CLS Aipmt 14 15 XI Che Study Package 2 SET 2 Chapter 6

Chapter
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)
(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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44
6.
Thermodynamics
Solution of Assignment (Set-2)
For the reaction PCl5(g) PCl3(g) + Cl2(g)

(1) H = E
(2)
H > E
(3)
H < E
(4)
Cant predicted
(4)
E = s
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
(3)
E = r
(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
(2)
E = r 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
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
Thermodynamics
45
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
(4)
H2 = (x1 + x) x3
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
D ; H = x. Steps involved are

13. For the given reactions, A
B ; H1 = x1
A
C ; H2 = ?
B
D ; H3 = x3
C
(1) H2 = x (x1 + x3)
(2)
H2 = x + x1 + x3
(3)
H2 = x1 x3 x
Sol. Answer (1)

Given reactions are
We know,
H1
H2
H3
H = H1 + H2 + H3
or, H2 = H H1 H3
= x (x1 + x3)
46
Thermodynamics
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
(3)
2x z = y
(4)
2z + x = y
(3)
x=
y
2
(4)
x y
Sol. Answer (4)
P yellow
P red
5
1
O2 g P2O5 s ; H1 9.91kJ
2
2
5
1
O2 g P2O5 s ; H2 8.78 kJ
2
2
Rearranging, we get
P yellow
5
O2 g P2O5 g ; H 9.91kJ
2
P2O5 Pred
5
O2 g ; H 8.78 kJ
2
Adding these two equations, we get
P yellow Pred ; 9.91 8.78 kJ 1.13 kJ

15. If the heat of formation of NO2 is x
[ 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
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.
(1) x = y
(2)
x = 2y
Thermodynamics
47
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 25C 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 Jk1 mol1 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
48
Thermodynamics
Sol. Answer (4)
Sr hombic O2 g SO2 g ; H 297.5 kJ
(1)
Smonoclinic O2 g SO2 g ; H 300 kJ
(2)
Subtracting (2) from (1),
Sr hombic Smonoclinic ; 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
SO2
1
O2 SO3
2
SO3 H2O H2SO 4
H2
1
O2 H2O
2
H = 298.2 kJ
H = 98.7 kJ
H = 130.2 kJ
H = 287.3 kJ
H' = 814.4 kJ
Additing all these, we get

H2 S 2O2 H2 SO 4
Hf = H' = 814.4 kJ
21. The volume of a gas expands by 0.25 m3 at a constant pressure of 103N m2. 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 m2
and, V = 0.25 m3
w = 103 Nm2 0.25 m3 = 250 J
So, work done by the gas is 250 J.
Thermodynamics
49
22. When 1 g of anhydrous oxalic acid is burnt at 25C, 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)

H2C2O 4 s
oxalic acid
1
O2 g 2CO2 g H2O l
2
We know,
Hcombustion = Amount of heat liberated when 1 mole of substance reacts with oxygen.
Mol. wt. of oxalic acid = 90 g mol1
1 g oxalic acid liberates 2.835 kJ
90 g (1 mole) oxalic acid liberates 2.835 90 kJ mol1 = 255.15 kJ
Heat involved = 255.15 kJ
23. The heat of neutralization of LiOH and HCl at 25C is 34.868 kJ mol1. 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.
Hne
4 LiCl H O
LiOH Li OH HCl
2
H = 34.868 kJ
x 57.1 kJ mol1 = 34.868 kJ mol1
or, x = (57.1 34.868) kJ mol1 = 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 25C 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)
(3)
(q2 q1)
Sol. Answer (3)

Maximum heat is absorbed by NH4NO3
H = + 16.08 (maximum positive value)
25. HA + OHH2O + A + q1 kJ
H+ + OH H2O + q2 kJ
The enthalpy of dissociation of HA is
(1) (q1 + q2)
(2)
(q1 q2)
(4)
(q1 + q2)
50
Thermodynamics
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
180 g
1560
180 kJ
100
wt. of 1 gram molecule

= 180 g which gives
1560 180
kJ = 2808 kJ
100
27. C6H12 (l) + 9O2(g) 6H2O(l) + 6CO2(g);H298= 936.9 kcal. Thus

