Solutions to Chemical and Engineering Thermodynamics, 5th ed Chapter 4

4
4.1 (a) System = Ball (1) + Water (2)
Energy balance: M1U1f + M 2U 2f − M1U1i − M 2U 2i = 0

c h c h
⇒ M1CV,1 T1 f − T1i + M 2CV,2 T2f − T2i = 0 ; also T1 f − T2f . Thus
M1CV,1T1i + M 2CV,2T2i 5 × 10 × 05
3
. × 75 + 12 × 103 × 4.2 × 5
Tf = =
M1CV,1 + M 2CV,2 5 × 103 × 05
. + 12 × 103 × 4.2
= 8.31° C
[Note: Since only ∆T s are involved, ° C were used instead of K)].
(b) For solids and liquids we have (eqn. 4.4-6). That ∆S = M CP
dT
T
T
z
= MCP ln 2 for the case in
T1
which CP is a constant. Thus

Ball: ∆S = 5 × 103 g × 05
J
× ln RS
8.31 + 27315
. UV
= −53161
J
.
g⋅K T
75 + 27315
.
.
W K
= −53161
. s

Water: ∆S = 12 × 103 g × 4.2

J
× ln RS
8.31 + 27315
.
= +596.22 UV
J
g⋅K T
5 + 27315
. KW
and
J J
∆S (Ball + Water ) = 596.22 − 53161
= 64.61
.
K K
Note that the system Ball + Water is isolated. Therefore
J
∆S = Sgen = 64.61
K
4.2 Energy balance on the combined system of casting and the oil bath

c h c h
M cCV,c T f − Tci + M oCV,o T f − Toi = 0 since there is a common final temperature.

20 kg × 0.5
kJ
kg ⋅ K
dT − 450iK + 150 kg × 2.6
f kJ
kg ⋅ K
dT f
− 450 K = 0 i
This has the solution Tf = 60oC = 313.15 K
Since the final temperature is known, the change in entropy of this system can be calculated
F
. + 60
27315 I . + 60
27315 FkJ I
from ∆S = 20 × 05. × ln
H
. + 450
27315 K
+ 150 × 2.6 × ln
. + 50
27315
= 4135
.
HK K
4.3 Closed system energy and entropy balances
dU dV dS Q 
= Q + Ws − P ; = + Sgen ;
dt dt dt T
dS
Thus, in general Q = T − TSgen and
dt
Solutions to Chemical and Engineering Thermodynamics, 5th ed Chapter 4

dU  dV dU dS dV
Ws = −Q+ P = −T + TSgen + P
dt dt dt dt dt

c
Reversible work: WsRev = WsRev Sgen = 0 =
dU
dt
−T
dS
dt
h+P
dV
dt
dU dV
(a) System at constant U & V ⇒ = 0 and =0
dt dt

 S
W  c
s gen = 0 = WS h
 Rev = −T dS
dt

dS dP dV d
(b) System at constant S & P ⇒ = 0 and = 0⇒ P = ( PV )
dt dt dt dt
so that

c h
Ws Sgen = 0 = WSrev =
dU d d
+ ( PV ) = (U + PV ) =
dt dt dt
dH
dt

4.4
700 bar, 600oC 10 bar, T = ?

Steady-state balance equations

dM  +M 
=0= M 1 2
dt
0
dU
=0= M  H + M  H + Q 0 + W 0 − P dV =M  H + M H
1 1 2 2 s 1 1 2 2
dt dt
or H 1 = H 2
Drawing a line of constant enthalpy on Mollier Diagram we find, at P = 10 bar, T ≅ 308° C

At 700 bar and 600° C At 10 bar and 308° C

V = 0.003973 m3 kg 
V ≈ 0.2618 m3 kg
H = 3063 kJ kg H ≈ 3063 kJ kg
S = 5522
. kJ kg K S = 7145
. kJ kg K
Also

 0
dS
=0= M  S + Q
 S + M + Sgen = 0
1 1 2 2
dt T

⇒ Sgen =M1 2 c
1
M  h
 S − S or Sgen = S − S = 7145
2 1
1
. − 5522
. = 1623
.
kJ
kg ⋅ K

