UNIT # 06

THERMODYNAMICS EXERCISE # 1
1. m Zn .S Zn .(T f – T i ) + m H O.S H .(T f – T i ) = 0 9. Reversible process-involve infinitesimally small
2 2O
(65.38 gm) (0.4 J/g°C) (T f – 20°C) + 180 gm driving force. Hence system and surrounding re-
(4.20 J/g°C) × (T f – 100°C) = 0 mains in equilibrium.
 [(65.38) (0.4) + 180(4.20)] (
T f = (65.38) (0.4) (20) + (180) (4.20) (100) 
)
 (65.38 )(0.4 )(20)  (180)(4.20)(100) 
Tf =    97.3 C PV
 (65.38 )(0.4 )  (180)(4.20)  10. temperature at 'a' = T 0 =
2. U = q + w R

heat absorb (q) = 45 joule P0 V0

at (a) T 0 = ...........(i)
w = –70 joule since R

Work done by the system. (2P0 )(4 V0 )

at (c) T C =  8 T0
(
) R

U = q + w = 45 – 70 = –25 joule 3
U = nC V (T f – T i ) = R (8 T0  T0 )
2
3. Decrease in internal energy = –U
(
) U 
21RT0
 10.5 RT0
2
work done by the system = –w
–U = –w  U = w  q = 0 12. Work done in adiabataic process (  
The process is adiabatic. ( 
) 
)
4. At constant volume w PV = 0 U = w = nC V T
 U  q first law w = (2)(12.5)(200 – 300)
5. The energy due to external field is not included in
13. The case of irreversible adiabatic process.
i nternal energy like gravitat ional field, ear th's
magnetic field etc. w = –P(V f – V i )
(
 nC V (T 2 – T 1 ) = – P(V f – V i ) n = 1

) 3
6. Heat and work are path dependent, or indefinite CV = R T1 = T
2
quantity.
( P(Vf  Vi ) (1atm )(2L  1L )
) T2 = T = T –
nC V 3
7. For monoatomic ideal gas total degree of freedom = 3 (R )
2
( 2 (L atm )
= 3) T 2 = T – 3  0.0821 (L atm k 1 mole 1 )
Three translational mode of motion (    V
V1

) 1 5 . V B > V A and T B > T A
P A B
1 3 5 H = nCP (TB – TA) > 0 1
V >V
CV = 3 × R = R CP = CV + R = R
2 2 2
w = –P ext (V B – V A ) < 0
CP 5
r =C 3 16. Heat of reaction at const. pressure =  r H
T
V

3 Heat of reaction at const. pressure =  r U

8. Ar = monoatomic ideal gas R CV =
2
At constant pressure q = H = nC P T  r H =  r U + n g RT

5 n g = –3
q = (0.25 mole) .(8.314 J / K mole) (16)
2  r H –  r U = (–3 RT)
18. Fusion and vaporisation are example of isothermal RT
25. Initial pressure P =
processes - V
(
) P = 300 R = (300 × 0.0821) atm
final pressure = 1 atm
R T final volume ; P f V f = P i V i
T

Q Pi Vi  (300) R   24.6 L
 Vf = = 
X Pf  1 
V2
Tf < Tb PQ – T f RT – T b S = nRT ln
V1
q q
19. H 2O(s) 
1
 H 2O(l) 
2
 H 2 O(l)  24.6 
0°C 0°C 25°C S = R ln  
 1 
 36  26. for spontaneous reactions S total > 0
q 1 = H fusion (kJ/mole)  mole 
 18  (
)
q 1 = 6.01 × 2 = 12.02 kJ
S total = S system + S surr
q 2 = mS T = (36 gm) (4.18 J/K gm)25
 X 
 (36)(25)(4.18)  S total = S system –  
q NET = q 1 + q 2 = 12.02   kJ  298 
 1000 
When ice   X
20.  liquid : the process is reversible S total > 0  S sys + 0
fusion. The fusion is isothermal process. 298
(  : 

