Thermodynamics 7.

Chapter 7 Thermodynamics
INTEXT EXERCISE: 1
1. Properties, which are amount independent, are 7. P × 1 = RT
intensive properties and others which are amount 3
Also, internal energy U = 2 RT
dependent are extensive properties.
3
U= 2P
2. An isolated system neither shows exchange of heat
nor matter with surroundings. or P = 3 U
2
3. KE = (3/2) RT. Since T is same, hence K.E. is same. 8. Temperature is a measure of intensity of energy,
Force extensive whereas heat is a measure of quantity of energy.
4. Pressure = Area i.e. extensive
9. Follow Zeroth law of thermodynamics.
capacity is intensive not heat capacity. 10. The water in beaker will be heated to 100oC but
5. During reversible process, the internal equilibrium will not boil as for boiling it requires latent heat of
evaporation. Water can be made to boil by lowering
always remains in the equilibrium state during this the external pressure. Regulation involves melting
process.
pressure. Ice can be sublimed by reducing external
6. At constant temperature U = 0. pressure to its vapour pressure.
INTEXT EXERCISE: 2
3. At constant volume P9V = 0, ` q = 9U
1. 9W =- # P9V = Area under PV curve
4. WAB = P9V =- 10 J; WBC = 0;
q = 9U + (- WT)
a 9U = 0 WT = q = 2.5J
- 2.5 = [WAB + WBC + WCA]
2.5 = [ 10 + 0 + WCA]
=- [4 + V]
1 or WCA = 7.5 J
=- [P0 (V1 - V0) + 2 (P1 - P0) × (V1 - V0)]
PV 1×22.44
5. At A : T1 = nR = 1×0.0821 = 273 K
1 1
=- [P0 (V1 - V0) + 2 P1 (V1 - V0) - 2 P0 (V1 - V0)] PV 1×44.88
At B : T2 = nR = 1×0.0821 = 546 K
=- : 2 P0 (V1 - V0) + 2 P1 (V1 - V0)D
1 1
PV 0.5×44.88
At C : T3 = nR = 1×0.0821 = 273 K
1 1
=- 2 [P0 + P1] [V1 - V0] =- 2 [(1 + 4)) ×105] ×[4 - 1]
Y -Y
=- 7.5×105 J 6. Equation of line AB is Y - Y1 = X1 - X2 (X - X1)
1 2
3Po - Po
2. P - 3P0 = V - 3V (V - V0) ...(i)
o o
nRT P0
V - 3P0 =- V0 (V - V0)
P
or nRT = 3P0 V - V0 V 2 + P0 V ...(ii)
Net work done = Area covered by the cycle 0

(clockwise) Differentiating w.r.t. V

1 nRdT 2P0 2P0
=- 2 [(4P - P) ×(3V - V)] dV = 3P0 - V0 V + P0 = 4P0 - V0 V
1 dT
=- 2 ×6PV For max. value of T, dV = 0
=- 3PV
7.2 Chemistry

P 01 :4 - V D = 0 or V = 2V0
2V CP 5R # n1 + 7R # n 2
` C V = 1.50 = 3R # n1 + 5R # n 2
m

0 m

Now from (ii) or 4.50 Rn1 + 7.5Rn 2 = 5Rn1 + 7Rn 2

P 0.5 Rn 2 = 0.5 Rn1
nRTmax = 6P0 V0 - V0 4V 02 + P0 2V0 = 4P0 V0
0 n1
4P0 V0 n2 = 1
Tmax = nR
8. 9H = 9U + P9V
3R 5R
n1 × 2 + n 2 × 2 3Rn + 5Rn 9H - 9U 50 - 113
7. C V = = 2 (n1 + n ) 2 P= 9V = - 10 = 6.3 K Nm -2
m
n1 + n 2 1 2

5 7R 9. In a cyclic process 9U = 0.
n1 × 2 + n 2 × 2 5Rn + 7Rn
CP = = 2 (n1 + n ) 2 5
m
n1 + n 2 1 2
10. 9U = n×C V ×9T = 1× 2 ×8.314×15 = 311.75J

INTEXT EXERCISE: 3
1. For isothermal process U = 0. or T3 - 2c = constant
dP
2. Slope of an isotherm in P V curve : dV =- V
P 3 - 2c = 0
3
dP P or c = 2
Slope of an adiabat in P V curve : dV =- c V
8. The work done by the gas during isothermal and
Slope of adiabat = slope of isotherm adiabatic expansions are shown schematically by
3. For adiabatic process TV 1 = constant the corresponding P V lines.
Given T(V)1/2 = constant Obviously, W2 > W1 > W3 since we are only talking
1 about the magnitude of work here.
1= 2
3
or c = 2 = 1.5
4. The given process is isothermal, hence U = 0
q= w
a q = 208 J
w= 208 J (i.e., work done by the system)
u rms T T1
5. u rms T = T2
1

2×u
u = T2
T1 b u rms T = u rms T l
1

22

T1 9. Let volume after compression be XV

or T = 4
2
P1V = P2 (XV)
T
i.e., T2 = 41 1.01 × 105 × V = 1.122 × 105 (XV)
X = b 1.122 l = b 1.122 l
From TV c - 1 = constant fro adiabatic expansion 1.01 1/c 1.01 1/1.667
= 0.94
T1 V1c - 1 = T2 V 2c - 1
Reduction in volume = V 0.94 V = 0.06 V
or : V1 D = T2 = 4
V c-1 T 1 0.06 V
2 1 % = V ×100 = 6
b V1 l = 4 & b V2 l = 4
1.4 - 1
1 V 5
2 10. CP CV = R
V2 1 R
CP CV = M
V2
or V = 32
1 C
Also, C P = c
6. q = m $ s $ 9T if 9T = 0, S = 3, As during melting V

or boiling there is no change in T. C R

C P - cP = M
if q = 0, S = 0, As q = 0 in adiabatic processes. R$c
C P = M (c - 1)
7. For adiabatic process Tc P(1 - c) = constant
CP
or Tc (T) 3(1 - c) = constant (a P \ T3)
pressure.
 Thermodynamics 7.3
INTEXT EXERCISE: 4
1. For free expansion, Pext = 0
w= P V = 0; For adiabatic process q = 0
v=q+w
q = 0, w = 0 T=0
2. Work done by gas = Pext × change in volume
= 10 (10
5 2
10 )
3

= 10 × 0.009 =
5
900 J
Hence, Wirreversible > Wreversible
3. Assuming P, T to be constant, V remains constant as
the no. of moles of gas remains unchanged. 7. q = n $ C p 3 T
100
4. T = KP0.4 = KP2/5 1000 = 18 ×75×9T
a PV = RT T = 2.4 K
or PV = R $ K $ P 2/5 8. The colling shows fusion process for 30 minute
P =K
3/5 I (40 10) at 400 K
PV5/3 = KII q = 0 0.4 × 103 × 30 = 12 kJ
5 9. w = P (Vg Vl) = PVg = nRT
PV = constant 1.66 = 3 for He
Thus, process is adiabatic H=0 103
= 18 ×8.314×373 = 172284.56 J
5. Wexp =- P×9V = 172.28 kJ
=- 1× (13 - 3) =- 10 atm dm3 70
10. Q P = C P $ 9T ` C P = 5 = 14 cal o C -1
6. In both the curves, work done on the gas is C P - C V = nR
represented by the shaded area and the area under the
C V = 14 - 2×2 = 10 cal K -1
curve is always more in irreversible compression.
Q V = C V $ 9T = 10×5 = 50 cal
INTEXT EXERCISE: 5
1. 9Ssyst =- ve 9SSurr =+ ve , as system loses heat Tsurr = 300 K
and surrounding gains heat. - 3×101.3
Ssurr = 300 = 1.013 J/K
9S T =- ve
q rev 8. At 100 C and 1 atmosphere pressure, water shows
o
2. Entropy change 9S = T
equilibrium in two phases as H 2 O (l) ? H 2 O (g)
` Unit of S is J K -1 mol -1 . and thus for equilibrium 9S total = 0 and
3. An exothermic reaction in which entropy of system 9Ssystem + 9SSurrounding = 0 For change of liquid to
is increasing is spontaneous at all temperatures. gases state, 9Ssys is + ve and therefore 9Ssurr. will
be ve.
H < 0, S > 0 always spontaneous.
9Ssystem > 0 and 9Ssurrounding < 0
4. 9S total = 9Ssys + 9Ssurr =+ ve for irreversible
process. 9. During compression for isothermal process
9S = nR ln V2 =- R ln 2 b V2 = 21 l
V V
T1 - T2 500 - 400 1
5. h = T1 = 500 =5 1
During heating for isochloric process
1 T
w = h×Q = 5 ×6×10 4 = 1.2×10 4 9S = nC V ln T2 = C V ln 2 (T2 = 2T1)
1
dq Work done by the gas (W) Thus, total change in entropy
6. - 9S = T = T = C V ln 2 - R ln 2 = (C V - R) ln 2
- 9S×PV
W =- 9S×T = nR Q rev
10. 9S = T
7. W = 3(2 1) = 3 L atm
a Q rev = 0 for adiabatic process
q = W = 3 L atm ( a u = 0 for isothermal)
Thus, 9S = 0
qsurr = 3 L atm = 3 × 101.3 J
Reversible Adiabatic processes are isoentropic.
7.4 Chemistry
INTEXT EXERCISE: 6
9H 540×18 6. For spontaneous change (work is being done by the
1. 9S = T = 373 cal mol -1
system)
= 26.06 cal K -1 mol -1 (dG)T, P - ve and (dS)V, U be + ve
2. All are acid and thus reaction will go in forward 7. - 9G o = RT In K C (Theoretical)
direction. However maximum for HI as their K
values are 10 3, 108, 1010 and 1017 for HF, HCl, HBr 8. G = H T S, since G = + ve at T = 273 K
and HI respectively. and H = + ve and at high temperature 373 K it
becomes spontaneous ( G = ve) even if H = +
3. 9G = 9H - T9S ve. This is possible only, if S = + ve because at
at equilibrium 9G = 0 high temperature T S > H to give G = ve.
9H 30×103 9. On adding more product, reaction will tend to move
T = 9S = 75 = 400 K
backward
4. 9G o = 9H o - T9S o
10. Given H = +ve; S = +ve
=- 382.64 - 298× (- 145.6×10 -3)
Thus, G is ve only when | H| < |T S|.
=- 339.3 kJ mol -1
9H 6×103
5. 9S f = T f = 273 = 21.98 J
INTEXT EXERCISE: 7
1. CH 4(g) + 2O 2(g) $ CO 2(g) + 2H 2 O(l) 5. 9H 2 - 9H1 = 9C P (T2 - T1)
9n g = 1 - 3 =- 2 9H 2 - 9H1 = 0×100
9H 2 = 9H1
9H o = 9U o + 9n g RT
6. Cgraphite Cdiamond Hreaction = fH(diamond) f
H(graphite)
9H o =- 393 + (- 2) RT
= 1.896 0.23 = 1.666 kJ/ mol.
9H o =- 393 - 2×8.314×10 -3 ×T
7. 9C P = C P of products - C P of reactants.
9H o < 9U o
100
2. No doubt (a) and (b) both represent heat of 8. 9H 2 = 9H1 + # 9C P $ dT
formations but standard heat of formation (91 H fo) 10
for CO2 will be from C(graphite) + O2 CO2 as C(graphite) 100

is most stable form of carbon. =- 142 + # [2.0 + 0.2T] $ dT

10
3. Subtracting (ii) from (i)
=- 14.2×103 + ;2.0×[100 - 10] + 0.2 :100 10 2 DE
2

