Thermodynamics 01 Solution 1673568756956

TOPIC
Exercise-(S-I)
1. Extensive properties G,
 mole, KE, U, H
Intensive
ntensive properties: V.P.
2. State function : U, H, S, P, T, V
Path function : q, w, molar heat capacity , Specific heat capacity
60
4. q= × 24 × 20 = 1.006 kJ
27
5. If vol. decreases then work will be done on system and w will be +ve and vice versa
(i) V = –ve (ii) V = +ve (ii) V = +ve (iv) V = +ve,

w = +ve w = –ve w = –ve w = –ve
6. w = – PV
w = –1 × (1.1 – 1.0) = – 0.1 L-atm
L = – 10 J
7. w = –  Pext dV
V4 1 1
3 3
= – KV dV
3
=–K× = –  × 80= – 4 L-atm
1
4 1
5 4
8. w= +8J
q = + 40 J
U = q + w = 48 J
9. q = + 200 J
w = –0.5 × (6 – 2) = –2
2 L-atm
L = –200 J
U = q + w = 0
10. q = + 50 J U
U = + 60 J
U = q + w
w = +10 J
11. U = 0 , q = + 84 – 60 = + 24 cal
U = q + w
w = –q = –24 cal
|w| = + 24 cal
12. q = – 65 J w = + 20 J
U = q + w = – 65 + 20 = – 45 J
H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

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13. qAB = + 80 J , wAB = –30
30 J
UAB = qAB + wAB = + 50 J
(a) UACB = UADB = + 50 J
UADB = qADB + wADB
+ 50 = qADB – 10  qADB = 60 J
(b) UBA = –50 J wBA = + 20 J

qBA = – 50 – 20 = –70 J
(c) UAB = UAD + UDB

50 = 40 + UDB UDB = 10 J
WADB = WAD + WDB
WAD = –10 J & WDB = 0
qAD = UAD – WAD = + 40 + 10 = 50 J
qDB = UDB– WDB = 10 J
14. q = + 180 kJ
20 100
w = –1 × (20) = –20 L-atm
atm = = –2 kJ
1000
U = 180 – 2 = + 178 kJ
15. U = 30 L-atm
H = U + (P2V2 – P1V1) = 30 + 14 = 44 L-atm
16. q = + 0.1 kcal

30
w = –1 × (1.5 – 1.2) = –0.3
– L-atm = – 30 J = = – 0.00723 kcal
4.2 1000
U
U = q + w = + 0.993 kcal
H = U + PV = + 0.993 + 0.007 = 1 kcal
17. U = – 742.7 kJ/mol

H = U + ngRT
0.5  8  300
 = – = –742.7 + 1.2 = –741.5 kJ/mol
1000
18. at const. vol. q = U

H = U + ngRT
8.3  300
U = – 20 – (–1) ×
1000
= – 17.5 kJ (for 2 mole of A)
17.5
U = × 0.4 (for 0.4 mole of A) = – 3.5 Kj
2
q =U = – 3.5 kJ

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19. w = – Pext V – nR(T2 – T1)
  = – 0.1 × 2 × (600 – 300) = – 0.1 × 2 × 300 = – 60 cal.
20. w = – nRT ln P1/P2

10
= – 1 × 8.314 × 300 ln = – 8.314 × 300 × 2.303 = – 5744.14 J
1
21. w = – Pext (V2 – V1)

12 100
= –4 × (1 – 4) = + 12 L-atm
L = = 1.2 kJ
1000
22. P1V1 = P2V2 ( for isothemal process)

process
7 × 1 = 1 × V2  V2 = 7
w = –1 × (7 – 1) = – 6 L--atm
wsurr = + 6 L-atm
23. H = nCPT
for isoT process T = 0 H = 0
24. For isoT process TT=0

If carried out irreversibly
U = nCvT= 0, HH = nCPT= 0
1 1 1 1 
wirrev =– Pext × × n × R ×T= –1 ×    × 5 × 8.314 × 300
P2 P1 1 4 
3
= × 5 × 8.314 × 300 = – 9353.25 J
4
qirrev = – wirrev = +9353.25 J
If carried out reversibly

U = nCvT= 0, HH = nCPT= 0
V 4
wrev = – nRT ln 1 = – 5 × 8.314 × 300 ln = – 17459.4
V2 1
qrev = – wrev= +17459.4
25. (i) If carried out reversibly

V
w = – nRT ln 1 = – 8 ln 2/20 = + 8 ln 10= + 18.424 bar-L
V2

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(ii) If carried out irreversibly
w = Pext (V2 – V1) = – 20 (0.4 – 4)
= + 20 × 3.6 bar-L = + 72 bar-L
(iii) w = –10 (0.8 – 4) – 20 (0.4 – 0.8)

