THERMODYNAMICS AND THERMOCHEMISTRY 1

EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTION

1. A reaction is non-spontaneous at the freezing point of H—H bonds are respectively, 414, 347, 615 and
water but is spontaneous at the boiling point of water, 435 kJ mol–1, the value of enthalpy change for the reaction,
then (2002) H2C CH2(g) + H2(g) H3C —CH3(g) at 298 K will be
DH DS (2003)
(a) + ve + ve (a) + 250 kJ (b) – 250 kJ
(b) – ve – ve (c) + 125 kJ (d) – 125 kJ
(c) – ve + ve Ans. (d)
(d) + ve – ve Sol.
Ans. (a)
Sol. Since the process is non-spontaneous at lower temperature
but becomes spontaneous at higher temperature, this
implies both D H and D S are positive. This is possible
because at high temperature, T D S > D H which gives a
negative value for D G.. DH reaction = å BEreactant – BE product
2. A heat engine absorbs heat q1 from a source at temperature =4 × 414 + 615 + 435 – (6 × 414 + 347)
T1 and heat q2 from a source at temperature T2. Work done
is found to be (q1 + q2)J. This is in accordance with =2706 – 2831 = – 125kJ
(2002) 6. The internal energy change when a system goes from state
A to B is 40 kJ/mol. If the system goes from A to B by a
(a) First law of thermodynamics reversible path and returns to state A by an irreversible
(b) Second law of thermodynamics path, what would be the net change in internal energy ?
(c) Joules equivalent law (2003)
(d) None of the above (a) 40 kJ (b) > 40 kJ
Ans. (d) (c) < 40 kJ (d) zero
Sol. It doesn’t violate the first law of thermodynamics, but Ans. (d)
violates the second law of thermodynamics . Sol. Reversible path
3. Heat required to raise the temperature of 1 mole of a
substance by 1º is called (2002)
(a) specific heat (b) molar heat capacity
(c) water equivalent (d) specific gravity
Ans. (b)
Sol. The amount of heat required to raise the temperature of
one mole of substance through 1°C is called molar heat
capacity..
4. The correct relationship between free energy change in a Irreversible path.
reaction and the corresponding equilibrium constant Kc is For a cyclic process, internal energy change is 0 and it is
(2003) independent of path taken.
(a) DG = RT ln Kc (b) –DG = RT ln Kc 7. The enthalpy change for a reaction does not depend upon
the (2003)
(c) DGº = RT ln Kc (d) – DGº = RT ln Kc
(a) physical state of reactants and products
Ans. (d)
(b) use of different reactants for the same product
Sol. Relationship between free energy and equilibrium constant,
- D G = RT ln Kc. (c) nature of intermediate reaction steps

5. If at 298 K the bond energies of C—H, C—C, C C and (d) difference in initial or final temperatures of involved
substances
Ans. (c)
 2 THERMODYNAMICS AND THERMOCHEMISTRY

Sol. Enthalpy change is a state function so it does not depend Now DG = –RT ln K
on the path taken by the reaction. it depends only on the
difference of final and initial values of enthalpy change. When K > 1, DG = –ve
8. The enthalpies of combustion of carbon and carbon Again DG0 = –nFE0
monoxide are – 393.5 and – 283 kJ mol–1 respectively. The
enthalpy of formation of carbon monoxide per mole is When E0 = + ve, DG0 = – ve

(2004) 11. If the bond dissociation energies of XY, X2 and Y2 (all

diatomic molecules) are in the ratio of 1 : 1 : 0.5 and DHf for
(a) 110.5 kJ (b) 676.5 kJ the formation of XY is –200 kJ mol–1. The bond dissociation
(c) – 676.5 kJ (d) – 110.5 kJ energy of X2 will be (2005)
Ans. (d) (a) 400 kJ mol–1 (b) 300 kJ mol–1

1 (c) 800 kJ mol–1 (d) None of these

Sol. C (s) + O 2 (g ) ® CO (g ) DH f = ?
2 Ans. (c)

C(s) + O 2(g) ® CO2(g) DH = -393.5kJ mol-1 ....(1) Sol. Let the bond dissociation energies of XY, X2 and Y2 be x,x,
and 0.5 x kJ respectively.
1
CO (g) + O 2(g ) ® CO 2(g ) DH = -283.0kJ mol-1 ...(2) 1 1
2 X 2 + Y2 ® XY ; DH f = –200kJ mol –1
2 2
Reversing equation (2)
DH(reaction)= (Sum of bond dissociation energies of
1 reactants)-
CO 2( g) ® CO (g) + O 2(g ) DH = +283.0kJ mol -1 ...(3)
2 (Sum of bond dissociation energies of products)
On adding equation (1)&(3)
é1 1 ù
1 = ê DH X2 + DH Y2 – DH xy ú
C(s) + O2(g) ® CO( g) DH = (-393.5 + 283) ë 2 2 û
2

= -110.5kJ mol -1 x 0.5

+ – x = –200
2 2
9. An ideal gas expands in volume from 1 × 10 –3 m3 to
1 × 10 –2 m3 at 300 K against a constant pressure of 200
1 × 105 Nm–2. The work done is (2004) \ x= = 800kJ mol –1
0.25
(a) – 900 J (b) – 900 kJ
12. Consider the reaction : N2 + 3H2 ® 2NH3 carried out at
(c) 270 kJ (d) 900 kJ constant temperature and pressure. If DH and DE are the
Ans. (a) enthalpy and internal energy changes for the reaction,
which of the following expressions is true ? (2005)
Sol. W = P DV
(a) DH > DE (b) DH < DE

æ 1ö (c) DH = DE (d) DH = 0
= -105 ´10 -2 ç1 - ÷
è 10 ø Ans. (b)
5 -2 9
= -10 ´10 ´ Sol. DH = DE + Dng RT
10
= -900J DH = DE – 2RT
DE > DH
10. For a spontaneous reaction the DG, equilibrium constant
(K) and Eºcell will be respectively (2005) \ Option(b)
(a) –ve, >1, –ve (b) –ve, <1, –ve 13. The standard enthalpy of formation (DHºf) at 298 K for
methane, CH4(g) is – 74.8 kJ mol–1.
(c) +ve, >1, –ve (d) –ve, >1, + ve
Ans. (d) The additional information required to determine the
average energy for C—H bond formation would be
Sol. For a spontaneous process, DG = –ve (2006)
THERMODYNAMICS AND THERMOCHEMISTRY 3