1 2 - 2
CO + 2 O 2 $ CO 2; 9H = X - Y
=- 14.2×10 + [180 + 1000 - 10]
3
Z=X Y
=- 14.2×103 + 1170 =- 13.03 kcal .
X=Y+Z
9. 9H = H G - H D =- ve , i.e., Graphite has lower
4. 9H = 9U + 9nRT
energy and thus more stable.
for (a), (b), (c) 9n = 0 and for (d) 9n =- 2
10. Br2 has 9f H o = 0 in liquid state.
INTEXT EXERCISE: 8
3 4. 9Hsol = 9H lattice + 9H hyd
1. S + 2 O 2 $ SO3; 9H =- 2x ...(i)
1 1 = 180 + 9H h
SO 2 + 2 O 2 $ SO3; 9H =- y ...(ii)
9H h =- 179 kcal
By eqs. [(i) (ii)]
9H Na (h) + 9H Cl (h) =- 179 kcal
+ -

S + O 2 $ SO 2; 9H = (y - 2x)
5
2. Two equivalents of each are used. 9H Na (h) + 6 9H Na (h) =- 179 kcal
+ +

3. H + + OH - ? H 2 O; 9H =- 57.46 kJ 6×(- 179)

9H Na (h) =
+
11 =- 97.64 kcal
+
` H 2 O ? H + OH ; -
9H =+ 57.46 kJ
 Thermodynamics 7.5
5. C6 H12 O6 (s) + 6O 2 (g) $ 6CO 2 (g) + 6H 2 O (l) 8. 9C H = 9C U + 9n(g) RT
9c H Co H6 12 O6 = 69f H CO
o
+ 69f H oH O(l) - 9f H Co H
2 2 6 12 O6 (s) 9C U =- 1364.47 kJ mol -1, 9n(g) = 2 - 3 = - 1
= 6×(- 400) + 6×(- 300) - (- 1300) 9C H =- 1364.47×103 + (- 1) ×8.314×298
=- 2900 kJ/mol =- 1364470 - 2477.57 =- 1366.95 kJ
Standard enthalpy of combution per gram of =- 1366.95 kJ mol -1
glucose
9. Heat required to dissociate 90% of the undissociated
- 2900 acid = 0.90 × 400 = 360 cal.
= 180 =- 16.11 kJ
6. 9Hsub
o
= 9H fusion
o
+ 9H ovap = 0.36 kcal.
9H cond
o
=- 9H ovap Hneut with strong base = 13.7 + 0.36
57.5 = 9H fusion
o
+ 42 = 13.34 kcal
9H fusion
o
= 15.5 kJ mol -1, 10. H B > H A H B - H A = 24
9H o
freezing =- 15.5 kJ mol -1
HC > H B H C - H B =- 18
7. q = 1.23×103 ×6.12 = 7.5×103 J H B > HC > H A
u= 7.5 kJ
3×8.314×343
H= 7.5 1000
= 16.08 kJ
INTEXT EXERCISE: 9
1. Bond energy is the amount of heat required to break Given: 9H fCO =- 393 kJ
2

1 mole bond to give isolated gaseous atoms. Resonance energy of CO2 = 393 538 kJ
= 931 kJ
2. Shorter is bond, more is bond energy.
8. A + O 2 $ Oxide of A or B; 9H =- 17 kJ
3. PH3 $ P + 3H; 9H = 228
228 B + O 2 $ Oxide of A or B; 9H =- 12 kJ
EP H = 3
A$B ; 9H =- 5 kJ
H2P PH2 2P + 4H; H = 355;
Thus A has higher energy than B and is less stable.
E P - P + 4×E P - H = 355
228 9. 9H =- [2 × EC - H + EC - C + [EC = C + E H - H]
E P - P + 4× 3 = 355
and EH H = 2 × heat of formation of H atom
E P - P = 51
=- [2 × 413 + 346] + 611 + 2 × 218
4. 9H =- [EC - C + 6×EC - H] + [EC = C + 4EC - H] + E H - H =- 125 kJ
5. EA A = a 10. 3C (s) + 3H 2 (g) $ C3 H6; 9H = 53.0 kJ mol -1 ..(i)
EA B = a
C (s) $ C (g); 9H = 715 ...(ii)
EB B = 0.5 a 1
1 1 2 H 2 (g) $ H (g); 9H = 218 ...(iii)
Also, 2 A 2 + 2 B 2 $ AB;
By eqs. 3×(ii) + 6×(iii)
9H =- 100 kJ mol -1
3C (s) + 3H 2 (g) $ 3C (g) + 6H (g);
1
9H =- [E A - B] + 2 [E A - A + E B - B] 9H = 2145 + 1308 = 3453 kJ mol -1 ..(iv)
1
=- a + 2 [a + 0.5a] By (iv) (i)
- 100 =- 0.25 a 3C (g) + 6H (g) $ C3 H6; 9H = 3400 kJ mol -1
a = 400 kJ mol -1 3C (g) + 3H 2 (g) $ CH2
6. Average bond energy of C - H bond is
H2C CH2
Dissociation energy of CH 4 X1
No. of bond broken = 4 9H = 3×EC - C + 6×C - H = 3×356 + 6×408
7. C + O 2 $ CO 2 = 1068 + 2448 = 3516 kJ mol -1
H f ]CO 2g = 3 Hsub ]Cg + EO = O - 2×EC = O Thus strain = 3516 - 3400 = 116 kJ
= 718 + 498 2 × 339 = 538 kJ
7.6 Chemistry
EXERCISE 1
1. U T for ideal gases It will be ( ) because work is done by the system.
2. Heat capacity at constant volume (Cv)=20 J/k
3. We know that work done
W =- nC V (T2 - T1); 3000 =- 1×20(T2 - 300)
4. 1 cal = 4.184 J and 1 J = 107 erg.
3000 =- 20T2 + 6000
5. Lower the energy more stable it is. 3000
20T2 = 3000; T2 = 20 = 150 K
6. u = K.E. and hence u \ T. Thus u is a state function.
20. Given that
7. Density tension is an intensive property which do
P1 = 10 atm, P2 = 1 atm, T = 300 K, n = 1
not depend upon the quantity of matter present in the
system. R = 8.314 J/K/mol

8. No exchange of mass or heat takes place in an Now, by using

isolated system. P
W = 2.303 nRT log10 P2
1
9. Surface tension is an intensive property which do 1
= 2.303×1×8.314×300 log10 10
not depend upon the quantity of matter present in the
system. W = 5744.1 Joule
10. First Law : u = Q + W 21. At constant volume, w = 0
u=q
11. u increases with temperature.
22.
12. q = u W if q = 0 for adiabatic process, than E =W.
23. 9H = 9u - W or 9H = 9u + P9V .
13. As the system is closed and insulated no heat enter
or leave the system, i.e. q = 0; 24. W =- P9V =- 1×105 (1×10 -2 - 1×10 -3)
u = Q + W = W. =- 1×105 ×9×10 -3 =- 900 J
14. We know that u = Q + W = 600 + ( 300) 25. W =- P9V; W =- 3×(6 - 4) = 6 L atm
= 600 + ( 300) = 300 J W =- 6×101.32 (` 1 L atm = 101.32 J)
W = 300, because the work done by the system. W =- 608 J
15. A monoatomic gas has only three translational 26. V ! 0 but w = Pext V = 0 as Pext = 0
degrees of freedom. Energy associated with each
1 27. When Stot = + ve the change is spontaneous.
degree of freedom = 2 kT . Hence internal energy
3 3 28.
of 1 mole of gas - 2 kT × N 0 2 RT . temperature.
16. U is a state function but w and q are not state 29. Mixing of non reacting gases increases randomness
functions. and so increase entropy.
p1
17. - W =+ 2.303 nRT log p 2 30. Stot > 0 as process is irreversible. Since the system
is isolated so Ssurr = 0 Ssys > 0
10
- W = 2.303×1×2×300 log 1 = 1381.8 cal
31. For the same suibstance in solid, liquid and gas, Ssolid
P2 < Sliquid < Sgas.
18. W = 2.303 nRT log P1
10 32. For adiabatic expansion q = 0 than according to the
= 2.303×1×2×300 log 2 = 965.84 q
S= T S = 0.
at constant temperature, u = 0.
33. If H > 0 and S < 0 then the process will be non
u = q + w; q = w= 965.84 cal.
spontaneous at all temperatures.
19. Given number of moles = 1
34. There are the assumptions in deriring the relation
Initial temperature = 27oC = 300 K H T S < 0 for spontaneous reaction.
Work done by the system = 3 KJ = 3000 K
35. Solid Liquid, S increases.
 Thermodynamics 7.7
q rev 56. H < 0.
36. 9S = T ` unit of S is JK 1mol 1.
57. H = U + ngRT
37. Both melting of ice and evaporation are spontaneous
at room temperature. Since ng = 2
(900×18) Then H = U 2RT.
38. 9S vap = 373 = 43.4 JK -1 mol -1 .
58. If n= ve than H < E.
9H 9.2
39. Tm = 9S fusion = 0.008 = 1150 K.
fusion 59. It is a combustion reaction, H = ve.
40. Formation of CO2 is,
60. The enthalpies of all elements in their standard state
C(s) + O2(g) CO2(g) at 25oC or 298 K are zero.
So = 213.5 5.690 205 = 2.81 JK 1. 61. E = H if ng = 0
41. Because solid solid, S is same and H is ve. 62. For this reaction n = 0 hence E = H.
3 H 2257×18
42. 3 S = T = 373 (As H is given in kJ/g) 63. Since H is a state function, therefore its value is the
= 108.91 JK mol
1 1 same when Reactants get converted into products
irrespective of the path followed by the reaction.
43.
but violates the II law of thermodynamics. 64. 9H - 9E = 9n g RT; 9n g =- 3
44. Given that, T1 = 500 K, T2 = 300 K so, 9H - 9E =- 3RT .
T -T 500 - 300 200 65. 9H - 9E = 9n g RT
By using, h = 1 T 2 = 500 = 500 = 0.4
1
also, 2NH3(g) " N 2(g) + 3H 2(g)
45. Since gas gets attached on solid surface therefore
entropy decreases. 9n g = 2 and T = 300 K