= + 10 × 3.2 + 20 × 0.4 = 32 + 8 = 40 bar-L
26. (i) In process A vol. is constant so it is ischoric process
V = 0 ; so w = 0
3 3
q = U = nCVT= 1 × R × 273 = R × 273
2 2
5
H = nCPT = 1 × R × 273
2
(ii) In process B, Temp is constant, so it is isothermal process.
T = 0 ; so U = nCV T
T = 0 & H = nCPT = 0
q = –w = + 1 × R × 546 ln 2 = –546 R ln 2
q = + 546 R ln 2
V1 V2
(iii) In process C, pressure is constant because 
T1 T2
3 3
U = nCVT = 1 × R × (546–
(546 273) = – R × 273
2 2
5 5
q = H = nCPT = = 1 × R × (546– 273) = – R × 273
2 2
w = –nR (T2 – T1) = + R × 273 = + 273R
27. n=1
At point – 1
P = 1 atm and V = 22.4 L So T = 273K
At point – 2
P = 1 atm and V = 44.8 L So T = 546K So
At point – 3
P = 0.5 atm and V = 44.8 L So T = 273K
Step-A isobaric process

5
q = H = nCPT = 1 × R × 273
2
3
U = nCvT =1
1× R × 273
2
w = – nR (T2 – T1) = – R × (546 – 273) = – 273R

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Step-B vol.
ol. is const. isochoric process
w=0
3
q = U = nCVT= –1 × R × 273
2
5
H = nCPT = –1 × R × 273
2
Step-C P1V1 = P2V2
so, it is isoT process
U = 0 ; H
H=0
1
w = –1 1 × R × 273 ln = + 273 R ln 2
2
q = – w = – 273 R ln 2
PV 26 1
28. (a) T1 = = 243.6 K
nR 1 0.0821
V1 V2
in process AB, pressure
pressur is constant so
T1 T2
So T2 = 2436K
(b) AB isobaric process (P is constant)
3
U = nCVT = 1 × R × 2192.4
2
5
q = nCPT = 1 × R × 2192.4
2
w = – 1 × R × 2192.4 = – 2192.4R
BC isochoric process (V is constant)
w=0
3
q = U = – R × 2192.4
2
CA isothermal process (Temp.
Temp. is constant
constant)
T = 0  U = nCvT= T= 0,
1
w = – R × 243.6 ln = + 243.6 R ln 10
10
q = – w= – 243.6 R ln 10
for overall process U

U = 0 so q = – w
w = 243.6 R ln 10 – 2192.4 R = – 1631.3 R = – 3262 cal

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29. (a) WAB =0
WBC = – PV=
V= – 15 × 4= – 60 L-atm
1
WAC = – (5 × 4 + × 10 × 4) = – 40 L-atm
2
(b) UAC = qAC + wAC = 200 – 40 = 160
UC – UA = + 160
UC = 160 + 10 = 170 J
(c) UAB = + 10 J
WAB = 0
q = U = + 10 J
30. for free expansion

Pext = 0 so, w = 0
31. U = w
For irreversible adiabatic process
nCVT = – Pext (V2 – V1)
3  T 30 
n × R (T2 – 30) = –2 2 ×  2   × nR  T2 = 42 K
4  2 1 
3
w = nCVT = 2 × R × (42 – 30) = 36 R = 72 cal
2
32. For irreversible adiabatic process q = 0

5  T 300 
n × R × (Tf – 300) = –1 1×  f   × nR  Tf = 270K
2  2 5 
5
w = U = nCVT = 2 × R × (270 – 300) = – 5R × 30 = – 1247.1 J
2
7
H = nCPT = 2 × R × (270 – 300) = – 7R × 30 = –210 R = – 1745.94 J
2
33. For irreversible adiabatic process q = 0

U = w
 T 400 
n × 3R × (Tf – 400) = –11×  f   × nR Tf = 310 K
 1 10 
w = 1 × 3R × (310 – 400) = – 270 R = – 2244.78 J

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4
34. =
3
T Vi
1
Ti Vi 1
= Tf Vf 1
 f
Ti Vf
4 1
Tf  1 3  1 3 1
1
   =     Tf = 100 K
300  27   27  3
w = 1 × 25.08 (100 – 300) = – 25.08 × 200 J = – 5.016 kJ
35. For reversible adiabatic process q = 0

U = w = nCVT = 3 × 27.5 × (250 – 200) = 4.125 KJ
H = nCPT = 3 × 35.814 × (250 – 200) = 5.3721 kJ
T  P 
 1
T P 1
T P 1
 i    f 
 Tf   Pi 
i i f f
 250   Pf  5 P 
 1 1.3 0.3
        f 
 200   2  4  2
1.3
5 3
Pf = 2 ×   = 2 × 2.61 = 5.22
4
Pi Vi Pf Vf 5.22  Vf
 3
3 × 0.0821 =  Vf = 11.8 L
Ti Tf 250
36. A  
P const.
B C
300 K 600 K T=?
20 L 40 L 110 L
Ti Vi1 = Tf Vf1
300 × (40)-1 = Tf × (110)-1
2
Tf  40  T  4 3
1
   f   
300  110  600  11 
600 T
Tf = = 300 K  f = 3K
2 100
37. For irreversible adiabatic process