(1) 936.9 = E (2103 298 3) kcal
(2)
+936.9 = E +(2103 298 3) kcal
(3) 936.9 = E (2103 298 2) kcal
(4)
936.9 = E +(2103 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 k1 mol1 298 K)
= U (3 2 298 103 ) 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
Thermodynamics
51
29. The heat of combustion of solid benzoic acid at constant volume is 321.3 kJ at 27C. The heat of combustion
at constant pressure is
(1) 321.3 300R
(2)
321.30 + 300R
(3)
321.3 150R
(3)
x1
(4)
321.3 + 900R
(4)
x1
Sol. Answer (3)
COOH
ng = 7
15
O2 g 7CO2 g 3H2O
2
15
1
=
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
30.
1
H2 (g) O2 (g)
H2O( )
2
H2O(l) H2O(g); H = x4
Given, EHH = x1
EO=O = x2
EOH = x3
HF of H2O vapour is
(1) x1
x2
x3 x 4
2
(2)
2x 3 x1
x2
x4
2
x2
2x 3 x 4
2
x2
2x 3 x 4
2
Sol. Answer (4)
H2 g
1
Hf
H2O g
O2 g
2
H
H2O ()
Now, for H2 g
x4
1
O2 g H2O ; H
2
H = (B.D.E)reactants (B.D.E)products = x1
Hf = H + x4 = x1
1
x 2 2x3
2
1
x 2 2x3 x 4
2
52
Thermodynamics
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
or, 1 mole of gas requires
9
mole of O2
2
If the gas is C2H4

C2H4 3O2 2CO2 2H2O
If the gas is propylene

C3H6
9
O2 3CO2 3H2O
2
It is clear that propylene (1 mole) requires
9
moles of oxygen. As per the data, 12 ml of gas requires 54
2
ml of oxygen and hence 1 part of gas requires
9
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 mol1 k1
CP = CV + R = 3 cal mol1 k1 + 2 cal mol1 k1 = 5 cal mol1 k1
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
Thermodynamics
53
34. Energy required to dissociate 4 g of gaseous H2 into free gaseous atoms is 872 kJ at 25C. 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
1mole (2g)
2H g ; H
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 mol1 and that of C2H6 (g) is 620 kcal mol1. The C C bond energy
(1) 260 kcal mol1
(2)
180 kcal mol1
130 kcal mol1
(3)
(4)
80 kcal mol1
Sol. Answer (4)
H
H
C
H
H
H
H CCH
H
H
C(g) + 4 H (g) ; H7
2 C(g) + 6 H (g) ; H2
Given: H1 = 360 kcal mol1 ; H2 = 620 kcal mol1

Also, H1 = 4 Bond energy of C H = 360 kcal mol1
Bond energy of C H = 90 kcal mol1
Now, H2 = 6 Bond energy of C H + Bond energy of C C
H2 = 6 90 kcal mol1 + Bond energy of C C
H2 = 620 kcal mol1
620 kcal mol1 = 540 kcal mol1 + Bond energy of C C or, Bond energy of C C = 80 kcal mol1
36. The enthalpy of reaction,
2HCCH + 5O2 4CO2 + 2H2O
If the bond energies of CH, CC, O=O, C=O and OH 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:
2H C C H + 5O = O 4O = C = O + 2
H is enthalpy of reaction.
H = (B.D.E)reactants (B.D.E)products
= 2 ECH ECH 2 ECC 5 EOO
4 ECO ECO 2 EOH EOH
= 4ECH 2 ECC 5 EOO 8ECO 4EOH

= 4p + 2q + 5r (8s + 4t)
54
Thermodynamics
37. Using bond energy data, calculate heat of formation of isoprene

5C(s) + 4H2(g)
H 2C = C CH = CH 2
CH3
Given CH, HH, CC, 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
5 C(s) + 4 H2(g)
C=CC=C
H
5x
C(g) + 4 H2(g)
Hf
C
H
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
Thermodynamics
55
40. For stretched rubber, Entropy

(1) Increases
(2)
First increases then decreases
(3) Decreases
(4)
First decreases then increases
(1) Ice
(2)
Liquid water
(3) Steam
(4)
Randomness is same in all
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
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.
43. The standard entropies of N2 (g), H2 (g) and NH3 (g) are 191.5, 130.5, 192.6 JK1 mol1. The value of S of
formation of ammonia is
(1) 98.9 JK1 mol1
(2)
Zero
(3)
+129.4 JK1 mol1
(4)
29.4 JK1 mol1
Sol. Answer (1)
1
3
N2 H2 NH3
2
2
S = SNH SH SN
3
2
2
3
1 191.5
JK 1
= (192.6 JK1 mol1 1 mol) 130.5 JK
2
2
= 192.6 JK1 195.75 JK1 95.75 JK1

= 98.9 JK1 for 1 mole of NH3
56
Thermodynamics
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
(4)
315 J
Sol. Answer (2)
Smix = n R 2.303 xH2 log H2 xO2 log O2
Total moles = (0.5 + 0.5) moles = 1 mole
xH2 xO2
1
2
moles of O2 =
11.2
= 0.5
22.4
moles of H2 =
11.2
= 0.5
22.4
S = 1 mol 8.314 JK1 (0.5 log 0.5 + 0.5 log 0.5)

