6 Thermodynamics

Chapter 6
Thermodynamics
Solutions
SECTION - A
Objective Type Questions
1. Tea placed in thermos flask is an example of
(1) Open system (2) Close system
(3) Isolated system (4) It can't act as system
Sol. Answer (3)
A thermos flask does not allow exchange of energy and matter. Hence, it is an isolated system.
2. Gaseous system is placed with pressure P1, volume V1 and temperature T1, it has undergone thermodynamic
changes where temperature is remaining constant, it is
(1) Adiabatic process (2) Isothermal process (3) Isobaric process (4) Isochoric process
Sol. Answer (2)
A system which undergoes change such that temperature remains constant. Such a change is called isothermal
process.
3. The respective examples of extensive and intensive properties are

(1) Enthalpy, Entropy (2) Entropy, Enthalpy
(3) Entropy, Temperature (4) Temperature, Entropy
Sol. Answer (3)
Entropy is an extensive property (mass dependent). Temperature is intensive since it is mass independent.
4. A thermally isolated, gaseous system can exchange energy with the surroundings. The mode of energy may
be
(1) Heat (2) Work (3) Heat and radiation (4) Internal energy
Sol. Answer (2)
Since the system is thermally isolated, energy can only be transferred through a non-thermal mode i.e. work.
5. Which of the following is a state function?

(1) q (2) w (3) q+w (4) All of these
Sol. Answer (3)
q (heat) and w (work done) are both path functions.
q + w = U, which is change in internal energy, which is a state function.
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46 Thermodynamics Solution of Assignment
6. For the reaction PCl5(g)  PCl3(g) + Cl2(g)

(1) H = E (2) H > E (3) H < E (4) Can’t predicted
Sol. Answer (2)
PCl5 (g)  PCl 3 (g)  Cl2 (g)
ng = 2 – 1 = 1
 H = U + ng RT
= U + RT
or, H > U. (∵ RT is positive)
where U = E i.e., change in internal energy.
7. If ‘r’ is the work done on the system and ‘s’ is heat evolved by the system then,
(1) E = r + s (2) E = r – s (3) E = r (4) E = s
Sol. Answer (2)
According to 1st law of thermodynamics,
U = q + w
w = +r (∵ work is done on the system)
q = –s (∵ heat is evolved out of system)
 U = r – s
8. For the reaction,
aA(s) + bB(g) 
 dD(s) + cC(g). Then
(1) H – E = (b – d) RT (2) H – E = (c – b) RT
(3) H – E = (a + b) – (c + d) RT (4) H – E = (a – d) RT
Sol. Answer (2)
For the reaction,
ng = (c – b) [∵ rest are solid substances]
We know,
H = U + ng RT
or, H = U + (c – b) RT
or, H – U = (c – b) RT
9. A system absorbs 10 kJ of heat and does 4 kJ of work. The internal energy of the system
(1) Decreases by 6 kJ (2) Increases by 6 kJ
(3) Decreases by 14 kJ (4) Increases by 14 kJ
Sol. Answer (2)
As per Ist law,
U = q + w
q = +10 kJ (heat is absorbed by the system)
w = –4 kJ (work is done by the system)
 U = q + w = 10 – 4 kJ = +6 kJ
Solution of Assignment Thermodynamics 47
10. In a reaction, all reactant and products are liquid, then
(1) H > E (2) H < E (3) H = E (4) Can't predicted
Sol. Answer (3)
∵ All reactants and products are liquid,
hence, ng = 0
where, ng signifies change in moles of gaseous substances.
 H = U + ng RT
or, H = U
11. Regarding the internal energy of the molecule, which of the following statement is correct?
(1) Its absolute value can be successfully calculated
(2) Its absolute value cannot be determined
(3) It is the sum of vibrational and rotational energies
(4) Both (1) & (3)
Sol. Answer (2)
The absolute value of internal energy cannot be determined since it is the sum total of all the energies at a
molecular level. These energies cannot be determined and hence the absolute value of U cannot be determined.
12. Consider the following reaction :

C (graphite) + O2(g)CO2(g) ; H = – x1 cal
C (diamond) + O2(g) CO2(g) ; H = – x2 cal
What is the heat of transition of graphite into diamond?
(1) x1 + x2 (2) x2 – x1 (3) x1 – x2 (4) x1 x 2
Sol. Answer (2)
Required equation
C graphite   C diamond
C graphite   O2  CO2  g ; H   x, cal
CO2  C diamond  O2  g ; H   x2 cal
Adding, we get C graphite   C diamond  H  x2 – x1 cal
13. For the given reactions, A 

 D ; H = x. Steps involved are
A 
 B ; H1 = x1
B 
 C ; H2 = ?
C 
 D ; H3 = x3
(1) H2 = x – (x1 + x3) (2) H2 = x + x1 + x3 (3) H2 = x1 – x3 – x (4) H2 = (x1 + x) – x3
Sol. Answer (1)
Given reactions are H1 H2 H3
A B C D
We know,
H = H1 + H2 + H3
or, H2 = H – H1 – H3
= x – (x1 + x3) H
14. The heats of combustion of yellow P and red P are –9.91kJ and –8.78kJ respectively. The heat of transition
of yellow to red phosphorus is
(1) –18.69 kJ (2) +1.13 kJ (3) +18.69 kJ (4) –1.13 kJ
Sol. Answer (4)
5 1
P yellow   O2  g  P2O5  s  ; H1   9.91kJ
2 2
5 1
P red  O2  g  P2O5  s  ; H2   8.78 kJ
2 2
Rearranging, we get
5
P yellow   O2  g  P2O5  g ; H   9.91kJ
2
5
P2O5  Pred  O2  g ; H   8.78 kJ
2
Adding these two equations, we get
P yellow   Pred ;  9.91  8.78  kJ   1.13 kJ
15. If the heat of formation of NO2 is ‘x’

[½ N2(g) + O2(g)  NO2(g)] the heat of reaction
N2(g) + O2(g)  2NO(g) is y and the heat of reaction
2NO(g) + O2(g)  2NO2(g) is z, then
(1) 2x + z = y (2) 2y + z = x (3) 2x – z = y (4) 2z + x = y
Sol. Answer (3)
Given:
⎛1 ⎞
2  ⎜ N2  g   O2  g   NO2  g  ; H  x ⎟
⎝ 2 ⎠
= N2  g  2O2  2NO2  g ; H1  2x
Also,
N2  O2  2NO  g ; H  y
2NO  O2  2NO2 ; H  z
Adding, we get
N2  2O2  2NO2 ; H2  y  z
∵ H1 = H2 (∵ H is state function)

 2x = y + z
16. In the reactions

HCl + NaOH  NaCl + H2O + x cal.
H2SO4 + 2NaOH  Na2SO4 + 2H2O + y cal.
y
(1) x = y (2) x = 2y (3) x= (4) x y
2
Sol. Answer (3)
HCl  NaOH  NaCl  H2 O  x cal
where x cal is the heat released due to neutralisation of 1 g equivalent of acid by 1 g equivalent base.
In the 2nd reaction,
H2SO4  2NaOH  Na2SO4  2H2O  y cal

Now, 2 g equivalents of strong acid reacts with 2 g equivalent of strong base, thus releasing double of energy
released in the 1st reaction.
 y = 2x
17. Hf C2H4 = 12.5 kcal

Heat of atomisation of C = 171 kcal
Bond energy of H2 = 104.3 kcal
Bond energy C – H = 99.3 kcal
What is C = C bond energy?
(1) 140.7 kcal (2) 49 kcal (3) 40 kcal (4) 76 kcal
Sol. Answer (1)
Given:
2C graphite   2H2  g  C2H4  g ; Hf
Hf = Bond dissociation enthalpy of reactants – Bond dissociation enthalpy of products

= 12.5 = (171 × 2) + 2 × 104.3 – (4 × 99.3 + BEC = C)
 BE(C = C) = 140.9 kcal
18. The difference between H and E for the reaction

2C6H6 (l) +15O2(g)  12CO2(g) + 6H2O (l) at 25°C in kJ is
(1) –7.43 kJ (2) +3.72 kJ (3) –3.72 kJ (4) +7.43 kJ
Sol. Answer (1)
Given reaction:
2C6H6  l  15O2  g  12CO2  g  6 H2O  l
ng = 12 – 15 = – 3 mol
H = U + ng RT
or, H – U = – 3 × 8.314 Jk–1 mol–1 × 298 K × mol = –7.432 kJ
19. S (rhombic) + O2 (g) SO2 (g); H = –297.5 kJ

S (monoclinic) + O2 (g) SO2(g); H = –300 kJ
The above data can predict that
(1) Rhombic sulphur is yellow in colour
(2) Monoclinic sulphur has metallic lustre
(3) Monoclinic sulphur is more stable
(4) H(Transition) of S(R) to S(M) is endothermic process
Sol. Answer (4)
Sr hombic   O2  g  SO2  g ; H  –297.5 kJ …(1)
Smonoclinic   O2  g  SO2  g ; H  –300 kJ …(2)
Subtracting (2) from (1),
Sr hombic   Smonoclinic  ; H   297.5  300  kJ   2.5 kJ
 This transition is endothermic.
20. If S + O2 SO2; H = –298.2 kJ

SO2 + 1/2O2 SO3; H = –98.7 kJ
SO3 + H2O H2SO4; H = –130.2 kJ
H2 + 1/2O2 H2O; H = –287.3 kJ
then the enthalpy of formation of H2SO4 at 298 K is
(1) –814.4 kJ (2) –650.3 kJ (3) –320.5 kJ (4) –433.5 kJ
Sol. Answer (1)
H2  g  S  2O2  g  H2SO4 ;  f
Given:
S  O2  SO2 ; H = – 298.2 kJ
1
SO2  O2  SO3 ; H = – 98.7 kJ
2
SO3  H2O  H2SO 4 ; H = – 130.2 kJ
1
H2  O2  H2O ; H = – 287.3 kJ
2
Additing all these, we get
H2  S  2O2  H2 SO 4 ; H' = – 814.4 kJ
 Hf = H' = – 814.4 kJ
21. The volume of a gas expands by 0.25 m3 at a constant pressure of 103N m–2. The work done is equal to
(1) 2.5 erg (2) 250 J (3) 250 watt (4) 250 newton
Sol. Answer (2)
We know, work done, w = – Pex + V.
Given, pressure is 103 N m–2
and, V = 0.25 m3
 w = – 103 Nm–2 × 0.25 m3 = – 250 J
So, work done by the gas is 250 J.
22. When 1 g of anhydrous oxalic acid is burnt at 25°C, the amount of heat liberated is 2.835 kJ. H combustion
is (oxalic acid : C2H2O4)
(1) –255.15 kJ (2) –445.65 kJ (3) –295.24 kJ (4) –155.16 kJ
Sol. Answer (1)
1
H2C2O 4  s   O2  g   2CO2  g   H2O  l 
 oxalic acid 2
We know,
Hcombustion = Amount of heat liberated when 1 mole of substance reacts with oxygen.
Mol. wt. of oxalic acid = 90 g mol–1
1 g oxalic acid liberates 2.835 kJ
 90 g (1 mole) oxalic acid liberates 2.835 × 90 kJ mol–1 = 255.15 kJ
 Heat involved = – 255.15 kJ
23. The heat of neutralization of LiOH and HCl at 25°C is 34.868 kJ mol–1. The heat of ionisation of LiOH will be
(1) 44.674 kJ (2) 22.232 kJ (3) 32.684 kJ (4) 96.464 kJ
Sol. Answer (2)
Let heat of ionization be a of LiOH.
x Hne
 LiOH  Li  OH  HCl 
4  LiCl  H O
2
H = – 34.868 kJ
 x – 57.1 kJ mol–1 = – 34.868 kJ mol–1