S syst > 
 X 


)  298 
Hence Ssyst can be negative but numerically smaller
dq dq
C =   X
dT 0 than .
21. U = q + w 298
P = constant since H = q p Ssyst 
202.6 = U + 1 atm (2 litres) X
  U = 202.6 – 2(L atm) (101.325 J/L atm)  
298
     U = 0 27. For dissociation reactions (
)
22. For reversible adiabatic process (  H > 0 and n g > 0   rS > 0
) 28. G = H – TS
q rev = 0  S system = 0
G = –33000 – [(–58)]
T V  G = –33000 + 58 T
23. S = nC V ln 2  nR ln  2 
T1  V1  spontaneous but less than certain temperature.
373  10  29. Formation of Fe 3 O 4
S = 5 ln  R ln  
298  1 
3Fe(s) + 2O 2(g)  Fe 3O 4 (s) ; G = ?
H transition 1 2
24. Using S transition = G = × (–19 kcal) + (–177 kcal)
Ttransition 3 3
H trans = –242.3 kcal/mole
S surr =
T
401.7 H 
S trans = 30. T =
368 S 
H° = – 110 – (–266.3)
401.7
Ssurr = ,  temperature of ice bath = 273K S° = 197.6 + 27.28 – 5.74 – 54.49
273
Above this temperature the process becomes
401.7 401.7
S total = + spontaneous. ( 
)
368 273
THERMODYNAMICS EXERCISE # 2
1. Intensive property (  
) 5. AB = isochoric heating
B
( )
extensive property ( 
)
=
extensive property P BC = isothermal expansion
pH  concentration = mole/volume ()
A C
though pH is a dimensionless number and intensive CA = isobaric cooling
property ( pH 
) 0 T ( 
)
energy C
EMF = = Intensive property AB = isochoric heating
ch arg e
Boiling point(Tb)= temperature = intensive property BC =
V
q extensive
entropy (s) = = = extensive property A B
T intensive
2. At constant T, the molecule with maximum atoms T
P0 V0
have greatest internal energy. 6. Temperature at A (T A) =
A B nR
 T  P0
 2P0 V0
TB =
3. q = 0 U = W nR
 3000 = C V (T 2 – T 1 )
D C 2P0 V0
3000 TC =
T2 – T1 =  150 T2 = T1 + 150 = 450 K nR
20
4. Irreverssible adiabatic process (  V0 2V0 4V0
)
(P0 / 2).2V0 PV
 nRT2 nRT1  TD = = 0 0  TA
W = –P ext  P  P  P2 = Pext = 2 atm nR nR
 2 1 
P 1 = 1 atm T 1 = 300 K now  T D – T A : U = H = 0

 2(R ).T2 2 R (350)   U  nC V T 

W = –(2 atm)   remember for ideal gas 
 2 atm 1 atm   H  nC P T 
5 Isochoric
and W = 2C V (T 2 – 350) = 2 × R (T2  350) heating
2 7. A (P 1 ,V 1 ,T 1)  B(P 2 ,V 1,T 2 )
5R(T 2 – 350) = (750 R – 2 RT 2 ) H 1
5T 2 – 1750 = 1400 – 2T 2
irr. adiabatic
7T 2 = 3150 T 2 = 450 K H2 process
W = 2 × C V (450 – 350) (q=0)
5
= 2 × R  (100) = 500 R
2 C(P ,V ,T )
H overall = H 1 + H 2 3 2 2
W = W AB + W BC + W CD
H 1 = U 1 + (P 2V 1 – P 1 V 1 )
V  P
= –P 0(V B – V A) – nRT B ln  C   0 (VD  VC ) H 1 = C V (T 2 – T 1) + (P 2 V 1 – P 1V 1 )
 VB  2
H 2 = U 2 + (P 3 V 2 – P 2 V 1 )
W = –P 0 (2V 0 –V 0 ) – 2P 0 V 0 ln
 4 V0  P0 H 2 = –P 3 (V 2 – V 1 ) + (P 3 V 2 – P 2V 1 )
   (2V0  4 V0 ) H 2 = P 3 V 1 – P 2 V 1
 2V0  2
W = – 2P 0 V 0 ln2 and q = –W ( U = 0) Hoverall = CV(T2 – T1) + (P2V1 – P1V1) + P3V1 – P2V1
q = 2 P 0 V 0 ln2 = C V (T 2 – T 1 ) + P 3 V 1 – P 1 V 1
 T2  T1  Tf 
8.  = S hot body = C V.ln  T 
T2  H
373 – 298  75  T 
 =   S cold body = C V.ln  f 
373  373 
 TC 
 × 100 =
 T T 
S Total = C V  ln f  ln f 
T2  T1  TH TC 
9.  =
T2 2
 T 
500 – 300 2 = C V  ln f 
 =   T .T
500 5  H C 
 (T  TC )2 
W by S Total = C V ln  f 
 =  W by = (n C) (q source )  4 TH .TC 
q source
14. G = H – TS
2 
=   (2 kcal) = 0.8 kcal
5  y = C + mX
10. H = q p  H = C