= 8.314 JK1 ( log 2) = + 5.76 JK1
45. Given S C2H6 = 225 J mol-1K1,
o
SC
= 220 J mol1K1, SH = 130 J mol1K1. Then S for the process
2H4
2
C2H4 + H2 C2H6 is
(1) +25 J
(2)
125 J
(3)
135 J
Sol. Answer (2)

For the reaction,
C2H4 H2 C2H6
S = SC2H4 SC2H4 SH2

= (225 220 130) JK1
46. For the melting of NaCl heat required is 7.26 kcal mol1 and S increases by 6.73 cal mol1k1. The melting
point of the salt is
(1) 805.75C
(2)
500 K
(3)
1.77 K
(4)
1.77C
Sol. Answer (1)

Let melting temperature = T
Sfusion =
Hfusion
T
Hfusion
T = S
fusion
7.26 cal mol1

6.73 cal mol1 k 1
= 1078.75 K
T = 1078.75 K or (1078.75 273)C = 805.75C

Thermodynamics
57
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)= 68.0JK1mol1 respectively is

(1) 318.4JK1mol1
(2)
318.4JK1mol1
(3)
31.84 JK1mol1
(4)
3.184 JK1mol1
Sol. Answer (1)
2H2 g O2 g 2H2O
S = 2 SH2O 2 SH2 SO2
1
1
1
1
= 2 68.0 JK1 mol1 2 126.6 J mol J K 201.20 J K mol
= [136 (253.2 + 201.2)] J K1 mol1 = 318.4 J K1 mol1

48. Which of the following is correct?
H
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
TS would always be positive
( T is positive always)
TS is always positive
H

Always Always
positive positive
G is always positive.
49. Entropy of vaporisation of water at 100C, if molar heat of vaporisation is 9710 cal mol1 will be
(1) 20 cal mol1 K1
(2)
26.0 cal mol1 K1
(3)
24 cal mol1 K1
(4)
28.0 cal mol1 K1
Sol. Answer (2)

Molar entropy of vaporisation of water,
Svap
Hvap m
T
9710 cal mol1

= 26.03 cal mol1 K1
373 K
50. A particular reaction at 27C 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 27C
58
Thermodynamics
Sol. Answer (2)

A reaction is spontaneous when G < 0,
We know,
G =
TS
H

Positive Negative
So, G < 0 only when

H < TS
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.
Thermodynamics
59
55. At 27C the reaction,

C6H6(l) + 15/2 O2(g) 6CO2(g) + 3H2O(l)
proceeds spontaneously because the magnitude of
(1) H = TS
(2)
H > TS
(3)
H < TS
(4)
H > 0 and TS < 0
(4)
Cp Cv = 0
Sol. Answer (2)

For the given reaction,
S = negative
( Lesser number of gaseous products are formed)
TS = positive
But H = ve
Since, it is a combustion reaction and hence exothermic.
G = H TS ; So for G to be negative, |H| > |TS|
SECTION - B
Objective Type Questions
1.
For two mole of an ideal gas

(1) Cp, m Cv, m = R
(2)
Cp Cv =
R
2
(3)
Cv Cp = 2R
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) Ca
1
O2 (g) CaO(s)
2
(3) C(s) + O2(g) CO2(g)
(2)
CaCO3(s) CaO(s) + 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.
60
4.
Thermodynamics
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 K1 mol1. 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 K1 mol1
To raise temperature by 1C (or 1 K), heat required is 75 J for 1 mole of water
i.e. 75 J for 18 g of H2O.
So for 1 g of H2O, heat required is
Specific heat capacity =
75
J
18
75
J g1 K1
18
q = mCT
or, T =
mC
1000 J
75
1000 g
J K 1 g1
18
18
K = 0.24 K
75
8.
Thermodynamics
61
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
n=
16000 g
32 g mol1
(Considering ideal behaviour)

500 mol
R = 2 cal mol1 K1
T = 273 K
w = 500 mol 2 273 cal mol1 K1 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 K1 respectively.
Predict the nature of reaction at 298 K is
(1) Spontaneous
(2)
Reversible
(3)
Irreversible
(4)
Non-spontaneous
262.12 K
(4)
562.12 K
Sol. Answer (1)

H = 2.5 103 cal
S = + 7.4 cal K1
H < 0 and S > 0
G < 0 Process is spontaneous
10. The temperature at which the given reaction is at equilibrium
Ag2O(s) 2Ag(s) +
1
O (g)
2 2
H = 30.5 kJ mol1 and S 0.066 kJ mol1 K1

(1) 462.12 K
(2)
362.12 K
(3)
Sol. Answer (1)

At equilibrium, G = 0
H = TS (at equilibrium)
T=
H
30.5 k J mol1
462.12 K
S 0.066 k J mol1 K 1
62
Thermodynamics
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
(4)
All of these
Sol. Answer (3)

Enthalpy is given as,
H = U + pV
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)
(3)
Sol. Answer (4)