or, x = (57.1 – 34.868) kJ mol–1 = 22.232 kJ
24. Which compound will absorb the maximum amount of heat when dissolved in the same amount of water?
(Integral heats of solution at 25°C in kcal/mol of each solute are given in brackets)
(1) HCl (H = –17.74) (2) HNO3 (H = –7.85)
(3) NH4NO3 (H = +16.08) (4) NaCl (H = +1.02)
Sol. Answer (3)
Maximum heat is absorbed by NH4NO3
 H = + 16.08 (maximum positive value)
25. HA + OH–H2O + A– + q1 kJ
H+ + OH–  H2O + q2 kJ
The enthalpy of dissociation of HA is
(1) (q1 + q2) (2) (q1 – q2) (3) (q2 – q1) (4) –(q1 + q2)
Sol. Answer (3)
HA  H  A  ; H
Given:
HA  OH  H2O  A   q1 kJ ; H  – q1 kJ
q2 kJ  H2O  H  OH ; H   q2 kJ
Adding, we get
HA  H  A  ; H   q2 – q1  kJ
26. An athlete takes 100 g of glucose of energy equivalent to 1560 kJ. How much amount of energy is uptaken
by 1 g molecule of glucose?
(1) 15.6 kJ (2) 2808 kJ (3) 1560 kJ (4) 28.08 kJ
Sol. Answer (2)
100 g 1560 kJ
1560
180 g  180 kJ
100
∵ wt. of 1 gram molecule
1560  180
= 180 g which gives kJ = 2808 kJ
100
27. C6H12 (l) + 9O2(g)  6H2O(l) + 6CO2(g);H298= – 936.9 kcal. Thus

(1) –936.9 = E –(2×10–3 × 298 × 3) kcal (2) +936.9 = E +(2×10–3 × 298 × 3) kcal
(3) –936.9 = E –(2×10–3 × 298 × 2) kcal (4) –936.9 = E +(2×10–3 × 298 × 2) kcal
Sol. Answer (1)
ng = 6 – 9 = – 3
 H = U + ng RT
or, U = H – ng RT
= – 936.9 kcal – (– 3 R × 298 K)
or, – 936.9 kcal = U + (– 3 × 2 cal k–1 mol–1 × 298 K)
= U – (3 × 2 × 298 × 10–3 ) kcal
U = E = change in internal energy.
28. For strong acid strong base neutralisation energy for 1 mole H2O formation is –57.1 kJ. If 0.25 mole of strong
monoprotic acid is reacted with 0.5 mole of strong base then enthalpy of neutralisation is
(1) –(0.25 × 57.1) (2) 0.5 × 57.1 (3) 57.1 (4) –(0.5 × 57.1)
Sol. Answer (1)
1 mole of strong monoprotich acid reacts with 1 mole of strong base to give – 57.1 kJ
 0.25 mol of strong acid will react with only 0.25 mol of strong base (and not 0.5 mol)
 Energy involved = – 57.1 kJ × 0.25
29. The heat of combustion of solid benzoic acid at constant volume is –321.3 kJ at 27°C. The heat of combustion
at constant pressure is
(1) –321.3 – 300R (2) –321.30 + 300R (3) –321.3 – 150R (4) –321.3 + 900R
Sol. Answer (3)
COOH
15
 O2 g  7CO2 g  3H2O
2
15 1
ng = 7 – =–
2 2
We know,
H = U + ng RT
H = qP
U = qV
 qP = qV + ng RT
⎛ 1 ⎞
= – 321.3 + ⎜   300 K  R ⎟
⎝ 2 ⎠
= – 321.3 – 150 R
1
30. H2 (g)  O2 (g) 
H2O( )
2
H2O(l)  H2O(g); H = x4
Given, EH–H = x1
EO=O = x2
EO–H = x3
HF of H2O vapour is
x2 x2 x2 x2
(1) x1   x3  x 4 (2) 2x 3  x1   x4 (3) x1   2x 3  x 4 (4) x1   2x 3  x 4
2 2 2 2
Sol. Answer (4)
1 Hf
H2 g  O2 g   H2O g
2
H
H2O ()
x4
1
Now, for H2  g  O2  g  H2O   ; H
2
1
H = (B.D.E)reactants – (B.D.E)products = x1  x 2  2x3
2
1
Hf = H + x4 = x1  x 2  2x3  x 4
2
31. A cylinder contains either ethylene or propylene. 12 ml of gas required 54 ml of oxygen for complete
combustion. The gas is
(1) Ethylene (2) Propylene
(3) 1 : 1 mixture of two gases (4) 1 : 2 mixture
Sol. Answer (2)
12 ml of gas requires 54 ml of O2
9
or, 1 mole of gas requires mole of O2
2
If the gas is C2H4
C2H4  3O2  2CO2  2H2O
If the gas is propylene
9
C3H6  O2  3CO2  3H2O
2
9
It is clear that propylene (1 mole) requires moles of oxygen. As per the data, 12 ml of gas requires 54
2
9
ml of oxygen and hence 1 part of gas requires parts of oxygen by moles.
2
 The gas is propylene
32. The specific heat of a gas is found to be 0.075 calories at constant volume and its formula wt is 40. The
atomicity of the gas would be
(1) One (2) Two (3) Three (4) Four
Sol. Answer (1)
Specific heat = 0.075 calories
 Molar specific heat capacity, CV = 0.075 × 40 = 3 cal mol–1 k–1
 CP = CV + R = 3 cal mol–1 k–1 + 2 cal mol–1 k–1 = 5 cal mol–1 k–1
CP 5
     1.66
CV 3
 Monoatomic gas.
33. H(g) + O(g)  O – H(g); H for this reaction is

(1) Heat of formation of O – H (2) Bond energy of O – H
(3) Heat of combustion of H2 (4) Zero at all temperatures
Sol. Answer (2)
H  g  O  g  O – H  g ; H
H = (B.D.E)reactants – (B.D.E)Products
= O – Bond energy of O – H
 H = – Bond energy of O – H
34. Energy required to dissociate 4 g of gaseous H2 into free gaseous atoms is 872 kJ at 25°C. The bond energy
of H-H bond will be
(1) 8.72 kJ (2) 4.36 kJ (3) 436 kJ (4) 43.6 kJ
Sol. Answer (3)
H2 g   2H  g ; H
1mole (2g)
H = (B.D.E)reactants – (B.D.E)Products = Bond energy of H2

Given that 4 g of H2 requires 872 kJ to dissociate
 2 g of H2 requires 436 kJ
 1 mole of H2 require 436 kJ
 H = +436 kJ = Bond energy of H2
35. The dissociation energy of CH4 (g) is 360 kcal mol–1 and that of C2H6 (g) is 620 kcal mol–1. The C – C bond energy
(1) 260 kcal mol–1 (2) 180 kcal mol–1 (3) 130 kcal mol–1 (4) 80 kcal mol–1
Sol. Answer (4)
H
C C(g) + 4 H (g) ; H7
H H
H
H H
H C–C–H 2 C(g) + 6 H (g) ; H2
H H
Given: H1 = 360 kcal mol–1 ; H2 = 620 kcal mol–1
Also, H1 = 4 × Bond energy of C – H = 360 kcal mol–1
 Bond energy of C – H = 90 kcal mol–1
Now, H2 = 6 × Bond energy of C – H + Bond energy of C – C
H2 = 6 × 90 kcal mol–1 + Bond energy of C – C
∵ H2 = 620 kcal mol–1
 620 kcal mol–1 = 540 kcal mol–1 + Bond energy of C – C or, Bond energy of C – C = 80 kcal mol–1
36. The enthalpy of reaction,

2HCCH + 5O2  4CO2 + 2H2O
If the bond energies of C–H, CC, O=O, C=O and O–H bonds are p, q, r, s, t respectively
(1) [8s + 4t] – [4p + q + 5r] (2) [4p + 2q + 5r] – [8s + 4t]
(3) [4p + 2q + 5r + 8s + 4t] (4) [2p + q + 5r] – [8s + 4t]
Sol. Answer (2)
Given: H H
2H – C  C – H + 5O = O  4O = C = O + 2 O
H is enthalpy of reaction.
H = (B.D.E)reactants – (B.D.E)products

= 2  ECH  ECH   2 ECC  5 EOO  –  4  ECO  ECO   2 EOH  EOH  
=  4ECH  2 ECC  5 EOO    8ECO  4EOH 
= 4p + 2q + 5r – (8s + 4t)
37. Using bond energy data, calculate heat of formation of isoprene
5C(s) + 4H2(g) H 2C = C – CH = CH 2
CH3
Given C–H, H–H, C–C, C = C and C(s)  C(g) respectively as 98.8 kcal, 104 kcal, 83 kcal,
147 kcal, 171 kcal
(1) – 21 kcal (2) 21 kcal (3) 40 kcal (4) 50 kcal
Sol. Answer (2)
Given
H
H H
Hf
5 C(s) + 4 H2(g) C=C–C=C
H H
5x C
H H
H H
C(g) + 4 H2(g)
 H = (B.D.E)reactants – (B.D.E)products
= 4 EH – H – (2 EC = C + 8 EC – H + EC – C)
 Hf = 5x + H (∵ H is a state function)
x = 171 kcal
 Hf = 5 × 171 kcal + [4 × 104 kcal – (2 × 147) – 8 × 98.8 kcal] – 2 × 83 kcal
= 855 kcal + (416 kcal – 294 kcal – 790.4 kcal – 166 kcal)
= 20.6 kcal  21 kcal
38. In a flask colourless N2O4 is in equilibrium with brown coloured NO2. At equilibrium when the flask is heated
at 100°, the brown colour deepens and on cooling it becomes less coloured. The change in enthalpy, H for
formation of NO2 is
(1) Negative (2) Positive (3) Zero (4) Undefined
Sol. Answer (2)

N2O4
2NO2
Upon heating, brown colour deepens, i.e. NO2 is formed.
 The reaction is as follows

N2O4  H
2NO2
The reaction is, hence, endothermic.
39. For which of these reactions will there be S positive?

