝑅 ln
𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙
𝑇𝑓𝑖𝑛𝑎𝑙 𝑉𝑓𝑖𝑛𝑎𝑙
Ans : We know entropy change ∆𝑆 = 𝑅 ∆𝑆 = 𝐶𝑣 ln + 𝑅 ln
𝑇𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙
𝑉𝑓𝑖𝑛𝑎𝑙
For isothermal process 𝑇𝑓𝑖𝑛𝑎𝑙 = 𝑇𝑖𝑛𝑖𝑡𝑖𝑎𝑙 ; So ∆𝑆 = 𝑅 ln
𝑉𝑖𝑛𝑖𝑡𝑖𝑎𝑙
1
(4) Consider the reaction C𝑂(𝑔)+ 𝑂2(𝑔) → 𝐶𝑂2(𝑔). The value of ∆U for the reaction
2
at 300 K is –281.8 𝑘𝐽𝑚𝑜𝑙𝑒 . The value of ∆H at same temperature is ______ 𝑘𝐽𝑚𝑜𝑙𝑒 −1
−1
1
∆𝐻 =– 281.8 × 103 𝐽𝑚𝑜𝑙𝑒 −1 − × 8.3 𝐽𝐾 −1 𝑚𝑜𝑙𝑒 −1 × 300𝐾 = 283.045 k𝐽𝐾 −1 𝑚𝑜𝑙 −1
2
1
(5) For the reaction 𝐻2(𝑔)+ 𝑂2(𝑔) → 𝐻2𝑂(𝑙), the following information is given
2