3  Tf 30 
n× R × (Tf – 30) = –2
2×    × nR
2  2 1 
1.5 Tf – 45 = –Tf + 60 2.5 Tf = 105

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105
Tf = = 42 K
2.5
3
w = 2 × R × 12 = 36 R = 72 cal
2
38. w = –nRT ln P1 / P2
= –1 × R × 298 ln 5 = –298 R ln 5 – 3.994 kJ
39. w = – PV
500  50 25 101.3
= –1 × = – 25 L-atm
L = = – 2.53 kJ
1000 1000
q = H = – 36.5 kJ
–36.5 = U + 1 ×8.314 ×300/1000
U = – 36.5 – 2.5 = – 39 kJ
40. PV–2 = K
On comparing with PVx = K x=–2
Ti Vix 1 = Tf Vfx 1
Tf 1 Tf 1
2 1 3
  Tf = 800 K
100 2 100  2 
q = nCT
R 3R R 3R R 11
C = Cv – = – =  = R
x 1 2 3 2 3 6
11
q= R × 700= 2566.66 cal
6
3
U = 1 × R × 700= 2100 cal
2
nRT 1 R 700
w= = – = – 466.66 cal
x 1 3
41. PV2 = k
On comparing with PVx = K x= 2
Ti Vix 1 = Ti Vfx 1
Tf  vi  1
x 1
Tf 1
2 1
    
Ti  vf  273  2  2
273
Tf = = 136.5 K
2
q = nCT

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R 3 R 3 R
C = Cv – = R– = R–R=
x 1 2 2 1 2 2
1 R 1 R 273
q=  × (136.5 – 273) = –   = – 0.25 L-atm
22.4 2 22.4 2 2
42. H2O()  H2O(g) , H

H = 40.66 kJ mol–1
1 8.314  373
40.66 = U +
1000
U
U = + 37.55 (for 1 mole H2O)
= + 37.55 × 2 (for 2 mole H2O) = + 75.11 kJ
43. q = + 1440 cal

w = + 1 × 0.0016
= + 0.0016 L-atm
atm = 0.0384 cal
U = 1440.0384 cal
for solid and liquid H  U = 1440.0384 cal

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Exercise-(S-II)
1.
V
D C
VD
VB B
A
0 T
TA TB
VB V
 GIVEN: n=2 ; = 2 ; D = 4 and TA = 300 K
VA VA
(A) For process AB  P = constant  V  T
VA VB V T
  B  B
TA TB VA TA
2×300 = TB  TB = 600 K
 TB = TC = 600 K
 TA = TD = 300 K
5
(B) QAB = nCPT = 2× ×R×(600 – 300) = 3000 cal = 3 kcal
2
V
BC  T= constant  QBC = –WBC = nRTln C = 2×R×600×ln2
VB
= 2×2×600×0.69 = 1.658 cal

3R
CD  V= constant  QCD = nCvT = 2× 3×2×300= –1.8 kcal
×(300 – 600) = –3×2×300=
2
V  1
DA  T= constant  QDA = –WDA = nRT  A  = 2×R×ln   = –2×2×300×2×0.69
 VD  4
= –1.658 kcal
(C) WNET = WAB + WBC + WCD WDA
= –nR(TB – TA) + (–Q
( BC) +0+ (–QDA)
2  2  300
= – 1.658 + 1.658
1000
= –1.2 kcal
Work done by gas = 1.2 kcal

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2. Given process is cyclic

ence for overall process H = U = 0  q = –W
Hence
W = WA + WB + WC
WA= 0 (Volume Constant)
WB= 0 (free expansion)
WC = –P(V2 – V1)
 nRT2 nRT1 
= –P    = –nR(T
nR(T2 – T1) = –nR(298 – 373)
 P P 
= +1×8.314×75== 623.55 J
W = 623.55 J
q = –W = –623.55 J
3. C2H2 + H2  C2H4
Vi 50 ml 50 ml 0
Vf 0 0 50 ml
U = H – PV
1.5  (50  103 )  100
= –0.31 – 0.31 +0.0075 = –0.3025 kJ
= –0.31 + 75 ×10–4 = –0.31
1000
n 2a
4. PV = nRT –
V
nRT n 2 a
P= – 2
V V
dW = –PdV
nRT n 2a
Vf
W= – dV
Vi
V V2
Vf 1 1
= nRT ln n 2a
Vi Vf Vi
5. Mole of gas
PV 3  22
n=  =2
RT 0.08  600
(i) processT = 0, H = 0, U = 0
For isoT reversible process
32
W = –2×2.303×2×600log
2×2.303×2×600log = –8290.8 Cal
1
q = –WW = +8290.8 Cal

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(ii) Rev. adiabatic qq = 0,
Ti Pi 1–
= Tf Pf 1–
1 2
Tf Pi Tf  32  5
    = (2)–2
Ti Pf 600  1 
600
Tf = = 150 K
4