(a) the dissociation energy of H 2 and enthalpy of ΔH-ΔU=Δn g RT

Sol.
sublimation of carbon
1
(b) latent heat of vaporisation of methane C+ O 2 ® CO
2
(c) the first four ionisation energies of carbon and electron
æ 1ö 1
gain enthalpy of hydrogen Δn g = 1 - ç1 + ÷ = -
è 2ø 2
(d) the dissociation energy of hydrogen molecule, H2
1
ΔH-ΔU = - ´ 8.314 ´ 298
Ans. (a) 2
Sol. C + 2H2 ® CH4 ; DH0 = – 74.8kJ mol–1 = -1238.78 Jmol-1
In order to calculate average energy for C-H bond 16. An ideal gas is allowed to expand both reversibly and
formation, we should know the following data: irreversibly in an isolated system. If T i is the initial
C(graphite) ® C(g) ; DHC0 = Enthalpy of sublimation of temperature and Tf is the final temperature, which of the
carbon. following statements is correct ? (2006)
(a) (Tf)irrev > (Tf)rev
H2(g) ® 2H2(g) ; D H0 = Bond disassociation energy of H 2
(b) Tf > Ti for reversible process but Tf = Ti for irreversible
14. The enthalpy changes for the following processes are listed process
below : (c) (Tf)rev = (Tf)irrev
Cl2 (g) ® 2Cl(g), 242.3 kJ mol–1 (d) Tf = Ti for both reversible and irreversible processes
I2(g) ® 2I(g), 151.0 kJ mol–1 Ans. (a)
ICl (g) ® I(g) + Cl (g), 211.3 kJ mol–1 Sol. If a gas was to expand by a certain volume reversibly,
then it would do a certain amount of work on the
I2(s) ® I2(g), 62.76 kJ mol–1 surroundings. If it was to expand irreversibly it would
Given that the standard states for iodine and chlorine are have to do the same amount of work on the surroundings
I2(s) and Cl2(g), the standard enthalpy of formation of to expand in volume, but it would also have to work against
ICl (g) is (2006) frictional forces.
(a) – 14.6 kJ mol–1 (b) – 16.8 kJ mol–1 Therefore the amount of work has greater modulus but -
ve sign.
(c) + 16.8 kJ mol–1 (d) + 244.8 kJ mol–1 17. In conversion of limestone to lime,
Ans. (c) CaCO3(s) ® CaO (s) + CO2 (g)
Sol. the values of DHº and DSº are + 179.1 kJ mol–1 and 160.2 J/K
respectively at 298 K and 1 bar. Assuming that DHº and
1 1 DSº do not change with temperature, temperature above
I 2(g) + Cl 2(g) ® ICl(g) which conversion of limestone to lime will be spontaneous
2 2
is (2007)
1
DH ICl ( g ) = éë DH I2(s) ®I2(g) + DH I - I + DH Cl - Cl ùû (a) 1008 K (b) 1200 K
2
(c) 845 K (d) 1118 K
-[DH I -Cl ]
Ans. (d)
1 Sol. For D G0 = D H0 – TD S0
= 62.76 + 151.0 + 242.3 - [211.3]
2 For a spontaneous proess D G0 < 0
= [31.38 + 75.5 + 121.15] - 211.3 i. e D H0 – T D S0 < 0
= 228.03 - 211.3 = 16.73kJ/mol D H0 < T D S0 or T D S0 > D H0

15. (DH – DE) for the formation of carbon monoxide (CO) from DH 0 179.1´ 1000
its elements at 298 K is (R=8.314 JK–1 mol–1) (2006) or T > i. e T >
DS 0 160.2
–1 –1
(a) – 1238.78 J mol (b) 1238.78 J mol
or T > 1117.9 K » 1118K
(c) – 2477.57 J mol–1 (d) 2477.57 J mol–1 18. Identify the correct statement regarding a spontaneous
Ans. (a) process. (2007)
(a) For a spontaneous process in an isolated system, the
change in entropy is positive
(b) Endothermic processes are never spontaneous
(c) Exothermic processes are always spontaneous
(d) Lowering of energy in the reaction process is the only
 4 THERMODYNAMICS AND THERMOCHEMISTRY
criterion for spontaneity 1
Ans. (a) The energy involved in the conversion of Cl (g) to
2 2
Sol. In an isolated system, there is neither exchange of energy o = 240 kJ mol -1
not matter between the system and surrounding. For a Cl– (aq) will be (using the data, Ddiss H Cl 2
spontaneous process in an isolated system, the change o -1
in entropy is positive, i.e. DS>0. D EA HoCl = -349kJ mol-1 , D hyd H Cl = -381 kJ mol )
Most of the spontaneous chemical reactions are (2008)
–1 –1
exothermic. A number of endothermic (a) + 152 kJ mol (b) – 610 kJ mol
reactions are spontaneous e.g. melting of ice (an (c) – 850 kJ mol–1
(d) + 120 kJ mol–1
endothermic process) is a spontaneous reaction. Ans. (b)
(i) tendency to acquire minimum energy
1
(ii) tendency to acquire maximum randomness. Sol. Cl2( g ) ® Cl( g ) :
2
19. Assuming that water vapour is an ideal gas, the internal
energy change (DE) when 1 mole of water is vaporised at 1 1 240
DH 1 = D diss Cl2 = = 120 KJ mol –1
bar pressure and 100ºC, (Given : molar enthalpy of 2 2
vaporisation of water at 1 bar and 373 K = 41 KJ mol–1 and
R = 8.3 J mol–1 K–1) will be (2007) Cl( g ) ® Cl(-g ) DH (+g ) = -349kJ mol -1
(a) 4.100 kJ mol–1 (b) 3.7904 kJ mol–1
Cl – ( g ) – aq ® Cl – ( aq) ;
(c) 37.904 kJ mol–1 (d) 41.00 kJ mol–1
Ans. (c) DH1 = D hyd H 2Q = –381KJ mol –1
Sol. D U = D H – DnRT
= 41000 –1 × 8.314 × 373 T
1 –
The required reaction is Cl ( g ) ® Cl( aq ) ; DH
=41000 – 3101.122 2
= 37898.878 J mol–1 = 37.9 kJ mol–1 1
20. Standard entropy of X2, Y2 and XY 3 are 60, 40 and Then DH1 = D diss H Q + D ( eg ) H Q + D hyd H 2Q
2
50 JK–1 mol–1, respectively. For the reaction,
=
120 + (–349) + (–381) = –610 kJ mol–1
1 3
X 2 + Y2 ® XY3 , DH = - 30 kJ, to be at equilibrium, 22. On the basis of the following thermochemical data
2 2 [DGº H+ (aq) = 0]
the temperature will be (2008)
+ –
(a) 1250 (b) 500 K H2O(l) ¾¾
® H (aq) + OH (aq); DH = 57.32 kJ
(c) 750 K (d) 1000 K
1
Ans. (c) H2(g) + O (g) ¾¾ ® H2O(l); DH = – 286.02 kJ
2 2
1 3
Sol. X 2 + Y2 ® XY3 The value of enthalpy of formation of OH– ion at 25ºC is
2 2
(2009)
D S0 reaction – DS0 products = D S0 reaction
0 1 3 (a) – 22.88 kJ (b) – 228.88 kJ
\ D S0 reaction = DS XY3 – DS 0 X 2 – DSY02
2 2 (c) + 228.88 kJ (c) – 343.52 kJ
1 3 Ans. (b)
= 50 – ´ 60 – ´ 40 JK –1mol –1 Sol. The reaction for the formatin of OH– (aq) is
2 2
And at equilibrium, DG = 0. Therefore,
1
H 2( g ) +O2( g ) ® H + (aq ) + OH - ( aq )
DH –30 ´ 1000 2
T= = = 750 K
DS –40 This is obtained by adding the two given equations.
21. Oxidising power of chlorine in aqueous solution can be
determined by the parameters indicated below : DH for the above reaction = 57.32 + (–286.2) = –228.88kJ
23. In a fuel cell methanol is used as fuel and oxygen gas is
1
1 D Ho Ho 3
Cl 2 (g) 2 diss ® Cl(g)
¾¾¾¾¾
D
EA
¾¾¾¾® used as an oxidiser. The reaction is CH3OH(l) + O (g)
2 2 2
hydD Ho - ¾¾ ® CO2(g) + 2H2O(l). At 298 K standard Gibb’s energies
Cl - (g) ¾¾¾¾ ® Cl (aq) of formation for CH3OH(l), H2O (l) and CO2(g) are – 166.2,
–237.2 and –394.4 kJ mol –1 respectively.
If standard enthalpy of combustion of methanol is
– 726 kJ mol–1, efficiency of the fuel cell will be (2009)
THERMODYNAMICS AND THERMOCHEMISTRY 5
(a) 80% (b) 87% value will be
(c) 90% (d) 97% (Given, DH of sublimation for N2O5 is 54 kJ mol–1) (2011)
Ans. (d) (a) – 165 kJ (b) + 54 kJ
(c) +219 kJ (d) – 219 kJ
Sol. For the given reaction,
Ans. (d)
D H = – 726 kJ mol–1
Sol. N2O5(s) ®N2O5(g) ; DH = 54 kJ/ ml
D G 0 å DG 0 products – å DG 0 reactants So,
N2O5(g) ® N2O5(s) ; DH = –54 kJ/ ml
0 -1
also DG f éëCH 3OH (1) ùû = -394.4 kJ mol for two mole DH = – 108kJ/ml ....(i)
D G 0 å DG 0 products – å DG 0 reactants Heat of reaction for
4NO2(g) + O2 ®2N2O5(g)
–394.4 + 2 ´ (–237.2) – (–166.2) is DrH = – 111 kJ ...(ii)
Adding both equation – 108 – 111 = –219 kJ
= –702.6kJ mol –1 \ Option (d)
\ Efficiency » 97% 27. The value of enthalpy change (DH) for the reaction
C2H5OH(l) + 3O2(g) ® 2CO2(g) + 3H2O(l),
24. For a particular reversible reaction at temperature T, DH at 27ºC is – 1366.5 kJ mol–1. The value of internal energy
and DS were found to be both +ve. If Te is the temperature change for the above reaction at this temperature will be
at equilibrium, the reaction would be spontaneous when
(2011)
(2010)
(a) – 1371.5 kJ (b) – 1369.0 kJ
(a) Te > T (b) T > Te
(c) – 1364.0 kJ (d) – 1361.5 kJ
(c) Te is 5 times T (d) T = Te
Ans. (c)
Ans. (b) Sol. DH = D U + D ngRT
Sol. According to Gibb’s formula, –1366500J = D U + (–1)8.314 × 300
DG = DH - T DS DU = –1364.0KJ/mol
ΔH and ΔS, both are positive for \Option(c)
28. The entropy change involved in the isothermal reversible
ΔG < 0 and T > Te expansion of 2 moles of an ideal gas from a volume of
25. The standard enthalpy of formation of NH3 is – 46.0 kJ mol–1. 10 dm3 to a volume of 100 dm3 at 27º C is (2011)
If the enthalpy of formation of H 2 from its atoms is (a) 38.3 J mol–1K–1 (b) 35.8 J mol–1K–1
– 436 kJ mol–1 and that of N2 is –712 kJ mol–1, the average (c) 32.3 J mol–1K–1 (d) 42.3J mol–1K–1
bond enthalpy of N—H bond in NH3 is (2010)
Ans. (a)
(a) – 964 kJ mol–1 (b) + 352 kJ mol–1
(c) + 1056 kJ mol–1 (d) – 1102 kJ mol–1 æV ö
Sol. DS = 2.303nR log ç 2 ÷
Ans. (b) è V1 ø
1 3 æ 100 ö
N 2 + H 2 ® NH 3 DS = 2.303 ´ 2 ´ 8.314 ´ log ç ÷
2 2 è 10 ø
Sol.
B.E - 712 - 436 = 38.294 Jmol -1 K -1

