CLS Aipmt 14 15 XI Che Study Package 2 SET 2 Chapter 6
CLS Aipmt 14 15 XI Che Study Package 2 SET 2 Chapter 6
CLS Aipmt 14 15 XI Che Study Package 2 SET 2 Chapter 6
Thermodynamics
Solutions
SECTION - A
Objective Type Questions
1.
(2)
Close system
(4)
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
(2)
Entropy, Enthalpy
(4)
Temperature, Entropy
A thermally isolated, gaseous system can exchange energy with the surroundings. The mode of energy may
be
(1) Heat
(2)
Work
(3)
(4)
Internal energy
(2)
(3)
q+w
(4)
All of these
44
6.
Thermodynamics
(2)
H > E
(3)
H < E
(4)
Cant predicted
(4)
E = s
ng = 2 1 = 1
H = U + ng RT
= U + RT
or, H > U.
( RT is positive)
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
q = s
U = r s
8.
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
Thermodynamics
45
(2)
H < E
(3)
H = E
(4)
Can't predicted
(2)
x2 x1
(3)
x1 x2
(4)
x1 x 2
(4)
H2 = (x1 + x) x3
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
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
H1
H2
H3
H = H1 + H2 + H3
or, H2 = H H1 H3
= x (x1 + x3)
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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
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
(2)
2y + z = x
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
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Thermodynamics
47
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,
(2)
49 kcal
(3)
40 kcal
(4)
76 kcal
(2)
+3.72 kJ
(3)
3.72 kJ
(4)
+7.43 kJ
48
Thermodynamics
(1)
(2)
(2)
650.3 kJ
(3)
320.5 kJ
(4)
433.5 kJ
H2 g S 2O2 g H2SO4 ; f
Given:
S O2 SO2
SO2
1
O2 SO3
2
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
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
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
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
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)
(4)
NaCl (H = +1.02)
(3)
(q2 q1)
(2)
(q1 q2)
(4)
(q1 + q2)
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50
Thermodynamics
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
1560 kJ
180 g
1560
180 kJ
100
1560 180
kJ = 2808 kJ
100
(2)
(4)
(2)
0.5 57.1
(3)
57.1
(4)
(0.5 57.1)
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
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
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
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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
(4)
1 : 2 mixture
9
mole of O2
2
9
O2 3CO2 3H2O
2
9
moles of oxygen. As per the data, 12 ml of gas requires 54
2
9
parts of oxygen by moles.
2
(2)
Two
(3)
Three
(4)
Four
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
(4)
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
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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
H2 g
1mole (2g)
2H g ; H
(2)
(3)
(4)
80 kcal mol1
H
H
C
H
H
H
H CCH
H
H
C(g) + 4 H (g) ; H7
2 C(g) + 6 H (g) ; H2
(2)
(4)
H is enthalpy of reaction.
H = (B.D.E)reactants (B.D.E)products
54
Thermodynamics
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
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
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)
(4)
N2(g) + 3H2(g)2NH3(g)
1 solid reactant gives 1 solid and 1 gaseous product and as a result increases disorder liness
S = positive
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Thermodynamics
55
(2)
(3) Decreases
(4)
(1) Ice
(2)
Liquid water
(3) Steam
(4)
(2)
ve
(3)
+ve
(4)
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)
(4)
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
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
xH2 xO2
1
2
moles of O2 =
11.2
= 0.5
22.4
moles of H2 =
11.2
= 0.5
22.4
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
(2)
500 K
(3)
1.77 K
(4)
1.77C
Hfusion
T
Hfusion
T = S
fusion
= 1078.75 K
Thermodynamics
57
2H2(g) + O2(g) 2H2O(l) at 300 K when SHo 2 (g) = 126.6, SO2 (g) = 201.20,
(2)
318.4JK1mol1
(3)
31.84 JK1mol1
(4)
3.184 JK1mol1
2H2 g O2 g 2H2O
1
1
1
1
= 2 68.0 JK1 mol1 2 126.6 J mol J K 201.20 J K mol
Nature of reaction
(1) ()
(+)
(2) (+)
()
(3) (+)
(+)
(4) ()
()
( 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)
(3)
24 cal mol1 K1
(4)
Svap
Hvap m
T
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)
(4)
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Thermodynamics
TS
H
Positive Negative
(2)
H is ve and S is +ve
(4)
H is ve and S is ve
(2)
G = 2.303 RT logK
(3) G = RT logK
(4)
G = RT logK
(2)
G > 0
(3) G < 0
(4)
G may be +ve or ve
Thermodynamics
59
(2)
H > TS
(3)
H < TS
(4)
(4)
Cp Cv = 0
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.
(2)
Cp Cv =
R
2
(3)
Cv Cp = 2R
When an ideal gas is compressed adiabatically and reversibly, the final temperature is
(1) Higher than the initial temperature
(2)
(4)
1
O2 (g) CaO(s)
2
(2)
(4)
60
4.