(1) H2O(g) H2O(l) (2) H2(g) + I2(g) 2HI(g)
(3) CaCO3(s) CaO(s) + CO2(g) (4) N2(g) + 3H2(g)2NH3(g)
Sol. Answer (3)
For the 3rd reaction,
CaCO3 (s)  CaO(s)  CO2 (g)
1 solid reactant gives 1 solid and 1 gaseous product and as a result increases disorder liness
 S = positive
40. For stretched rubber, Entropy
(1) Increases (2) First increases then decreases
(3) Decreases (4) First decreases then increases
Sol. Answer (3)
For stretched rubber, entropy decreases.
∵ Upon releasing , it regains its original shape
 Spontaneous process, S = positive
So, for the reverse process (stretching),
S must have been negative.
41. The least random state of H2O is

(1) Ice (2) Liquid water
(3) Steam (4) Randomness is same in all
Sol. Answer (1)
Least random state of H2O would be its solid state, i.e. ice.
42. S for the reaction: MgCO3(s)  MgO(s) + CO2(g)

(1) Zero (2) –ve (3) +ve (4) 
Sol. Answer (3)
MgCO3  s   MgO  s   CO2  g
S = SCO  SMgO  SMgCO

2 3
∵ MgO and MgCO3 are solids, so their entropy is almost same.
 S = SCO i.e., S is positive.

2
43. The standard entropies of N2 (g), H2 (g) and NH3 (g) are 191.5, 130.5, 192.6 JK–1 mol–1. The value of Sº of
formation of ammonia is
(1) –98.9 JK–1 mol–1 (2) Zero (3) +129.4 JK–1 mol–1 (4) –29.4 JK–1 mol–1
Sol. Answer (1)
1 3
N2  H2  NH3
2 2
S° = SNH  SH  SN

3 2 2
⎛3 1 191.5 ⎞
= (192.6 JK–1 mol–1 × 1 mol) – ⎜  130.5 JK  JK 1 ⎟
⎝ 2 2 ⎠
= 192.6 JK–1 – 195.75 JK–1 – 95.75 JK–1

= – 98.9 JK–1 for 1 mole of NH3
44. What is the increase in entropy when 11.2 L of O2 are mixed with 11.2 L of H2 at STP?
(1) 0.576 J/K (2) 5.76 J/K (3) 7.56 J/K (4) 2.76 J/K
Sol. Answer (2)

Smix = – n R × 2.303 xH2 log H2  xO2 log O2 
Total moles = (0.5 + 0.5) moles = 1 mole
1
xH2  xO2 
2
11.2
∵ moles of O2 = = 0.5
22.4
11.2
moles of H2 = = 0.5
22.4
S = – 1 mol × 8.314 JK–1 (0.5 log 0.5 + 0.5 log 0.5)
= – 8.314 JK–1 (– log 2) = + 5.76 JK–1

45. Given S C2H6 = 225 J mol-1K–1,

SC 2H4
o
= 220 J mol–1K–1, SH = 130 J mol–1K–1. Then S° for the process
2
C2H4 + H2  C2H6 is
(1) +25 J (2) –125 J (3) 135 J (4) 315 J
Sol. Answer (2)
For the reaction,
C2H4  H2  C2H6
 S° = SC2H4  SC2H4  SH2
= (225 – 220 – 130) JK–1
46. For the melting of NaCl heat required is 7.26 kcal mol–1 and S increases by 6.73 cal mol–1k–1. The melting
point of the salt is
(1) 805.75°C (2) 500 K (3) 1.77 K (4) 1.77°C
Sol. Answer (1)
Let melting temperature = T
Hfusion
 Sfusion =
T
Hfusion
 T = S
fusion
7.26 cal mol1

= = 1078.75 K
6.73 cal mol1 k 1
 T = 1078.75 K or (1078.75 – 273)°C = 805.75°C
47. The S for the reaction
o
2H2(g) + O2(g)  2H2O(l) at 300 K when SHo 2 (g) = 126.6, SO2 (g) = 201.20,
SH 2O (l)= 68.0JK–1mol–1 respectively is
(1) –318.4JK–1mol–1 (2) 318.4JK–1mol–1 (3) 31.84 JK–1mol–1 (4) 3.184 JK–1mol–1
Sol. Answer (1)
2H2  g  O2  g  2H2O  

 S = 2  SH2O – 2  SH2  SO2 
 1 1 1
= 2 × 68.0 JK–1 mol–1 – 2  126.6 J mol J K  201.20 J K mol
1

= [136 – (253.2 + 201.2)] J K–1 mol–1 = – 318.4 J K–1 mol–1
48. Which of the following is correct?

H S Nature of reaction
(1) (–) (+) Spontaneous only at high temperature
(2) (+) (–) Nonspontaneous regardless of temperature
(3) (+) (+) Spontaneous only at low temperature
(4) (–) (–) Spontaneous at all temperatures
Sol. Answer (2)
If H > 0 and S < 0
 – TS would always be positive (∵ T is positive always)
 
H 
 TS is always positive

Always Always
positive positive
 G is always positive.
49. Entropy of vaporisation of water at 100°C, if molar heat of vaporisation is 9710 cal mol–1 will be
(1) 20 cal mol–1 K–1 (2) 26.0 cal mol–1 K–1 (3) 24 cal mol–1 K–1 (4) 28.0 cal mol–1 K–1
Sol. Answer (2)
Molar entropy of vaporisation of water,
 Hvap m 9710 cal mol1

 Svap m 
T

373 K
= 26.03 cal mol–1 K–1
50. A particular reaction at 27°C for which H > 0 and S > 0 is found to be non-spontaneous. The reaction may
proceed spontaneously if
(1) The temperature is decreased (2) The temperature is increased
(3) The temperature is kept constant (4) It is carried in open vessel at 27°C
Sol. Answer (2)

A reaction is spontaneous when G < 0,
We know,
G = 
H 
 TS

Positive Negative
So, G < 0 only when

H < TS
So, the reaction would proceed only when temperature is high.
51. It is impossible for a reaction to take place if

(1) H is +ve and S is +ve (2) H is –ve and S is +ve
(3) H is +ve and S is –ve (4) H is –ve and S is –ve
Sol. Answer (3)
It is impossible for a reaction to occur when G > 0 which is possible only when H > 0 and when S < 0.
52. The standard free energy change G° is related to K (equilibrium constant) as
(1) G° = –2.303 RT logK (2) G° = 2.303 RT logK
(3) G° = RT logK (4) G° = –RT logK
Sol. Answer (1)
We know,
G = G° + RT ln Q ; Q = Reaction quotient.
At equilibrium, G = 0 ; Q = K
 0 = G° + RT ln K
or, G° = – RT ln K = – 2.303 RT log K
53. The sole criterion for the spontaneity of a process is

(1) Tendency to acquire minimum energy
(2) Tendency to acquire maximum randomness
(3) Tendency to acquire minimum energy and maximum randomness
(4) Tendency to acquire maximum stability
Sol. Answer (4)
The sole criterion for the spontaneity of a process is the tendency to acquire maximum stability.
54. For an endothermic reaction to be spontaneous

(1) G = 0 (2) G > 0
(3) G < 0 (4) G may be +ve or –ve
Sol. Answer (3)
Whatever the process be (endothermic or exothermic), G has to be negative for the process to be
spontaneous.
55. At 27°C the reaction,
C6H6(l) + 15/2 O2(g) 6CO2(g) + 3H2O(l)
proceeds spontaneously because the magnitude of
(1) H = TS (2) H > TS (3) H < TS (4) H > 0 and TS < 0
Sol. Answer (2)
For the given reaction,
S = negative (∵ Lesser number of gaseous products are formed)
 –TS = positive
But H = –ve
Since, it is a combustion reaction and hence exothermic.
∵ G = H – TS ; So for G to be negative, |H| > |TS|
SECTION - B
Objective Type Questions
1. For two mole of an ideal gas
R
(1) Cp, m – Cv, m = R (2) Cp – Cv = (3) Cv – Cp = –2R (4) Cp – Cv = 0
2
Sol. Answer (1)
For two, three or even thousand moles of an ideal gas,
Cp, m – Cv, m = R ; where Cp, m is molar heat capacity at const. pressure while Cv, m is molar heat capacity at
const. volume.
2. When an ideal gas is compressed adiabatically and reversibly, the final temperature is
(1) Higher than the initial temperature (2) Lower than the initial temperature
(3) The same as the initial temperature (4) Dependent on the rate of compression
Sol. Answer (1)
When an ideal gas is compressed adiabatically and reversibly,
Then q = 0
 According to 1st law:
U = q + w = w
∵ Gas is compressed  work done is positive i.e. w is positive in magnitude
 U is positive
 T is positive as well.
3. S° will be highest for the reaction
1
(1) Ca  O2 (g)  CaO(s) (2) CaCO3(s)  CaO(s) + CO2(g)
2
(3) C(s) + O2(g)  CO2(g) (4) N2(g) + O2(g)  2NO(g)
Sol. Answer (2)
S° would be highest for the reaction for which ng is most positive.
In this case, CaCO3  s   CaO  s   CO2  g
ng = +1 which is maximum for this case.
4. In an irreversible process, the value of

Ssystem + Ssurr is
(1) +ve (2) –ve (3) Zero (4) All of these
Sol. Answer (1)
For any process, whether reversible or irreversible,
Suniverse > 0
 Ssystem + Ssurroundings > 0.
5. A closed flask contains a substance in all its three states, solids, liquids and vapour at its triple point. In this
situation the average KE of the water molecule will be
(1) Maximum in vapour state (2) Maximum in solid state
(3) Greater in the liquid than in vapour state (4) Same in all the three states
Sol. Answer (4)
The triple point for water exists at a particular temperature.
∵ Temperature is same  K.E. of water is also same.
6. In thermodynamics a process is called reversible when

(1) System and surrounding change into each other
(2) There is no boundary between system and surrounding
(3) The surroundings are always in equilibrium with the system
(4) The system changes into the surroundings spontaneously
Sol. Answer (3)
A process is reversible only when the system and surroundings are always in equilibrium with each other.
7. The molar heat capacity of water at constant pressure P is 75 J K–1 mol–1. When 1.0 kJ of heat is supplied
to 1000 g of water, which is free to expand, the increase in temperature of water is
(1) 1.2 K (2) 2.4 K (3) 4.8 K (4) 0.24 K
Sol. Answer (4)
Molar heat capacity of water is 75 J K–1 mol–1
 To raise temperature by 1°C (or 1 K), heat required is 75 J for 1 mole of water
i.e. 75 J for 18 g of H2O.
75
So for 1 g of H2O, heat required is J
18
75
 Specific heat capacity = J g–1 K–1
18
 q = mCT
q 1000 J
or, T = 
mC 75
1000 g  J K 1 g1
18
18
= K = 0.24 K
75
8. 16 kg oxygen gas expands at STP (1 atm) isobarically to occupy double of its original volume. The work done
during the process is nearly
(1) 260 kcal (2) 180 kcal (3) 130 kcal (4) 271 kcal
Sol. Answer (4)
We know, work done,
w = – Pex + V
= – P V (∵ pressure is constant)
= – P(2V – V) ; where V is initial volume
= – PV
= – nRT (Considering ideal behaviour)
16000 g
n=  500 mol
32 g mol1
R = 2 cal mol–1 K–1