é1 3 ù 29. For complete combustion of ethanol,

\ DH ° f NH 3 = ê B.E.N2 + B.E.H 2 – 3BE.N – H ú
ë2 2 û C 2 H5 OH(l ) + 3O 2 (g) ® 2CO 2 (g) + 3H 2 O(l ),
é1 3 ù the amount of heat produced as measured in bomb
–46 = ê B.E.N 2 + B.E.H2 – 3B.E.N – H ú
ë 2 2 û calorimeter, is 1364.47 kJ mol–1 at 25ºC. Assuming ideality
– 46 = 356 + 654 – B.E.N–H the Enthalpy of combustion, D CH, for the reaction will be :
3 B.E.N– H = 1056
(R = 8.314 kJ mol–1) (2014)
1056 (a) –1361.95 kJ mol –1
(b) –1460.50 kJ mol –1
B.E.N–H = = 352 kJ mol–1
3 (c) – 1350.50 kJ mol –1
(d) – 1366.95 kJ mol–1
26. Consider the reaction
Ans. (d)
4NO2(g) + O2(g) ® 2N2O5(g), DrH = – 111 kJ. If N2O5(s) is
formed instead of N2O5(g) in the above reaction, the DrH
 6 THERMODYNAMICS AND THERMOCHEMISTRY

Sol. It is an exothermic combustion reaction. CH4 (g) 186.2 J K–1 mol–1

O2 (g) 205.0 J K–1 mol–1
DH = DU + Dng RT
CO2 (g) 213.6 J K–1 mol–1
218
DH = -1364.47 + -1 ´ 8.314 ´ H2O (l) 69.9 J K–1 mol–1
1000
The entropy change (DSo) for the reaction
ΔH=-1366.95 kJ/mol
CH4(g) + 2O2(g) ® CO2(g) + 2H2O (l) is:
30. The standard enthalpy of formation of NH3 is –46.0 kJ (Online 2014 Set-3)
mol–1. If the enthalpy of formation of H2 from its atoms is (a) –37.6 J K–1 mol–1 (b) –312.5 J K–1 mol–1
–436 kJ mol–1 and that of N2 is – 712 kJ mol–1, the average (c) –242.8 J K–1 mol–1 (d) –108.1 J K–1 mol–1
bond enthalpy of N — H bond in NH3 is:
Ans. (c)
(Online 2014 Set-1)
(a) – 1102 kJ mol–1 (b) – 964 kJ mol–1 Sol. DSo = (Entropy of products)-(Entropy of reactants)
–1 –1
(c) + 352 kJ mol (d) + 1056 kJ mol DSo=(213.6 + 2 x 69.9)-(186.2 + 2 x 205)
Ans. (c)
= –242.8 J K–1 mol–1
1 3 33. The DH and DS for a reaction at one atmospheric pressure
Sol. N 2 (g)+ H 2 ( g ) ® NH 3 (l ) DH=-46.0 kJ/mole are +30.558 kJ and 0.066 kJk–1 respectively. The temperature
2 2
at which the free energy change will be zero and below of
2H(g) ® H 2 DH=-436.0 kJ/mole this temperature the nature of reaction would be
(Online 2015 Set-1)
2N(g) ® N 2 DH=-712 kJ/mole
(a) 483 K, spontaneous (b) 443 K, spontaneous
(c) 463 K, spontaneous (d) 463 K, non-spontaneous
é1 3 ù
DH f = ê B.E.( N 2 ) + B.E.( H 2 ) ú Ans. (d)
ë 2 2 û
-3B.E.( N - H ) Sol. DG = DH - T DS
é1 3 ù 0 = 30.558 - T ´ 0.066
-46 = ê ´ 712 + ´ 436ú - 3B.E.( N - H )
ë2 2 û 30.558
T=
B.E.(N-H)=352 kJ/mol 0.066
T = 463K
31. The molar heat capacity (Cp) of CD2O is 10 cals at 1000K.
The change in entropy associated with cooling of 32g Hence DG > 0 for T > 463K
of CD2O vapour from 1000 K to 100 K at constant 34. A reaction at 1 bar is non-spontaneous at low temperature
pressure will be: (Online 2014 Set-2) but becomes spontaneous at high temperature. Identify
(D = deuterium, at. Mass = 2 u) the correct statement about the reaction among the
following : (Online 2016 Set-1)
(a) 2.303 cal deg–1 (b) 23.03 cal deg–1
(c) –23.03 cal deg–1 (d) –2.303 cal deg–1 (a) Both “H and “S are negative.

Ans. (c) (b) Both “H and “S are positive.