U = W = nCVT= 2× R×(150 – 600) = –3R×450= –2700 Cal
2
5
H = nCPT = 2× R×(150 – 600) = –5R × 450= –4500 Cal
2
(iii) isoT and adiabatic  Free expansion

T = 0, U = 0, w = 0, q = 0, H = 0
(iv) For irrev. adiabatic
nCV (Tf – Ti) = –Pext(V2 – V1)
3 T 600
n× R×(Tf – 600) = –1×
1× f ×nR
2 1 32
Tf = 367.5 K
3
q = 0, W = U = 2× R×(367.5 – 600) = –1395 Cal
2
5
H = 2× R×(367.5 – 600) = –2325 Cal
2
(v) For irrev. isoT
T = 0, U = H = 0
1 1 
W = –1×    ×2×2×600 = –2325 Cal
 1 32 
q= +2325 Cal
P
6.
V
1
W=( ×10×10–3×1000×100) + (1×10×10–3×100) = 501 J
2
U = W = 501 J

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H = U +(P2V2–P1V1) =501
= 1×1000×10 ×100)] = 99.5 KJ
+ [(1001××990×10 ×100) – (1×1000×10
–3 –3
7. ddiamond = 3g/ml, dgraphite = 2g/ml

2g/m
P = 500 Kbar, Temperature = T
Graphite  Diamond
(1mol) (1mol)
H = U + P2V2 – P1V1
(H – U) = P(V2 – V1)
m m  12 12 
= 500×10–3 = 500×10–3    ×10–3×100 = 500×10–3 (6 – 4)×0.1 = 100 kJ
d2 d1 2 3
3R 5R
8. Cv = , Cp = n =2
2 2
Process -1 Reversible adiabatic compression
P1 = 1atm, T1 = 300 K
P2 = 4 2 atm, T2 = T
P11  T1 = P21  T2
1 2
Tf Pi Tf 1

5
Ti Pf 300 4 2
2
Tf =(300)1.67× 4 2 = 600 K
5
nR(T2  T1 ) 2 R(600 300)

W= = = 900 R
 1 5
1
3
Process – 2 Reversible Isotherma
sothermal
Pi 4 2
W= –nRTln = –2×R×600ln
2×R×600ln = –3000×Rln2
Pf 1

Process – 3 Isobaric
W= –nR(Tf – Ti) = –2R(300
(300 – 600) = 600R
Wnet = 900 R+ (–3000×Rln2)+
3000×Rln2)+ 600R = – 600R

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9. (I) T1 = 300K, Vi = V, P1 = P
T2 = 600 K, V2 = V, P2 = 2P
W1–2 = 0
(II) T2 = 600 K, P2 = 2P, V2 = V
T3 = 600 K, P3 = P, V3 = 2V
2V
W2–3 = –1×R×600ln = – 600Rln2
V
(II) P3 = P, V3 = 2V ,T3 = 600 K,
P4 = P, V4 = V/2 , T4 = 600 K
V1
T3 T4 T4
   2  T4 = 150 K
V3 V4 600 2V1
W3–4 =–nR(Tf – Ti) = – 1×R(150 – 600) = 450 R
 Vrms 1
3RT1
10. =
M
 Vrms 2
3RT2
=
M
 Vrms 1
  Vrms 2 =
T1
T
T2 =
2 4
Reversible adiabatic expansion
T1V1–1 = T2V2–1
V 
 1
T
T1V1–1 = 1 V2–1   2  =4
4  V1 
 V2 
   V2 = 32V1
1
  = 4  1 = (4)
5/2
V
 1
EXERCISE (O-I)
(O
1. Intensive property B.P., pH, density
2. Enthalpy, internal energy and volume all are extensive properties.
3. AB vol. const.  isochoric

AC Temp const.  isothermal
CA  pressure const.  isobaric
5. When liquid is freezed heat is given by system q < 0

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6. (i) P1, V2P1,V
vol. is constant so,w = 0
(ii) P, V1P1,2V1
w = – P × (2V1 – V1) = – PV1
7. |w| = Area enclosed

1
= × 2V1 × 5P1
2
= 5 P1V1
8. If liquid is stirred work is done on system

w>0
q = 0 (thermally insulated)
9. w=0
for vacuum Pext = 0
10. w = –1 × (13 – 3)
= –10 atm dm3
11. w = –  P dv
If P is variable.
12. Process AB and CD volume is constant so w = 0

amount of work done in process BC and DA is equal but sign is opposite.
So wnet = 0
13. U = q + w
If work done by sys is w
U = q – w
14. q = + 600 J & w = –300

300 J
U = q + w = 300 J
15. q = 0.5 kJ
U = 300 J = 0.3 kJ
U = q + w
w = 0.3 – 0.5 = – 0.2 kJ
–200 = –1 × V × 100 V
 =2
17. qv = U = + 200 J
18. q = – 450 J
w = + 600 J