T = 273 K
 w = – 500 mol × 2 × 273 cal mol–1 K–1 × K = – 273 cal
 work done by oxygen gas is 271 cal.
9. The enthalpy and entropy change for a chemical reaction are –2.5 × 103 cal and 7.4 cal K–1 respectively.
Predict the nature of reaction at 298 K is
(1) Spontaneous (2) Reversible (3) Irreversible (4) Non-spontaneous
Sol. Answer (1)
H = – 2.5 × 103 cal
S = + 7.4 cal K–1
∵ H < 0 and S > 0
 G < 0  Process is spontaneous
10. The temperature at which the given reaction is at equilibrium
1
Ag2O(s)  2Ag(s) + O (g)
2 2
H = 30.5 kJ mol–1 and S 0.066 kJ mol–1 K–1

(1) 462.12 K (2) 362.12 K (3) 262.12 K (4) 562.12 K
Sol. Answer (1)
At equilibrium, G = 0
 H = TS (at equilibrium)
H 30.5 k J mol1
T=   462.12 K
S 0.066 k J mol1 K 1
11. One mole of a non ideal gas undergoes a change of state (2.0 atm, 3.0 L, 95 K)  (4.0 atm, 5.0 L, 245 K)
with a change in internal energy U = 30.0 L atm. The change in enthalpy of the process in L atm is
(1) 40.0 (2) 42.3 (3) 44.0 (4) 56.0
Sol. Answer (3)
Enthalpy is given as,
H = U + pV
This can be rewritten as
H = U + (pV)
= U + (p2V2 – p1V1)
= 30.0 L atm + (4.0 atm × 5.0 L – 2.0 atm × 2.0 L)
= (30.0 + 14.0) L atm = 44.0 L atm
12. Which of the following can be zero for isothermal reversible expansion?
(1) E (2) H (3) T (4) All of these
Sol. Answer (4)
For an isothermal reversible expansion,
T = 0
 U or E = 0
Also, H = m CpT
∵ T = 0
 H = 0
13. In an insulated container water is stirred with a rod to increase the temperature. Which of the following is true?
(1) U = W  0, q = 0 (2) U = W = q  0
(3) U = 0, W = q  0 (4) W = 0, U = q  0
Sol. Answer (1)
∵ Container is isolated
 q=0
 According to first law,
U = q + W
or U = W
 U and W are both same in magnitude
∵ T increases
 U is positive
 U + W = 2 U = positive and hence non-zero.
14. Two atoms of hydrogen combine to form a molecule of hydrogen gas the energy of the H2 molecule is
(1) Greater than that of separate atoms (2) Equal to that of separate atoms
(3) Lower than that of separate atoms (4) Sometimes lower and sometimes higher
Sol. Answer (3)
2 atoms of hydrogen forms bond to form H2 molecule.  Bond is formed  Attractive forces  Energy is
released during the process.
15. The temperature of 15 ml of a strong acid increases by 2°C when 15 ml of a strong base is added to it. If 5
ml of each are mixed, temperature should increase by
(1) 0.6°C (2) 0.3°C (3) 2°C (4) 6°C
Sol. Answer (3)
Heat of neutralization, H depends upon number of gram equivalents of strong acid and strong base.
Number of g equivalents depends upon volume of acid/base taken.
 H  g equivalents of acid and base
 H  volume of acid and base
Also, H = qp = mCPT
H
or, T =
mCp
Cp is intensive variable
m
and = d  m = dV
V
H 1
 T = 
V Cp  d
We know, H  V
 H = KV (where K is proportionality constant)
K
 T =  Change in temperature remains constant when all these conditions are same.
Cp  d
16. The standard heat of formation of NO2(g) and N2O4(g) are 8.0 and 4.0 kcal mol–1 respectively. The heat of
dimerisation of NO2 in kcal is
(1) –12 kcal (2) 12 kcal (3) 4 kcal (4) 16 kcal
Sol. Answer (1)
1
N2  g   O2  g  NO2  g  ; H  8.0 kcal mol1
2
Reversing and multiplying 2,
2NO2  N2  2O2 ; H  – 16 kcal
Also,
N2  2O2  N2O4 ; H  4 kcal
Adding, we get
2NO2  N2O 4 ; H   12 kcal
1 1
17. If X2O(s)  X(s) + O2(g); H = 90 kJ. Then heat change during reaction of metal X with one mole of O2
2 4
to form oxide to maximum extent is
(1) 360 kJ (2) –360 kJ (3) –180 kJ (4) +180 kJ
Sol. Answer (2)
1 1
Given,  X2O  s   X  s   O2  g  ; H  90 kJ
2 4
1 1
 X  s  O2  g  X2O  s  ; H   90 kJ
4 2
Multiplying with 4, we get
4X  s   O2  g  2X2O  s  ; H   360 kJ
18. For a gaseous reaction :

A(g) + 3B(g)  3C(g) + 3D(g)
E is 17 kcal at 27°C. Assuming R = 2 cal K–1 mol–1 the value of H for the above reaction will be
(1) 15.8 kcal (2) 16.4 kcal (3) 18.2 kcal (4) 20.0 kcal
Sol. Answer (3)
Given: A  g  3B  g  3C  g  3D  g
ng = 6 – 4 = 2
We know,
H = U + pV
Considering ideal behaviour, we have
H = U + ngRT
= 17 kcal + 2 × 2 cal K–1 × 298 K
= (17000 + 4 × 298) cal
= 18192 kcal = 18.2 kcal
19. A mixture of 2 mole of CO and 1 mol of O2 is ignited. Correct relationship is

(1) H = U
(2) H > U
(3) H < U
(4) The relationship depends upon the capacity of vessel
Sol. Answer (3)
2CO  g  O2  g  2CO2  g
ng = 2 – 3 = –1
We know,
H = U – 1 × RT
 H = U – RT ⎡8  10  2 ⎤
⎢ ⎥
 H < U ⎣⇒ 8  10 ⎦
20. Bond dissociation energy of XY, X2 and Y2 (all diatomic molecules) are in the ratio of 1 : 1 : 0.5 and Hf of
XY is –200 kJ mol–1. The bond dissociation energy of X2 will be
(1) 800 kJ mol–1 (2) 200 kJ mol–1 (3) 300 kJ mol–1 (4) 400 kJ mol–1
Sol. Answer (1)
B.D.E of XY, X2 and Y2 are in the ratio 1 : 1 : 0.5
Let B.D.E. of XY be x, X2 be x and Y2 be 0.5 x.
Now, X2  g  Y2  g  2XY  g ; H
 H = – 2 × (B.D.E)XY + B.D.E X2
 B.D.E. Y
2

= – 2x + (x + 0.5 x) = – 0.5x
Also, Hf of XY is – 200 kJ mol–1
1 1
i.e. X2  g   Y2  g  XY  g ; Hf
2 2
 H = 2 × Hf = 2 × – 200 kJ mol–1 = – 400 kJ

So, 0.5x = + 400 kJ
 x = 800 kJ
21. Vapour density of a gas is 8. Its molecular mass will be

(1) 8 (2) 16 (3) 32 (4) 64
Sol. Answer (2)
We know,
Molecular mass of substance

Vapour density =
Molecular mass of H2
 Molecular mass of substance = 8 × 2 = 16
22. If x mole of ideal gas at 27°C expands isothermally and reversibly from a volume of y to 10y, then the work done is
y
(1) w = x R 300 ln y (2) w = – 300x R ln 10 y
1
(3) w = – 300x R ln 10 (4) w = 100x R ln y
Sol. Answer (3)
V2
Work done, w = – nRT ln V
1
10 y
= – x × R × 300 ln y
= – x × R × 300 ln 10
= – 300x R ln 10
23. Enthalpy of formation of NH3 is – X kJ and HH–H, HN–H are respectively Y kJ mol–1 andZ kJ mol–1. The value of
HN  N is
X
(1) Y – 6Z + (2) – 3Y + 6Z – 2X (3) 3Y + 6Z + X (4) Y + 6X + Z
3
Sol. Answer (2)
1 3
N2  g  H2  g  NH3  g ; Hf  – x kJ
2 2
Hf = H = (B.D.E)reactants – (B.D.E)products
1 3
= HN2  HH2  3NH
2 2
HNN 3
=  XY  3XZ
2 2
We have,
HNN 3Y
–X=  3 Z
2 2
⎛ 3Y ⎞
or, HNN = ⎜ 3Z   X ⎟  2 = 6Z – 3Y – 2X
⎝ 2 ⎠
24. A system X undergoes following changes
X  W  Z  X
(P1V1T1 ) (P2 V2T1 ) (P3 V2T2 ) (P1V1T1 )
The overall process may be called as

(1) Reversible process (2) Cyclic process
(3) Cyclic reversible process (4) Isochoric process
Sol. Answer (2)
∵ The system returns to its original state, the whole process is called a cyclic process.
25. The heat of neutralisation for strong acid and strong base forming 2 moles of water is
(1) – 2 × 57.1 kJ
(2) – 57.1 kJ
57.1
(3)  kJ
2
(4) Strong acid and strong base will not undergo neutralisation
Sol. Answer (1)
When 1 mole of water is formed upon neutralization, – 57.1 kJ is released when 2 moles of water are formed,
– 57.1 × 2 kJ of energy is released.
26. The value of H° in kJ for the reaction will be
CS2(l) + 4NOCl(g)  CCl4(l) + 2SO2 (g) + 2N2(g)
if
Hf (CS2 )   x Hf (NOCl)   y
Hf (CCl4 )   z Hf (SO2 )   r
(1) x + 4y – z – 2r (2) r + z + 4y – x
(3) 2r + z + 4y + x (4) x + 4y + z – 2r
Sol. Answer (4)
For the reaction,
CS2  l   4NOCl  g  CCl4  l   2SO2  g  2N2  g



 


H° = HfCCl4  HfSO2  2  HfN2  2  HfCS2 (l)   HNOCl   4
= z + 2(–r) + 2(0) – (– x) – (– y)
= x – 2r + x + y
Hf of N2(g) is o since if is in its reference state.
27. The heat liberated on complete combustion of 1 mole of CH4 gas to CO2(g) and H2O(l) is 890 kJ. Calculate the heat
evolved by 2.4 L of CH4 on complete combustion.
(1) 95.3 kJ (2) 8900 kJ (3) 890 kJ (4) 8.9 kJ
Sol. Answer (1)
CH4  g  2O2  g  CO2  g  2H2O  l  ; H
H is 890 kJ for 1 mole CH4