(c) “H is positive while “S is negative.
dqrev (d) “H is negative while “S is positive
Sol. DS = ò
T
100 Ans. (b)
C p dT
= ò
1000 T Sol. DG = DH - T DS
100
DS = C p ln T 1000
At low temp. reaction is non-spontaneous.
DS = 10 ´ 2.303 ´ 2 - 3
= -23.03 caldeg -1

32. The entropy (So) of the following substances are:

THERMODYNAMICS AND THERMOCHEMISTRY 7
DG > 0, so DH is positive, TDS is positive of negative
Sol. DH = DU + Dng RT
where DH > T DS . At high temperatures DG < 0,
-3RT = DU - 1RT
-3RT + RT = DU
and DH is positive, TDS is positive. Hence DH < T DS
-2 RT = DU
35. For the reaction, A(g) + B(g) ® C(g) + D(g), DH° and DS° \ D H > DU
are respectively, –29.8 kJ mol–1 and –0.100 kJ K–1 mol–1 at
298 K. The equilibrium constant for the reaction at 38. What is the value of change in internal energy at 1 atm
298 K is : (Online 2016 Set-1) in the process?
(a) 1.0 × 10–10 (b) 1.0 × 1010 H 2 O(l,323K) ® H 2 O(g, 423K)
(c) 10 (d) 1 Given :
Ans. (d) Cv, m (H 2O, l) ® 75.0 JK -1mol-1 ;
Sol. DG ° = DH ° - T DS ° Cp,m (H 2O,g) = 33.314 JK -1mol-1 ;
= -298 - 298 ´ (-1) = 0 DHvap at 373 K = 40.7 kJ/mol (Online 2017 Set-1)
DG ° = 0 (a) 42.91 kJ/mol (b) 43086 kJ/mol
(c) 42.6 kJ/mol (d) 49.6 kJ/mol
0 = - RT ln keq
Ans. (c)

keq = 1
DU1
Sol. H 2 O(l,323K) ¾¾¾ ® H 2 O (l,373K)
36. lf 100 mole of H 2O2 decompose at 1 bar and 300 K, the DU 2 DU 3
work done (kJ) by O2(g) as it expands against 1 bar ¾¾¾ ® H 2 O(g,373K) ¾¾¾ ® H 2 O (g,423K)
pressure is : C v , m (H 2 O,g) =33.314-8.314=25J/K.mol
(C p -Cv =R)
ˆˆ† 2H 2 O(l) + O 2 (g)
2H 2 O2 (l) ‡ˆˆ
DU 2 = DH 2 - Dng RT = 37.6
-1 -1
(R = 8.3 JK mol ) (Online 2016 Set-2) DU total = DU 1 + DU 2 + DU 3
= C v,m (l )DT + DU vap + Cv , m ( g )DT
(a) –62.25 (b) –124.50
75 ´ 50 25 ´ 25
(c) –249.00 (d) –498.00 = + 37.6 +
1000 1000
Ans. (b) = 42.6kJ / mol
Sol. W = -Pext Dv
39. An ideal gas undergoes isothermal expansion at constant
W = -Dn g RT pressure. During the process :
(Online 2017 Set-2)
W = -50 ´ 8.3 ´ 300 (a) enthalpy increases but entropy decreases.
W = -124.5kJ (b) enthalpy remains constant but entropy increases.
(c) enthalpy decreases but entropy increases.
37. For a reaction, A(g) ® A(l); H = –3RT. The correct
(d) Both enthalpy and entropy remain constant.
statement for the reaction is : (Online 2017 Set-1)
Ans. (c)
(a) D H = D U ¹ 0 (b) D H = D U = 0
Sol. During isothermal process, enthalpy is constant,
(c) | D H| < | D U| (d) |DH| > |DU| but as gas expands its volume increases & entropy
increases.
Ans. (d)
40. A gas undergoes change from state A to state B. In this
process, the heat absorbed and work done by the gas is
5J and 8J, respectively. Now gas is brought back to A by
 8 THERMODYNAMICS AND THERMOCHEMISTRY
1
another process during which 3J of heat is evolved. In H 2 (g) + O 2 (g) ® H 2 O(l); DrH° = – 285.8 kJ mol–1 (2)
this reverse process of B to A : (Online 2017 Set-2) 2
CO2(g) + 2H2O(l) ® CH4(g) + 2O2(g); DrH° = +890.3 kJ
(a) 10J of the work will be done by the gas.
mol–1 (3)
(b) 6J of the work will be done by the gas.
(c) 10J of the work will be done by the surrounding on Adding (1)+2(2)+(3), we get C(graphite)+ 2H2 (g)®CH4(g)
gas. DrH° = -393.5+2(-285.8)+890.3 kJ/mol
(d) 6J of the work will be done by the surrounding on = -74.8 kJ/mol
gas.
Ans. (d) 43. The combustion of benzene (l) gives CO2(g) and H2O(l).

Sol. DU = q + w = 5 - 8 = - 3 J Given that heat of combustion of benzene at constant

DU is state function, so in the reverse reaction. volume is –3263.9 kJ mol–1 at 25°C; heat of combustion (in
kJ mol–1) of benzene at constant pressure will be:
DU = q + w
3 = -3 + w (R = 8.314 JK–1 mol–1) (2018)

w = +6 J (a) – 3267.6 (b) 4152.6

So work is done by the surrounding on the gas. (c) –452.46 (d) 3260
41. DU is equal to : (2017)
Ans. (a)
(a) Isobaric work (b) Adiabatic work
(c) Isothermal work (d) Isochoric work 15
Sol. C6 H 6 (l)+ O 2 ( g ) ® 6CO 2 (g)+3H 2 O(l)
2
Ans. (b)
Sol. From first law, DU = q + w ΔH=ΔU+Δn g RT

In adiabatic process, q=0 æ 15 ö 298

ΔH=-3263.9 + ç 6 - ÷ 8.314 ´
Hence DU = w è 2ø 1000
42. Given
= -3267.6 kJ/mol
C(graphite) + O2 (g) ® CO2(g) ; 44. For which of the following reactions, DH is equal to DU?
(Online 2018 Set-1)
DrH° = –393.5 kJ mol–1
(a) N2(g) + 3H2(g) ® 2NH3(g)
1 (b) 2HI(g) ® H2(g) + l2(g)
H 2 (g) + O 2 (g) ® H 2 O(l);
2 (c) 2NO2(g) ® N2O4(g)
DrH° = – 285.8 kJ mol–1 (d) 2SO2(g) + O2(g) ® 2SO3(g)
Ans. (b)
CO2(g) + 2H2O(l) ® CH4(g) + 2O2(g);
DrH° = +890.3 kJ mol–1 Sol. DH = DU + Dng RT , so in the reaction:
Based on the above thermochemical equations, the 2HI(g) ® H2(g) + l2(g)
value of DrH° at 298 K for the reaction
C(graphite) + 2H2(g) ® CH4(g) will be : (2017) Dng = 0
(a) + 144.0 kJ mol–1 (b) –74.8 kJ mol–1 \DH = DU
–1 –1
(c) –144.0 kJ mol (d) +74.8 kJ mol 45. An ideal gas undergoes a cyclic process as shown in
Ans. (b) Figure.

Sol. C(graphite) + O2 (g) ® CO2(g) ; DrH° = –393.5 kJ mol–1 (1)