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U = 150 J
U2 – U1 = 150
U2 = 150 + U1
19. q = + 200 kJ
1 1.5  103  100
|w| = 1 × 1 + × 1 × 1 = 1.5 bar m3= = 150 kJ
2 103
w = –150 kJ (expansion)
U = q + w = 200 – 150 = + 50 kJ
20. q = – 124 J
2  (177  377) 2  200
w= = × 100= + 40 J
1000 1000
U = – 84 J
21. In process A  B
TB > TA H = +ve
PA = PB so T V
VB > VA  expansion so w < 0
22. q = H = 202.6 J
H = U + PV
202.6 = U
U + 1 × 2 × 101.3 U = 0
1
23. CO(g) + O2(g) CO
CO2(g)
2
 ng = – 0.5
H < U
24. N2(g) + 3H2(g) 2

2 NH3(g) 
ng = – 2
H = U – 2RT
25. H = U
if ngRT = 0 ng
ng = 0
26. qp = H = –28 kcal mol–11

qv = U
1 2  300
H = U +
1000
–28 = U + 0.6 U = –28.6
– kcal mol–1

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27. ng = 0
H = U = – 185 kJ/mol (for 1 mole H2)
= – 185 × 3= – 555 kJ (for 3 mole H2)
28. C2H4(g) + HCl(g)  C2H5Cl(g)

2.5 mol 2 mol
(LR)
1 8.314  300
–72.3 = U +
1000
U = – 72.3 – 2.5= – 74.8 kJ
for 2 mol HCl
U = – 74.8 × 2 = – 149.6 kJ
1 10 4  5
29. 
300 T2
T2 = 600 K
50  300
q = CT = = + 15 kJ
1000
1 3 100
w= = – 0.3 kJ
1000
U = = q + w=14.7 kJ
10 100
= 14.7 + = + 15.7 kJ
1000
30. For isoT T = 0

U = 0 and H = 0
31. For isochoric process

V = 0 ,w = 0 and q = U

32. T = 0 , U = 0
33. w = – 1 × R × 298 ln2

= – 298 R ln2
= – 298 × 8.31 × 2.303 log 2 × 107 ergs.
34. For process BC

4V0
wBC = – 2 P0 V0 ln
2V0
= – 2 P0 V0 ln2

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P0
wCP = × (2V0 – 4V0) = + P0 V0
2
wAB = – P0 × (2V0 – V0) = – P0V0

wnet = – 2 P0V0 ln2
35. I II III
8 bar 2 bar 1 bar
4L 16 L 32 L
300 K 300 K 300 K
Process I II and II III are isothermal
iso
So U = 0 ; q = –w
w I II = –2 × (16 – 4) = –2 × 12 = –24 bar-L
w II III = – 1 × (32 – 16) = – 1 × 16 = –16 bar-L
wnet = – 40 bar-L= – 4000 J
q = –w = + 4000 J
36. W12 = – 300 R ln2

W23 = – R × (600 – 300) = – 300 R
10
W34 = – 600 R ln = + 1200 R ln2
ln
40
W41 = 0
Wnet = 900 R ln2 – 300R
= 300 R = 660 cal
37. q = + 100 cal= 420 J

w = – 209 J
U = + 211 J
nC T 420
=2
nCv T 211
C
= 2 C = 5R
5 / 2R
38. for isothermal process T = 0 so q = –w

for cyclic process
U = 0 (state function)
for adiabatic process q = 0 so U = w
for free expansion w = 0
39. for adiabatic q = 0
40. In adiabatic compression Tf > Ti
42. |slope| = |– P/V|

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slope 
 He > H2
5  T 300 
43. n× 2×  f 
R × (Tf – 300) = –2  × nR
2  2 5 
3.5 Tf = 870
870
Tf = = 248.57 K
3.5
5  T 350 
44. n× 2×  f 
R × (Tf – 350) = –2  × nR
2  2 1 
2.5 Tf – 875 = –Tf + 700
3.5 Tf = 1575
Tf = 450 K
5
w = 1 × R × (450 – 350) = 2.5 R × 100 = 250 R
2
45. Ti Vi = Tf Vf1
1
Tf  Vi 
2
 1 5 1
1
T
   f   
Ti  Vf  600  32  4
Tf = 150 K
7
H = nCPT = 1 × R × (150 – 600) = –1575 R
2
46. w = nCVT
–3 × 1000 = 1 × 20 × (Tf – 300)
Tf = + 150 K
47. Ti Vi1 = Tf Vf1

Tf  Vi 
1
 
Ti  Vf 
Tf 1 1
4/3 1
300 8 2
Tf = 150 K
w = nCVT
= 1 × 3R × (150 – 300)
= – 450 R = – 900 cal