For an isothermal reversible expansion,
T = 0
U or E = 0
Also, H = m CpT
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.
Thermodynamics
63
15. The temperature of 15 ml of a strong acid increases by 2C when 15 ml of a strong base is added to it. If 5
ml of each are mixed, temperature should increase by
(1) 0.6C
(2)
0.3C
(3)
2C
(4)
6C
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 = mCPT
or, T =
H
mCp
Cp is intensive variable
m
= d m = dV
V
and
T =
H
1
V Cp d
We know, H V
H = KV (where K is proportionality constant)
T =
K
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 mol1 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 mol1
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
64
Thermodynamics
1
1
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
17. If
(1) 360 kJ
(2)
360 kJ
(3)
180 kJ
(4)
+180 kJ
Sol. Answer (2)

Given,
1
1
X2O s X s O2 g ; H 90 kJ
2
4
X s
1
1
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 27C. Assuming R = 2 cal K1 mol1 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 + pV
Considering ideal behaviour, we have
H = U + ngRT
= 17 kcal + 2 2 cal K1 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 + ngRT
H = U 1 RT
H = U RT
H < U
8 10 2
8 10
Thermodynamics
65
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 mol1. The bond dissociation energy of X2 will be
(1) 800 kJ mol1
(2)
200 kJ mol1
(3)
300 kJ mol1
(4)
400 kJ mol1
(3)
32
(4)
64
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
= 2x + (x + 0.5 x) = 0.5x
Also, Hf of XY is 200 kJ mol1
i.e.
1
1
X2 g Y2 g XY g ; Hf
2
2
H = 2 Hf = 2 200 kJ mol1 = 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
Sol. Answer (2)

We know,
Vapour density =
Molecular mass of substance

Molecular mass of H2
Molecular mass of substance = 8 2 = 16

22. If x mole of ideal gas at 27C expands isothermally and reversibly from a volume of y to 10y, then the work done is
(1) w = x R 300 ln y
(2)
y
w = 300x R ln 10 y
(3) w = 300x R ln 10
(4)
1
w = 100x R ln y
Sol. Answer (3)
V2
Work done, w = nRT ln V
1
= x R 300 ln
10 y
y
= x R 300 ln 10
= 300x R ln 10
66
Thermodynamics
23. Enthalpy of formation of NH3 is X kJ and HHH, HNH are respectively Y kJ mol1 andZ kJ mol1. The value of
HN N is
X
3
(3)
3Y + 6Z + X
(1) Reversible process
(2)
Cyclic process
(3) Cyclic reversible process
(4)
Isochoric process
(1) Y 6Z +
(2)
3Y + 6Z 2X
(4)
Y + 6X + Z
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 3NH
2
2
HNN 3
XY 3XZ
2
2
We have,
X=
HNN 3Y
3 Z
2
2
3Y
X 2 = 6Z 3Y 2X
or, HNN = 3Z
2
24. A system X undergoes following changes
(P1V1T1 )
(P2 V2T1 )
(P3 V2T2 )
(P1V1T1 )
The overall process may be called as
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
(3)
57.1
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.
Thermodynamics
67
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) HNOCl 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
2.4 L
means 1 mol
means
1
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
68
Thermodynamics
We know,
w = pV = ngRT
= 2 mol 2 cal mol1 K1 300 K
= 1.2 kcal
So, work done = 1.2 kcal
29. Which statement is correct?
dH
dE

(1)
dT P dT V
(2)
dH
dE

R
dT
P dT V
dE
for ideal gas is zero
(3)
dV T
(4)
All of these
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
30. A schematic representation of enthalpy changes for the C( graphite )

The missing value is
Cgraphite + O2(g)
393.5 kJ
CO2(g)
(1) + 10.5 kJ
1
O (g) CO (g) reaction, is given below.
2 2
(2)
11.05 kJ
??
CO(g) + O(g)
283.0 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
Thermodynamics
69
32. Different types of systems are given below
Surrounding
Surrounding
Work
Heat
System
Matter
Energy
System
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
1 g yields
1 g yields
75.6 kcal
60 g
745.6 4.2
kJ g1 52.2 kJ g1
60
Hence, calorific value of ethane is 52.2 kJ g1

70
Thermodynamics
SECTION - C
Previous Years Questions
1.
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?
(1) Mg(s)
1
O2 (g)
MgO(s)
2
(3) C (graphite)
1
O2 (g)
CO(g)
2
(2)
1
1
1
C (graphite) O2 (g)
CO2 (g)
2
2
2
(4)
CO(g)
1
O2 (g)
CO2 (g)
2
Sol. Answer (3)