4.5 1 2
System
Ws
Energy balance

c h c
∆U = U 2f − U 2i + U1f − U1i = Q h adiabatic
z constant
+ WS − PdV volume
Solutions to Chemical and Engineering Thermodynamics, 5th ed Chapter 4

c h c
Ws = MCp T2f − T2i + MCp T1 f − T1i = MCp T2f − T2i + T1 f − T1i h c h c h
Ws
but T1 f = T2f = T f ⇒ = 2T f − T1i − T2i
MCP
Entropy balance
adiabatic

c h c
∆S = S2f − S2i + S1f − S1i = h z  0
Q
T
dt +Sgen
0 for maximum work

cS 2
f
h c h
− S2i + S1f − S1i = 0 = MCP ln
T2f
T2i
+
Tf
MCP ln 1 i
T1

or ln
RS T T UV = 0 ; T T = T T ; but T
2
f
1
f
f f i i f
= T2f = T f
TTT W i i
2 1
1 2 1 2 1

⇒ cT h = cT T h or T = T T and
f 2 i i
1 2
f i i
1 2

Ws
= 2T f − T1i − T2i = 2 T1i T2i − T1i − T2i
MCP

1 bar 10 bar
4.6
290 K 575 K

(a) Entropy change per mole of gas

T P
∆S = CP ln 2 − R ln 2 eqn. (4.4-3)
T1 P1
J 575 J 10 J
Thus ∆S = 29.3 ln − 8.314 ln = 0.9118
mol K 290 mol K 1 mol K
(b) System = contents of turbine (steady-state system)
dN
Mass balance = 0 = N 1 + N 2 ⇒ − N 2 = N 1 = N
dt
dU dV 0
= 0 = N 1 H 1 + N 2 H 2 + Q
0
Energy balance + Ws − P
dt dt
a
Ws = N H 2 − H 1 = NC T −T
P 2 f 1 a f

W
a
W = s = CP T2 − T1 = 29.3
N
J
mol K
f
× (575 − 290)K

J
= 83505
.
mol
(c) In Illustration 4.5-1, W = 7834.8 J mol because of irreversiblitities (∆S ≠ 0) , more work is
done on the gas here. What happens to this additional energy input? It appears as an increase of
the internal energy (temperature) of the gas.

4.7 Heat loss from metal block

dU dT
= CP = Q
dt dt
Solutions to Chemical and Engineering Thermodynamics, 5th ed Chapter 4

−W =
T − T2 
Q(−1)
RS
Q = heat out of metal
T T
−Q = heat into heat engine
a
dT T − T2 f
= −W ⇒ − Wdt
 =C
2
T
z
t T

z FH I
CP
dt T 0
P
T
1 − 2 dT
T
1
K
a T
f T
−W = CP T2 − T1 − CP ⋅ T2 ln 2 = CP T2 − T1 − T2 ln 2
LMa f OP
T1 T1 N Q
−W = CPT2 1 −
LMFG T1 TIJ
− ln 2
OP
NH T2 T1K Q
z
T2
Q = CPdT = CP T2 − T1 = CPT2 1 − a f FG T1 IJ
T1
H T2 K
Alternate way to solve the problem

T2

System is the metal block + heat engine (closed)

dU dT
E.B.: = CP = Q + W
dt dt
dS Q
S.B.: = 2 +Sgen
dt T
0 for maximum work
dS dU dS  C
Q = T2 ; = T2 + W ; dU = CPdT ; dS = P dT
dt dt dt T
W =
dU dS C T F I
dt
− T2
dt
= CPdT − T2 P dT = CP 1 − 2 dT
T T H K
z
 = C 1 − T2 dT = C
T2
T
z F I I z FH
T2
W = Wdt
T
P
T
P
T
1 − 2 dT
T
1
H K K 1

a T
W = CP T2 − T1 − T2CP ln 2 f LF T I T O
= C T MG1 − J − ln P
NH T K T Q
1 2
P 2
T1 2 1

4.8 This problem is not well posed since we do not know exactly what is happening. There are several
possibilities:
(1) Water contact is very short so neither stream changes T very much. In this case we have the
Carnot efficiency

−W Thigh − Tlow 22 22
η= = = = = 0.0733 = 7.33%
Q Thigh 27 + 273 300

(2) Both warm surface water (27°C) and cold deep water (5°C) enter work producing device, and
they leave at a common temperature.