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48. R
I
S
II
Case I: If process I is isothermal, Then temperature

t of R and S should be equal
If process II is adiabatic then temperature
temp of R and S should not be equal.
temperature of R and S should not be equal.
Case II: If process I is adiabatic then temp
If process II is isothermal,Then temperature
t of R and S should be equal
V I V
49.
II
P III
V
I – isobaric ,II– isothermal and III – adiabatic
w3 > w1 > w2 (area under the curve)
50. For same initial volume to same final volume through adiabatic reversible and adiabatic
irreversible
Tf irrev > Tf rev
T rev > T irrev
H2 > H1 (magnitude)
P
51. PVx = k slope = x
V
Vi
P PV =k2
PV2 =k1
V
PV2 = k1 (process I)
PV = k2 (process II)
|w2| > |w1| (area under the curve)
52. PV = k (isothermal)
PV = k (adiabatic)
P
Pf
vf , adia vf , isoT V

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In case of expansion
for isothemal Tf = Ti and for adiabatic Tf < Ti
if Pf is same, then Vf will be greater for the process which has more Tf.
53. I – isothemal reversible (PV = K

K)
II – PV = const.
1/2
III – PV = const.

IV – Irreversible adiabatic
i
1
p PV1/2 =k
2
3 PV =k
4 PV =k
v
point 3 is for irreversible adiabatic because same final volume so (Pf) irrev > (P
( f) rev
54. PV = k (process I)

PV2 = k (process II)
I
II (Pf) II > (Pf) I so (Tf) II > (Tf) I
P
V
55. T = kV
PV
= kV
nR
P= constant
5
Cm = Cp = R.
2
56. H2O (s) H2O ()
V < 0 so w > 0
57. H2O () H2O (s) – Hfusion

at constant P
q = H = – nHfustion

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(O-II)
3. For isoT process if stating from same Vi and to same Vf
 Tf irrev = Tf rev
U rev = U irrev
|Wrev| > |Wirrev|
Wrev < Wirrev (with sign)
w = –q
qrev > qirrev
4. For isothermal process
T = 0, H = 0, U = 0
5. |Slope|B > |Slope|A

For adiabatic process
P
|Slope| =
V
Slope of the curve will be more for the gas has higher value of r.
6. In adiabatic expansion
Tf < Ti
PV = K (Valid only for rev. adiabatic)
For irrev. Adiabatic U
U = w = –Pext V
U = Pext – V = 0
H < 0
7. n1CV(Tf – T1) + n2CV(Tf – T2) = 0

P1V1 PV
(Tf – T1) + 2 2 (Tf – T2) = 0
RT1 RT2
 PV P V  PV P V
Tf  1 1  2 2  = 1 1  2 2
 RT1 RT2  R R
T T (P V  P V )
Tf = 1 2 1 1 2 2
P1V1T1  P2 V2T2
8. Heat given by water = Heat taken by ice

00 9
×75.6×20 = n× ×6×103
18 18
n = 14

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9. At point B T = 500 K
Process BC is isochoric
PB PC
So 
TB TC
PB 
 PB = 2 bar
500 250
3
UBC = nCV TBC = 2× R×(250 – 500) = –750 R
2
V = –Pext(V2 – V1)
3  T 250 
n× R×(Tf – 250) = –3×  f   ×nR
2  3 1 
2.5 Tf = 1125 Tf = 450 K
5
HCD = nCPT= 2× R×200 = 1000 R
2
10. If T = 0 H= 0
For ideal gas H = f(T)
11. For any substance

H = f(V,T) = f(P,T) = f(P,V)
For vacuum Pext = 0, w = 0
If process is carried our isothermaliy in vacuum T = 0, U
U = 0, q = 0
For isobaric compression V  T V, T
12. For adiabatic process

W = U
For adiabatic rev and irrev. process.
If Tf rev = Tf irrev then from W = nCVT Wrev = Wirrev
For rev. adiabatic expansion Temperature of system decreases.
For same change in volume in adiabatic and isobaric expansion
Tf isobaric = Tf adiabatic
13. H2O(l)  H2O(g)

At constant temperature
KE = constant but PE increase so U increase
H2O(s)  H2O(l)
H  U for solid and liquid volume chanang is negligible.
Cp and Cv are temperature dependent.

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14. If volume is doubled then
For isoT expansion Ti = Tf
For adiabatic expansion Ti < Tf
For free expansion Ti = Tf
For isobaric expansionTf > Ti
Tf adiabatic < Tf isoT = Tf free expansion< Tf isobaric
E4 > E3 = E2 > E1
Wsys
16. n=–  100
q supplied
qAB = H = nCPT = +750 R
qBC = U = nCPT = –450450 R
qCA = –300 Rln2
WAB = –1×R×(600 – 300) = –300 R
WBC = 0
WCA = +300Rln2
Wnet = 300Rln2 – 300R = –300R×0.3
300R  0.3
n=  100 = 12%
750R
17. Sec. B is adiabatic
PV
i i = Pf V f
Pf Vf
=
Pi Vi
Pf
= (8)5/3 Pf = 32 atm
1
Pf Vf Pi Vi
18. 
Tf Ti
32  22.4  15 / 8 1  22.4
=
Tf 27.3
15
Tf = 32× ×27.3 = 1638 K
8
5
19. H = nCpT = 0.1× R×1610.7 = 80.53 Kcal
2
20. For rev. isoT
V P
W = nRTln 2 = –nRTln
nRTln 1
V1 P2
For rev. adiabatic/irrev. adiabatic
W = nCv(T2 – T1)
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V2
For irrev. IsoT W = Pext dV = –Pext(V2 – V1)