since H is state function H will remain same from m = –S

both path-isobaric and non-isobaric
from intercept C > 0  H > 0
qp
A B m < 0  –S < 0
isobaric
path   S > 0
non-isobaric path
q 15. Melting of H2O(s) at 0°C and 1 atm is a reversibly
But q = q p only when path was isobaric. procers  S Total = 0

H = q p only for isobaric path. Vaporisation of H 2 O(l) at 373 K is a reversible

process S Total = 0
11. Greater the n g greater the value of S.
Below 0°C – H2O(s)  H2O(l) is non spontane-
T  ous not feasible.
12. S = nC V ln  2  for isochoric change.
 T1 
H 2O(l)  H 2O(s) (freezing) is feasible above 0°C
 3   573 
S = 2 ×  R  ln   H 2O(s)  H 2O(l)
 2   473 
feasibly  G = –ive for melting process  STotal
 573 
S = 3R ln   increases
 473 
13. The net heat absorbed by hot and cold body is equal 19. G = H + E
to zero. G = – 3000 – 1 × 2 × 300 + 3000
qH + qC = 0 = – 6000 cal
Let C V is the total heat capacity of hot and cold 20. H 2O(l)   H 2O(g)
body.
373 K 373 K
C V (T f – T C ) + C V (T f – T H) = 0
1atm 1atm
T  TH H vap
 Tf = H
2 S =
T
Entropy change S Total = S hot body + S cold body
G = H f – H i = 0
THERMODYNAMICS EXERCISE # 3
COMPREHENSION # 1 3. U = q + w  100J = q – 80J

1. U =  V Here U = Kinetic energy of ideal gas q = 180 J

()

U = nC V T COMPREHENSION # 2

PV
 nC VT =  V ...(i) T = ...(ii) 1.  r S° = S°(CH 3 OH, g)
nR

sub. (2) in (1) – [S°(CO, g) + 2 × S°(H 2 , g)]

 CV  = 240 – 198 – 29 × 2 = – 16 J/K-mole

 R  .PV   V
 

 .R  1 2.  r H° =  f H°(CH 3 OH, g)

 P = C 
 V  V
–  f H°(CO, g) = – 201 – (114) = –87 kJ/mol
 R  dV
w = –  PdV = –  C  
 V V T2
3.  r S T2   r S T1  C P ln
T1
1 V2
= – () (– 1). ( V )
(1 / 2)  V1
C°P = C P,m (CH 3 OH)   C P,m (CO)  2C P,m (H 2 ) 
= 44 – (29.4 + 2 × 28.8) = – 43 J/K-mol
w = –2() ( – 1)  V2 – V1 
work done by the gas = – w = 2() 320
 r S T2 – (–16) = (–43) ln
300
( – 1)  V2 – V1 
 r S T2 = – 13.225 J/K-mol
2. For diatomic gas with no vibrational degree of
freedom

4.  r H T2   r H T1   r C P (T2  T1 )

3 1
CV = R + 2× R
2 2

C V =5/2 R  r H T2 – (–87) = –43(320 – 300)

U =   V2 – V1  = 100 J
 r H T2 = –87.86 kJ/mol

w = 2() ( – 1)  V2 – V1  = (2) ( – 1) × 100

5.  r G° =  r H T2 – T T S T2
CP 7
  = C 5
V

= –87860 – 320 (–13.225)

7  2 
( – 1)=  – 1    
5  5 
= –81.91 kJ/mol
2 
w = (2)   (100)J = 80J
5 
 THERMODYNAMICS EXERCISE # 4[A]
1.(i) H 2O (g)  H 2 O() 5. H = 1 kcal
V (g) > V () H = E + PV
3 5 –3
W = –P ext (V () – V (g)) 1 × 10 × 4.18 = E + 1.013 × 10 × 3 × 10
W = +ve  4149.61 
E = (4180 – 30.39) Joule =   cal
(ii) H 2 O (s)  H 2 O(g)  4.18 
V (g) > V (s) E = 0.993 kcal