TH
TO
TL
Solutions to Chemical and Engineering Thermodynamics, 5th ed Chapter 4

M.B.:
dM
dt
=0= M  +M
H
 +M
L
 ⇒M
0
 =− M
0
 +M
H

L b g
dU  H + M H + M  H + W = 0
E.B.: =0= M H H L L 0 0
dt
 H − M
W = − M H H
 H + M
L L
 +M
H
 H
L 0 b g
=M H 0 H L 0c
 H − H
 H − H + M
L h c h
 C T −T + M
=M H P 0 H
 C T −T
L P 0 L a f a f
 0 0
S.B.:
dS
=0= M  S + M  S + M S + Q +Sgen
H H L L 0 0
dt T
      
M H SH + M L SL − M H + M L S0 = 0 b g
H Hc h
 S − S + M
M 0 L L 0
 C ln TH + M
 S − S = 0 ⇒ M
H P
T0
L P c
 C ln TL = 0
T0
h
FG T IJ FG T IJ 
M H

M L

= 1 or TH M H TL M L = T0 M H + M L
  
HT K HT K
H L

0 0

T0 = H

M
TH H
L
TL L H
b M 
+M g 
M b M 
+M L g
From this can calculate T0 . Then

W = M
 C T −T + M
H P 0 H
 C T −T
L P 0 L a f a f
This can be used for any flow rate ratio.
(3) Suppose very large amount of surface water is contacted with a small amount of deep water, i.e.,
 >> M
M  . Then T ~ T
H L 0 H

W = M H P H a
 C T −T + M
H
 C T −T ~ M
L P H L
 C T −T
L P H Lf a f a f
(4) Suppose very large amount of deep water is contacted with a small amount of surface water, i.e.,
 << M
M  , T ~T .
H L 0 L
W = M
 C T −T + M
H P a
 C T −T ~ M
L H f
 C T −T
L P a L L f H P a L H f
4.9 System = contents of the turbine. This is a steady-state, adiabatic, constant volume system.
dM  +M  or M  = −M 
(a) Mass balance =0= M 1 2 2 1
dt
Energy balance
constant
dU
=0= M  H + M  H + Q adiabatic +W − P dV volume
1 1 2 2 s
dt dt
Entropy balance

dS
=0= M  S + M S + Q +Sgen
1 1 2 2
dt T
0, by problem statement
Thus
M = −M = −4500 kg h M.B.
2 1

W = − M H − H

S

1 c 1 2 h E.B.
S2 = S1 S.B.
Solutions to Chemical and Engineering Thermodynamics, 5th ed Chapter 4

State T1 = 500° C Steam H 1 = 3422.2 kJ kg

1  →
P1 = 60 bar Tables S = 68803
. kJ kg
1

State P2 = 10 bar Steam T2 ≅ 240.4° C

2  →
Tables
S2 = S1 = 68803
.
kJ H 2 ≈ 29205
. kJ kg
kgK
kg kJ kJ
Ws = 4500 × (29205 . − 3422.2) = −2257650 = −6271 . kW
h kg h
a
(b) Same exit pressure P2 = 10 bar , and still adiabatic f
⇒ W = − M
s 1c
 H − H .
1 2 h
Here, however,
Ws = 08
. Ws ( Part a) = 08. −2.258 × 106 c kJ
h
h
= 4500 H 2 − 3422.2
kJ
h
c h
⇒ H 2 = 30208 . kJ kg Steam T2 ≅ 286.7 K
 →
P = 10 bar Tables S2 ≈ 7.0677 kJ kg K
Thus
Sgen = − M 1 1 c 2
h
h
 S − S = −4500 kg × (68803 . − 7.0677)
kJ
kg K
= 8433
.
kJ
K⋅h
(c) Flow across valve is a Joule-Thompson (isenthalpic expansion) ... See Illustration 3.4-1.
Thus, H into valve = H out of valve , and the inlet conditions to the turbine are

H 1 = H out of valve = H into valve = 3422.2 kJ kg

P1 = 30 bar

Steam T1 ≈ 484.8° C
 →
Tables S1 ≈ 71874
. kJ kg K

Flow across turbine is isentropic, as in part (a)

S2 = S1 = 71874

. kJ kg K Steam T2 ≅ 3181
. °C
 → 
P2 = 10 bar Tables H2 ≈ 3090.4 kJ kg

kg kJ kJ
Ws = 4500 × (3090.4 − 3422.2) = −1493
. × 106 = −414.8 kW
h kg h
4.10 Since compression is isentropic, and gas is ideal with constant heat capacity, we have