46. G is a measure of the Chemical Potential. 66. PCl5 (g) PCl3 (g) + Cl2 (g)
For this reaction ng = 2 1=1
47. At equilibrium, G = 0.
ng = is positive, i.e., there is an increase in the
48. 9G o =- 2.303 RT log K number of gaseous moles then H > E.
- 4.606 =- 2.303×0.002×500 log K 1
67. H 2 + 2 O 2 " H 2 O 9H =- 188kJ/mole ...(i)
log K = 2, K = 100.
H 2 + O 2 " H 2 O 2; 9H =- 286kJ/mole ...(ii)
49. 9G = 9H - T9S, T = 25 + 273 = 298 K
By 2 × (i) and (ii)
= 11.7×103 - 298× (- 105)
2H 2 + O 2 " 2H 2 O; 9H =- 376kJ/mole ...(iii)
= 19590 J = 19.59 kJ
2H 2 + 2O 2 " 2H 2 O 2 H =- 572kJ/mole ...(iv)
50. If 9G =- ve reaction is spontaneous. By (iii) (iv)
51. 9G = 9H - T9S 2H 2 O 2 " 2H 2 O + O 2 9H =+ 196kJ .
9G =- 382.64 - (- 145.6) ×10 -3 ×298 68. H for C2H6 = 341.1 kcal.
=- 339.3 KJmol -1 - 341.1
= 30 =- 11.37 kcal/g.
52. 9G = 9H - T9S = 31400 - 1273×32 H for C2H2 = 310.0 kcal
= 31400 - 40736 =- 9336 cal - 310.0
= 26 =- 11.92,
53. 9G = 9H - T9S
hence C2H2 is a better fuel.
0 =+ 30.558 - T×0.066
69. For the decomposition of 9gm of water heat required
30.558
or T = 0.066 = 463 K =142.5 kJ
54. dG = VdP We know H2O = 2 + 16 = 18
55. 2CO(g) + O2(g) 2CO2(g) Therefore heat required for decomposition of 18gm
18
ng = 2 3= 1 water = 9 ×142.5 = 285 KJ
Now, H = u + ngRT. Since ng < 0 Than, enthalpy of formation of water is reverse of
heat required =- 285 kj.
H> u
7.8 Chemistry
70. C(s) + 2H 2(g) " CH 4(g) ...(i) 9H comb. (CH 4)
C(s) + O 2(g) " CO 2(g) 9H =- 94 kcalmol -1
... (ii) = 9H f (CO 2) + 29H f (H 2 O) - 9H f (CH 4) - 29H f (O 2)
1
H 2(g) + 2 O 2(g) " H 2 O(l) 9H =- 68kcal mol -1 ..(iii) & - 890.4 =- 395.5 + 2 (- 285.5) - 9Hf (CH 4) - 2 # 0
CH 4 + 3/2 O 2 " CO 2 + 2H 2 O H 9H f (CH 4) =- 76.7 kJ mol -1 .
= 213 kcalmol 1
...(iv) 76. S + O 2 " SO 2, 9H f =- 4.6 kJ
to obtain equation (i) operate (ii) + 2 x (iii) (iv). a 0.5 gm of sulphu on burning produce 1gm of
H of equation (i) = 94 + 2 ( 68) ( 213) SO2
= 17 kcal/mol. 32 gm of sulphur on burning produce 64gm of
SO2
71. C(s) + O2(g) CO2(g) H = 393.5 KJmol 1
...(i)
9H = (- 4.6 kJ) ×64 =- 294.4 kJ .
CO(g)+1/2O2(g) CO2(g) H = 393.5 KJmol ..(ii) 1
77. No doubt heat evolved during neutralization of
On substracting equation (ii) from equation (i) 250 cm3
We get evolved during neutralization of 50 cm3 of each acid
C(s) + O2(g) CO2(g); H = 110.5 KJmol 1 and base but the quantity of solution taking heat is
The enthalpy of formation of carbon monoxide per
mole = 110.5 KJmol 1 78. Given: Weight of iron burnt = 4g; Heat liberated =
29.28 KJ and atomic weight of iron (Fe) = 56. We
72. C + O 2 " CO 2; 9H = q
know that in ferric oxide (Fe2O3), 2 moles of iron
C + 1/2O 2 " CO; 9H =- 12 ...(i) or 2 × 56 = 112 gram of iron are burnt. We also
CO + 1/2O 2 " CO 2; 9H =- 10 ...(ii) know that when 4 grams of iron are burnt, then
additing equation (i) and (ii) we can get heat liberated = 29.28 KJ, therefore when 112
grams of the iron are burnt, then heat liberated
9H =- 12 + (- 10) =- 22 29.28×112
= 4 =- 819.8 kJ (Minus sign due to
25
73. C8 H18 + 2 O 2 " 8CO 2 + 9H 2 O liberation of heat).
3 H orxn = 8H fo ]CO 2g + 9H fo ]H 2 Og - H fo ]C8 H18g 79. C + O 2 " CO 2(g), 9H fo =- 393.5 kJ mol1 ...(i)
=8( 490) + 9 ( 240) 160 1
C + 2 O 2 " CO(g), 9Hf =- 110.5 kJ mol
o -1
...(ii)
3H o
rxn = 3920 2160 160 = 6240 KJ/mol 1
H 2 + 2 O 2 " H 2 O(g), 9Hfo =- 241.8 kJ mol -1 ...(iii)
3H o
rxn = for 6 moles of octane = 6240 × 6
By (ii) + (iii) (i)
= 37440 KJ /mol = 37.4 KJ
CO 2(g) + H 2(g) " CO(g) + H 2 O(g), 9H =+ 41.2 .
3
74. 2Fe + 2 O 2 " Fe 2 O3; 9H =- 193.4 kJ ...(i)
80. XY $ X(g) + Y(g); 9H =+ a kJ/mol ...(i)
1 X 2 $ 2X; 9H =+ a kJ/mol
Mg + 2 O 2 " MgO; 9H =- 140.2 kJ ...(ii) ...(ii)
On multiplying eq. (ii) by 3 Y2 $ 2Y; 9H =+ 0.5 a kJ/mole ...(iii)
3 1 1
3Mg + 2 O 2 " 3MgO; 9H =- 420.6 kJ ...(iii) 2 ×(ii) + 2 ×(iii) - (i), gives
Resulting equation can be obtained by subtracting 1 1
eq. (i) from (iii) 2 X 2 + 2 Y2 $ XY ;
9H = b + 2 + 2 a - a l kJ/mole
3 a 0.5
3Mg + 2 O 2 " 3MgO; 9H =- 420.6 kJ
3 a 0.5 a
2Fe + 2 O 2 " Fe 2 O3; 9H =- 193.4 KJ + 2 + 2 - a =- 200
Subtraction: a = 800 .
3Mg + Fe 2 O3 " 2Fe + 3MgO; 9H =- 227.2 KJ 81. 4g H2 = 2 moles, Bond energy for 1 mole of
75. CH 4 + 2O 2 " CO 2 + 2H 2 O, 9H =- 890.4 kJ .(i) H2 = 208 / 2 = 104 kcal.
C + O 2 " CO 2, 9H =- 395.5 kJ ...(ii)
1 82. is resonance stabilized and hence the
H 2 + 2 O 2 " H 2 O, 9H =- 285.8 kJ ...(iii) :
from (i), (ii), (iii). C H bond is easier to break than CH4 to form CH3
 Thermodynamics 7.9
83. N N is the strongest bond among the given options. - 166
86. 4 =- 41.5 kJ/mole EC H = 41.5 kJ/mol.
1 1
84. Aim: 2 H 2 + 2 Cl 2 " HCl 1 1
87. 2 H 2 + 2 Cl 2 " HCl, 9H =- 90 KJ
9H = /B.E.(Products) - /B.E.(Reactants) 1 1
9H = 2 f H - H + 2 fCl - Cl
= B.E (HCl) - : 2 B.E. (H 2) + 2 B.E. (Cl 2)D
1 1
1 1
or - 90 = 2 ×430 + 2 ×240 - f HCl
=- 103 - : 2 (- 104) + 2 (- 58)D
1 1
f H - Cl = 425 kJmol -1 .
=- 103 - (- 52 - 29) =- 22 kcal . 88. CH 4 " C + 4H, 9H = 320
85. First ionization potential of Li = 5.4 eV fC - H = 80 cal
C 2 H6 " 2C + 6H, 9H = 520
We have H = I.P. E.A. 520 = fC - C + 6fC - H
= 5.4 3.61 = 1.80 eV = 1.80 × 1.6 × 10 22
kJ fC - C = 520 - 480 = 40 cal.
H = 2.86 × 10 22
kJ, 89. H - H + Br - Br " 2H - Br
for 1 mol H = 625 728 = 103 kJ
H = 2.86 × 10 22
× 6.02 × 10 = 170 kJ/mole.
23

EXERCISE
1. Test tube is open to atmosphere.
2. (i), (ii), (iii), (iv)
3. (ii), (iii), (iv), (v), (vi), (vii), (viii)
4. Insulated container of rigid walls will not show any
change in temperature.
5.
6. Case (i) 9V = 0, W = 0
Case (ii) P = constant, W =- P (2V1 - V1) =- PV1
7. W = +ve because work done on system.
q = 0 because thermally insulated container.
2
C D : Isochoric decrease in P, T
D A : Isothermal compression as PV is constant
14. From graph we know that VB > VA, so expansion has
taken place so w will be with –ve sign and H will
be +ve as T has increased.
15. If system returns to initial state after multiple
processes then it is a cyclic process.
16. Work done by the gas in the
cyclic process = Area bounded
(ABCA) = 5P1V1

8. Freezing of liquid is always an exothermic process Since Vol. is in X axis and loop is clockwise
in which the system loses heat.
Sign of W is negative
9. U = Q + W = 600 + ( 300) = 300 J
17. At constant vol. or decreasing volume, T is increasing
W = 300, because the work done by the system. thus pressure must be increasing.
10. U=q+2=q Pext (V2 V1) When V, T both increasing, P is decreasing as slope
300 = 500 1 ( V) × 100 is greater than 45o.
500 - 300
9V = 100 = 2 lit.
18.
11. Formation of bonds results from attractive forces i.e.
decrease in potential energy. Since u = P.E. + K.E.
therefore as P.E. decreases, u also decreases.
12. A B, volume is not changing (Isochoric) PV = const = K
B C Isobaric log P + log V = log K
C A Temperature is constant (Isothermal) Y + X = K as T - K-
Hence intercept on co ordinate axes will increase
13. A B : Isochoric increase in P, T
T2 > T1
B C : Isothermal expansion as PV is constant
7.10 Chemistry
V nR 32. P2V2 = 20 L atm P1V1 = 3 L atm
19. Slope = T = P
(PV) = 17 L atm
as slope increses, P must u = 40 L atm H = u + (PV) = 57 L atm
be decreasing
PA < PB 33. H = heat given. So process is isobaric.