W = – ve 3
6. NH 4CN(s) + O (g)  N 2(g) + CO 2(g) + H 2O()
(iii) H 2O ()  H 2O(s) 2 2
V (s) > V ()
1
H298 = E + ngRT = –742.7 + × 8.314 × 298
W = –P ext (V (s) – V ()) 2
= –ve = –742.7 + 1.239
(iv) 3H 2 (g) + N 2(g)  2NH 3 (g) H 298 = –741.46
W = –P ext (V 2 – V 1 ) 7. H =1440 cal
= –P ext (n 2 RT – n 1RT) H = E + P(V 2 – V 1 )
= –n gRT 5
1440=E+1.013× 10 (0.0180 – 0.0196) × 10
–3

W = +Ve E = 1440 – 1.013 × 0.0016 × 10

–3

(v) CaCO 3 (s)  CaO (s) + CO 2 (g)

E = 1440.168
W = –P ext V
8. W   Pext dV
V > 0
= –ve 5
=   P (V2  V1 ) = – 1.01 × 10 (0.1) × 10
–3

2. E = –65 J w = 20 J
W = –10.1 J
q = V – w –65 = V – 20 + 2+
9. Zn(s) + 2H (aq) Zn (aq) + H 2 (g)
V = –45 J
H = –36.5 kJ
3. H glucose = –2808 kJ mol
Q = E – W –36.5 kJ
(a) Energy need to climb 3m = Mgh= 62.5 × 10 × 3
5 –6
= E + 1.01 × 10 (500 × 50 × 10 )
q = 1875 Joule
E = –39.03 kJ
Now useful energy from 1 mole of glucose
5 –6
1 W=–P ext (V 2 –V 1 )=–1.013× 10 × 500 × 50 × 10
= 2808 × = 702 kJ
4 W = –2.53
1875
 No. of mole of glucose required =  P2   1
702  10 3 10. Wirr = –nRT  1   = – 5 × 8.314 × 300  1  
 P1   4
–3
= 2.67 × 10 mole W irr = –9.353 kJ
–3
grams of glucose = 180 × 2.67 × 10 =0.4807 gm  V2 
W rev = –2.303 nRT 1og  
(b) Energy need tp climb 3000 m will be 10 time.
3  V1 
3 W re v = –2.303 × 5 × 8.314 × 300 log4
 wt. should be 10 time = 0.4807 kg
4. q p = q v + n gRT W rev = –17.29 kJ

40.66 × 2 = q v + 2 × 8.314 × 373 and q = E – W

 q v = (81.32 – 6.202) kJ at T  0E  0 H  0

   q v = 75.118 kJ W rev = –q = 17.29 kJ

11. n1 = 1 State - 3
–1 –1
T 1 = 300 V 2 = 27 V 1 T 1V 1 = T 2V 2 P 1 V 1 = P 2V 2
1
 1 2 × 22.4 = 44.8 × P 2
 T1   V2   1 3
T V  T2 = 300  
 27 
P 2 = 1 atm
 2  1
T 2 = 100 K
Adiabatic condition Q = 20 E=W=nC V(T 2–T 1) Step Name of process q w E H
3 3 5
W = 1 × 25 × –200 W = –5.000 kJ/mole A Isochoric 2 R(273) 0 2 R(273) 2 R(273)
B Isotherm 546R ln2 –546R ln2 0 0
12. Process reversibly adiabatic C Isotherm –5 R(273) 3 –5
2 R(273) 2 R(273) 2 R(273)
T 1 = 298.15 K V 2 = 2V 1 overall
 