We know, 22.4 L means 1 mol
1
2.4 L means  2.4 mol = 0.107 mol
22.4
 H = 890 kJ × 0.107 = 95.23 kJ
28. The work done in an open vessel at 300 K, when 112 g iron reacts with dil HCl to give FeCl2, is nearly
(1) 1.1 kcal (2) 0.6 kcal (3) 0.3 kcal (4) 0.2 kcal
Sol. Answer (1)
2Fe  s   4HCl  2FeCl2  2H2
 ng = 2 mol
We know,
w = – pV = – ngRT
= – 2 mol × 2 cal mol–1 K–1 × 300 K
= – 1.2 kcal
So, work done = 1.2 kcal
29. Which statement is correct?
⎛ dH ⎞ ⎛ dE ⎞ ⎛ dH ⎞ ⎛ dE ⎞
(1) ⎜ ⎟ ⎜ ⎟ (2) ⎜ ⎟ ⎜ ⎟ R
⎝ dT ⎠P ⎝ dT ⎠ V ⎝ dT ⎠P ⎝ dT ⎠ V
⎛ dE ⎞
(3) ⎜ ⎟ for ideal gas is zero (4) All of these
⎝ dV ⎠ T
Sol. Answer (3)
For an ideal gas,
dU or dE = 0 when T is constant
⎛ dU ⎞ dU
 ⎜ dV ⎟ i.e., at constant volume is 0.
⎝ ⎠T dV
1
30. A schematic representation of enthalpy changes for the C( graphite )  O (g)  CO (g) reaction, is given below.
2 2
The missing value is
Cgraphite + O2(g)
??
CO(g) + ½O(g)
– 393.5 kJ
– 283.0 kJ
CO2(g)
(1) + 10.5 kJ (2) – 11.05 kJ (3) – 110.5 kJ (4) – 10.5 J

Sol. Answer (3)
Since enthalpy is state function,
H + (– 283.0 kJ) = – 393.5 kJ
or, H = – 110.5 kJ
31. Which of the following equations represent standard heat of formation of CH4?
(1) C(diamond) + 2H2(g)  CH4(g) (2) C(graphite) + 2H2(g)  CH4(g)
(3) C(diamond) + 4H(g)  CH4(g) (4) C(graphite) + 4H(g)  CH4(g)
Sol. Answer (2)
Standard heat of formation is enthalpy change when 1 mole of substance is formed from its constituents
elements in their reference states.
Reference state of carbon  graphite
 C graphite   2H2  CH4  g
32. Different types of systems are given below
Surrounding Surrounding
Work Matter
Heat Energy
System System
A B
The A and B systems respectively are
(1) Open system, Closed system (2) Isolated system, Closed system
(3) Adiabatic system, Isolated system (4) Closed system, Isolated system
Sol. Answer (4)
A  Both energy and matter is exchanged
B  Neither energy nor matter is exchanged
 A  open, B  isolated
33. Set of intensive properties is shown by

(1) Mole fraction, standard electrode potential, heat capacity
(2) Viscosity, refractive index, specific heat
(3) Density, Gibbs free energy, internal energy
(4) Number of moles, molarity, electrode potential
Sol. Answer (2)
Viscosity, refractive index, and specific heat do not depend upon mass and hence are intensive properties.
34. For the expansion occurring from initial to final stage in finite time, which is incorrect?
(1) Equilibrium exist in initial and final stage
(2) Work obtained is maximum
(3) Driving force is much greater than the opposing force
(4) Both (1) & (2)
Sol. Answer (2)
Work obtained is maximum in case of reversible process (i.e. process occurring in infinite time)
Hence, work done infinite time is not maximum.
35. Calorific value of ethane, in kJ/g if for the reaction

2C2H6 + 7O2  4CO2 + 6H2O; H = –745.6 kcal
(1) –12.4 (2) –52 (3) –24.8 (4) –104
Sol. Answer (2)
In the reaction, 2 moles of ethane yielded – 745.6 kcal
i.e., 2 × molar mass of C2H6 = 60 g
 60 g yields – 745.6 kcal
75.6 kcal
 1 g yields –
60 g
745.6  4.2
 1 g yields kJ g1  –52.2 kJ g1
60
Hence, calorific value of ethane is – 52.2 kJ g–1
SECTION - C
Previous Years Questions
1. For the reaction, X2O4(l)  2XO2(g)
U = 2.1 k cal, S = 20 cal K–1 at 300 K
Hence, G is [AIPMT-2014]
(1) 2.7 kcal (2) –2.7 kcal (3) 9.3 kcal (4) –9.3 kcal
Sol. Answer (2)
G = 0  H = TS
H 40630
 T=  K = 373.4 K
S 108.8
2. In which of the following reactions, standard reaction entropy change (S°) is positive and standard Gibb's
energy change (G°) decreases sharply with increasing temperature ? [AIPMT (Prelims)-2012]
1 1 1 1
(1) Mg(s)+ O (g)MgO(s) (2) C graphite + O2(g) CO2(g)
2 2 2 2 2
1 1
(3) C graphite + O (g)CO(g) (4) CO(g)+ O (g)CO2(g)
2 2 2 2
Sol. Answer (3)

For the reaction
1
C graphite   O2  g  CO  g
2
1 1
ng = 1  
2 2
 S is positive
and hence G decreases with increase in temperature
∵ G = H – TS
3. Standard enthalpy of vapourisation vapH(0) for water at 100C is 40.66 kJmol–1.The internal energy of vapourisation
of water at 100C (in kJmol–1) is [AIPMT (Prelims)-2012]
(1) +43.76 (2) +40.66 (3) +37.56 (4) –43.76
(Assume water vapour to behave like an ideal gas)
Sol. Answer (3)
We know,
or, U = H – ngRT
The reaction is
H2O  l   H2O  g
 ng = +1
 U = 40.66 kJ mol–1 – 1 mol × 8.314 J mol–1 K–1 × 373 K
= 40.66 – 3101 J
= + 37.56 J
4. The enthalpy of fusion of water is 1.435 kcal/mol. The molar entropy change for the melting of ice at 0C is
[AIPMT (Prelims)-2012]
(1) 5.260 cal/(mol K) (2) 0.526 cal/(mol K) (3) 10.52 cal/(mol K) (4) 21.04 cal/(mol K)
Sol. Answer (1)
Hfus
Sfus 
T
1.435  103 cal mol1


273 K
= 5.26 cal mol–1 K–1
5. Equal volumes of two monoatomic gases, A and B, at same temperature and pressure are mixed. The ratio
of specific heats (Cp/Cv) of the mixture will be [AIPMT (Mains)-2012]
(1) 0.83 (2) 1.50 (3) 3.3 (4) 1.67
Sol. Answer (4)
6. Which of the following is correct option for free expansion of an ideal gas under adiabatic condition?
(1) q = 0, T < 0, w  0 (2) q = 0, T  0, w = 0
(3) q  0, T = 0, w = 0 (4) q = 0, T  0, w = 0
Sol. Answer (4)
Free expansion  Pext = 0
 w=0
 U = w + q = q (∵ w = 0)
∵ Expansion is adiabatic
 q=0
Hence U = 0
 T = 0 (∵ U is proportional to temperature)
7. If the enthalpy change for the transition of liquid water to steam is 30 kJ mol–1 at 27°C, the entropy change
for the process would be [AIPMT (Prelims)-2011]
(1) 100 J mol –1 K–1 (2) 10 J mol –1 K–1 (3) 1.0 J mol –1 K–1 (4) 0.1 J mol –1 K–1
Sol. Answer (1)
Hvap 30000 J mol1

Svap    100 J mol1 K 1
T 300 K
8. Enthalpy change for the reaction, 4 H(g) 2H2 (g) is –869.6 kJ. The dissociation energy of H – H bond is
(1) + 217.4 kJ (2) – 434.8 kJ (3) – 869.6 kJ (4) + 434.8 kJ
Sol. Answer (4)
Given reaction:
4 H  g  2 H2  g
 H = B.D.E. of reactants – B.D.E. of products

= 0 – 2 × HH–H = – 2HH–H
This is equal to – 869.6 kJ
 – 2HH–H = – 869.6 kJ
 HH–H = + 434.8 kJ
9. Consider the following process

H(kJ/mol)
1
A B + 150
2
3B  2C+D – 125
E + A  2D + 350
For; B + D  E + 2C, H will be [AIPMT (Mains)-2011]
(1) –325 kJ/mol (2) 325 kJ/mol (3) 525 kJ/mol (4) –175 kJ/mol
Sol. Answer (4)
Given:
1
A  B ; H = + 150 kJ mol–1
2
 A  2B ; H = + 300 kJ mol–1 …(1)
Also given:
3B  2C  D ; H = – 125 kJ mol–1 …(2)
E  A  2D ; H = + 350 kJ mol–1
 2D  E  A ;H = – 350 kJ mol–1 …(3)
Adding (1), (2) and (3), we get
B  D  E  2C ; H = – 175 kJ
1 3
10. Standard entropies of X2, Y2 and XY3 are 60, 40 and 50 JK–1 mol–1 respectively. For the reaction X2  Y2 
2 2
XY3;H = –30kJ to be at equilibrium, the temperature should be [AIPMT (Prelims)-2010]
(1) 750 K (2) 1000 K (3) 1250 K (4) 500 K
Sol. Answer (1)
For the reaction to be at equilibrium,
G = 0
 H = TS
⎛1 3 ⎞
Now, S =  ⎜ S X2  S Y2 ⎟  S XY3
⎝ 2 2 ⎠
⎛ 60 3 ⎞
= ⎜ 50    40 ⎟ J K 1
⎝ 2 2 ⎠
= – 40 J K–1
H 30000 J
 T=   750 K
S 40
11. Match List-I (Equations) with List-II (Type of process) and select the correct option [AIPMT (Mains)-2010]
List-I List-II
(Equations) (Type of process)
a. Kp > Q (i) Non-spontaneous
b. G< RT ln Q (ii) Equilibrium
c. Kp = Q (iii) Spontaneous and endothermic
H
d. T > (iv) Spontaneous
S
(1) a(i), b(ii), c(iii), d(iv) (2) a(iii), b(iv), c(ii), d(i) (3) a(iv), b(i), c(ii), d(iii) (4) a(ii), b(i), c(iv), d(iii)
Sol. Answer (3)
12. Three moles of an ideal gas expanded spontaneously into vacuum. The work done will be
[AIPMT (Mains)-2010]
(1) Infinite (2) 3 Joules (3) 9 Joules (4) Zero
Sol. Answer (4)

For a spontaneous process,
G = H– TS < 0
or, H < TS
H
or, T
S
For a non-spontaneous process,