V1
21. (A) For isothermal vaporisation of water

T = 0, U U > 0, q > 0, H > 0, W < 0
(B) isoT rev. expansion
T = 0, U = 0, H = 0, W < 0, q > 0
(C) Adiabatic free expansion
q = 0, Pext = T, W = 0, U = 0, T = 0, H = 0
(D) Isochoric heating
V = 0, W = 0, T T > 0, U > 0, H > 0, q > 0
22. For rev. isoT

P1
q = –W = 2.303 nRT ln
P2
For rev. adiabatic PVr = K
For isochoric process VV = 0, W = 0
For irrev. IsoT q = –W
W = Pext (V2 – V1)
P
23. (i)
1/V
– q = +ve, U = 0
For isoT expansion W = –ve,
P PV = constant
(ii)
V
isoT expansion W < 0, T
T = 0, U = 0, q > 0
P
(iii)
1/V
T < 0, W > 0, q < 0
For isobaric compression

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P
(iv)
V
For cyclic process U
U = 0, W = +ve, q = –ve
JEE-MAIN
1. U is state function
UAB = +40 kJ/mol
UBA = –40 kJ/mol
2. ng < 0
H < U
3. Tf irrev > Tf rev
4. H2O(l) 
 H2O(g)
ng = 1
1  8.3  373
41 = U +
1000
U = +37.9041 kJ mol–1
5. C2H5OH (l) + 3O2(g)  2CO2(g) + 3H2O(l)

ng = –1
1  8.314  300
–1366.5 = U –
1000
U = –1366.5 + 2.4942 = –1364.0058 kJ
6. 2C6H6(l) + 15O2(g)  12CO2(g) + 6H2O(l)
ng = –3
H – U = ngRT
3  8.314  300
= = –7482.6 J mol–1
1000

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7. For rev. isothermal process
V
W = –q = –nRT ln 2
V1
U = 0
8. W = –ngRT = –1×8.3×300
1×8.3×300 J = –2.49 kJ

q = 0, U = W
10. ng = –1
|U| > |H|
11. qAB = +5J

WAB = –8J
UAB = qAB + WAB = –3J
3J
UBA = +3J
qBA = –3J
WBA = UBA – qBA = +6 J
12. U = UAB + UBC + U UCA = 0

UAB = –5 + 2 = –33 kJ mol–1
–5 – 3 + UCA = 0
UCA = +8 KJ mol–1
qCA = UCA – WCA = 8 – 3 = +5 kJ mol–1
14. W = –4×(1 – 5) = +16 J

q = CmT
2
16 = 1×24×T T = K
3
15. CP is defined at constant P only.
U = f(T)
CV is defined at constant V only.
CP and CV = f (T)
16. For isoT process

PVm = Constant
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PVm
P
1/Vm P
U
P
Vm Vm
 nC dT = 
T1 1000
17. H = p 3(23  0.01T) dT = 61950 J= 62 kJ
T2 300

q = 0  U
U=W
19. 5 mole ideal gas is given,

Cw,m = 28 J k–1 mol–1, R = 8J k–1 mol–1
100 K  200 K
U = ncv,mdT = 5 × 28 × 100
= 14000 J
= 14 kJ
(pv) = P2V2 – P1 V1
= nRT2 – nRT1
= 5 × 8 × 100= 4kJ
20. Both work (w) and heat (q) are state function.
21. From 1st low of thermodynamics

U = q + w
w = 10 kJ ( work is done on spring)
q = –2kJ ( Heat rejected into surrounding)
U = –2 + 10 = 8 kJ
22. C7 H16(l) + 11O2(g)  7C2(g) + 8H2O(l)

ng =  – 11 = –4
H = U = –4RT
23. As process is Irreversible

w = –Pext (dv)
= –1 × 9
= –9 lit. bar

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JEE ADVANCE
1. T i Vi –1
= TfVf –1
300×(1.25) –1
= Tf×(2.5) –1
 1.25 
r 1
Tf = 300×  
 2.5 
300
= 2/3 = 188.5 K
2
H = nCpT= T= 0.05×20.8×(188.5 – 300) = –115.41 J
2. Work is path function.
3. H = U + P2V2 – V1 P1 = 30 + (5×4 – 3×2) = 30 + 14 = +44 L-atm

atm
P
1 2
1atm
4.
0.5atm 3
20 L 40 L V
Wnet = w1 + w2 + w3
= –1×20
1×20 + 0 + 20 ln2= 20(ln2 –1) = –20×0.307 L-atm = –6.14 L--atm
q = –w = + 6.14 L-atm
for cyclic process H
H = 0, U= 0, S = 0
5. He molecule is monoatomic so it just has three degree of freedom at all temperature but H2 is
diatomic molecule at hisher temperature vibrational degree of freedom is also considered.
6. For adiabatic
U = W
W = –PV
= 100×10–3
= +0.1 bar-L
H = U + P2V2 – P1 V1
= +0.1 + (100×99 – 1×100) ×10–3
= +9.9 bar-L