For the reaction
C graphite
ng = 1
1
O2 g CO g
2
1
1
2
2
S is positive
and hence G decreases with increase in temperature
G = H TS
2.
Standard enthalpy of vapourisation vapH for water at 100 C is 40.66 kJmol1. The internal energy of
vapourisation of water at 100C (in kJmol1) is
(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,
H = U + ngRT
or, U = H ngRT
The reaction is
H2O l H2O g
Dng = +1
U = 40.66 kJ mol1 1 mol 8.314 J mol1 K1 373 K
= 40.66 3101 J = + 37.56 J
3.
The enthalpy of fusion of water is 1.435 kcal/mol. The molar entropy change for the melting of ice at 0C is
(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)

Sfus
Hfus 1.435 103 cal mol1
T
273 K
= 5.26 cal mol1 K1

4.
Thermodynamics
71
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
5.
( U is proportional to temperature)
If the enthalpy change for the transition of liquid water to steam is 30 kJ mol1 at 27C, the entropy change
for the process would be
(1) 100 J mol1 K1
(2)
10 J mol1 K1
(3)
1.0 J mol1 K1
(4)
0.1 J mol1 K1
Sol. Answer (1)

Svap
6.
Hvap
T
30000 J mol1
100 J mol1 K 1
300 K
Enthalpy change for the reaction, 4H(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
(3)
525 kJ/mol
(4)
175 kJ/mol
Sol. Answer (4)

Given reaction:
4 H g 2 H2 g
H = B.D.E. of reactants B.D.E. of products
= 0 2 HHH = 2HHH
This is equal to 869.6 kJ
2HHH = 869.6 kJ
HHH = + 434.8 kJ
7.
Consider the following process

H(kJ/mol)
1
A B
2
+ 150
3B 2C + D
125
E + A 2D
+ 350
For B + D E + 2C, H will be

(1) 325 kJ/mol
(2)
325 kJ/mol
72
Thermodynamics
Sol. Answer (4)

Given:
1
A B ; H = + 150 kJ mol1
2
A 2B ; H = + 300 kJ mol1
(1)
Also given:
3B 2C D ; H = 125 kJ mol1
(2)
E A 2D ; H = + 350 kJ mol1
2D E A ;H = 350 kJ mol1
(3)
Adding (1), (2) and (3), we get

B D E 2C ; H = 175 kJ
8.
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 TS
= + 48 kJ 400 135 J K1
( Reaction has to be endothermic)
= (+ 48000 54000) J = 6000 J

G < 0
9.
Which of the following are not state functions?

(I) q + w
(II)
(III)
(IV) H TS
(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.
10. Three thermochemical equations are given below:
(i) C(graphite) + O2(g) CO2(g); rH = x kJ mol1
(ii) C(graphite) +
(iii) CO (g) +
1
O (g) CO(g); rH = y kJ mol1
2 2
1
O (g) CO2(g); rH = z kJ mol1
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
Thermodynamics
73
Sol. Answer (3)

Subtracting equation (ii) from (i), we get
CO
1
O2 CO2 ; H x y kJ
2
Also, H = z kJ mol1
xy=z
or, x = (y + z)
11. Bond dissociation enthalpy of H2, Cl2 and HCl are 434, 242 and 431 kJmol1 respectively. Enthalpy of formation
of HCl is
(1) 245 kJmol1
(2)
93 kJmol1
(3)
245 kJmol1
(4)
93 kJmol1
Sol. Answer (4)

H2 Cl2 2HCl ; H
H = HHH + HClCl 2HHCl

= (434 + 242 2 431) kJ
= 186 kJ
So, for 2 moles of HCl, H = 186 kJ
for 1 mole of HCl, H = 93 kJ
12. For the gas phase reaction, PCl5 (g) PCl3(g) + Cl2 (g), which of the following conditions is correct?
(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)
13. 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.
74
Thermodynamics
14. When 5 litres of a gas mixture of methane and propane is perfectly combusted at 0C 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 mol1, Hcomb (C3H8) = 2220 kJ mol1) 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
x
Volume reacted:
2 O2 g CO2 g 2H2O l
2x
For propane,
Volume reacted:
C3H8 5O2 2CO2 4H2O

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
mol
22.4
Moles of methane combusted =
Energy due to methane combusted =
3
890 kJ
22.4
Volume of propane combusted = 2 L

Moles of propane combusted =
2
mol
22.4
Energy due to propane combusted =
2
2220 kJ
22.4
Total energy released

2
3
890
2220 kJ
=
22.4
22.4
1
3 890 4440 kJ
22.4
1
2670 4440 kJ = 317.41 kJ
22.4
15. If enthalpies of formation for C2H4(g), CO2(g) and H2O(l) at 25C 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
Thermodynamics
75
Sol. Answer (4)