Thermodynamics
(2)
ve
(3)
Zero
(4)
All of these
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)
(4)
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
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
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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
( pressure is constant)
16000 g
32 g mol1
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
1
O (g)
2 2
(2)
362.12 K
(3)
T=
H
30.5 k J mol1
462.12 K
S 0.066 k J mol1 K 1
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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
(2)
(3)
(2)
U = w = q 0
(3) U = 0, w = q 0
(4)
w = 0, U = q 0
(2)
(4)
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
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
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
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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
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
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
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
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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
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
(2)
16
(2)
y
w = 300x R ln 10 y
(3) w = 300x R ln 10
(4)
1
w = 100x R ln y
V2
Work done, w = nRT ln V
1
= x R 300 ln
10 y
y
= x R 300 ln 10
= 300x R ln 10
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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
(2)
Cyclic process
(4)
Isochoric process
(1) Y 6Z +
(2)
3Y + 6Z 2X
(4)
Y + 6X + Z
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
(P1V1T1 )
(P2 V2T1 )
(P3 V2T2 )
(P1V1T1 )
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.
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Thermodynamics
67
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
= 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
means 1 mol
means
1
2.4 mol = 0.107 mol
22.4
(2)
0.6 kcal
(3)
0.3 kcal
(4)
0.2 kcal
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
dU
dU
dV i.e.,
at constant volume is 0.
T
dV
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
(2)
(4)
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Thermodynamics
69
Surrounding
Surrounding
Work
Heat
System
Matter
Energy
System
(2)
(4)
(2)
52
(3)
24.8
(4)
104
75.6 kcal
60 g
745.6 4.2
kJ g1 52.2 kJ g1
60
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
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
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)
(4)
21.04 cal/(mol K)
T
273 K
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
( 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
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
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.
+ 150
3B 2C + D
125
E + A 2D
+ 350
(2)
325 kJ/mol
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Thermodynamics
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)
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)
(4)
G = H TS
= + 48 kJ 400 135 J K1
(II)
(III)
(IV) H TS
(2)
(3)
(4)
(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
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Thermodynamics
73
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
(2)
H = 0 and S < 0
(4)
(2)
+, +,
(3)
+, , +
(4)
, +,
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
CH4 g
x
Volume reacted:
2 O2 g CO2 g 2H2O l
2x
For propane,
Volume reacted:
3
890 kJ
22.4
2
mol
22.4
2
2220 kJ
22.4
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
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Thermodynamics
75
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)
(2)
S must be negative
(4)
(3)
y 2x
y 2x
2
(2)
2x y
(4)
2x y
2
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
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Thermodynamics
(2)
Zero
(3)
163.7 cal
(4)
9 L atm
(2)
(x y)
(3)
(x + y)
(4)
(y 2x)
(4)
0.977 J/molK
(4)
H = E 2RT
Given : S
and,
3
O2 SO3 : H1 2x kcal
2
SO3 SO2
1
O2 : H2 y kcal
2
(2)
10.77 J/molK
(3)
9.07 J/molK
9.77 J mol1 K 1
T
300 K
(2)
H = E + RT
(3)
H = E + 2RT
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
Given:
H2 O2 H2O2 ; H1 188 kJ mol1
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
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?
(1) x > y
(2)
x < y
(3)
x = y
(4)
xy
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
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Thermodynamics
CO2 2H2O CH 3 OH
3
O2 ; H' y
2
(2)
1
O2 CH3 OH ; H x y
2
We know, H < 0
xy<0
|x|>|y|
(2)
J mol1
(3)
J1 K1 mol1
(4)
JK mol1
(2)
E = W = q 0
(3) E = 0, W = q 0
(4)
W = 0, E = q 0
(2)
(3)
(4)
9.2
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
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Thermodynamics
79
Given;
C O2 CO2 ; H1
(1)
2 H2 O2 H2O ; H2
2
(2)
(3)
(2)
3RT
(3)
+ 3RT
(4)
RT
(2)
2.013
(3)
2.198
(4)
21.98
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)
(4)
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
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
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)
(4)
(2)
608 J
(3)
+304 J
(4)
304 J
(2)
(4)
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Thermodynamics
81
(2)
(4)
(2)
(4)
57.33 kJ mol1
(Week base)
(2)
285.7 K
(3)
273 K
(4)
450 K
or, T =
30000 J mol1
H
285.7 K
=
S
105 J K 1 mo1
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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
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
5
O 2 (g) 2CO2(g) + H2O(l), H = +X4 kJ mol1
2
(2)
X4 kJ mol1
(3)
+X1 kJ mol1
(4)
X2 kJ mol1
(3)
501 J
(4)
731 J
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
(2)
1317 J
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Thermodynamics
83
S2 2 O2 2 SO2 ; G 408 J
Adding, we get
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
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
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
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
d.
H
S
(iv) Spontaneous
(2)
(4)
(2)
3 joules
(3)
9 joules
(4)
Zero
H
T
S
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85
(2)
393.4 K
(3)
373.4 K
(4)
293.4 K
(3)
10.3 kJ
(4)
+6.2 kJ
(2)
43.3 kJ
Given:
Fe2O3 3CO 2 Fe 3CO2 ; 1
(1)
FeO CO Fe CO2 ; 2
(2)
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.
Intensive
m Extensive
Heat capacity, S =
q
T
q is extensive
S is also extensive
3.
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.
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Thermodynamics
87
fructose
H2
1
O2 H2O ; Hf
2
Hf = (B.E.)reactants (B.E.)products
Hf = (Hf)reactants + (Hf)products
Comparing, (Hf) = B.E.
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Thermodynamics
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