THERMODYNAMICS AND THERMOCHEMISTRY 9
2Fe2O3(s) + 6CO(g) ® 4Fe(s) + 6CO2(g) will be :
(Online 2018 Set-2)
(a) -112.4 kJ mol-1 (b) -56.2 kJ mol-1
(c) -168.2 kJ mol-1 (d) -208.0 kJ mol-1
Ans. (b)
Sol. 2Fe 2 O3 (s) ® 4 Fe( s) + 3O2 ( g )
DrG0 = + 1487.0 kJ mol-1–A
DUBC = –5 kJ mol–1, qAB = 2 kJ mol–1
WAB = –5 kJ mol–1, WCA = 3 kJ mol–1 2CO(g) + O2(g) ® 2CO2(g) ; DG°= -514.4 kJ mo l-1 –B
Heat absorbed by the system during process CA is : Equation A+ 3(Equation B),
(Online 2018 Set-1)
DGrxn = 1487 + 3(-514.4)
-1
(a) -5 kJ mol (b) +5 kJ mol-1 = -56.2kJ / mol
(c) 18 kJ mol-1 (d) -18 kJ mol-1
48. For which of the following processes, DS is negative ?
Ans. (b)
(Online 2018 Set-3)
Sol. DU AB = q AB + wAB = -3kJ / mol (a) H2(g) ® 2H(g)
DU BC = -5kJ / mol (b) N2(g, 1 atm) ® N2(g, 5 atm)
for cyclic process DU = 0. So (c) C(diamond) ® C(graphite)
DU AB + DU BC + DU CA = 0 (d) N2(g, 273 K) ® N2(g, 300 K)
DU CA = -DU AB - DU BC Ans. (b)
= -(-3) - (-5) = 8kJ / mol Sol. When pressure increases, attraction between N2 molecules
increases.
DU CA = qCA + wCA
49. At 320 K, a gas A2 is 20 percent dissociated to A(g).
8 = qCA + 3 Þ qCA = 5kJ / mol The standard free energy change at 320 K and 1 atm in
46. DfG0 at 500 K for substance ‘S’ in liquid state and gaseous J mol-1 is approximately :
state are +100.7 kcal mol -1 and +103 kcal mol -1 , (R=8.314 JK–1 mol–1; ln 2=0.693; ln 3=1.098)
respectively. Vapour pressure of liquid ‘S’ at 500 K is
approximately equal to : (R = 2 cal K-1 mol-1) (Online 2018 Set-3)
(Online 2018 Set-2) (a) 4763 (b) 2068
(a) 0.1 atm (b) 1 atm (c) 1844 (d) 4281
(c) 10 atm (d) 100 atm Ans. (d)
Ans. (a) Sol. A 2 ƒ 2A
Sol.
At 20% dissociation, 80% A2 remains.
0 0 0
DGrxn = DGvapour - DGliquid
80
= 103 - 100.7 = 2.3kcal / mol A 2 = 1´ = 0.8M
100
DG 0 = - RT ln k A = 2 ´ 0.2 = 0.4M
ln k = 2.3 A
2

k = 0.1atm k=
A2
47. Given 0.4 2
k= = 0.2
(i) 2Fe2O3(s) ® 4Fe(s) + 3O2(g); DrG0 0.8

= + 1487.0 kJ mol-1
(ii) 2CO(g) + O2(g) ® 2CO2(g) ; = -514.4 kJ mo l-1
Free energy change, for the reaction
 10 THERMODYNAMICS AND THERMOCHEMISTRY
DH fus 334
DG0 = -RTln k Sol. As we know, DSfus = = = 1.22
273 273
= -8.314 ´ 320 ´ ln(0.2)
DH vap 2491
DG0 = 4281J / mol Also, DSvap = = = 6.67
373 373
50. Consider the reversible isothermal expansion of an ideal
æ T2 ö
gas in a closed system at two different temperatures T1 Also, DSvap = mC ln ç T ÷
è 1ø
and T2(T 1 < T 2). The correct graphical depiction of the
dependence of work done (w) on the final volume (V) æ 373 ö
= 4.2 ´ ln ç ÷ = 1.31
è 273 ø
is: (2019)
æT ö
Now, DSvap = m C ln ç 2 ÷
è T1 ø

(a) (b) æ 383 ö

= 2 ´ ln ç ÷ = 0.05
è 373 ø
\ Total entropy change
DS = 9.26kJ kg -1 K -1

52. A process has DH = 200J mol-1 and

(c) (d) DS = 40J K -1 mol-1 . Out of the values given below,,
choose the minimum temperature above which the
process will be spontaneous: (2019)
Ans. (b) (a) 20 K (b) 12 K
Sol. For reversible isothermal expansion, (c) 5 K (d) 4 K
V V
w = - nRT ln 2 Þ w = nRT ln 2 Ans. (c)
V1 V1
w = nRT ln V2 - ln V1 DH = 200J mol-1
Sol.
DS = 40J K -1 mol -1
w = nRT ln V2 - nRTV1
For spontaneous reaction,
y = mx + c
DG < 0
So, slope of curve 2 is more than curve 1 and intercept
of curve 2 is more negative than curve I. DH - TDS < 0; DH < TDS
51. The entropy change associated with the conversion of DH 200
< T; <T
1 kg of ice at 273 K to water vapours at 383 K is: DS 40
(Specific heat of water liquid and water vapour are 4.2 kJ 5<T
So, minimum temperature is 5 K.
K–1 kg–1 and 2.0 kJ K–1 kg–1: heat of fusion and
vaporisation of water are 334 kJ kg–1 and 2491 kJ kg–1. 53. The process with negative entropy change is: (2019)
respectively). (2019) (a) Dissociation of CaSO4(s) to CaO(s) and SO3(g)
(log 273 = 2.436, log 373 = 2.572, log 383= 2.583) (b) Sublimation of dry ice
(a) 790kJ kg -1 K -1 (b) 2.64kJ kg -1 K -1 (c) Dissolution of iodine in water
(c) 8.49kJ kg -1 K -1 (d) 9.26kJ kg -1 K -1 (d) Synthesis of ammonia from N2 and H2
Ans. (d)
Ans. (d)
THERMODYNAMICS AND THERMOCHEMISTRY 11

Sol. In the process of synthesis of ammonia from N2 and H2, Ans. (a)

number of moles decreases which implies that the T1 + T2

Sol. Final temperature = , let T2 > T1
change in entropy will be negative 2
dq C p dT
N 2 g + 3H 2 g ® 2NH3 g dS = =
T T
54. An ideal gas undergoes isothermal compression from 5
æT +T ö æT +T ö
m3 to 1 m3 against a constant external pressure of DSTotal = CP ln ç 1 2 ÷ + CP ln ç 1 2 ÷
4 Nm–2. Heat released in this process is used to increase
è 2T1 ø è 2T2 ø
2
the temperature of 1 mole of Al. If molar heat capacity of é T +T ù
= CP ln ê 1 2 ú
Al is 24J mol–1 K–1 the temperature of Al increases by:
êë 4T1T2 úû
(2019)
56. For the chemical reaction X ƒ Y the standard
3 reaction Gibbs energy depends on temperature T(in K)
(a) K (b) 2 K 3
2 -1
as D r Gº ln kJmol = 120 - T .
8
2
(c) K (d) 1 K The major component of the reaction mixture at T is:
3
(2019)
Ans. (c)
Sol. We known that, (a) Y if T = 300 K (b) Y if T = 280 K

w = -Pext Vf - Vi (c) X if T = 350 K (d) X if T = 315 K

w = -4Nm -2 1 - 5 m3 Ans. (d)

w = 16Nm Þ 16J 3
For isothermal compression, Sol. At 315K, DGº = 120 - T
8
DU = q + w DGº = 120 - 118.125 = positive
From calorimetry, Since DGº is positive then Keq < 1
Heat given = nCDT
y
So <1
1´ 24J ´ DT x
So, 16 = mol K
x > y
2
\ Change in temperature, DT = 3 K 57. The reaction MgO s + C s ® Mg s + CO g , for

55. Two blocks of the same metal having same mass and at which DHº = +491.1kJ mol –1 and DSº = 198.0 K -1 mol –1 ,
is not feasible at 298 K. Temperature above which
temperature T1, and T2, respectively, are brought in reaction will be feasible is
contact with each other and allowed to attain thermal (2019)
equilibrium at constant pressure. The change in (a) 2040.5 K (b) 1890.0 K
entropy, DS , for this process is: (2019)
(c) 2480.3 K (d) 2380.5 K
1
2 é ù Ans. (c)
é T1 + T2 ù T + T2 2
C p ln ê 1 ú
(a) C p ln ê 4T T ú (b) ê 4T1T2 ú
êë 1 2 úû êë Sol. MgO s + C s ® Mg s + CO g
ûú
é T1 + T2 ù é T1 + T2 ù For a reaction to be spontaneous
(c) 2C p ln ê 4T T ú (d) 2Cp ln ê 2T T ú
ë 1 2 û ë 1 2 û
 12 THERMODYNAMICS AND THERMOCHEMISTRY