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7. H = nCpT
For isoT T = 0
8. For irrev. adiabatic

nCvT = –Pext(V2 – V1)
3
1× R(Tf – T) = –1×(2 – 1)
2

Tf = T –
3  0.0821
9. H = U + VP
–560 = U + 1×(40 – 70) × 0.1
–560 = U – 3
U = –557 kJ mol–1
10. PV–1 = K
3 R 3 R
C= R– = R+ = 2R
2 2 2 2
11. State function - U, H

path function - W
12. Intesive properties : molar conductivity,

conductivity EMF
Extensive properties : Resistance , Heat capacity
V 5.5
13. Ws = –2.303RT log 2 = –2.303×log
V1 0.5
= –4.606 log 1.1= –4.8 L--atm
3  2 5 26
Wd = –4× + (–1×1) =      =  L-atm
2  3 2 3
Wd
= 1.8  2.0
Ws
14. T1 = T2 > T3
T1 > T3
W isoT < Wadia (with sign)
U isoT > U adia.

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15. Isochoric process vol. constant
16. KL  P constant
V, T 
LM – V constant
P, T
MN – P constant
V, T
NK – V constant
P, T
17. For free expansion

w = 0, q = 0 T = 0
T1 = T2
P1V1 = P2V2
(P1V1T1)
rev. isoT
P rev. adiabatic
18.
V
(A) During irrev. compression maximum work is done on the gas.
(B) For expansion of ideal gas from same Vi to same Vf |WisoT| > |Wadia|
(C) If T1 = T2 TT = 0, U = 0
For rev. adiabatic expansion T2 < T1 U = –ve
(D) For free expansion
Pext = 0 ,w = 0
If it is carried out isothemally U = 0 ,q = 0
 it is adiabatic also
19. A-C isochoric process

A-B isoT process
B-C isobaric process
qAC = UAC= nCv(T2 – T1) = UBC
V
wAB = –nRT1ln 2
V1

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wBC = –P2(V1 – V2) = P2(V2 – V1)
qBC = HBC = nCP(T2 – T1) = HAC
UCA = nCV(T1 – T2)

HCA < UCA

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Thermodynamics 01 Solution 1673568756956

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Thermodynamics 01 Solution 1673568756956

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Thermodynamics 01 Solution 1673568756956

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TOPIC

(i) V = –ve (ii) V = +ve (ii) V = +ve (iv) V = +ve,

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

(b) UBA = –50 J wBA = + 20 J

(c) UAB = UAD + UDB

16. q = + 0.1 kcal

17. U = – 742.7 kJ/mol

18. at const. vol. q = U

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

19. w = – Pext V – nR(T2 – T1)

  = – 0.1 × 2 × (600 – 300) = – 0.1 × 2 × 300 = – 60 cal.

20. w = – nRT ln P1/P2

21. w = – Pext (V2 – V1)

22. P1V1 = P2V2 ( for isothemal process)

for isoT process T = 0 H = 0

24. For isoT process TT=0

If carried out reversibly

25. (i) If carried out reversibly

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

(iii) w = –10 (0.8 – 4) – 20 (0.4 – 0.8)

(ii) In process B, Temp is constant, so it is isothermal process.

Step-A isobaric process

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

for overall process U

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

30. for free expansion

32. For irreversible adiabatic process q = 0

33. For irreversible adiabatic process q = 0

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

35. For reversible adiabatic process q = 0

37. For irreversible adiabatic process

1.5 Tf – 45 = –Tf + 60 2.5 Tf = 105

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

42. H2O()  H2O(g) , H

43. q = + 1440 cal

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

= 2×2×600×0.69 = 1.658 cal

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

2. Given process is cyclic

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

(iii) isoT and adiabatic  Free expansion

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

7. ddiamond = 3g/ml, dgraphite = 2g/ml

nR(T2  T1 ) 2 R(600 300)

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

2. Enthalpy, internal energy and volume all are extensive properties.

3. AB vol. const.  isochoric

5. When liquid is freezed heat is given by system q < 0

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

7. |w| = Area enclosed

8. If liquid is stirred work is done on system

12. Process AB and CD volume is constant so w = 0

14. q = + 600 J & w = –300

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

24. N2(g) + 3H2(g) 2

26. qp = H = –28 kcal mol–11

H.O. 92, Rajeev Gandhi Nagar, Kota (Raj.) Mob. 97831-97831,

28. C2H4(g) + HCl(g)  C2H5Cl(g)