FG T IJ = FG P IJ R CP

HT K H PK
2 2

1 1

So that T2 = T1
FG P IJ FG 3 × 10 IJ
R CP
= 29815
6 8.314 36.8
= 326.75 K . Now using, from solution to
HPK H 2 × 10 K
2
. 6
1
 aT − T f
Problem 3.31, that W = NC s P 2 1
Solutions to Chemical and Engineering Thermodynamics, 5th ed Chapter 4

kg 1 mol J 1000 g
Ws = 125 × × 368
. × (326.75 − 29815
. )K ×
s 16 g mol K kg
= 8.23 × 106 J s

The load on the gas cooler is, from Problem 3.31,

Q = NC a
 T −T
p 3 2 f
125 kg s × 1000 g kg J
= × 368
. × (29815
. − 326.75) K
16 g mol mol K
= −8.23 × 10+6 J s

4.11 (a) This is a Joule-Thomson expansion

⇒ H (70 bar, T = ?) = H (10133
. bar, T = 400° C) ≈ H (1 bar, T = 400° C)
= 3278.2 kJ kg
and T = 447° C , S = 6.619 kJ kg K
c h
(b) If turbine is adiabatic and reversible Sgen = 0 , then Sout = Sin = 6.619 kJ kg K and P = 1013
.
bar. This suggests that a two-phase mixture is leaving the turbine

S V = 7.3594 kJ kg K
Let x = fraction vapor
S L = 13026
. kJ kg K
Then x(7.3594) + (1 − x)(13026
. ) = 6.619 kJ kg K or x = 08778
. . Therefore the enthalpy of
fluid leaving turbine is

kJ
H = 08788
. × .
26755 + (1 − 08778
. )× 417.46 = 2399.6
H V (sat’d, 1 bar ) H L (sat’d, 1 bar ) kg

Energy balance

0
 H + M
0= M  H + Q 0 +W − P dV
in in out out s
dt

 = −M
but M 
in out

Ws kJ
⇒− = 3278.2 − 2399.6 = 878.6
M kg
in
(c) Saturated vapor at 1 bar

S = 7.3594 kJ kg K ; H = 26755
. kJ kg
Ws
− = 3278.2 − 26755
. = 602.7 kJ kg

M in Actual
602.7 × 100
Efficiency (% ) = = 68.6%
878.6
Sgen
= 7.3594 − 6.619 = 0.740 kJ Kh
M 
in
Solutions to Chemical and Engineering Thermodynamics, 5th ed Chapter 4

(d) W  +M
0= M  ⇒M = −M

1 2 2 1

Steam Water 1 1 c
 H − H + W + Q − P dV
0= M 2 s
dt
h
70 bar 1 bar

447° C 25° C 0= M1 1 c 2
Q
 S − S + + S
T
gen h
Q

Simplifications to balance equations

dV
Sgen = 0 (for maximum work); P = 0 (constant volume)
dt
Q Q
= where T0 = 25° C (all heat transfer at ambient temperature)
T T0
kJ  kJ
H (sat' d liq, 25° C) = 104.89 ; S (sat' d liq, T = 25° C) = 0.3674
kg kg K
 −Ws
Q
M c h
= T0 S2 − S1 ;
M c h c h c
= H 1 − H 2 + T0 S2 − S1 = H 1 − T0 S1 − H 2 − T0 S2 h
max

−Ws
. × 6.619 − 104.89 − 29815
= 3278.2 − 29815 . × 0.3674

M max
= 1304.75 + 4.65 = 1309.4 kJ kg

4.12 Take that portion of the methane initially in the tank that is also in the tank finally to be in the
system. This system is isentropic S f = Si .
(a) The ideal gas solution

FP I
= TG J
R Cp
F 35. I 8.314 36
S f = S i ⇒ Tf = 300
H 70 K = 150.2 K
f
HPK
i
i
PV PV Pf V
N= ⇒ Ni = i = 1964.6 mol; N f = = 196.2 mol
RT RTi RTf
∆N = N f − Ni = −1768.4 mol

(b) Using Figure 2.4-2.