(a) DU = 14kJ; D pV = 18kJ

DG < 0
DHº -TDSº < 0 (b) DU = 14kJ; D pV = 0.8kJ
DHº 491.1´ 100 (c) DU = 14kJ; D pV = 4kJ
ÞT> =T> = T > 2480.3K
DSº 198
(d) DU = 14kJ; D pV = 8.0 kJ
58. The standard reaction Gibbs energy for a chemical
Ans. (c)
reaction at an absolute temperature T is given
Sol. DU = nC v DT = 5 ´ 28 ´ 100 = 14 kJ
by D r G o = A - BT Where A and B are non-zone
constants. Which of the following is TRUE about this D PV = nR T2 - T1 = 5 ´ 8 ´100 = 4 kJ
reaction? (2019)
(a) Exothermic if B < 0 61. Among the following, the set of parameters that
represents path functions, is: (2019)
(b) Endothermic if A > 0
I. q + w II. q
(c) Endothermic if A < 0 and B < 0
III. w IV. H – TS
(d) Exothermic if A > 0 and B < 0
(a) II and III (b) II, III and IV
Ans. (b)
(c) I and IV (d) I, II and III
Sol. DGº = A - BT
A and B are non-zero constants Ans. (a)

DGº = DHº -TDSº = A - BT Sol. We know that heat and work are not state functions but
Reaction will be endothermic if DHº > 0 is a state function. H–TS (i.e. G) is also a state function.
59. Which one of the following equations does not H – TS(i.e. G) is also a state function.

correctly represent the first law of thermodynamics for 62. During compression of a spring the work done is 10 kJ
the given processes involving an ideal gas? (Assume and 2 kJ escaped to the surroundings as heat. The
non-expansion work is zero) (2019) change in internal energy, DU (in kJ) is: (2019)

(a) Cyclic process: q = –w (a) –12 (b) –8

(b) Adiabatic process: DU = - w (c) 8 (d) 12

(c) Isochoric process: DU = q Ans. (c)
(d) Isothermal process: q = - w Sol. w = 10 kJ
Ans. (b)
q = –2 kJ
Sol. From first law thermodynamics, DU = q + w
DU = q + w = -2 + 10 = 8kJ
For adiabatic process, q = 0
63. A process will be spontaneous at all temperature if:
\ DU = w
For isothermal process, DU = 0 (2019)
For cyclic process, DU = 0 (a) DH < 0 and DS < 0
For isochoric process, w = 0
(b) DH > 0 and DS < 0
60. 5 moles of an ideal gas at 100 K are allowed to undergo
(c) DH < 0 and DS > 0
reversible compression till its temperature becomes 200
K. If Cv = 28J K–1 mol–1, calculate DU and D(pV) for this (d) DH > 0 and DS > 0
process. (R = 8.0 Jk–1 mol–1) (2019) Ans. (c)
Sol. A reaction is spontaneous if DG sys is negative.
THERMODYNAMICS AND THERMOCHEMISTRY 13
DG sys = DHsys - TDSsys Ans. (a)
A reaction will be spontaneous at all temperatures if
DH sys is negative and DH sys is positive.

64. The difference between DH and DU DH - DU ,

when the combustion of one mole of heptane(l) is Sol.
carried out at a temperature T, is equal to: (2019)
(a) –4 RT (b) –3 RT

(c) 4 RT (d) 3 RT DH atomisation = DH vap + y

Ans. (a)
x - y = DH vap
D
Sol. C7 H16 l + 11O2 g ¾¾
® 7CO2 g + 8H 2 O l
67. The true satement amongst the following (2020)
DH - DU = Dn g RT (a) S is a function of temeprature but DS is not a function
Dn g = no. of moles of product in gaseous state- no. of of temperature
moles of reactant in gaseous state. (b) Both DS and S are functions of temperature
QDn g = -4 (c) Both S and DS are not functions of temperature
\DH - DU = -4RT (d) S is not a function of temperature but DS is a function
of temperature
65. Enthalpy of sublimation of iodine is 24 cal g–1 at 200oC.
Ans. (b)
If specific heat of I2(s) and I2(vap) are 0.055 and 0.031
Sol. Entropy is a function of temperature, at any temperature,
cal g–1 K–1 respectively, then enthalpy of sublimation of
the entropy can be given as :
iodine at 250oC in cal g–1 is: (2019)
T nCdT
(a) 2.85 (b) 5.7 ST = ò
0 T
(c) 22.8 (d) 11.4 Change in entropy is also a function of temeprature, at
any temperature, the entropy change can be given as :
Ans. (c)
dq
Sol. Heat or reaction depend upon temperature i.e., it varies DS = ò
T
with temperature, as given by Kirchoff’s equation,
68. For one mole of an ideal gas, which of these statements
T2 must be true? (2020)
DH T2 = DH Ti + ò DC p dT (i) U and H each depends only on temeprature.
T1
(ii) Compressiblity factor z is not equal to 1
where DC P = C P of product –CP of reactant
(iii) Cp.m - Cv,m = R
\ DC P = 0.031 - 0.055 = -0.024cal / g
(iv) dU = CvdT for any process
Now, DH T2 - DH T1 = DCP T2 - T1 (a) (i), (iii) and (iv) (b) (i) and (iii)

DH 250 - DH 200 = -0.024 523 - 473 (c) (iii) and (iv) (d) (ii), (iii) and (iv)
Ans. (a)
DH 250 = 24 - 50 ´ 0.024 = 22.8cal / g
Sol. For ideal gas U = f(T), H = f(T)
66. If enthalpy of atomisation for Br2(l) is x kJ /mol and bond Z=1
enthalpy for Br2 is y kJ/mol, the relation between them :
CP - CV = R
(a) is x > y (b) is x < y
dU = CV–dt
(c) is x = y (d) does not exist
Hence, option (a) is correct.
(2020)
69. The process that is not endothermic in nature is: (2020)
 14 THERMODYNAMICS AND THERMOCHEMISTRY
72. The magnitude of work done by gas that undergoes a
(a) H (g) + e - ® H (g)
-
reversible expansion along the path ABC shown in figure
is ________. (2020)
(b) Na (g) ® Na (g+ ) + e-

(c) Ar(g) + e - ® Ar(g)

-

-
(d) O(g) + e - ® O(g)
2-

Ans. (a)

Sol. H (g) + e - ® H (g)

-

Ans. (48.00)
is an exothermic reaction.
Sol. Wok done by the gas = The area under the curve
Numerical Value Type Questions
= (Area of the square) + (Area of the triangle) = 48 J
70. For the reaction A(l) ® 2B(g)
73. At constant volume, 4 mol of an ideal gas when heated
DU = 2.1kcal, DS = 20 Cal K -1 at 300 K, Hence DG in from 300 to 500 K changes its internal energy by 5000 J.
kcal (numeric value) is (2020) The molar heat capacity at constant volume is _____ .
Ans. (2.70) (2020)

Sol. DH = DU + DngRT Ans. (6.25)

Sol. DU = nC v DT
DH = 2100 + (2 ´ 2 ´ 300)(R = 2 Cal K -1mol -1 )
5000 = 4 × Cv(500-300)
= 3300 cal
Cv = 6.25 JK-1 mol-1
DG = DH - T DS
74. The internal energy change (in J) when 90 g of water
DG = 3330 - (300 ´ 20) = -2.7kcal undergoes complete evaporation at 100oC is