20. C p - C v = nR for non molar heat capacity W =- Pext (9V) =- 1×2 litre atm =- 202.6 J
C p,m - C v,m = R for non molar heat capacity Hence, q = 202.6 J = 9H and 9U = q + w = 0

21. Isochoric rocess w=0 34. Because two states of a system can not be connected
by one adiabatic & one isothermal path.
u=q
35. q = 0 ` 9U = w
22. For Isothermal Process u = 0
nC v,m (T2 - T1) =- Pext : P 2 - P 1 D
nRT nRT
q+w=0 q= w 2 1

C v,m [T2 - T1] = Pext $ R : P1 - P2 D

Now work done by the system = w T T
work done by the system = q 1 2

5 : 300 T2 D
23. During adiabatic expansion P, T both decrease. 2 R [T2 - 300] = 2×R 5 - 2
24. T1 V1c - 1 = T2 V2c - 1 & 300×V1/3 T2 = 248.5 K .
T2 (8V) 1/3 & T2 = 150 K 36. |Wrev |>| WIrr |
W = nC v (T2 - T1) = 1×3R (150 - 300) Tfinal(rev) < Tfinal(Irr)
3×2 (- 150) =- 900 cal 9Trev > 9TIrr
25. Magnitude of work done 9H \ 9T | Hrev| > | HIrr| but as T decreases
is maximum for largest during adiabatic expansion so H is < 0 Hrev
area under the P.V. curve < HIrrev
with the V axis. 9H rev > 9H Irr
26. Slope of adiabatic curve is greater than isothermal 37. State 1 $ State 2
curve
(1L, 10 atm, 300 K) (4L, 5 atm, 600 K)
27. TV c - 1 = constant q
a C = 3 T q = 50 × (600 300) = 15000 J
5 2
c= 3 `c-1 = 3 W =- Pext (V2 - V1) =- 1 (4 - 1) =- 3L atm =- 300 J
300× (8) 2/3 = 250× (V2) 2/3 9u = q + W = 15000 - 300 = 14700 J
(V2) = 4.8
2/3
9H = 9u + P2 V2 - P1 V1
V2 = (4.8) 3/2
10.5 L = 14700 J + (20 - 10) ×100 J = 15.7 KJ
28. At A and D the temperatures of the gas will be equal, 38. 9U = 9W
so 9u = 0, 9H = 0 nCv (T2 - T) =- P×(V2 - V1)
Now W = WAB + WBC + WCD 3
=- P0 V0 - 2P0 V0 2 R (T2 - T) =- 1
2
ln 2 + P0V0 T2 = T - 3×0.0821

= 2 + P0V0 ln 2 and q = W = 2 + P0V0 ln 2. 39. Since work done on the system, is maximum in
single stage compression hence all other adiabatic
29. In isothermal reversible process ideal gas has points will fall between 1 and 2.
constant temperature and so U=0 and H = U=0.
40. Final temperature of gas must be double of the initial
30. The product PV is increasing so temperature will temperature as P remains constant and V doubles.
keep or increasing in the process, hence H = u + Initially PV = 1 bar L = 100 J
(PV) will increase constantly
9H = 9u + 9 (PV) = nC v 9T + 9 (PV)
31. (PV) = 40 L atm = 40 × 100 J = 4000 J
a 9T = Tf - T1 = T1
u = 200 J nR 3
= (c - 1) T1 + 9 (PV) = 2 ×100 + 100 = 250 J.
H= u+ PV = 4200 J = 4.2 kJ
 Thermodynamics 7.11
401.7
Ssur = 273 = 1.47 J/K
41.
9S(universe) =- 1.09 + 1.47 = 0.38 JK -1
59. 9S reaction = 6 (87) - 4x - 205 =- 266
& x = 145.75 J moleK
60. Gibb’s free energy is expressed in kJ/mol or J/mol
and hence is an intensive property.
42. Vwater < Vice for ice to water V < 0 61. For spontaneity G < 0, which is possible when H
Now W = P V and V<0 < 0, S > 0.
W>0 62. Equilibrium at standard state means Go = 0 K=1.
43. During freezing Hfusion amount of heat is lost by the 63. Once curd formation beings in milk, the entire milk
system to freeze 1 mole water. gets converted to curd on its own i.e. spontaneously.
25 0.0821×373
44. W = P V. Now Vsteam = 18 × = 42.53 L 64. At 100oC and 1 atm water and steam are at
1 equilibrium, Hence G = 0.
4250
W = 1 × 42.5 L atm = - 4.18 cal = 1030 cal 65. It is because of the fact that for spontaneity, the value
25
q = H = 9270 × 18 = 13500 of G ( H T S) should be < 0. If S is – ve, the
value of T S shall have to be less than H or the
a H = u w at constant pressure 9H x
value of S has to be less than T i.e., 298 .
u = 13500 1030 = 12470 cal
66. H= 33 × 103 J and S = 58 J/k
45. Molecules of gas are most free to move about and
hence possess the highest entropy. For spontaneity : H T S<0
33000 T ( 58) < 0
46. ng is + ve
or, 58 T < 33000
47. Mixing of non reacting gases increases randomness
T < 568.96 k
and so increase entropy.
1
48. ng is most ve 67. K = 4
1
49. Reaction is endothermic and no. of moles increases Go = RT ln KP = RT ln KP = RT ln 4 = RT ln 4
on decomposition. 68. G for 3Fe (s) + 2O 2 (g) $ Fe3 O 4 (s) can be
50. NaNO3 is a solid, which is converted to liquid ions. 1
obtained by taking [(2) + 4×(1)] × 3
51. Greater value of ng more entropy change. 1
Hence, we get 9G f = [- 19 + 4×(- 177) × 3
52. Second Law of Thermodynamics can also be =- 242.3 K cal for 1 mole Fe3 O 4
stated as Entropy of the universe is continuously
increasing as the universe is expanding. 69. 9G o = 9H o - T9S o
For spontaneous process 9G o < 0
53. S (gas) is always > S (liquid)
So, 9H o - T9S o < 0
T 5 600
54. 9S = nC p,m ln T2 = 2× 2 R ln 300 = 5R ln2 Hence, T < 339 K or < 66 o C .
1

55. 9S gas = nC v,m ln T2 = 2× b 2 - 1 l R ln 2

T 5 70. G at equilibrium = 0.
1

= 3R ln 2. 71. 9H o = 9U o + 9n g RT
1×2×500
T 3 573
56. 9S gas = nC v,m ln T2 = 2× 2 R ln 473 = 3 R - 4.6 = 9U o -1000 & 9U =- 3.6 kCal
o
1

= 3R ln b 473 l .
573 72. w =- Pext 9V =- 9n g RT and 9n g is Ve for I and
II also 9V =- ve for IV. Hence, w is + ve.
V 73. 9n g = 0 & 9H o = 9U o
57. 9S gas = nR ln V2 = R ln 3
1

1× - 401.7 For 2 mole 9U o =- 370 kJ .

58. 9S(system) = 368 =- 1.09 JK - 1
The ice water both absorbs the 401.7 J
7.12 Chemistry
74. Sublimation would involve absorption of heat and 83. Combustion reaction of solid boron
thus, the temperature of the air inside the balloon wil 3 1
decrease. B (s) + 4 O 2 (g) $ 2 B 2 O3 (s)
u < 0. 1
9H 0r = 9H 0c = 2 H 0f (B 2 O3, s) - 9H 0f (B, s)
75. Using H = E + ng RT, if ng ! 0 the H ! u 3
- 4 9H 0f (O 2, g)
76. 3C(s) + 3H 2(q) + O 2(q) $ CH3 COOCH3 (,) 9H 0f of element in standard state is assumed to be
9H fo =- 442.91 zero.
1
9U = 9H - 9n q RT where nh = 4 HoC (B(s)) = 2 Hof (B2O3(s))

u = b - 442.91 - (- 4) ×8.314× 1000 l kJ mole -1 84. Heat evolved from 1 mole of sucrose (342 g)
298
= 1350 kcal
=- 433 kJ mole -1
Heat evolved from 17.1 g of sucrose
77. 2C + O 2 " 2CO; 9H =- 220 KJ 1350
= 342 ×17.1 = 67.5 kcal.
This reaction does not represent complete
combustion of carbon, hence heat of combution of 85. S + O2 SO2 H = 298.2 KJ/mole ...(1)
carbon will not be equal to 110 kJ. The negative 1
sign of H indicates that this reaction is exothermic. SO2 + 2 O2 SO3 H = 98.7 KJ/mole ...(2)
Also, despite being spontaneous reaction, it requires SO3 + H2O H2SO4 H = 130.2 KJ/mole ...(3)
initiation.
1
H2 + 2 O2 H 2O H= 287.3 KJ/mole ...(4)
78. C (s) $ C (g) can be obtained as,
1
9H = 9H1 - 9H 2 - 2 9H3 + 9H 4 Adding (1), (2), (3) and (4) we get desired equation.
5644
79. We have 86. nC H = 1411 = 4
2 4

H 2 O (l) " H 2 O (g) 9H = 40.63 kJ mol

o -1
C2H4 + 3O2 2CO2 + 2H2O nO needed = 4 × 3
2

9U = 9H - (9n g) RT,
o o
3 ng = 1 VO = 4 × 3 × 22.4 = 268.8 L
2

uo = 40.63 kJ mol 1
(8.314 × 10 3 × 373) 9H
87. = mol.wt
= (40.73 3.10) kJ mol 1

341
= 37.63 kJ mol 1 for ethane (C 2 H6) =- 30 =- 11.37
80. H represents heat of reaction. 310
for ethyne (C 2 H 2) =- 26 =- 11.9
81. H2(g) + Br2(g) 2HBr(g) H = Ho1 ... (i) H2.
2
Br2(g) Br2( ) H= H o
2
... (ii) 88. MgCl2 $ H2O MgCl2(aq) H1 = ?
[eq1 eq2]
MgCl2(aq) Mg2+(aq) + 2Cl (aq) H1= 30 cal/mol
H2(g) + Br2( )
2HBr(g) H = H o
2
1 1 MgCl2 $ H2O(s) Mg2+(aq)+2Cl (aq) H3= 25cal/mol
Required equation, 2 H 2 (g) + 2 Br2 (,) $ HBr (g)
a R1 = R3 R2.
9H = ; 9H1 - 9H 2 E
0 0

2 H1 = H3 H2 = 25 + 30 = + 5 cal/mol.
82. C (diamond) + O2 CO2(g); H = 94.3 kcal/mol 89. Since process is exothermic thus heat is evolved. So,
C (graphite) + O2 CO2(g); H = 97.6 kcal/mol temperature of water increases.
C (diamond) C (graphite) H = 3.3 kcal 90. C 2 H 2 (g) + H 2 (g) $ C 2 H 4 (g)
Heat required to convert 12 gram diamond to 9H = 9U + 9n g RT = 9U + P9V
graphite = 3.3 100
- 0.5 = 9U + 1.5 (- 5) × 1000
Heat required to convert 1 g diamond to graphite
3.3 9U =- 0.5 + 0.75
= 12 = 0.275
9U = 0.25 kJ
 Thermodynamics 7.13
91. KBr (s) $ K + (g) + Br - (g) 97. Given
& 9H = H 2 (g) $ 2H (g); 9H = 104 kcal ...(1)

92. 9H 0f (LiCl) =- q = 9Hsub (Li) + 1 2 9H diss Cl 2 (g) $ 2Cl (g); 9H = 58 kcal ...(2)