T 2 = 248.44 K Pv = K PV = nRT State - A  (Isochoric)
T  –1 –1
.V  K T 1V 1 = T 2V 2 W = 0 q = E
V
 1 3
 T1   V2   1 × R (273)
T V   298.15  1
   2. 2
 2  1   248.44  5
1.2 = 2
–1
log 1.2 = log 2 . (–1) H = nC pdT H = 1 × R (273)
2
log1.2 State - B  (Isothermal)
 – 1 =  – 1 = 0.263
log 2 E = 0 H = 0
P2 V2  P1 V1
No w nC V (T 2 – T 1 ) =  H = E + PV
 1
is Q = – w = +2.303 × 1 × 8.314 log(2) × 546
 R  nR (T2  T1 )
C V1 m =   Q = 546 R ln2 W = –546 R ln2
  1  (   1)
8.314 E = nC V T W = nR(T 2 – T 1 )
C V1 m = C V1 m = 31.61
0.263 State - C  (Isobaric)
 P1  q = E – w = E + P(V 2 – V 1 )
13. W = – 2.303 nRT log  
 P2  5
R ( 273)
or H = E +PV =
1  2
= –2.303 × 1 × 8.314 × 298 log   1
5  15. H 2 (g) + O (g)  H 2O()
W = –3.988 kJ 2 2
1
C p = C pH O()
– C pH (g)
– C p O (g)
V reaction 2 2 2 2
44.8L 3 1
= 75.312 – 38.83 – × 29.16
C
B 2
C p = 21.90 kJ
14. 22.4L 2 reaction
1 A H 373 = H 298 + nC p T
273K 546K T –3
= (–285.76 + 1 × 21.9 × 75 × 10 ) kJ
H 373 = – 284.12 kJ
Table-1 –3 –1 –1
16. C P = 22.34 + 48.1 × 10 T JK mol
State P V T
n 1 T2
1 1 22.4L 273 3

2 2atm 22.4 546K

H =  nC p dT =  (22.34  48.1  10 T ) dT =
T1

3 1atm 44.8 546K 48.1  10 –3  298  3

22.34 × 298 + × 298
State - 1 2
PV = nRT  P = 1 atm
H = 13.064 kJ/mole
State - 2
W = – P(V 2 – V 1) = – nR(T 2 – T 1 )
P1 P2

T1 T2    P 2 = 2 atm W = – 20477
546 E = 13.064 – 2.477
P2 =  1atm
273 E = 10.587 kJ
17. S = 28.8 J/K H = 30.5 kJ 21. 
H 2 O (g) + CO(s)  H 2 (g) + CO 2(g)
3
30.5  10
H = TS = T = 1059 K (i)  rH° 298
28.8
nC p dT = rH 2 (g) +  rH CO 2 (g) –  rH CO –(s)  r H 2O(g) =
18. S =
T
25.5 –3 –7 –94.05 + 26.42 + 57.8 = – 9.83 k cal/mol
=1 ×  ( + 13.6 × 10 – 42.5 × 10 T) dT
T
–3
= 2.303 × 25.5 log2 + 13.6 × 10 × 300 – 42.5 (ii)  rG = –94.24 + 0 + 32.79 + 54.64

(600 2  300 2 )
–7  rG = –6.81
× 10
2
S = 20.618 kJ (iii)  rG =  rH – T rS –6.81 = –9.83 – 298  rS
19. Br 2() + Cl 2(g)  2BrCl(g) , H° = 29.3 kJ
9.83  6.81
S Br = 152.3 S Cl = 223.0   r S
2 (g) 298
–1 –1
S BrCl(g) = 239.7 J mol K
 rS = –10.13 cal/ mole
S R = 2 × 239.7 – 223 – 152.3 = 104.4
 rG = H – TS (iv) but at constant P
= 29300 – 298 × 104.4 = –1721.8 J
H = E + PV  n g = 0
20. CCl 4()   CCl 4(g)
P=1atm  rH =  rE 298 = – 9.83 k cal/mol
–1
T = 298 K S = 94.98 JK (v) S° 298 [H 2O(g)]
 rH = H p – H r = (–106.7 + 139.3) kJ
 rS =  s H 2O(g) + S CO –  rS H –  rS CO
= 32.6 kJ/mol 2

 rG = H R – TS –10.13 = – rS H 2 O(g) + 47.3 + 31.2 + 51.1

3
 r G = 32.6 × 10 – 298 × 94.98
 rS H O(g) = 45.13 cal/ K mole
 r G = 4.296 kJ/mol 2

THERMODYNAMICS EXERCISE # 4[B]