C2H4 3 O2 2 CO2 2 H2 O ; Hr
Hr = Enthalpy of combustion
Now,
2 C s 2 H2 g C2H4 g ; H1
2 C s O2 g CO2 g ; H2
(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
16. For a reaction to occur spontaneously
(1) H must be negative
(2)
S must be negative
(3) (H TS) must be negative
(4)
(H + TS) must be negative
(3)
y 2x
Sol. Answer (3)

For a reaction to occur spontaneously,
G should be negative
H TS should be negative
17. Given that C + O2 CO2, H = x kJ
2CO + O2 2CO2, H = y kJ
What is heat of formation of CO?
(1)
y 2x
2
(2)
2x y
(4)
2x y
2
Sol. Answer (1)
C s
1
O2 CO ; Hr
2
C O2 CO2 ; H x kJ
CO2 CO
1
y
O2 ; H kJ
2
2
Adding, we get
1
y
y 2x
O2 CO : Hr x
2
2
2
76
Thermodynamics
18. 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 0C, 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.
19. 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. Mol1K1)
(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
20. 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)
(4)
0.977 J/molK
(4)
H = E 2RT
Sol. Answer (4)

S O2 SO2 : H
Given : S
and,
3
O2 SO3 : H1 2x kcal
2
SO3 SO2
1
O2 : H2 y kcal
2
Adding, S O2 SO2 : H H1 H2 y 2x kcal

21. At 27C latent heat of fusion of a compound is 2930 J/mol. Entropy change is
(1) 9.77 J/molK
(2)
10.77 J/molK
(3)
9.07 J/molK
Sol. Answer (1)

Sfusion
Hfusion 2930 J mol1
9.77 J mol1 K 1
T
300 K
22. 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
Sol. Answer (1)

We know,
H = U + pV
For an ideal gas,
H = U + ngRT
For the given reaction, ng = 2 3 = 1
H = U + (1) RT
= U RT
Thermodynamics
77
23. 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 mol1
2 H2O2 H2 O2 ; H1 188 kJ mol1
and 2 H2 O2 H2O ; H2 286 kJ mol1

2
Adding, we get
2H2O2 2H2O O2 ; Hr 2 2 2 1
= [ 286 2 + 2(188)] kJ
= ( 572 + 376) kJ = 196 kJ
24. 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
O CH3OH is negative. If enthalpy of combustion of CH4 and CH3OH are x and y
2 2
respectively. Then which relation is correct?
25. Enthalpy of CH4 +
(1) x > y
(2)
x < y
(3)
x = y
(4)
xy
Sol. Answer (1)
CH4
1
O2 CH3 OH ; H 0
2
Given:
CH4 2 O2 CO2 2 H2O ; H1 x
CH3 OH
(1)
3
O2 CO2 2 H2O ; Hr y
2
78
Thermodynamics
CO2 2H2O CH 3 OH
3
O2 ; H' y
2
(2)
Adding (1) and (2), we get

CH4
1
O2 CH3 OH ; H x y
2
We know, H < 0
xy<0
|x|>|y|
26. Unit of entropy is

(1) JK1 mol1
(2)
J mol1
(3)
J1 K1 mol1
(4)
JK mol1
Sol. Answer (1)

Unit of molar entropy is J K1
Unit of entropy is J K1
Entropy is represented in terms of molar entropy to make it an intensive variable.
27. 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]
28. 2 mole of ideal gas at 27C temperature is expanded reversibly from 2 lit. to 20 lit. Find entropy change (R =
2 cal/mol K)
(1) 92.1
(2)
(3)
(4)
9.2
Sol. Answer (4)

We know,
V
S = 2.303 nR log 2
V1
Given: V2 = 20 L ; V1 = 2 L
n = 2 mol., R = 2 cal mol1 K1
S = 2.303 2 mol 2 cal mol1 K1 log
20
= 9.2 cal K1
2
29. 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
Thermodynamics
79
Sol. Answer (1)

C 2H2 CH4 ; H
Given;
C O2 CO2 ; H1
(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 2H2 H3
= [ 94 + 2 ( 68) ( 213)] kcal

= 17 kcal
30. 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
31. What is the entropy change (in JK1 mol1) when one mole of ice is converted into water at 0C? (The enthalpy
change for the conversion of ice to liquid water is 6.0 kJ mol1 at 0C)
(1) 20.13
(2)
2.013
(3)
2.198
(4)
21.98
Sol. Answer (4)

Sfusion
Hfusion 6.0 kJ mol1
21.98 J mol1 K 1
T
273 K

32. 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
80
Thermodynamics
33. The molar heat capacity of water at constant pressure, C, is 75 J K1 mol1. 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 K1 mol1
We know, qp = Cp , m n T
or, T =
qp
Cp,m n
1000 J
75 J K
mol
100
mol = 2.4 K
18
34. Standard enthalpy and standard entropy changes for the oxidation of ammonia at 298 K are
382.64 kJ mol1 and 145.6 J mol1, respectively. Standard Gibbs energy change for the same reaction at
298 K is
(1) 221.1 kJ mol1
(2)
339.3 kJ mol1
(3)
439.3 kJ mol1
(4)
523.2 kJ mol1
Sol. Answer (2)