(Cl 2) + 9H IP (Li) + 9H EA (Cl) + 9H L.E. HCl 2 (g) $ H (g) + Cl (g); 9H = 103 kcal ...(3)
244 Heat of formation of HCl
- 400 = 160 + 2 + 520 - 365 + 9H L.E.
1 1
9H L.E. =- 400 - 437 =- 837 kJ mole -1 2 H 2 (g) + 2 Cl 2 (g) $ HCl (g) ; 9H = ?
Divide equation (1) and (2) by 2, and then add
93. Strong acid and strong base neutralization heat is
1 1
equal to – 13.7 kcal. 2 H 2 (g) + 2 Cl 2 (g) $ H (g) + Cl (g);
94. HCOOH is a weak acid so heat of neutralization is 9H = 81 kcal .... (4)
less than X. Subtracting equation (3) from equation (4)
+ -
95. H + OH $ H 2 O (,) 9H = 013.7 kcal ...(i) HCl (g) $ H (g) + Cl (g) ; 9H = 103 kcal ...(3)
CHCl 2 COOH $ CHCl 2 COO + H - + 1 1
2 H 2 (g) + 2 Cl 2 (g) $ HCl (g) ; 9H =- 22.0 kcal
9H = 0.7 kcal ...(ii) Enthalpy of formation of HCl gas =- 22.0 kcal
CHCl2COOH + OH CHCl2COO + H2O( ) H = ? 1 1
98. 2 A - A + 2 B - B " AB 9H =- 100 KJ/mole
Adding equation (i) and (ii) H = 13 kcal.
1 1
The required heat released will be (13.7 heat 2 x + 2 (0.5x) - x =- 100
required to dissociate CHCl2COOH = 13.0 kcal. x
& 2 + 0.25x -+ x =- 100
96. CH 4 $ C + 4H
&- 0.25 x =- 100
9H = 320 = 9H C - H; 9H C - H = 80
& x = 400 KJ/mole
C 2 H6 $ 2C + 6H
bond enthalpy = 400 kJ/mol.x
9H = 600 = 9H C - C + 69H C - H
600 = 9H C - C + 6×80
9H C - C = 120 cal
EXERCISE 3
1. There is a decrease in the magnetic potential energy TV = C’
which will be compensated by an increase in the T1V1 = T2V2
K.E. of the water molecules. Thus, temperature of
300 × 1 = T2 × 3 T2 = 100 K
the water will increase.
U = nCv, m T
2. From the graph it can be derived that the PV work
5R
of the system is zero. Thus, we can say that dw = 0 U = 1 × 2 (T2 T1)
only if non PV work is aso zero. 5×R
= 1 × 2 × (100 300)
3. Degrees of freedom : O3 > N2 > Ne and we know
1 1×5×R
that K.E. = f × 2 RT = - 2 ×200 =- 500R =- 4.2 kJ
4. The latent heat of vapourization is used to break the 7. Since ice water ratio is maintained as 1 : 1. So, T=0
bonds between the liquid molecules. In other words, as on supplying q, ice melts, hence C = 3 .
it is used to increase the potential energy of the
8. w =- nR9T =- 2×8.314×100 =- 1662.8 J
system. This is so because when there are forces of
400 400
attraction between particles P.E. < 0, and if there are
no interactions then P.E. = 0.
9U = n # C V,m dT = 2× # (20 + 10 -2 T) dT
300 300

= 2 :20×100 + 102 (400 2 - 300 2)D = 4700 J

-2
5. a The process is of free expansion thus W = 0, as
pext = 0.
4700 = q 1662.8
6. For polytropic process (n = 2)
q = 6362.8 J.
PV2 = C
7.14 Chemistry
9. Latent heat of vaporisation of water = 2.25×106 J/kg. 16. H 2 O (,) $ H 2 O (g) 9H vap = 9S vap TB.P. = x1 T1
H = 2.25 × 106 J/kg. 9H f (H 2 O, g) = 9H f (H 2 O, ,) + 9H vap = x 2 + x1 T1

105 b 0.6 - 1000 l

1 1 Hreaction = 2 Hf(CO2,g)+3 Hf(H2O,g) Hf(C2H6,g)
work done = Pext (V2 V 1) =
Hreaction= 2x3 + 3 (x2 + x1 T1) x4
= 0.166 × 106 J/kg
= 2x3 + 3x2 + 3x1 T1 x4.
= U= H V= H+w
17. Less negative the Gof lesser its stability and more
= 2.08 × 106 J/kg
easily it can decompose.
10. Volume = 5×10×3 = 150m3 = 150×103 L ;
18. The compressor has to run for longer time releasing
T = 27 o C = 300 K; P = 1 atm more heat to the surroundings.
PV = nRT 1 × 150 × 103 = n × 0.082 × 300 V
19. 9Ssystem = nR ln V2 = 2×R×ln2 = 11.52 J/K
n = 6097.6 1
3.41×1000
Total energy released per second 9Ssurrounding =- 310 =- 11 J/K
= 150 × 50 = 7500 J/sec. 9S total =+ 11.52 - 11 = 0.52 J/K
Amount of energy released by persons = energy T V
20. 9S = nC v,m ln T2 + nR ln V2
gained by air [7500] tsec = nC [dT] 1 1

= C v,m ln2 + R ln b 2 l = (C v,m - R) ln 2

7 1
& 7500tsec = 6097.6× 2 ×8.312×15
354.87 21. As dew formation is spontaneous process, therefore,
& tsec = 354.87sec. = 60 = 5.91 minutes. entropy or randomness of the universe will increase.
As randomeness of the system has decreased but
11. At constant volume 9U = q v = nC vm 9T randomness of the surrounding will increase larger
3 so that in Suiverse is positive.
= 2 R×300 = 450 R
At constant pressure 9H = q p = nC p,m 9T 22. Sliding of layers in possible in graphite due to
5 weak Vanderwaal’s forces between layers of carbon
= 2 R (- 150) =- 375 R
atoms. Within a layer each carbon atom is covalently
12. a H = U + PV and 9H = 9U + P9V bondid to 3 other carbon atoms.
P9V = nR9T P
23. 9S (gas) = nR ln P1 = 3×8.314×ln 2
2
3 H = 9U + nR9T = 17.29 J/K (at constant temperature)
For isothermal and reversible process Since T = 0, therefore, U = 0,
So, q = W = + pext V = +P2(V2 V1)=P2V2 b1 - V1 l
T=0 V
2
H=0
= nRT :1 - P D, as V = P
P2 V1 P2

13. In isolated system, the expansion of gas is carried 1 2 1

out adiabatically. Since heat exchange between q = T×12.47 J/K

system and surrounding is not possible i.e. q = 0 and q
9Ssurr =- T =- 12.47 J/K
secondary Wrev is always greater than WIrr therefore
9S tot = 17.29 - 12.47 =+ 4.82 J/K
for reversible process there must be comparatively
higher decreases in internal energy i.e. U for 24. 0.40 = aT13 + bT1
reversible process will be more negative. Hence, & 0.40 = a×(1000) + b×10
& 0.4 = 1000a + 10b ...(1)
smaller than irreversible process.
0.92 = aT 23 + bT2
(Tf)irrev > (Tf)rev
& 0.92 = a×8000 + 20b ...(2)
14. 9S = nC p,m ln T2 = 2.5×18×4.2 ln b 300 l
T 360
1 from Eqs. (1) and (2)
= 34.02 J/K a = 2×10 -5, b = 0.038
20
15. Reversible adiabatic processes are called Isoentropic aT3 + bT a [T 23 - T13] 020
as Ssys = 0 for such processes.
Sm = # T $ dT = 3 + b [T2 - T1] 020
0

= 0.813 J/K - mol

 Thermodynamics 7.15
25. 9G o200 = 9H o200 - T9S o200 31. Au(OH)3+4HCl HAuCl4+3H2O, H= 28 kcal
9H o200 = 20 -= 16 kJ/mol HAuBr4+3H2O Au(OH3+4HBr, H= 36.8 kcal

9H oT = 9H oT + 9C P [T2 - T1]
2 1
HAuBr4+4HCl HAuCl4+3H2O, H= 8.8 kcal
20×200
9H o400 = 9H o200 + 1000 kJ/mol When 100% conversion, heat absorbed = 8.8 Kcal
0.44
= 16 + 4 = 20 kJ/mol . % converstion = 8.8 ×100 = 5%
26. H3 PO3 $ 2H + + HPO32-; 9 r H = ? 32. Let mixture contain x mole of steam & y mole
2H + + 2OH - $ 2H 2 O; H = 55.84 × 2 oxygen then, since temperature is constant.
9 r H =+ 55.84×2 - 106.68 So, amount of heat released = amount of heat gain
9 r H = 5 kJ/mol. x 220 1.66
x×132 = y (220) y = 132 = 1
27. CS 2 (,) + 3O 2 (g) $ CO 2 (g) + 2SO 2 (g) x : y = 1:0.6
9H =- 256 Kcal
Let 9H f (CO 2, g) =- 4 x and 9H f (SO 2, g) =- 3 x 33.
Hreaction = Hf(CO2,g)+2 Hf(SO2,g) Hf(CS2,l)
256 = 4x 6x 26
x = + 23.9
H=4 + HIoni[Xe Xe+] Heg [F F ]
9H f (SO 2, g) = 3 x =- 71.7 Kcal/mol. Xe F F F