G > 0
or, G° + RT ln Q > 0 [∵ G = G° + RT ln Q]
∵ RT ln Q > 0
So, G° has to be greater in magnitude than RT ln Q for the reaction to be spontaneous.
∵ G° < RT ln Q Non spontaneous
kp = Q  G = 0
i.e. process is at equilibrium.
When kp > Q.
 Reaction will move in forward direction
 Spontaneous.
13. For vaporization of water at 1 atmospheric pressure, the values of H and S are 40.63 kJ mol–1 and 108.8
JK–1 mol–1 respectively. The temperature when Gibbs energy change (G) for this transformation will be zero,
is [AIPMT (Mains)-2010]
(1) 273.4 K (2) 393.4 K (3) 373.4 K (4) 293.4 K

Sol. Answer (3)
∵ Pext = 0
 w=0
14. The following two reactions are known :

Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g) ;
H = –26.8 kJ
FeO(s) + CO(g)  Fe(s) + CO2(g); H = –16.5 kJ
The value of H for the following reaction
Fe2O3(s) + CO(g)  2FeO(s) + CO2(g) is [AIPMT (Mains)-2010]
(1) +10.3 kJ (2) –43.3 kJ (3) –10.3 kJ (4) +6.2 kJ
Sol. Answer (4)
Fe2O3  CO  2 FeO  CO2 ;  r

Given:
Fe2 O3  3CO  2 Fe  3CO2 ; 1 …(1)
FeO  CO  Fe  CO2 ;  2

Multiplying by (2), and reversing, we get
2 Fe  2 CO2  2 FeO  2CO ;   2  2 …(2)
Adding 1 and 2, we get
Fe2O3  CO  2 FeO  CO2 ; Hr  H1 – 2 H2
= [– 26.8 – (2 × – 16.5)] kJ = + 6.2 kJ
15. The values of H and S for the reaction, C(graphite) + CO2(g)  2CO(g) are 170 kJ and 170 JK–1 respectively.
This reaction will be spontaneous at [AIPMT (Prelims)-2009]
(1) 910 K (2) 1110 K (3) 510 K (4) 710 K
Sol. Answer (2)
Reaction will be spontaneous at higher temperature when G < 0
At 1110 K
H – TS
G = (17000 J – 1110 × 170 J) = – 171.7 kJ i.e., G = – ve
16. From the following bond energies

H–H bond energy : 431.37 kJ mol–1
C = C bond energy : 606.10 kJ mol–1
C – C bond energy : 336.49 kJ mol–1
C – H bond energy : 410.50 kJ mol–1
Enthalpy for the reaction,
H H H H
C=C+H–H H–C–C–H
H H H H
will be [AIPMT (Prelims)-2009]
(1) –243.6 kJ mol–1 (2) –120.0 kJ mol–1 (3) 553.0 kJ mol–1 (4) 1523.6 kJ mol–1
Sol. Answer (2)
Given reaction :
H H H H
C=C +H–H H C C H ; Hr
H H H H
Hr = (B.D.E)reactants – (B.D.E)products
= HC = C + 4 HC – H + HH – H – Hc – C – (HC – H) × 6
= (606.10 + 4 × 410.5 + 431.37 – 336.49 – 6 × 410.5) kJ mol–1
= – 120.0 kJ mol–1
17. Bond dissociaton enthalpy of H2, Cl2 and HCl are 434, 242 and 431 kJ mol–1 respectively. Enthalpy of formation
of HCl is [AIPMT (Prelims)-2008]
(1) 245 kJ mol–1 (2) 93 kJ mol–1 (3) –245 kJ mol–1 (4) –93 kJ mol–1
Sol. Answer (4)
H2  Cl2  2HCl ; H

 H = HH–H + HCl–Cl – 2HH–Cl
= (434 + 242 – 2 × 431) kJ
= – 186 kJ
So, for 2 moles of HCl, H = – 186 kJ
 for 1 mole of HCl, H = – 93 kJ
18. For the gas phase reaction,

PCl5(g)
PCl3(g) + Cl2(g), which of the following conditions is correct ? [AIPMT (Prelims)-2008]
(1) H > 0 and S < 0 (2) H = 0 and S < 0

(3) H > 0 and S > 0 (4) H < 0 and S < 0
Sol. Answer (3)
PCl5  g  PCl3  g  Cl2  g
ng = 2 – 1 = + 1 S = positive

And since it is a decomposition reaction
 Bonds need to be broken
 Endothermic reaction (H = positive)
19. Which of the following are not state functions ?

(I) q + w
(II) q
(III) w
(IV) H-TS [AIPMT (Prelims)-2008]
(1) (II) and (III) (2) (I) and (IV) (3) (II), (III) and (IV) (4) (I), (II) and (III)
Sol. Answer (1)
q (heat) and w (work done) depend on path and hence are path functions.
20. Consider the following reactions :

(i) H+(aq) + OH– (aq) = H2O(l); H = –X1 kJ mol–1
1
(ii) H2(g) + O (g) = H2O(l); H = –X2 kJ mol–1
2 2
(iii) CO2(g) + H2(g) = CO(g) + H2O(l);
H = –X3 kJ mol–1
5
(iv) C2H2(g) + O (g) = 2CO(g) + H2O(l);
2 2
H = +X4 kJ mol–1
Enthalpy of formation of H2O(l) is [AIPMT (Prelims)-2007]
(1) +X1 kJ mol–1 (2) +X2 kJ mol–1 (3) +X3 kJ mol–1 (4) +X4 kJ mol–1
Sol. Answer (2)
21. Given that bond energies of H–H and Cl – Cl are 430 kJ/mol and 240 kJ/mol respectively and fH of HCl is –90
kJ/mol. Bond enthalpy of HCl is [AIPMT (Prelims)-2007]
(1) 245 kJ mol–1 (2) 2909 kJ mol–1 (3) 380 kJ mol–1 (4) 425 kJ mol–1
Sol. Answer (4)
22. Identify the correct statement for change of Gibbs energy for a system (Gsystem) at constant temperature and
pressure [AIPMT (Prelims)-2006]
(1) If Gsystem > 0, the process is spontaneous
(2) If Gsystem = 0, the system has attained equilibrium
(3) If Gsystem = 0, the system is still moving in a particular direction
(4) If Gsystem < 0, the process is not spontaneous
Sol. Answer (2)
23. Assume each reaction is carried out in an open container. For which reaction will H = E?
(1) H2(g) + Br2(g)  2HBr(g) (2) C(s) + 2H2O(g)  2H2(g) + CO2(g)
(3) PCl5(g) PCl3(g) + Cl2(g) (4) 2CO(g) + O2(g) 2CO2(g)
Sol. Answer (1)
24. The enthalpy and entropy change for the reaction

Br2(l) + Cl2(g)  2BrCl(g)
are 30 kJ mol–1 and 105 JK–1 mol–1 respectively. The temperature at which the reaction will be in equilibrium
is [AIPMT (Prelims)-2006]
(1) 285.7 K (2) 273 K (3) 450 K (4) 300 K
Sol. Answer (1)
At equilibrium,
G = 0
 H = TS
H 30000 J mol1
or, T = =  285.7 K
S 105 J K 1 mo 1
25. The enthalpy of combustion of H2, cyclohexene (C6H10) and cyclohexane (C6H12) are – 241, –3800 and –3920
kJ per mol respectively. Heat of hydrogenation of cyclohexene is [AIPMT (Prelims)-2006]
(1) – 121 kJ per mol (2) + 121 kJ per mol (3) + 242 kJ per mol (4) – 242 kJ per mol
Sol. Answer (1)
26. A reaction occurs spontaneously if [AIPMT (Prelims)-2005]

(1) TS < H and both H and S are +ve (2) TS > H and both H and S are +ve
(3) TS = H and both H and S are +ve (4) TS > H and H is +ve and S is –ve
Sol. Answer (2)
A reaction is spontaneous if G < 0.
 H – TS < 0
or, TS > H
Also, reaction is spontaneous when,
TS > H and H and S are +ve.
Reaction is never spontaneous if H is +ve and is -ve
27. Which of the following pairs of a chemical reaction is certain to result in a spontaneous reaction ?
(1) Exothermic and decreasing disorder (2) Endothermic and increasing disorder
(3) Exothermic and increasing disorder (4) Endothermic and decreasing disorder
Sol. Answer (3)
A chemical reaction is certainly spontaneous
if
H < 0 and S > 0
for which G < 0 at all temperature.
28. The absolute enthalpy of neutralisation of the reaction

MgO(s) + 2HCl(aq)  MgCl2(aq) + H2O(l)
will be [AIPMT (Prelims)-2005]
–1 –1
(1) Less than – 57.33 kJ mol (2) –57.33 kJ mol
(3) Greater than –57.33 kJ mol–1 (4) 57.33 kJ mol–1
Sol. Answer (1)
For this reaction,
MgO  s   2 HCl  aq   MgCl2  H2O

(Week base)
∵ MgO is weak, so extra energy is

required for its complete dissociation
Hence, Hn < 57.1 kJ mol–1
29. Which reaction, with the following values of H, S, at 400 K is spontaneous and endothermic?
(1) H = –48 kJ; S = + 135 J/K (2) H = –48 kJ; S = – 135 J/K
(3) H = +48 kJ; S = + 135 J/K (4) H = +48 kJ; S = – 135 J/K
Sol. Answer (3)
∵ G = H – TS
= + 48 kJ – 400 × 135 J K–1 (∵ Reaction has to be endothermic)
= (+ 48000 – 54000) J = – 6000 J
 G < 0
30. Three thermochemical equations are given below:

(i) C(graphite) + O2(g)  CO2(g); rH° = x kJ mol–1
1
(ii) C(graphite) + O (g)  CO(g); rH° = y kJ mol–1
2 2
1
(iii) CO (g) + O (g)  CO2(g); rH° = z kJ mol–1
2 2
Based on the above equations, find out which of the relationship given below is correct:
(1) x = y – z (2) z = x + y (3) x = y + z (4) y = 2z – x
Sol. Answer (3)
Subtracting equation (ii) from (i), we get
1
CO  O2  CO2 ; H  x  y kJ
2
Also, H = z kJ mol–1
 x–y=z
or, x = (y + z)
31. Following reaction occurring in an automobile 2C8H18(g) + 25O2(g)  16CO2(g) + 18H2O (g). The sign of H,
S and G would be
(1) –, +, + (2) +, +, – (3) +, –, + (4) –, +, –
Sol. Answer (4)
For the reaction, ng = 18 + 16 – 25 – 2 = + 7
 S = positive
It is a combustion reaction, H = negative
 G is negative, H is negative and S is positive.
32. When 5 litres of a gas mixture of methane and propane is perfectly combusted at 0°C and 1 atmosphere, 16
litre of oxygen at the same temperature and pressure is consumed. The amount of heat released from this
combustion in kJ (Hcomb (CH4) = 890 kJ mol–1, Hcomb (C3H8) = 2220 kJ mol–1) is
(1) 32 (2) 38 (3) 317 (4) 477
Sol. Answer (3)
Let volume of methane be x L
 volume of propane be (5 – x) L
For methane,
CH4 g  2 O2 g  CO2 g  2H2O l 

Volume reacted: x 2x
For propane,
C3H8  5O2  2CO2  4H2O

Volume reacted: 5  x  5 5  x 
We know, 16 L of oxygen is consumed.