G = H TS
145.6
= 382.64 298 K 1000 kJ mol1
= 339.3 kJ mol1
35. 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
36. 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
37. Which of the following pairs of a chemical reaction is certain to result in a spontaneous reaction?
(1) Exothermic and increasing disorder
(2)
Exothermic and decreasing disorder
(3) Endothermic and increasing disorder
(4)
Endothermic and decreasing disorder
Thermodynamics
81
Sol. Answer (1)

A chemical reaction is certainly spontaneous
if
H < 0 and S > 0
for which G < 0 at all temperature.
38. A reaction occurs spontaneously if
(1) TS < H and both H and S are +ve
(2)
T S > H and H is +ve and S is ve
(3) T S > H and both H and S are +ve
(4)
T S = H and both H and S are +ve
Sol. Answer (3)

A reaction is spontaneous if G < 0.
H TS < 0
or, TS > H
Also, reaction is spontaneous when,
TS > H and H and S are +ve.
Reaction is never spontaneous if H is +ve and is -ve
39. The absolute enthalpy of neutralisation of the reaction
MgO(s) + 2HCl(aq) MgCl2(aq) + H2O(l) will be
(1) 57.33 kJ mol1
(2)
Greater than 57.33 kJ mol1
(3) Less than 57.33 kJ mol1
(4)
57.33 kJ mol1
Sol. Answer (3)

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 mol1
40. The enthalpy and entropy change for the reaction : Br2(l) + Cl2(g) 2BrCl(g) are 30 kJ mol1 and 105 JK1
mol1 respectively. The temperature at which the reaction will be in equilibrium is
(1) 300 K
(2)
285.7 K
(3)
273 K
(4)
450 K
Sol. Answer (2)

At equilibrium,
G = 0
H = TS
or, T =
30000 J mol1
H
285.7 K
=
S
105 J K 1 mo1
82
Thermodynamics
41. The enthalpy of hydrogenation of cyclohexene is 119.5 kJ mol1. If resonance energy of benzene is 150.4
kJ mol1, its enthalpy of hydrogenation would be
(1) 358.5 kJ mol1
(2)
508.9 kJ mol1
(3)
208.1 kJ mol1
(4)
269.9 kJ mol1
Sol. Answer (3)

Enthalpy of hydrogenation of cyclohexene = 119.5 kJ mol1
Expected enthalpy of hydrogenation of benzene = ( 119.5 3) kJ mol1
non-resonated benzene
Eres
resonated benzene
Energy
E
cyclohexane
E + Eres = Expected heat of hydrogenation
or, E = ( 119.5 3 + 150.4) kJ mol1
= 208.1 kJ mol1
42. Consider the following reactions
(i) H+(aq) + OH(aq) H2O(l), H = X1 kJ mol1
(ii) H2(g)+
1
O (g) H2O(l), H =X2 kJ mol1
2 2
(iii) CO2(g) + H2(g) CO(g) + H2O, H = X3, kJ mol1

(iv) C2H2(g) +
5
O 2 (g) 2CO2(g) + H2O(l), H = +X4 kJ mol1
2
Enthalpy of formation of H2O(l) is

(1) +X3 kJ mol1
(2)
X4 kJ mol1
(3)
+X1 kJ mol1
(4)
X2 kJ mol1
(3)
501 J
(4)
731 J
Sol. Answer (4)
H2 g
1
O g H2O l ; H X2 kJ mol1
2 2
Elements in
reference states
1 mole of substance
is formed
Hf = X2 kJ mol1
43. 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
Thermodynamics
83
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

44. From the following bond energies
HH bond energy : 431.37 kJ mol1
C=C bond energy : 606.10 kJ mol1
CC bond energy : 336.49 kJ mol1
CH bond energy : 410.50 kJ mol1
Enthalpy for the reaction,
H
C=C+HHHCCH
H
will be
(1) 553.0 kJ mol1
(2)
1523.6 kJ mol1
(3)
243.6 kJ mol1
(4)
120.0 kJ mol1
Sol. Answer (4)

Given reaction :
H
H
C=C
H
H
H
H C
H
+HH
H
H ; Hr
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 mol1
= 120.0 kJ mol1
45. The values of H and S for the reaction, C(graphite) CO2 (g) 2CO(g) are 170 kJ and 170 JK1,
respectively. This reaction will be spontaneous at
(1) 510 K
(2)
710 K
(3)
910 K
(4)
1110 K
Sol. Answer (4)