= 4×34 + 279 - 85 - 38 = 136 + 279 - 123

28. Required reaction & 6C(graphite) + 3H 2(g) $ C6 H6(g) = 415 - 213 = 292 kcal/mole.
1. For formation of C6H6(g) from gaseous C and H
34. FeO + Fe 2 O3
atoms
2x x
9H1 =- (6×9H C - H + 39H C - C) 1
Fe + 2 O 2 $ FeO 9H fo =- 65 Kcal/mole
=- (6×416 + 3×591 + 3×331)
3
=- 5262 kJ mole -1 2Fe + 2 O 2 $ Fe 2 O3 9H 0f =- 197 Kcal/mole
2. Formation of gaseous C atoms from graphite 1
2FeO + 2 O 2 $ Fe 2 O3
6C(graphite) $ 6C(g) 9H 2 = 6×718 = 4308 9H =- 197 + 65×2 & 9H =- 67 Kcal/mole
3. Formation of atomic H atoms from H2 1
2FeO + 2 O 2 $ Fe 2 O3
3H 2(g) $ 6H(g) 9H3 = 3×436 = 1308
2 1
Adding (1) + (2) + (3) 3 3
6C(graphite) + 3H 2(g) $ C6 H6(g) 2 1
3 - 2x 3 +x
9H = 9H 0f (C6 H6, (g)) = 9H1 + 9H 2 + 9H3 2
= 354 kJ mole -1 3 - 2x = 1 x= 5
1
Hence resonance energy 1 2
3 +x
= 9H f (cal.) - 9H fo (theo) = 354 - 83 1
So, energy released = 5 ×67 = 13.4 kcal/mole
= 271 kJ mole -1
35. The heat evolved in the second case is half of the
25
29. C8 H18 (,) + 2 O 2 (g) $ 8CO 2 (g) + 9H 2 O (,)
25 16 - 25 9 mass of solution in the second case is also half,
9n g = 8 - 2 = 2 =- 2 =- 4.5 therefore the increase in temperature is the same.
4.5×8.314×298
9H - 9U = 9n g RT =- 1000
36.
=- 11.15 kJ
30. CH 2 = CH 2 + H 2 " CH3 - CH3 9H = x1
So, Hydrogenation energy of benzene should be 3x1
H calculated = 3x1 1 Wrev | > | Wirrev | but as the process is expansion so
So, Resonance energy = [3x1 x2] W is negative.
Hence Wirrev > Wrev. Also as q = W qrev > qirrev.
7.16 Chemistry
37. In adiabatic expansion, q = 0. So U = W = Pext V 48. At constant pressure heat of reaction = H and at
Irreversible adiabatic So PV constant not valid. constant volume heat of reaction = u.
Since q = 0, so gas does work by utilizing its internal since both u, H are state functions therefore value
energy. of heat of reaction is independent of method or steps
So, T decreases and also enthalpy (H) decreases. followed : Hess’ Law.
38. System surroundings are aways separated by a 49. Combustion reaction are exothermic, hydrogenation
boundary. This boundary is real in case of closed of alkenes are exothermic and graphite is
systems and imaginary in case of open systems. A thermodynamically more stable.
perfectly isolated system is impossible to create.
50. Heat of formation is H of that reaction in which 1
During a reversible process system and surrounding
mole of the substance is formed from its constituent
are always in equilibrium. Hence, it is called quasi
elements in their standard elemental states.
static.
51. (a) Correct : BE > 0
39. PV = constant for isothermal process
(b) Correct : n > 0 S>0
PV = constant for adiabatic process so more value
of , more decrease in pressure as volume increases. (c) Incorrect : It depends on T
(d) Incorrect : H = E + RT > E
40. For sublimation, q > 0 and process is always
endothermic H > 0. Also, for sublimation S>0 52. Ho.reaction = Hof only for formation reactions. i.e.
as solid gas. Thus T S > 0. are mole of the product should be formed from its
Now, G = H T S and for spontaneity G < 0. constituent elements and these constituent elements
Also, H = H + ng RT G = u + ngRT T S should be in their standard elemental states.
For G < 0, u > 0 at low T and at hight T it is 53. Since, Hof (C2H6(g)) = 218 HH H = 436
possible to have G < 0 even if u < 0. 2C + 3H2 C2H6
41. T = 0, E = 0, H = 0 Also H (C2H6(g)) = 2 × 718 + 3 × 436
o
f
a 6b
42. During ice(s) water (l) or vapourization of (9H C - C = a, 9H C - H = b)
comphour, it is easy to understand that entropy of a + 6b = 2829
the system increases as Ssolid < Sliquid < Sgas. However 3C + 4H2 C2H8
in case of rusting of iron: 4Fe + 3O2 2Fe2O3 the
entropy of the universe is increasing dispite the H (C2H6(g)) = 3 × 718 + 4 × 436
o
f
2a 8b
decrease in the entropy of the system. 2a + 8b = 4002
43. For isothermal expansion, T is constant so: a = 345 & b = 414 kJ.
H = 0, U = 0, G = T. S, T = TInitial 54. Formation reaction of CH4 can be obtained by:
44. Liquid solid is generally an exothermic process R1 + 2R2 R3 Hof (CH4) = Ho1 + 2 DHo2 DHo3
and also SLiquid > SSolid. = 394 568 + 892 = 70 kJ
45. q = 0 for reversible adiabatic Ssys = 0 = 16.607 kcal.
Isoentropic. For irreversible adiabatic : Ssurr = 0
Stot = Ssys > 0 55. Refer Q. 50.
For free expansion also, Ssurr = 0 and Ssys > 0 56. Strong acid with strong base heat of neutralization is
For isothermal compression qsys < 0 57.32 kJ (b 13.7 kcal) .
qsurr > 0 Ssurr > 0
57.
46. Molar entropy depends upon the degrees of freedom expansion is more than single stage expansion.
of a gas III – Single stage process is a irreversible process.
As atomicity increases Cv, Cp increases S
increases IV – We have 5 points on PV diagram.
For ideal gases there are no forces of interaction 58. All are examples of non PV work.
between molecules.
a) electrical work
47. Boiling of a liquid at normal boiling point is a b) Mechanical work
equilibrium process and on decreasing the pressure
c) Gravitational work
equilibrium will go forward and G will be negative
and vice versa. d) Magnetic work
 Thermodynamics 7.17
59. 1 × Vf = 5 × R × 546 = 224 L 66. a, b, : Factual
W= Pext ( V) = 1atm (224 L) = 224 L atm c : Dissolution of ionic salt is an example where
work done by system = 224 L atm S > 0 although ng = O
V
Enthalpy change ( H) = q = 273 × 5 d : For isothermal process S = nRln V2 &
1
V2 P1
= 1365 L atm V = P
1 2

U = q + W = 135 224 = 1141 L atm 67. (a) Incorrect : For an isothermal change, E = 0
(b) Correct : Precise and accurate measurement of
60. a) Linear compound will have more entropy than
state function is impractical.
cyclic compound.
(c) Correct : E is a state function. In cyclic process,
b) S is same for both
E=0.
c) S at 300 K < S at 300oC (573 K)
(d) Incorrect : E is a state function.
d) More H bonding in CH3OH than C2H5OH
S = nCV ln b Tf l + nR ln b Vfi l
T V
68.
61. OH = (n1 C p,m + n 2 C p,m ) OT
1 2 i

= b0.5 # 2 R + 0.5 # 4R l (- 100) =- 375 R and

373
7 = 5 ln 298 + 2 ln 10
H = nCP T = n (CV + R) T = 1 × 7 × 75 = 525 cal
OU = b0.5 # 2 R + 0.5 # 3R l (- 100) =- 275R.
5
69. Electrical work is done in b and d.
62. From graph, slope = 1
70. a) ng > 0, so V > 0 W is negative
eq & log10 V + log10 T = constant
b) ng = 0 V=0 w=0
VT = constant or PV2 = constant
c) Redox reaction non
R of change, electrical work
a C = CV + 1 - n
5R R 3R d) Dissolution of salt Wnon PV ! 0
C = 2 +1-2 = 2
71. For ACB u = q + w = 80 30 = 50
3R
q = nC T = 3 × 2 × (1000 100) = 4050 R So for ADB, u = 50 J as u is state function
5R
U = nCV T = 3 × 2 × (1000 100) = 6750 R 50 = q 10 q = 60 J
72. For B to A
W= U q = 6750 R 4050 R = 2700 R
u= 50 J as uB A
= uA B
63. H = 4 KJ
w = + 20 J
H = U + (PV)
q= 50 20 = 70 J
U = 4 P (V2 V1)
70 J heat is liberated.
105 (18 - 19) # 10 -6
= 4-
103 73. In ADB process, DB process is isochoric so WDB = 0
= 4 + 1 × 10 4
So, UAD = qAD + WAD
= 4.0001 KJ
40 = qAD + ( 10); qAD = 30 J
64. V T curve for a given mass of the gas is given Now, qAB = qAD + qDB; 60 = 30 + qDB
PV = nRT; V = b P l T
nR qDB = 90 J
74. G= H T S
T S dominates H at high temperature, thus G<0.
Hence, CaCO3 decomposes at high temperature.
75. G= H T S = 2.1 × 103 20 × 298 < 0.

a V 3 = V1 P3 > P1 as T3 > T1 76. For reaction to be spontaneous

G <O H T S<0
65. NO, NO2, N2O4 have positive heats of formation
100 # 103
Also, Hof (F2O) = 24.5 kJ/mol. T> & T > 2000 K.
.05 # 103
Combustion reactions are always exothermic
7.18 Chemistry
77. Clearly at 400 K, reaction is in equilibrium 87. Let moles of C2H8 = x, moles of X2H2 = y & moles
9H 40000 of CO2 = z.
& 9G = 0 & 9S = T =- 400 =- 100 cal K -1
Calculation of 9H fo of C3 H8 (g)
78. Use 9G = 9H - T9S
3C (s) + 4H 2 (g) $ C3 H8 (g)
300 # (- 7.2)
9G =- 15 - 1000 =- 12.84 Kcal mol -1 9H fo of C3 H8 (g)
79. 9H Nutralization = 9H Ionization - (H + OH - $ H 2 O) =[3(718) + 4(435)] – [2(347) + 8 (416)]
=- 49.86 - (- 55.84) kJ/mole =3894 4022 = 128 kJ / mol.
= 5.98 kJ/mole Calculations of 9H fo of C2H2(g)
80. 9H o = 2 # (- 55.84) kJ/mole =- 111.68 kJ 2C (s) + H 2 (g) $ C 2 H 2 (g)
81. For max. rise in temp.; max. neutralization of H+ and 9H fo C 2 H 2 (g) = [2(718) + (435)] – [(812) + 2(416)]
OH required. = (1436 + 435) – [1644]
If we take equal volume, all H+ (5 m mole) will = 227 kJ/mol.
react with all OH (5 m mole). Calculations of 9H fo of C2H4(g)
82. Work done in isothermal process will be more than 2C (s) + 2H 2 (g) $ C 2 H 4 (g)
PV2 = const, process whatever be the value of K1 9H fo of C2H4(g) = 2 (718) + 2 (435)–[615 + 4(416)]
and K2 as is shown in the diagram.
= 2306 – 2279 = 27 kJ/mol.
Calculations of 9H Comb
o
of C2H4(g)
C3 H8 (g) + O 2 (g) $ 3CO 2 (g) + 4H 2 O (,)
9H Comb
o
of C3H8(g)
= [39H f (CO 2) + 49H f (H 2 O, ,)] - 9H f (C3 H8, (g)
o o o

= [3 (–394) + 4 (–286)] – (–128)

83. Clearly (Vf)Isothermal > (Vf)adiabatic = –2198 kJ/mol.
Calculations of 9H Comb
o
of C2H2(g)
C 2 H 2 (g) + 2.5O 2 (g) $ 2CO 2 (g) + H 2 O (,)
9H Comb
o
of C2H2
= [29H f (CO 2) + 9H f (H 2 O, ,)] - 9H f (C 2 H 2)
o o o

= [2 (–394) + (–286)] – 227

84. Work done “by” the gas in isothermal process = –1301 kJ/mol.
is more than in adiabatic process as shown in the Hcomb (C3H8) + Hcomb (C2H2)
diagram above.
= 2198 + ( 1301) = 3499 kJ/mol
85. For isothermal irreversible process (T = constant)
88. Now total heat released during combustion
Po
P o V o = P ' 2V o & P = 2 2198 x + 1301 y = 4800 ...(i)
For P2V = constant Iron volume of CO2 : 3x + 2y = z = 10 ...(ii)
Po Total moles of H 2 O (,) formed = 4x + y.
P o2 V o = P 2 2V o & P =
2
3808
Final pressure of isothermal process > Final Moles of C2H4(g) to be prepared 22.4 = 170 .
pressure of adiabatic process and Final pressure of Total heat absorbed during evaporation of water
irreversible adiabatic process > Final pressure of formation of 170 moles C2H4 = 4800.
reversible adiabatic process. [(4x + y) × 0.875 x 40] + (170 x 27) = 4800
4x + y = 6 ...(iii)
on solvent (i), (ii) and (iii)
86. Hr = f C / C + f H - H ( fC = C + 2 fC - H ) we get x = 1, y = 2, and z = 3.
or Hr = 812 + 435 (615 + 2 × 416)
89. Extensive properties are
Hr = 200 kJ/mol.
(i) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (x)
 Thermodynamics 7.19
90. State function are (i) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) 9S =- 15 J/mol K
(ix) and (x) are constants and not variables 98. For the formation reaction above
9S fo = S oNH Cl - b 2 S oN + 2S oH + 2 SCl
91. Ist procese is isobaric, volume become double so, 1 1 o l
4 2 2 2

T is also doubled
= 94.6 - [1 2 (191.5) + 2 (130.6) + 1 2 (223.0)]
So, for adiabatic Ti = 2 × 300 = 600 =- 373.85 J K -1 mol -1
Vi = 40 Now that we have H and G,
Tf = ?, Vf = 110 9G f = 9H f - T9S t
o o o

for reversible adiabatic process TV 1

= constant = 313×103 J mol 1 (298 K)×( 373.85 J K 1 mol 1)
Ti V i
5/3 - 1
= Tf V f
2/3 =- 201.6 # 103 J mol -1 or - 201.6 kJ mol -1
600 # (40) 2/3 = Tf # (40) 2/3 = Tf # (110) 2/3 =- 48 Kcal mol -1 .