1. Step-1 (  -1) Step-5 (  -5)
Ice (200 K)  Ice (273 K) Steam (373 K)  Steam (400 K)
(200 K)  (273 K)
(373 K)  
(400 K)
T 273
S 1 = m C p ln 2 = 1 × 2.09 × 10 3 ln 400
T1 200 S 5 = 1 × 2.09 × 10 3 ln = 146.06 J/°C
373
S 1 = 650.312 J/°C
S T = 9383.4 J/°C
Step-2 (  -2)
5
Ice (273 K) 
 Water (273 K) 2.  = , P 1 = 1 atm, T 1 = 300 K, P 2 = 2 atm
3
5

S 2 =
H f 3.34  10
= = 1223.44 J/°C (a) PV  = constant ( )
273 273
P 1 –  T  = constant
Step-3 (  -3)
TP (1 – )/ = constant
Water (273 K)  Water (373 K)
T 1P 1(1 – )/ = T 2P 2(1 – )/
373 2 / 5
S 3 =1 × 4.18 × 10 3 ln = 1304.6 J/°C 1 
273 T 2 = 300   = 395.85
2 
Step-4 (  -4) 3
 w = U = n C v dT = 1 × × 8.314 × 95.85
Water (373 K)  Steam (373 K) 2
 (373 K) 
 
 (373 K) w = 1195.37 J
nRT 2
H v 22.6  10 5 V2 =  16.25L
S 4 = = = 6058.98 J/°C P2
373 373
(b) U = w (ii) S sys. = 9.134 J/K
1 × 1.5 × 8.314 (T 2 – 300) q irrev.  q rev.  836.6 
S surr. = = – 
 RT2 RT1  T  298
= – 2 × 101.3  
 P2 P1  = – S sys. + 2.807
S T = S sys. + (–S sys. + 2.807) = 2.807 J/K
 T 
(T 2 – 300) = 1.333  300  2  (iii) For free expansion system doesn't absorb any heat
 2 
so q = 0
nRT2
T 2 = 420 K V2 =P2
 17.24L (
w = U = 1.5 × 8.314 (420 – 300) q = 0)
w = 1496.52 J S sys. = 0
3. V 1 = 20 L,  = 7/5, T 1 = 673 K, S T = S sys. = 2.807 J/K
P 1 = 0.2 MPa = 2 atm, P 2 = 0.7 MPa = 7 atm 5.(i) S sys. = 0, S surr. = 0, S T = 0
(ii) U = w,  n C v (T 2 – T 1 ) = – P 2((V 2 – V 1 )
P1 V1
n =  2.5 0.5 × 1.5 × 8.314 (T 2 – 473)
RT1
(i) U = H = 0  T2 473 
= –101.3 × 2 × 0.5 × 0.0821   
2 5 
P1 7
q = –w = nRT ln = 2.5 × 8.314 × 673 ln  T2 
P2 2 T 2 – 473 = – 1.333   94.6 
q = 17.52 kJ w = –17.52 kJ 2 
T 2 = 359.49 K
(ii) P1 V 1 = P 2V 2 
7(20)  = 2(V 2 )   V 2 = (3.5) 5/7 = 48.92 L  T P 
S sys. = n  C p ln 2  R ln 1 
PV  T1 P2 
T 2 = 2 2  470.46 K
nR  359.49 5
q = 0, w = U = 2.5 × 2.5 × 8.314(470.46 – 673) = 0.5 2.5  8.314 ln  8.314 ln 
 473 2
w = U = – 10.524 kJ S sys. = 0.957 J/K
since no heat is transfered (
H = 2.5 × 3.5 × 8.314 (470.46–673)= – 14.73kJ
(iii) q = w = U = H = 0
(iv) q = 0, U = w
) q= 0
S surr. = 0
2.5 × 2.5 × 8.314 (T 2 – 673)
S T = S sys. = 0.957 J/K
 T2 T1 
= – 101.3 × 2 × 2.5 × 0.0821    (iii) In free expansion (  ) 
q = w = U = 0
2 7 
 T2  T is constant. (T  )
T 2 – 673 = – 0.79   96.142 
2  P1 5
S sys. = nR ln = 0.5 × 8.314 × ln =3.81 JK
T 2 = 536.91 K P2 2
w = U = 2.5 × 2.5 × 8.314 (–136) = – 7.1 kJ S surr. = 0
H = 2.5 × 3.5 × 8.314 (–136) = – 9.9 kJ S T = S sys = 3.81 J/K
(v) U = H = 0 6. P 1 = 1 atm, V 1 = 1 L
nRT 2.5  0.821  673 P 2 = 1001 atm, V 2 = 0.99L Let P = a + bV
V2 =
P2
=
2
= 69 L On finding  
a = 100001, b = –105
w = –P 2 (V 2 – V 1 ) = –2 × 49 = –98.13 L-atm so
w = –98.13 × 101.3 = –9940.9 J P = (100001 – 10 5 V)
w = – 9.94 kJ q = –w = 9.94 kJ V2
5
w =   PdV  V (100001  10 V )dV
4.(i) The entropy change of the system S sys. will be 1