71. The standard heat of formation (D f H 298o ) of ethane (in (Given : DH vap for water at 373 K = 41 kJ / mol, R = 8.314
JK-1 mol-1) (2020)
kJ/mol), if the heat of combustion of ethane, hydrogen
and graphite are -1560, -393.5 and -286 kJ/mol, respectively, Ans. (189494.39)
is __________. (2020)
Sol. H 2 O(l) ® H 2 O(g)
Ans. (-192.50)
DE vap = DH vap - DngRT
Sol. C(graphite) + O 2 (g) ® CO2 (g) DHco = -286kJ / mol......(1)
= 41000 ´ 5 - 5 ´ 8.314 ´ 373 = 189494.39
H 2 (g) + 0.5O 2 (g) ® H 2 O(l) DH co = -393.5 kJ / mol ....(2)
75. The heat of combution of ethanol into carbon dioxide and
C 2 H 6 (g) + 3.5O 2 (g) ® 2CO 2 (g) + 3H 2 O(l) DHc o = water is -327 kcal at constant pressure. The heat evolved
(in cal) at constant volume and 27oC (if all gases behave
-1560kJ / mol ....... (3) ideally) is (R = 2 cal mol-1 K-1) .......... . (2020)

2C(graphite) + 3H 2 (g) ® C2 H6 (g); DH of = ? Ans. (-326400.00)

By inverting (3) and multiplying (1) by 2 and (2) by 3 and Sol. DH 0c [C2 H5 OH] = -327kcal
adding, we get,
C 2 H5 OH(l) + 3O 2 (g) ® 2CO 2 (g) + 3(H 2 O)(l)
2 × (-286) + 3 × (-393.5) - (-1560) = -192.5 kJ/mol
DE 0c = DH 0c - DngRT
= -327 × 1000 - (-1) × 2 × 300
= -327000 + 600 = -326400
THERMODYNAMICS AND THERMOCHEMISTRY 15

76. For a dimerization reaction, 2A(g) ® A 2 (g) at 298 K, -742.24 kJ mol-1. The magnitude of DH 298 for the reaction
DU ° = -20 kJ mol -1 , DS° = -30 kJ mol-1 , then the 3
NH 2 CN(s) + O2 (g) ® N 2 (g) + CO2 (g) + H 2 O(l)
DG ° will be ....... j. (2020) 2
Ans. (-13538.00) is _____ kJ. (Rounded off to the nearest integer)
Sol. 2A ® A 2 [Assume ideal gas and R = 8.314 J mol-1 K-1]
(2021-02-25/Shift - 1)
DU° = -20kJ
Ans. (741.00)
DH° = -2000 + (-1)R ´ 298
Sol. DH oreaction = DUoreaction + Dn g RT
DG° = -20000 - 298 + 30 ´ 298
æ 90 - 25 ö æ -1 ö é 8.314 ù
DG° = -20, 000 + 298 ç = -742.14 + ç ÷ ´ ê ú ´ 298
÷ è 2 ø ë 1000 û
è 3 ø
= -743.4KJ / mol
208 ´ 65
DG° = 20,000 + = -743.4 ; 743
3

DG ° = -13538J 79. Five moles of an ideal gas at 293 K is expanded isothermally

from an initial pressure of 2.1 MPa to 1.3 MPa against at
77. During which of the following processes, does entropy constant external pressure 4.3 MPa. The heat transferred
decrease? in this process is ______ kJ mol-1. (Rounded-off to the
(A) Freezing of water to ice at 0oC nearest integer) [Use R = 8.314 J mol-1 K-1]
(B) Freezing of water to ice at - 10oC (2021-02-25/Shift - 2)

(C) N 2 (g) + 3H 2 (g) ® 2NH 3 (g) Ans. (15.00)

(D) Adsorption of CO(g) on lead surface. 5 ´ 8.314 ´ 293

Sol. Vf = = 9369.23 ´ 10-6
1.3 ´ 106
(E) NaCl(s) ® Na + (aq) + Cl - (aq)
Choose the correct answer from the options given 5 ´ 8.314 ´ 293
Vi = = 5800 ´10 -6
below : (2021-03-17/Shift - 2) 2.1 ´ 106
(a) (A), (C) and (E) only W = -Pext (Vf - Vi )
(b) (A), (B), (C) and (D) only
= -4.3 ´ 106 (9369.23 - 5800) ´ 10-6 Jmol -1
(c) (A) and (E) only
(d) (B) and (C) only = -4.3 ´ 3569.23 J mol-1
Ans. (b) = 1537.7 J mol-1
Sol. A, B ® Freezing of water will decrease entropy as = -15.34 kJ mol-1 = Q = -W
particle will move closer and forces of attraction will
increase. This leads to decrease in randomness. So 15
Q= = 3KJ / mol
entropy decrease. 5
C ® No. of moleucles decreasing Q = 15 k J for g mol
D ® Adsorption will lead to decrease in randomness
of gaseous particles. 80. ˆˆ† C + D
For a chemical reaction A + B ‡ˆˆ
(2021-02-26/Shift - 1)
E ® NaCl(s) ® Na + (aq) + Cl- (aq) DS > 0
So, (A,B,C,D) decreases entropy (D r Hy = 80 kJ mol -1 ) the entropy change D r Sy
depends on the temperature T (in K) as
78. The reaction of cyanamide, NH2CN(s) with oxygen was
run in a bomb calorimeter and DU was found to be D r Sy = 2T(JK -1 mol-1 ).
 16 THERMODYNAMICS AND THERMOCHEMISTRY
Minimum temperature at which it will become
50
sponatneous is ________ K. (Integer) =- ´ 8.31´ 298 = -2218.05J
55.85
Ans. (200.00)
Nearest integer = –2218
Sol. For a reaction to be spontaneous
83. The standard enthalpies of formation of Al2O3 and CaO
DG = (DH - TDS) < 0 are -1675 kJ mol-1 and -635 kJ mol-1 resepectively

As DH = + ve & DS = + ve For the reaction

So reaction will be spontaneous above equilibrium 3CaO + 2Al ® 3Ca + Al2O3 the standard reaction enthalpy
temeprature. D r H o = ........kJ (2021-03-17/Shift - 1)
At equilibrium DH - T DS = 0 (Round off to the Nearest Integer).

T[2T] Ans. (230.00)

80 - =0
1000 Sol. DH of = DH of (Products) - DH of (Reactants)

2T 2 = DH of (Al2 O3 ) - 3 ´ DH of (CaO)
80 =
1000 = -1675 - 3 (-635) = 230 kJ
2 3
T = 40 ´10 84. For the reaction C 2 H 6 ® C 2 H 4 + H 2 the reaction
T = 200 K enthalpy D r H = ..........kJ mol-1. (Round off to the Nearest
81. The average S - F bond energy in kJ mol-1 of SF6 is ______. Integer) . (2021-03-18/Shift - 1)
(Rounded off to the nearest integer)
[Given : Bond enthalpies in kJ mol-1 : C - C = 347, C = C =
[Given : The values of standard enthalpy of formation of 611; C - H = 414, H - H = 436]
SF6(g), S(g) and F(g) are -1100, 275 and 80 kJ mol-1
Ans. (128.00)
respectively.] (2021-02-26/Shift - 2)
Sol. C2H6 ® C2H4 + H2
Ans. (309.00)
DH = ?
DH oreaction = 6(BES- F )
= 2 × EC-H - EC=C- EH-H + EC-C
Sol.
= DH s0 (F, g) + DH f0 (F, g) - DH f0 (SF6 , g) = 2 × 414 + 347 - 611 - 436
= 275 + 6 × 80 -(-1100) = 1855 = 828 + 347 - 1047
= 128 kJ/mol
æ 1855 ö
BES-F = ç ÷ = 309.17kJ / mol » 309kJ / mol 85. An average person needs about 10000 kJ energy per day.
è 6 ø
The amount of glucose (molar mass = 180.0 g mol-1) needed
82. At 25oC, 50 g of iron reacts with HCl to form FeCl2, The to meet this energy requirement is _____ g. (nearest
evolved hydrogen gas expands against a constant
integer) (Use : D C H(glucose) = -2700 kJ mol -1 )
pressure of 1 bar. The work done by the gas during this
expansion is (Round off to the Nearest Integer). (2021-07-20/Shift - 1)
-1 -1
[Given : R = 8.314 J mol K . Assume, hydrogen is an Ans. (667.00)
ideal gas] (2021-03-16/Shift - 2)
Sol. Given - D C H(glucose) is - 2700 kJ mol-1
[Atomic mass of Fe is 55.85 u]
It means that on combustion of one mole of glucose (180g),
Ans. (–2218.00)
2700 kJ energy is produced.
Sol. Fe + 2HCl ® FeCl 2 + H 2 (g) Thus, the mass of glucose required to produce 10000 kJ
50g 10000
energy = ´180 = 666.66 » 667g
2700
50
Moles of Fe = mol = moles of H 2
55.85 86. For a given chemical reaction A ® B at 300 K the free
energy change is -49.4 kJ mol-1 and the enthalpy of reaction
Wirrrev = -Pext .DV = - moles of H2 × RT
T
THERMODYNAMICS AND THERMOCHEMISTRY 17