Tf = 600× b 11 l = 300K
4 2/3 99. C6 H12 O6 (s) + 6O 2 (g) $ 6CO 2 (g) + 6H 2 O (,)
0.36
300 No. of Mole of C6 H12 O6 = 180 = 2 # 10 -3 mole
Ans. 100 = 3 .
q
3 C = 9T ` q = C # 9T = 600 # 10 J = 6 kJ
92. w =- # PdV 6
1 Heat released per mole = = 3 # 103 kJ
2 # 10 -3
w =- # KV3 dV = :- K V4 D = 4 [81 - 1]
3
4 3
-K = 3 MJ
1
1 9U =- 3 MJ
1
- 5 # 4 # 80 =- 4 L atm w by the gas = 4 L atm 9H = 9U + 9n g RT here 9n g = 0
93. U = 30.0 L atm 9H = 9U =- 3 MJ mole -1
H = U + (PV)
100. Fe 2 O3 (s) + 3H 2 (g) $ 2Fe (s) + 3H 2 O (I)
= 30 + (P2V2 + P1V1) o
= 30 + ( 4 × 5 2 × 3) = 30 + 14 = 44 L atm 9H300K =- 35kJ
9H =- 26 KJ
o

94. Ssys = nR ln3 = 9 J/K

9C P = 2C P (Fe, s) + 3C P (H 2 O, ,) - C P (Fe 2 O3, s)
V
q = w = nRT ln V2 - 3C P (H 2, g)
1
qrev = 8.314 × 300 × ln3 = 2700 J 9C P = 80
qirrev = 2700 900 = 1800 J Ssurr Using Kirchoff’s Equation:
1800
= - 300 =- 6 - 26 # 103 =- 80 # 26720 + 80 (9T)
Stot = 9 6 = 3 J/K 9T = 9
95. Hdissolution = H(Lattice energy) + H(hydration) 101. On mixing CaCl2(aq) and Na2CO3
= 780 775 = 5 kJ mol 1
CaCl2 + Na2CO3 CaCO3 + 2NaCl
Gdissolution = Hdissolution T Sdissolution Solutions are very dilute and thus. 100 % dissociation
= 5000 300 × 40 = 7000 J = 7 kJ mol 1 occurs.
96. 9H fo = 2 # (- 10) =- 20 kcal Ca +2 (aq) + 2Cl - (aq) + 2Na + (aq) + CO3-2 (aq)
9S = 90 - (40 + 90) =- 40 cal K -1 " CaCO3 .+ 2Na + (aq) + 2Cl - (aq)
300x - 40 or Ca +2 (aq) + CO3-2 (aq) " CaCO3 (s)
9G = 9H - T9S =- 20 - 1000 = 8 kcal
9H = / H oProducts - / H oreactants
97. Given : 9H =- 217.77 kJ K -1 mol -1 or 9H = 9H fo CaCO - [9H fo Ca 9H fo CO ]
3
+2 -2
3

9G =- 213.3 kJ mol -1 9H o of a compound = 9H formation

o

T = 273 + 25 = 298 K =- 288.5 - (- 129.80 - 161.7) = 3 kcal

9G = 9H - T9S
40 # (- 1.25) # 100
- 213.3 # 103 =- 217.77 # 103 - 298 # 9S 102. 9H = 9U + 1000
- (217.77 # 103 - 213.3 # 103) 9U =- 92 + 5
or 9S = 298 9U =- 87 kJ.
7.20 Chemistry
103. Required equation is : = 2970 J
C 2 H 2(g) + H 2(g) $ C 2 H 4(g) 9H = V.i.t
1 9H 2970
H 2(g) + 2 O 2(g) $ H 2 O (,) 3 H o =- 67.8 ...(1) t = V.i = 11.4×.5
t = 540 second
5
C 2 H 2(g) + 2 O 2(g) $ 2CO 2 + H 2 O (,) 3 H o t = 9 minute.
=- 310.1 ...(2)
108. C(graphite) C(diamond)
C 2 H 4 + 3O 2(g) $ 2CO 2(g) + 2H 2 O (,) 3 H o
1 mole 1 mole
=- 337.2 ...(3)
t = 2 g/cm t = 3 g/cm3
3

Reg. Eq. = (1) + (2) (3) 12 12

V = 2 ml V = 3 ml
& C 2 H 2(g) + H 2(g) $ C 2 H 4(g)
9H = 9U + P9V
9H rxn = –67.8–310.1 + 337.2 = –40.7 kcal 9U - 9H =- P9V
9H = 9U + 9n^gh RT
=- 5×105 b 3 - 2 l ×103 L. bar
12 12
–40.7 = 9U + (–1) ×2×10 –3 ×350
- 12
9U = –40.7 + .7 =- 5×105 × 6 ×10 -1 J = 100 KJ/mole
9U = –40 kcal/mole 9U - 9H 100
20 = 20 = 5 .
104. 2C (g) + 3H 2 (g) " C 2 H6 (g)
n1 C V,m + n 2 C V,m
9H reaction = 9H fo (C 2 H6) ...(i) 109. Avg.C V,m =
1 2

n1 + n 2
2C (s) " 2C (g) 9H1 = 2×170 kcal ...(ii) 3
1×3R + 2× 2 R
equations (i) + (ii) = = 2R & c = 3 2
3
2C (s) + 3H 2 (g) " C 2 H6 (g)
T1 V1c - 1 = T2 V 2c - 1 & 320×1 2 - 1 = T2 × ]4g3/2 - 1
3

9H reaction = 9H fo (C 2 H6)
& T2 = 160 K
= 9H1 + 39H H–H –69H C–H –9H C–C
9U = (n1 + n 2) C V.avg 9T
–20 = 340 + 3×104–6×99–9H C–C
9H C–C = 78 kcal. = 3×2R×(160 - 320) =- 960 R
10 10 |(9U/10R) | = |- 960 R/10R | = 96
105. 9W = # Pdv =- 20 # dv
V =- 20 [,n (V))] 1
10
110. This is adiabatic irreversible process so, for this
1 1
process
=- 20 In (10) =- 4605 J
PV = Constant, is not applicable
9q = 9U - 9W w =- Pext (V2 - V1)
= 400 - (- 4605) = 5005 J c 5 kJ. But for adiabatic process
w = dU = c 2 c2 - 11 1 m
106. n = 4 P V -PV
V1 = 20 lit. V2 = 80 lit.
PV = nRT
9w =- Pext (V2 - V1)
& 10×10 = n×0.082×273 & n = 4.47 moles
- 125
- Pext (V2 - V1) = c 2 c2 - 11 1 m
=- 1000 ×(80 - 20) ×100 =- 750 J. P V -PV
In case of adiabatic process q = 0
1×V2 - 10×10
U = 0 + Dw = 750 J &- 1×(V2 - 10) = 1.67 -1
nCV = T V2 - 100
& (10 - V2) = 0.67
3
4× 2 ×R9T =- 750
& 6.7 - 0.67 V2 = V2 - 100
9T =- 15 K & 106.7 = 1.67 V2
7.8 & V2 = 64.
107. moles = 78 = 0.1
V T
9H = n×9H vap 111. 9Ssys = nRln V2 + nC V ln T2
1 1

= 0.1×29.7 KJ V
9Ssystem = nR ln V2 = 2×8.314 ln 7.5
1
= 2.97 KJ
= 33.6 J = 8 Cal .
 Thermodynamics 7.21
112. (i) In case of adiabatic reversible expansion, (c) Irreversible adiabatic expansion of an ideal gas
dq rev = 0 & 9S = 0. nR (T2 - T1)
w= c-1
(ii) In case of free expansion (Adiabatically) (d) Irreversible isothermal compression of an ideal
w = 0, q = 0, gas 9H =- (as 9T = 0)
9U = 0 & nC V (T2 - T1) = 0 & T2 = T1 117.
called reversible process
9S = nR ln b V2 l = 2R ln (3) = 18 J/K.
V
1 (b) A process in which no heat enters or leaves the
113. Heat generated = C T 9T = 2108×1 cal. system is called adiabatic process
2108×1 (c) A process carried out at constant temperature is
nCH = 210.8×103 = 0.01
4 called isothermal process
PV (d) In a cyclic process, state function have no change
n total = RT = 0.04
in their value.So, 9U = 0, 9H = 0 .
0.01
mol% = 0.04 ×100 = 25%
118. (a) 9Gsys = 0 & equilibrium and free energy is zero.
114. 2C(s) $ 5C(g) So, no useful work.
9H1 = 5×718 = 3590 (b) 9S universe > 0 & Spontaneous process and able to
do useful work.
4H 2(g) $ 8H(g)
(c) 9S universe < 0 & Nonspontaneous process and
9H 2 = 4×435 = 1740
unable to do useful work.
5C(g) + 8H(g) $ C5 H8(g)
(d) 9Gsys > 0 & Nonspontaneous process and
9H3 = – (8×913 + 2×348 + 2×615) = –5230 unable to do useful work.
(1) + (2) + (3)
5C(s) + 4H 2(g) $ C5 H8(g) 119. (a) For reversible process 9S universe = 0 and for
adiabatic process 9Ssystem = 0
9H r×n = 9H f (C5 H8) = 9H1 + 9H 2 + 9H3 = 100
(b) For reversible process 9S universe = 0 , and in
So resonance energy = 79 - 100 =- 21 kJ mole -1 vaporisation entropy of system increases
Hence resonance energy in Kcalmole 1 = 5 (c) Number of gaseous moles decreases. So, entropy
115. Hion = Hneut of WA + SB Hneut of SA + SB of system decreases and N2 is more stable. So,
process is spontaneous. For spontaneous process
=- 56.1 - (- 57.3) = 1.2 KJ eq -1 9S universe > 0
Enthalpy of ionization for making 100% ionization (d) Number of gaseous moles increases. So, entropy
when there is no ionization at all = 1.5 KJ eq -1 of system increases.
1.5 - 1.2
% of ionization = 1.5 ×100 = 20% 120. (a) This is combustion reaction as well as formation
reaction of CO2.
116. (a) Reversible isothermal expansion of ideal gas
V (b) This is sublimation, atomization as well as
w = 2.303 nRT log V2 and U= H=0 (as T=0) formation reaction of C(g).
1
(b) Reversible adiabatic compression of an ideal gas (c) This is combustion reaction of CO (g).
nR (T2 - T1) (d) This is atomization of CH4(g).
PV c = constant and w = c-1
P V -PV
= 2 c2 - 11 1