 2x + 5 (5 – x) = 16
or, 2x + 25 – 5x = 16
or, 25 – 3x = 16
 x=3
So, volume of methane combusted = 3 L
3
 Moles of methane combusted = mol
22.4
3
Energy due to methane combusted =  890 kJ
22.4
Volume of propane combusted = 2 L
2
 Moles of propane combusted = mol
22.4
2
 Energy due to propane combusted =  2220 kJ
22.4
 Total energy released
⎛ 3 2 ⎞
= ⎜  890   2220 ⎟ kJ
⎝ 22.4 22.4 ⎠
1
=  3  890  4440  kJ
22.4
1
=  2670  4440  kJ = 317.41 kJ
22.4
33. If enthalpies of formation for C2H4(g), CO2(g) and H2O(l) at 25°C and 1 atm pressure are 52, –394 and –286
kJ/mol respectively, then enthalpy of combustion of C2H4(g) will be
(1) + 14.2 kJ/mol (2) + 1412 kJ/mol (3) – 141.2 kJ/mol (4) – 1412 kJ/mol
Sol. Answer (4)
C2H4  3 O2  2 CO2  2 H2O ; Hr
Hr = Enthalpy of combustion

Now,
2 C  s   2 H2  g  C2H4  g ; H1

2  C  s   O2  g   CO2  g  ; H2  …(1)
⎛ 1 ⎞
2  ⎜ H2  O2  g   H2O  g  ; H3 ⎟ …(2)
⎝ 2 ⎠
Also, we have,
C2H4  2 C  s   2 H2  g ; – H1 …(3)
Adding (1), (2), (3), we get
C2H4  3 O2  2 CO2  2 H2O ; Hr  – H1  2 H2  2 H3
Hr = [– 52 + 2 × (– 394) + 2 × (– 286)] kJ/mol

= – 1412 kJ./mol
34. For a reaction to occur spontaneously
(1) H must be negative (2) S must be negative
(3) (H – TS) must be negative (4) (H + TS) must be negative
Sol. Answer (3)
For a reaction to occur spontaneously,
G should be negative
 H – TS should be negative
35. Given that C + O2  CO2, H° = –x kJ

2CO + O2  2CO2, H° = –y kJ
What is heat of formation of CO?
y  2x 2x  y
(1) (2) 2x – y (3) y – 2x (4)
2 2
Sol. Answer (1)
1
C  s  O2  CO ; Hr
2
C  O2  CO2 ; H   x kJ
1 y
CO2  CO  O2 ; H  kJ
2 2
Adding, we get
1 y y  2x
C O2  CO : Hr   x 
2 2 2
36. Identify the correct statement regarding entropy

(1) At absolute zero of temperature, the entropy of all crystalline substances is taken to be zero
(2) At absolute zero of temperature, the entropy of a perfectly crystalline substance is +ve
(3) At absolute zero of temperature, entropy of a perfectly crystalline substance is taken to be zero
(4) At 0°C, the entropy of a perfectly crystalline substance is taken to be zero
Sol. Answer (3)
3rd law of thermodynamics states that at 0 K, entropy of a perfectly crystalline substance is zero.
37. One mole of an ideal gas at 300 K is expanded isothermally from an initial volume of 1 litre to 10 litres. The E for
this process is (R = 2 cal. Mol–1K–1)
(1) 1381.1 cal (2) Zero (3) 163.7 cal (4) 9 L atm
Sol. Answer (2)
 The process is isothermal, T = 0 and, U  T
 U = 0
38. In the reaction : S + 3/2 O2  SO3 + 2x kcal and SO2 + 1/2 O2  SO3 + y kcal, the heat of formation of
SO2 is
(1) (2x + y) (2) (x – y) (3) (x + y) (4) (y – 2x)
Sol. Answer (4)
S  O2  SO2 : H
3
Given : S  O2  SO3 : H1   2x kcal
2
1
and, SO3  SO2  O2 : H2  y kcal
2
Adding, S  O2  SO2 : H  H1  H2  y  2x kcal
39. At 27°C latent heat of fusion of a compound is 2930 J/mol. Entropy change is
(1) 9.77 J/mol·K (2) 10.77 J/mol·K (3) 9.07 J/mol·K (4) 0.977 J/mol·K
Sol. Answer (1)
Hfusion 2930 J mol1

Sfusion    9.77 J mol1 K 1
T 300 K
40. For the reaction

C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l), which one is true?
(1) H = E – RT (2) H = E + RT (3) H = E + 2RT (4) H = E – 2RT
Sol. Answer (1)
We know,
H = U + pV
For an ideal gas,
For the given reaction, ng = 2 – 3 = – 1
 H = U + (–1) RT = U – RT
41. Change in enthalpy for reaction, 2H2O2 (l )  2H2O (l ) +O2 (g) if heat of formation of H2O2(l ) and H2O(l ) are –188 and
–286 kJ/mol respectively, is
(1) –196 kJ/mol (2) +196 kJ/mol (3) +948 kJ/mol (4) –948 kJ/mol
Sol. Answer (1)
2H2O2  2H2O  O2 ; Hr
Given:
H2  O2  H2O2 ; H1   188 kJ mol1
 
2  H2O2  H2  O2 ; – H1  188 kJ mol1 
⎛ 1 ⎞
and 2  ⎜ H2  O2  H2O ; H2  – 286 kJ mol1 ⎟
⎝ 2 ⎠
Adding, we get
2H2O2  2H2O  O2 ; Hr  2 2  2  – 1 
= [– 286 × 2 + 2(188)] kJ
= (– 572 + 376) kJ = – 196 kJ
42. When 1 mol of gas is heated at constant volume temperature is raised from 298 to 308 K. Heat supplied to
the gas is 500 J. Then which statement is correct?
(1) q = U = –500 J, w = 0 (2) q = U = 500 J, w = 0
(3) q = w = 500 J, U = 0 (4) U = 0, q = w = –500 J
Sol. Answer (2)
∵ Volume is constant
 V = 0
 – pex + V = 0
 w=0
As per 1st law of thermodynamics,
U = q + w = q = +500 J
1
43. Enthalpy of CH4 + O  CH3OH is negative. If enthalpy of combustion of CH4 and CH3OH are x and y
2 2
respectively. Then which relation is correct?
(1) x > y (2) x < y (3) x = y (4) xy
Sol. Answer (1)
1
CH4  O2  CH3 OH ; H  0
2
Given:
CH4  2 O2  CO2  2 H2 O ; H1   x …(1)
3
CH3 OH  O2  CO2  2 H2O ; Hr  y
2
3
 CO2  2H2O  CH 3 OH  O2 ; H'   y …(2)
2
Adding (1) and (2), we get
1
CH4  O2  CH3 OH ; H  x  y
2
We know, H < 0
 x–y<0
∵ |x|>|y|
44. Unit of entropy is

(1) JK–1 mol–1 (2) J mol–1 (3) J–1 K–1 mol–1 (4) JK mol–1
Sol. Answer (1)
Unit of molar entropy is J K–1
Unit of entropy is J K–1
Entropy is represented in terms of molar entropy to make it an intensive variable.
45. In a closed insulated container a liquid is stirred with a paddle to increase the temperature which of the following
is true?
(1) E = W  0, q = 0 (2) E = W = q  0
(3) E = 0, W = q  0 (4) W = 0, E = q  0
Sol. Answer (1)
Since container is insulated,
q=0
According to 1st Law,
U = q + W = W  0 [work is done]
46. 2 mole of ideal gas at 27°C temperature is expanded reversibly from 2 lit. to 20 lit. Find entropy change (R =
2 cal/mol K)
(1) 92.1 (2) 0 (3) 4 (4) 9.2
Sol. Answer (4)
We know,
V2
S = 2.303 nR log
V1
Given: V2 = 20 L ; V1 = 2 L
n = 2 mol., R = 2 cal mol–1 K–1
20
 S = 2.303 × 2 mol × 2 cal mol–1 K–1 × log = 9.2 cal K–1
2
47. Heat of combustion for C(s), H 2 (g) and CH 4 (g) are –94, –68 and –213 kcal/mol, then H for
C(s) + 2H2(g)  CH4(g) is
(1) –17 kcal (2) –111 kcal (3) –170 kcal (4) –85 kcal
Sol. Answer (1)
C  2H2  CH4 ; H
Given;
C  O2  CO2 ; H1 …(1)
⎛ 1 ⎞
2  ⎜ H2  O2  H2O ; H2 ⎟ …(2)
⎝ 2 ⎠
CH4  2 O2  CO2  2 H2O ; H3
 CO2  2 H2O  CH4  2 O2 …(3)
Adding (1), (2) and (3), we get
C  2 H2  CH4 ; H  H  2H2 – H3
= [– 94 + 2 (– 68) – (– 213)] kcal

= – 17 kcal
48. For the reaction
C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l)
at constant temperature, H – E is
(1) + RT (2) – 3RT (3) + 3RT (4) – RT
Sol. Answer (2)
For the reaction,
ng = 3 – (5 + 1) = – 3
 H = U + ngRT
 H – U = –3RT
49. What is the entropy change (in JK–1 mol–1) when one mole of ice is converted into water at 0°C? (The enthalpy
change for the conversion of ice to liquid water is 6.0 kJ mol–1 at 0°C)
(1) 20.13 (2) 2.013 (3) 2.198 (4) 21.98
Sol. Answer (4)
Hfusion 6.0 kJ mol1

Sfusion    21.98 J mol1 K 1
T 273 K

50. For which one of the following equations is Hreact equal to Hf for the product?
(1) N2(g) + O3(g)  N2O3(g) (2) CH4(g) + 2Cl2(g)  CH2Cl2(l) + 2HCl(g)

(3) Xe(g) + 2F2(g)  XeF4(g) (4) 2CO(g) + O2(g)  2CO2(g)
Sol. Answer (3)
In the 3rd reaction,
All the reactants are in their referance states and 1 mole of product is formed.
Hence, Hf = Hreaction
51. The molar heat capacity of water at constant pressure, C, is 75 J K–1 mol–1. When 1.0 kJ of heat is supplied
to 100 g of water which is free to expand, the increase in temperature of water is
(1) 1.2 K (2) 2.4 K (3) 4.8 K (4) 6.6 K
Sol. Answer (2)
Given: Cp, m = 75 J K–1 mol–1
We know, qp = Cp , m × n T
qp 1000 J 100
or, T =   mol = 2.4 K
Cp,m  n 1 1 18
75 J K mol
52. Standard enthalpy and standard entropy changes for the oxidation of ammonia at 298 K are
–382.64 kJ mol–1 and –145.6 J mol–1, respectively. Standard Gibb’s energy change for the same reaction at
298 K is
(1) –221.1 kJ mol–1 (2) –339.3 kJ mol–1 (3) –439.3 kJ mol–1 (4) –523.2 kJ mol–1
Sol. Answer (2)