Reaction will be spontaneous at higher temperature when G < 0
At 1110 K
H TS
G = (17000 J 1110 170 J) = 171.7 kJ i.e., G = ve
84
Thermodynamics
46. Standard entropies of X 2, Y 2 and XY 3 are 60, 40 and 50 JK 1 mol 1 respectively. For the reaction
1
3

X Y
XY3 , H 30kJ to be at equilibrium, the temperature should be
2 2 2 2
(1) 500 K
(2)
750 K
(3)
1000 K
(4)
1250 K
Sol. Answer (2)

For the reaction to be at equilibrium,
G = 0
H = TS
Now,
3
1
S = S X2 S Y2 S XY3
2
2
60 3
40 J K 1
= 50
2 2
= 40 J K1
T=
H 30000 J
750 K
S
40
47. Match Column-I (Equations) with Column-II (Type of process) and select the correct option
Column-I
Column-II
Equations
Type of processes
a. Kp > Q
(i) Non-spontaneous
b. G < RT ln Q
(ii) Equilibrium
c. Kp = Q
(iii) Spontaneous and endothermic
d.
H
S
(iv) Spontaneous
(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)

48. Three moles of an ideal gas expanded spontaneously into vacuum. The work done will be
(1) Infinite
(2)
3 joules
(3)
9 joules
(4)
Zero
Sol. Answer (4)

For a spontaneous process,
G = H TS < 0
or, H < TS
or,
H
T
S
Thermodynamics
85
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.
49. For vaporization of water at 1 atmospheric pressure, the values of H and S are 40.63 kJ mol1 and 108.8
JK1 mol1, respectively. The temperature when Gibbs energy change (G) for this transformation will be zero,
is
(1) 273.4 K
(2)
393.4 K
(3)
373.4 K
(4)
293.4 K
(3)
10.3 kJ
(4)
+6.2 kJ
Sol. Answer (3)

Pext = 0
w=0
50. 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
(1) +10.3 kJ
(2)
43.3 kJ
Sol. Answer (4)

Fe2O3 CO 2 FeO CO2 ; r
Given:
Fe2O3 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

86
Thermodynamics
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
Heat capacity, S =
q
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 eq1
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.
Thermodynamics
87
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 100C
H is +ve, S must be +ve for G to be ve
7.
A : For an isolated system G = TStotal.

R : For an isolated system q = 0.
Sol. Answer (2)

For an isolated system,
H = 0
G = TStotal
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
H2
1
O2 H2O ; Hf
2
Hf = (B.E.)reactants (B.E.)products
Hf = (Hf)reactants + (Hf)products
Comparing, (Hf) = B.E.
88
Thermodynamics
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.


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Chapter

Tea placed in thermos flask is an example of

(3) Isolated system

It can't act as system

Sol. Answer (3)

Sol. Answer (2)

The respective examples of extensive and intensive properties are

(3) Entropy, Temperature

Sol. Answer (3)

Heat and radiation

Sol. Answer (2)

Which of the following is a state function?

Sol. Answer (3)

Solution of Assignment (Set-2)

For the reaction PCl5(g) PCl3(g) + Cl2(g)

Sol. Answer (2)

where U = E i.e., change in internal energy.

Sol. Answer (2)

( work is done on the system)

( heat is evolved out of system)

For the reaction,

Sol. Answer (2)

[ rest are solid substances]

Sol. Answer (2)

Solution of Assignment (Set-2)

10. In a reaction, all reactant and products are liquid, then

Sol. Answer (3)

Sol. Answer (2)

D ; H = x. Steps involved are

Sol. Answer (1)

Solution of Assignment (Set-2)

Sol. Answer (4)

Adding these two equations, we get

P yellow Pred ; 9.91 8.78 kJ 1.13 kJ

Sol. Answer (3)

Solution of Assignment (Set-2)

Sol. Answer (3)

H2SO4 2NaOH Na2SO4 2H2O y cal

Sol. Answer (1)

2C graphite 2H2 g C2H4 g ; Hf

BE(C = C) = 140.9 kcal

18. The difference between H and E for the reaction

Sol. Answer (1)

2C6H6 l 15O2 g 12CO2 g 6 H2O l

Solution of Assignment (Set-2)

Sol. Answer (4)

Sr hombic O2 g SO2 g ; H 297.5 kJ

Smonoclinic O2 g SO2 g ; H 300 kJ

Subtracting (2) from (1),

Sr hombic Smonoclinic ; H 297.5 300 kJ 2.5 kJ

Sol. Answer (1)

SO3 H2O H2SO 4

Additing all these, we get

Sol. Answer (2)

Solution of Assignment (Set-2)

Sol. Answer (1)

Sol. Answer (2)

(3) NH4NO3 (H = +16.08)

Sol. Answer (3)

Solution of Assignment (Set-2)

Sol. Answer (3)

Sol. Answer (2)

wt. of 1 gram molecule