1. H 2 O]s g DS1
H 2 O] l g DS 2
H 2 O] l g 2491
273k 273k 373k 3 S3 = 373

DS3
H 2 O ^g h DS 4
H 2 O ^g h 383
3 S 4 = 1× 2 × ln 373
373k 383k
Stot = S1 + S2 + S3 + S4
334
3 S1 = 273
Stot = 9.26 kJ kg 1K 1.
373
3 S 2 = 1× 4.2 × ln 273
7.22 Chemistry
2. G= H–T S 8. C 2 H5 OH (,) + 3O 2 (g) $ 2CO 2 (g) + 3H 2 O (,)
For a spontaneous reaction, 9U =- 1364.47 KJ/mol.
G = –ve thus, H < T S 9H = 9U + 9n g RT
DH 200 9n g =- 1
< T , 40 < T
DS
9H =- 1364.47 + :
- 1×8.314×298 D
Thus, T should be greater than 5 K. 1000
3. C6 H6 ] l g + 2 O 2 ^g h 6CO 2 ^g h + 3H 2 O ] l g =- 1364.47 - 2.4776 =- 1366.94 KJ/mol.
15
9. 4NO2(g) + O2(g) 2N2O5(g), H = 111 kg
3 n g =- 3
2 . 54 × 2
3 H 0C = Heat of combustion at const. press 2N2O5(s)
3 E0C = Heat of combustion at const. vol. H1 = 111 54 × 2
3 H 0C = 3 E0C + 3 n g RT 219 kJ
3 H 0C =- 3263.9 KJ/mol. - 3/2 # 8.314 # 298 10. The process is isothermal expansion Hence,
=- 3267.6 KJ/mol . q= w as u = 0
4. From 1st law: q = + 208 J
U=q+w w= 208 J (expansion work)
For adiabatic process: 11. 9G o = 9H o - T9S o
q=0 - RTlnK = 9H o - T9S o
U=w 9H o - T9S o
lnK =- RT
Work in adiabatic process is at the expense of
12. C 2 H5 OH (,) + 3O 2 (g) $ 2CO 2 (g) + 3H 2 O (,)
change in internal energy of the system.
9n g = 2 - 3 =- 1
5. C (s) + O 2 (g) " CO 2 (g); 9H =- 393.5 kJ/mol.
9U = 9H - 9n g RT
1
CO (g) + 2 O 2 (g) " CO 2 (g); 9H =- 283.5 kJ/mol. 8.314
=- 1366.5 - (- 1) × ×300
103
1 =- 1366.5 + 0.8314×3 =- 1364 KJ
C(s) + 2 O2(g) CO(g); H = 393.5+283.5 kJ/mol
= 110 kJ/mol. 3
13. N 2 (g) + 2 H 2 (g) $ NH3 (g);
6. CH 4 (g) $ C (g) + 4H (g) 9H fo =- 46.0 kJ mol -1
& 4×fC - H = 360 KJ/Mol. 2H (g) $ H 2 (g); 9H fo =- 436 kJ mol -1
& fC - H = 90 KJ/Mol. 2N (g) $ N 2 (g); 9H fo =- 712 kJ mol -1
and C 2 H6 (g) $ 2C (g) + 6H (g) 1 3
NH3 (g) $ 2 N 2 (g) + 2 H 2 (g);
& fC - C + 6×90 = 620
9H =+ 46
& fC - C = 80 kJ/mol
3 3
hc 2 H 2 $ 3H ; 9H =+ 436× 2
& NA × = 80×1000 J
m
1 1
6.02×10 23 ×6.62×10 -34 ×3×108 2 N 2 $ N; 9H =+ 712× 2
m= 80000
NH3 (g) $ N (g) + 3H (g); 9H =+ 1056 kJ mol -1
= 14.9×10 -7 m = 1.49×10 -6 m = 1.49×103 nm . 1056
Average bond enthalpy of N - H = 3
7. 29G f(NO
o
) - [29G f(NO) 9G f(O )] = 9G r =- RT,n K p
o o o
=+ 352 kJ mol -1
2 2

29G o
f(NO 2) - [2×86,600 + 0] =- RT,n K p
9G o
f(NO 2) = 0.5 [2×86, 600 - R (298) ,n (1.6×1012)]
 Thermodynamics 7.23

2. As G = useful work
10. Ssys is a state function but
3G
G= P V P = -3 V
w is a path function.
From given data, G = 2.9 kJ and V = 2 x 10 6 m3
2.9 ×103
P= ×109Pa=×1.45×104 bar
2 ×10 -6
P = 14500 bar
(A) 9S x " z = 9S x - y + 9S y " z (Correct)
3. For H 2 O (,) " H 2 O (g) at T = 100 o C, 1 atm
(B) Wx " y = Wx - y + Wy " z (Incorrect)
equilibrium exists. ` 9G = 0, 9H - T9S = 0
(C) Wx " y " z = Wx - y (Correct)
9H = T9S > 0 for system, since evaporation is
endothermic Because y z is an iso choric process
qsurr (D) 9S x " y " z = 9S x - y (Incorrect)
` (9S) system > 0, also (9S) surrounding = T
surr
Heat gained by system = heat lost by surroundings 11. Since the vessel is thermally insulated so
` qsurr. < 0 ` (9S) surr < 0 q=0
pext = 0, so w = 0
4. C6 H12 O6 (s) + 6O 2 (g) $ 6CO 2 (g) + 6H 2 O (,)
so U = 0 (ideal gas)
9C H = 6×9f H (CO 2) + 69f H (H 2 O)
Hence T = 0
- 9f H (C6 H12 O6) - 69f (O 2, g)
& 9T = 0
= 6×(- 400 - 300) - (- 1300) - 0
& T2 = T1
=- 4200 + 1300
& P2 V2 = P1 V1
=- 2900 KJ/mol
The process is however adiabatic irreversible.
For one gram of glucose, enthalpy of combustion
2900 So we cannot apply P2 V 2c = P1 V1c
=- 180 =- 16.11 KJ/g.
Hence ans is (A), (B), (C)
5.
12.

9H =+ 140 + 330 - (350×2) - EC / C =+ 225

EC / C = 1740 - 700 - 225 =+ 815 KJ/mol.
6. Statement 2 is IInd law of thermodynamics which
concludes that total heat can never be converted into
equivalent amount of work.
7. Standard enthalpy of formation of a compound is
the standard enthalpy when one mole of a compound (A) T1 = T2 (due to isothermal)
is formed from the elements in their stable state of
(B) T3 > T1 (incorrect) cooling will take place in
aggregation.
adiabatic expansion)
8. (c) Internal energy is a state function and if T1 ! T2
then u ! 0. Hence c is incorrect. (C) WIsothermal > Wadiabatic {with sign, this is incorrect}

9. Go = RT ln K = Ho T So (D) 9U Isothermal = 0 > 9U adiabatic =- ve

3 So 3 Ho So, answer is (A,D).
or, lnK = R - RT
On increasing T, value of ln K increases if Ho
is positive i.e. reaction is endothermic.
7.24 Chemistry
13. Let the heat capacity of insulated beaker be C. 16. Process shown by solid line is reversible isothermal
Mass of aqueous content in expt. 1 = 200 g So, work Ws =- 4×0.5 ln (5.5/0.5)
Total heat capacity = (C + 200×4.2) J/K =- 2 ln 11 L atm.
Moles of acid, base neutralized in expt. 1 = 0.1 For dotted process (3 step irreversible) work done is
2
Heat released in expt. 1 = 0.1×57 = 5.7 KJ Wd =- {4×1.5 + 1×1 + 3 ×2.5} L atm.
& 5.7×1000 = (C + 200×4.2)×9T. 5 26
=- {6 + 1 + 3 }L atm. =- 3 L atm.
5.7×1000 = (C + 200 + 4.2) ×5.7
W 26
& (C + 200×4.2) = 1000 so, Wd = 3×2 ln 11 . 2.
s

In second experiment, nCH COOH = 0.2, n NaOH = 0.1

3
17. (A) H 2 O (,) $ H 2 O (s) at 273 K & 1 atm
Total mass of aqueous content = 200 g 9H =- ve = q
Total heat capacity = (C + 200×4.2) = 1000 9Ssys < 0, 9G = 0.
Heat released = 1000×5.6 = 5600 J. w ! 0 (as water expands on freezing), 9U ! 0
Overall, only 0.1 mol of CH3 COOH undergo (B) Free expansion of ideal gas. q=0
neutralization.
- 5600 w=0
& 9H neutralization of CH3 COOH = 0.1
9U = 0
=- 56000 J/mol =- 56 KJ/mol.
9Ssys > 0
& 9H Ionization of CH3 COOH = 57 - 56 = 1 KJ/mol
9G < 0
14. Final solution contain 0.1 mole of CH3 COOH and (C) Mixing of equal volume of ideal gases at constant
CH3 COONa each. pressure & temp in an isolated container
[CH3 COO -] q = 0, w = 0, 9U = 0 , 9Ssys > 0, 9G < 0
pH = pK a + log [CH COOH]
3
Reversible
0.1 (D) H 2 (g) 300K Heating, 1 atm
= 5 - log 2 + log 0.1 = 4.7
Re versible
600 K Cooling, 1 atm
300 K.
1
15. (i) 2Cu(s)+ 2 O2(g)— Cu2
q = 0, w = 0, 9U = 0 , 9G = 0, 9Ssys = 0
1
(ii) H2(g)+ 2 O2(g)— H2
18. (A) CO 2 (s) $ CO 2 (g)
(i) – (ii) then
It is phase transition. The process is endothermic
2Cu(s) + H2O (g) — Cu2O(s) + H2(g) (sublimation). Gas is produced, so entropy increases.
(B) On heating CaCO3 decomposes. So, process is
Now for the above reaction endothermic. The entropy increases as gaseous
product is formed.
n c PH m
P 2

H O 2 (C) 2H : $ H 2 (g)
To prevent the above reaction : Entropy decreases as number of gaseous particles
decreases.

n c PH m > 0
P 2 (D) It is phase transition.
H O 2
White and red P are allotopes.
10 ^,nPH - ,nPH Oh > - 105
4
Red P is more stable than white. So 9H is – ve.
2 2

,nPH > - 10 + ,nPH O

2 2

> - 10 + 2.3 log (0.01)

,nPH > - 10 + 4.6
2

,nPH > - 14.6

2

Minimum ,nPH =- 14.6 2