same in all the three process as it is state function. 10 5 2

w = – 100001 (V 2 – V 1 ) + (V2  V12 )
(
S 2
10 5

) w = – 100001 (–0.01) + ( 0.0199) = 5.01
2
V2 L-atm
S sys. = nR ln = 1 × 8.314 ln 3 = 9.134 J/K
V1 w = 501J U = w = 501J
For reversible process (  ) H = U + (P 2 V 2 – P 1 V 1 )
S T = 0 = 501 + (1001 × 0.99 – 1 × 1) × 100 = 99500J
S surr. = – S sys. = – 9.134 J/K H = 99.5 kJ
 T2 3 1000 3
7.(i) S sys. = n C v ln = 1 × R ln  R ln10  8.368  10 2 
T1 2 100 2 q=H=2 12.552(250)  212500 
 2 
S T = 0 (Reversible process ( 
))
q = H = 24.04 kJ
3
S surr. = –S sys. =  R ln10
2 Cv = C p – R = 4.238 + 8.368 × 10 –2 T
3
(ii) S sys. = R ln10 U = nC v dT = 19.9 kJ
2
w = 0 (iii) w = 0
3 q = U = 19.9 kJ
q = U =  R (900)
2
H = nC p dT = 24.04 kJ
q 3R (900) 3
S surr. =  = =  R (0.9)
T 2  1000 2 10. At 298 K,

3 3 G° = – 6333 kJ/mole

3
S T = R ln10  R (0.9) = R (1.402)
2 2 2 H° = – 5737 kJ/mole
8. G = H – TS = U + PV – TS
& G° = H° – TS°
dG = dU + PdV + VdP – TdS – SdT
so S° = 2 kJ/mole
w = 0, dV = 0, dV = dq = T dS so
dG = TdS + VdP – TdS – SdT At 310 K

dG = VdP – SdT  G = VP   S dT G = – 5737 – 2 × 310 = –6357 kJ/mole

VdP = V (P 2 – P 1 ) Additional non-PV work (  -PV 

) =
P2 P1 |G – G°| = 24 kJ/mole
 P2 1 4

T2 T1  400 300  P 2 = 3
11.  rC p = 33.305 – 75.312 = – 42.007 J/K mole
VdP = 24.6 (4/3 – 1) = 8.2 L-atm = 820 J
H 40639
T2  r S 323 = = = 108.95 J/K mole
2
SdT=  (10  0.01T ) dT=10(T 2 –T 1 )+0.005(T –T ) 2 T 323
T1 2 1

SdT = 10(100) + 0.005 (400 2 – 300 2 ) = 1350  r C p dT

d( rS) =
T
G = 820 – 1350 = – 530 J
9. n = 2 T2
 rS 373 –  rS 323 =  rC p ln
T1
2  0.0821  300
V1 = = 49.26 L
1  373 
 r S 373 = 108.95 –  42.007 ln 
 323 
V1 T2 49.26 V2

T1 V2  300 = 550  V 2 = 90.31 L = 115 J/K mole

(i) w = – PV = 1(90.31 – 49.26) = – 41.05 L-atm

d ( rH) =  r C pdT
w = – 41.05 × 101.3 = – 4158.36 J = –4.15 k
 rH 373 –  rH 323 = –42.007 (50)
q = H = n C p dT
 r H 373 = 42739.35 J/mole
 8.368  10 3 2
= 2 12.552(T2  T1 )   T2  T12   r G 323 = 42739.35 – 323 (115)
 2 
= 5594.35 J = 5.59 kJ/mole