G = H – TS
⎡ ⎛ 145.6 ⎞ ⎤
= ⎢ 382.64  298 K ⎜ 1000 ⎟ ⎥ kJ mol–1
⎣ ⎝ ⎠⎦
= – 339.3 kJ mol–1
53. Considering entropy (S) as a thermodynamic parameter, the criterion for the spontaneity of any process is
(1) Ssystem + Ssurroundings > 0 (2) Ssystem – Ssurroundings > 0
(3) Ssystem > 0 only (4) Ssurroundings > 0 only
Sol. Answer (1)
For a spontaneous process,
Suniverse > 0
or, Ssystem + Ssurrounding > 0
54. The work done during the expansion of a gas from a volume of 4 dm3 to 6 dm3 against a constant external
pressure of 3 atm is (1 L atm = 101.32 J)
(1) –6 J (2) –608 J (3) +304 J (4) –304 J
Sol. Answer (2)
We know,
w = – pext V
= – 3 atm (6 L – 4 L )
= – 3 × 2 L atm
= – 6 × 101.32 J
= – 607.92 J
55. The enthalpy of hydrogenation of cyclohexene is –119.5 kJ mol–1. If resonance energy of benzene is –150.4
kJ mol–1, its enthalpy of hydrogenation would be
(1) –358.5 kJ mol–1 (2) –508.9 kJ mol–1 (3) –208.1 kJ mol–1 (4) –269.9 kJ mol–1
Sol. Answer (3)
Enthalpy of hydrogenation of cyclohexene = – 119.5 kJ mol–1
 Expected enthalpy of hydrogenation of benzene = (– 119.5 × 3) kJ mol–1
non-resonated benzene
Eres
resonated benzene
Energy
E
cyclohexane
 E + Eres = Expected heat of hydrogenation
or, E = (– 119.5 × 3 + 150.4) kJ mol–1
= – 208.1 kJ mol–1
56. 2Zn + O2  2ZnO; G° = –616 J
2Zn + S2  2ZnS; G° = –293 J
S2 + 2O2  2SO2; G° = –408 J
G° for the following reaction
2ZnS + 3O2  2ZnO + 2SO2 is
(1) –1462 J (2) –1317 J (3) –501 J (4) –731 J
Sol. Answer (4)
Given:
2 Zn  O2  ZnO ; G  – 616 J
2 ZnS  2 Zn  S2 ; G   293 J
S2  2 O2  2 SO2 ; G   408 J
Adding, we get
2 ZnS  3 O2  2 ZnO  2 SO2 ; G   616  293  408  J   1462 J
SECTION - D
Assertion - Reason Type Questions
1. A : Cdiamond  Cgraphite
H and U are same for this reaction.
R : Entropy increases during the conversion of diamond to graphite.
Sol. Answer (2)
For the reaction, ng = 0
 H = U
Also, graphite is more disordered because of sp2 hybridization and  electrons.
 S is +ve
2. A : Specific heat is an intensive property.

R : Heat capacity is an extensive property.
Sol. Answer (2)
q
Specific heat C = m T
q Extensive
  Intensive
m Extensive
q
Heat capacity, S =
T
∵ q is extensive
 S is also extensive
3. A : All reactions which are exothermic are spontaneous.

R : All reactions in which entropy increases are spontaneous.
Sol. Answer (4)
Not all exothermic reactions are spontaneous. Neither those reactions in which entropy increases. Only those
reactions are spontaneous for which G < 0.
4. A : Enthalpy of neutralisation of 1 equivalent each of HCl and H2SO4 with NaOH is same.
R : Enthalpy of neutralisation is always the heat evolved when 1 mole acid is neutralised by a base.
Sol. Answer (3)
1 eq of strong acid and strong base gives out – 57.1 kJ g eq–1
Enthalpy of neutralisation is heat evolved when 1 g equivalent of acid reacts with 1 g equivalent of base.
5. A : q and w are path function.

R : q + w is a state function.
Sol. Answer (2)
q and w are path functions, while, q + w = U is a state function and do not depend upon path.
6. A : Dissolution of sugar in water proceed via increases in entropy.

R : Entropy decreases when egg is hard boiled.
Sol. Answer (3)
Dissolution of sugar in water results in increase in entropy
C12H22O11  H2O  C6H12O6  C6H12O6

Glucos e fructose
When egg is boiled, bonds are broken
and egg attains a more disordered state
 S = +ve
Also, egg is boiled  spontaneous process.
So, G < 0 at 100°C
∵ H is +ve, S must be +ve for G to be –ve
7. A : For an isolated system G = –TStotal.

R : For an isolated system q = 0.
Sol. Answer (2)
For an isolated system,
H = 0
 G = – TStotal
8. A : Combustion is an exothermic process.

R : Combustion is a spontaneous process.
Sol. Answer (2)
Combustion is exothermic and also spontaneous.
Since G < 0.
9. A : Total enthalpy change of a multistep process is sum of H1 + H2 + H3 + .....
R : When heat is absorbed by the system, the sign of q is taken to be negative.
Sol. Answer (3)
∵ H is a state function, So for multistep process,
H = H1 + H2 + H3 + ……
Also, when heat is absorbed by the system, q is +ve.
10. A : Bond energy is equal to enthalpy of formation with negative sign.

R : Bond energy is energy required to dissociate 1 mole single bond.
Sol. Answer (3)
Bond energy is the energy required to dissociate 1 mole of bonds (can be single, double or triple)  Reason
is false.
Now, Hr = (B.E.)reactants – (B.E.)products
Lets take an example, of H2O
1
H2  O2  H2O ; Hf
2
Hf = (B.E.)reactants – (B.E.)products
Hf = – (Hf)reactants + (Hf)products
Comparing, (Hf) = – B.E.
11. A : H is positive for endothermic reactions.

R : If total enthalpies of reactants and products are HR & HP respectively then for an endothermic reaction HR <
HP.
Sol. Answer (1)
If HR and HP are total enthalpies of reactants and products respectively, then for an endothermic reaction
HR < HP
or, HP – HR < 0
 H < 0
12. A : The energy of the universe is constant, whereas the entropy of the universe is continuously increasing.
R : For spontaneous process S > 0.
Sol. Answer (2)
For universe, energy is constant while
S > 0
Also, for a spontaneous process,
Suniverse > 0
13. A : A non-spontaneous process becomes spontaneous when coupled with a suitable spontaneous reaction.
R : The overall free energy of coupled spontaneous reaction is negative.
Sol. Answer (1)
Overall free energy change for coupled spontaneous reaction is –ve.
Also, A non spontaneous reaction becomes spontaneous if coupled with another reaction so that
Goverall < 0.
14. A : An ideal crystal has more entropy than a real crystal.

R : An ideal crystal has more disorder.
Sol. Answer (4)
An ideal crystal has lesser entropy (more ordered) than a real crystal.
15. A : Work done in an irreversible isothermal process at constant volume is zero.

R : Work is assigned negative sign during expansion and is assigned positive sign during compression.
Sol. Answer (2)
Work done at constant volume = 0
∵ w = – pext V
Also, according to 10 PAC convention,
expansion  w = –ve
compression  w = +ve.


6 Thermodynamics

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6 Thermodynamics

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Chapter 6

3. The respective examples of extensive and intensive properties are

5. Which of the following is a state function?

6. For the reaction PCl5(g)  PCl3(g) + Cl2(g)

PCl5 (g)  PCl 3 (g)  Cl2 (g)

8. For the reaction,

12. Consider the following reaction :

C graphite   C diamond

C graphite   O2  CO2  g ; H   x, cal

CO2  C diamond  O2  g ; H   x2 cal

Adding, we get C graphite   C diamond  H  x2 – x1 cal

13. For the given reactions, A 

P yellow   Pred ;  9.91  8.78  kJ   1.13 kJ

15. If the heat of formation of NO2 is ‘x’

= N2  g  2O2  2NO2  g ; H1  2x

2NO  O2  2NO2 ; H  z

N2  2O2  2NO2 ; H2  y  z

∵ H1 = H2 (∵ H is state function)

16. In the reactions

HCl  NaOH  NaCl  H2 O  x cal

H2SO4  2NaOH  Na2SO4  2H2O  y cal

17. Hf C2H4 = 12.5 kcal

2C graphite   2H2  g  C2H4  g ; Hf

Hf = Bond dissociation enthalpy of reactants – Bond dissociation enthalpy of products

18. The difference between H and E for the reaction

2C6H6  l  15O2  g  12CO2  g  6 H2O  l

19. S (rhombic) + O2 (g) SO2 (g); H = –297.5 kJ

Sol. Answer (4)

Sr hombic   O2  g  SO2  g ; H  –297.5 kJ …(1)

Smonoclinic   O2  g  SO2  g ; H  –300 kJ …(2)

Subtracting (2) from (1),

Sr hombic   Smonoclinic  ; H   297.5  300  kJ   2.5 kJ

 This transition is endothermic.

20. If S + O2 SO2; H = –298.2 kJ

H2  g  S  2O2  g  H2SO4 ;  f

S  O2  SO2 ; H = – 298.2 kJ

SO3  H2O  H2SO 4 ; H = – 130.2 kJ

H2  S  2O2  H2 SO 4 ; H' = – 814.4 kJ

 Hf = H' = – 814.4 kJ

 x – 57.1 kJ mol–1 = – 34.868 kJ mol–1

Sol. Answer (3)

HA  OH  H2O  A   q1 kJ ; H  – q1 kJ

q2 kJ  H2O  H  OH ; H   q2 kJ

∵ wt. of 1 gram molecule

27. C6H12 (l) + 9O2(g)  6H2O(l) + 6CO2(g);H298= – 936.9 kcal. Thus

C2H4  3O2  2CO2  2H2O

If the gas is propylene

33. H(g) + O(g)  O – H(g); H for this reaction is

H = (B.D.E)reactants – (B.D.E)Products = Bond energy of H2

36. The enthalpy of reaction,

37. Using bond energy data, calculate heat of formation of isoprene

39. For which of these reactions will there be S positive?

CaCO3 (s)  CaO(s)  CO2 (g)

41. The least random state of H2O is

42. S for the reaction: MgCO3(s)  MgO(s) + CO2(g)

MgCO3  s   MgO  s   CO2  g

S = SCO  SMgO  SMgCO

∵ MgO and MgCO3 are solids, so their entropy is almost same.

 S = SCO i.e., S is positive.

S° = SNH  SH  SN