70 bar ≈ 7 MPa, T = 300 K . kJ kg K = S f
Si = 505
3
m 0.7 m3
Vi = 0.0195 , so that mi = = 3590
. kg.
kg m3
0.0195
kg
g
35.90 kg × 1000
kg
Ni = = 1282 mol
g
28
mol
Solutions to Chemical and Engineering Thermodynamics, 5th ed Chapter 4

At 3.5 bar = 0.35 MPa and S f = 505

. kJ kg K ⇒ T ≈ 138 K. Also,
m3 0.7 m3
Vf = 0192
. , so that m f = = 3646
. kg.
kg m3
0192
.
kg
g
3646
. kg × 1000
kg
Nf = = 130.2 mol
g
28
mol

∆N = N f − Ni = 130.2 − 1282 = −11518

. mol
dT dV
4.13 dS = C +R eqn. (4.4-1)
T V

∆S = z LMN
(a − R) + bT + cT 2 + dT 3 +
T PQO
e dT
2
T
+R
dV
V z
so that

a f a f
S T2 , V 2 − S T1, V 1 = (a − R) ln
T2
T1
f c a h
c
+ b T2 − T1 + T22 − T12
2

+ cT − T h − cT − T h + R ln
d 3 e 3 V −2 −2 2
2 1 2 1
3 2 V 1

Now using

V 2 T2 P1
PV = RT ⇒ = ⋅ ⇒
V 1 T1 P2

a f a f
S T2 , P2 − S T1, P1 = a ln
T2
T1
a c
+ b T2 − T1 + T22 − T12
2
f c h
d
3
c e
2
h c P
+ T23 − T13 − T2−2 − T1−2 − R ln 2
P1
h
Finally, eliminating T2 using T2 = T1 P2 V 2 PV
1 1 yields

a f a f
S P2 ,V 2 − S P1,V 1 = a ln
FG P V IJ + b a P V − PV f
2
H PV K R
2
2 2 1 1
1 1

+
c
2R
a P V f − a PV f
2 2 2
2
1 1
2

+
d
3R
a P V f − a PV f
3 2 2
3
1 1
3

eR 2
−
2
d
P2V 2 −2 − PV
1 1
−2 P
− R ln 2
P1
i d i
Solutions to Chemical and Engineering Thermodynamics, 5th ed Chapter 4

4.14 System: contents of valve (steady-state, adiabatic, constant volume system)

Mass balance 0 = N 1 + N 2
0 dV 0
Energy balance 0 = N 1 H 1 + N 2 H 2 + Q 0 + Ws − P
dt
⇒ H1 = H 2
Q 0
Entropy balance 0 = N 1 S 1 + N 2 S 2 + Sgen +
T
Sgen
⇒ ∆S = S 2 − S 1 =
N
(a) Using the Mollier Diagram for steam (Fig. 3.3-1a) or the Steam Tables

T1 = 600 K P2 = 7 bar T2 ≈ 293° C

 ⇒ 
P1 = 35 bar H2 = 30453
. J g S2 = 7.277 J g K

H 1 = H 2 = 30453
. J g . Thus S1 = 65598
. J g K ; Texit = 293° C
  
∆S = S − S = 0.717 J g K
2 1
(b) For the ideal gas, H 1 = H 2 ⇒ T1 = T2 = 600 K

a f a f
∆ S = S T2 , P2 − S T1, P1 = Cp ln
T2
T1
P
− R ln 2
P1
P2
= − R ln = 1338
. J mol K ⇒
P1
∆S = 0.743 J mol K

4.15 From the Steam Tables

P = 15538
. MPa
V = 0.001157 m3 / kg VV = 012736
L
. m3 / kg
U L = 850.65 kJ / kg U V = 25953
. kJ / kg
At 200oC,

H = 852.45 kJ / kg
L 
H = 27932
L
. kJ / kg
S = 2.3309 kJ / kg ⋅ K S = 6.4323 kJ / kg ⋅ K
L V

∆H vap = 1940.7 kJ / kg ∆S vap = 41014

. kJ / kg ⋅ K
(a) Now assuming that there will be a vapor-liquid mixture in the tank at the end, the properties
of the steam and water will be
P = 0.4578 MPa
V L = 0.001091 m3 / kg VV = 0.3928 m3 / kg
U L = 63168
. kJ / kg U V = 2559.5 kJ / kg
o
At 150 C,
H = 632.20 kJ / kg
L
H V = 27465
. kJ / kg
S L = 18418
. kJ / kg ⋅ K 
S = 68379
V
. kJ / kg ⋅ K
∆H = 2114.3 kJ / kg ∆S vap = 4.9960 kJ / kg ⋅ K
 vap

(b) For simplicity of calculations, assume 1 m3 volume of tank.