is 51.4 kJ mol-1. The entropy change of the reaction is DU = q + w = 150 - 200 = -50J
_____ J K-1 mol-1. (2021-07-20/Shift - 2)
90. When 400 mL of 0.2 M H2SO4 solution is mixed with 600
Ans. (336.00) mL of 0.1 M NaOH solution, the increase in temperature
Sol. DG = DH - T DS of the final solution is ______ × 10-2 K. (Round off to the
nearest integer). (2021-07-27/Shift - 2)
Þ -49400 = 51400 - 300DS
[Use : H+(aq) + OH-(aq) ® H2O : D r H = -57.1 kJ mol -1 ]
Þ 300 DS = 51400 + 49400 = 1, 00,800
Specific heat of H2O = 4.18 J K-1 g-1
1, 00,800 Density of H2O = 1.0 g cm-3
Þ DS = = 336 J K -1mol-1
300
Assume no change in volume of solution on mixing.
1, 00,800 Ans. (82.00)
Þ DS = = 336 J K -1mol-1
300 Sol. m moles of H+ = 2 × 400 × 0.2 = 160 m moles
87. If the standard molar enthalpy change for combustion of m moles of OH- = 600 × 0.1 = 60 m moles
graphite powder is 2.48 × 102 kJ mol-1, the amount of heat Thus, 60 m moles of H+ will react with 60 m moles of OH-.
generated on combustion of 1 g of graphite powder is
_____kJ. (Nearest Integer) (2021-07-22/Shift - 2) Amount of heat liberated = 60 × 10-3 × 57.1 × 103 = 3426 J
Total volume of water = 400 + 600 = 1000 mL
Ans. (–21.00)
Thus, total mass of water = 1000 g
o
Sol. D c H (standard molar enthalpy change for combustion )
Now, q = msDT
is defined as the amount of heat liberated on combustion
of one mole of a substance. q 3426
Þ DT = = = 81.96 ´ 10 -2 K
12g of graphite powder on combustion gives 2.48 × 10 kJ 2 ms 1000 ´ 4.18
energy.
91. For water at 100oC and 1 bar,
Thus 1 g of graphite powder on combustion will give
D vap H - D vap U = ___________´ 102 Jmol-1
2.48´100
- = -20.67kJ energy = – 21.00 kJ.
12 (Round off to the Nearest Integer) [Use : R = 8.31 J mol-1
K-1]
88. At 298 K, the enthalpy of fusion of a solid (X) is 2.8 kJ mol-
1
and the enthalpy of vaporization of the liquid (X) is [Assume volume of H2O(l) is much smaller than volume of
98.2 KJ/mol–1. The enthalpy of sublimation of the H2O (g). Assume H2O(g) treated as an ideal gas].
substance (X) in KJ mol-1 is _______ . (in nearest (2021-07-27/Shift - 1)
integer)
Ans. (31.00)
(2021-07-25/Shift - 1)
Sol. The equation corresponding to vapourisation of water is
Ans. (101.00) written as -
Sol. Sublimation can be sum of as a combustion of fusion and
H 2 O(l) ® H 2 O(g)
vaporization
D sub H = D fus H + D vap H Now, D vap H - D vap U = Dn g RT = 1 ´ 8.31 ´ 373

Þ D sub H = 2.8 + 98.2 = 101 kJ mol -1 = 3099.63 = 30.9963 ´102 Jmol-1

89. A system does 200 J of work and at the same time absorbs 92. For water D vap H = 41kJmol-1 at 373 K and 1 bar pressure.
150 J of heat. The magnitude of the change in interval Assuming that water vapour is an ideal gas that occupies
energy is ________ J. (2021-07-25/Shift - 2) a much larger volume than liquid water, the internal energy
Ans. (–50.00) change during evaporation of water is ____ kJ mol-1
Sol. q = 150 J
w = -200 J
 18 THERMODYNAMICS AND THERMOCHEMISTRY

[Use : R = 8.3 J mol-1 K-1] (2021-08-26/Shift - 2)

æ DH o ö
Ans. (38.00) Sol. Tmin = ç o ÷
è DS ø
Sol. Given equation is

kJ D o H rxn = [ Df0 H(Fe) + D f0 H(CO)] -

H 2 O(l) ® H 2 O(g) : DH = 41
mol
[D 0f H(FeO) + D0f H(C(graphite) )]
Þ From the relation : DH = DU + Dn g RT
= [0 - 110.5] - [-266.3+ 0] = 155.8 kJ /mol
kJ 8.3
41 = DU + (1) ´ ´ 373 D o Srxn = [ Do S(Fe) + D o S(CO)] -
mol 1000

Þ DU = 41 - 3.0959 » 38kJ / mol [D oS(FeO) + D oS(C(graphite) )]

93. 200 mL of 0.2 M HCl is mixed with 300 mL of 0.1 M NaOH. = [27.28 + 197.6] - [57.49 + 5.74] = 161.65 J/mol - K
The molar heat of neturalization of this reaction is
-57.1 kJ. The increase in temperature in oC of the system 155.8 ´103 J / mol
on mixing is x × 10-2. The value of x is ______. (Nearest Tmin = = 963.8K » 964K
161.65J / mol - K
integer) [Given : Specific heat of water = 4.18 J g-1 K-1
Density of water = 1.00 g cm-3] Assume no volume change (nearest Integer)
on mixing) : (2021-08-27/Shift - 1)
95. ˆˆ† N 2 O4 (g), when
For the reaction 2NO 2 (g) ‡ˆˆ
Ans. (82.00)
-1
Sol. Millimoles of HCl = 200 × 0.2 = 40 DS = -176.0JK -1 and DH = -57.8 kJ mol , the
Millimoles of NaOH = 300 × 0.1 = 30 magnitude of DG at 298 K for the reaction is ____ kJ
mol-1. (Nearest integer) (2021-09-01/Shift - 2)
æ 3 ö Ans. (–5.00)
Heat released = ç ´ 57.1´ 1000 ÷ = 1713J
è 1000 ø
Sol. DG = DH - T DS
Mass of solution = 500 ml × 1 gm/ml = 500 gm
298(-176)
DG = -57.8 -
q 1713J 1000
Þ DT = = = 0.8196
m´C J
500g ´ 4.18 DG = -5.352kJ / mole
g.K
[Nearest integer value] = –5
= 81.96 × 10-2 K
94. Data given for the following reaction is as follows :
FeO(s) + C(graphite) ® Fe (s) + CO (g )
Substance DH o (kJ mol -1 ) DSo (J mol -1K -1 )

FeO(s) -266.3 57.49

C(graphite) 0 5.74
Fe(s) 0 27.28
CO(g) -110.5 197.6

The minimum temperature in K at which the reaction

becomes spontaneous is _______. (Integer answer)
(2021-08-27/Shift - 2)
Ans. (964.00)