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Shown at the bottom is a PV diagram with two adiabatic lines 1 → 2 and 2 → 3, assumed to intersect at
point 2. A cycle is formed by an isothermal line from 3 → 1. An engine traversing this cycle would
produce work. For the cycle U = 0, and therefore by the first law, Q + W = 0. Since W is negative, Q
must be positive, indicating that heat is absorbed by the system. The net result is therefore a complete
conversion of heat taken in by a cyclic process into work, in violation of Statement 1a of the second law
(Pg. 160). The assumption of intersecting adiabatic lines is therefore false.
W = QH
TC
= 1−
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TH
T 323 K
W = 1− C Q = 1− 250 kJ s-1 = 148.8 kJ s -1
H
T 798 K
H
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TC 300 K
= 1− = 1− = 0.6
TH 750 K
QC T 303
thermal = 1 − = 1− C = 1 − = 0.514
QH TH 623
T 303
thermal = 0.55 1 − C = 0.55 1 − = 0.35
TH TH
Differentiate:
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Since TC/TH is less unity, the efficiency changes more rapidly with TC than with TH. So in theory it is
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more effective to decrease TC. In practice, however, TC is fixed by the environment, and is not subject
to control. The practical way to increase η is to increase TH. Of course, there are limits to this too.
TC 113.7 K
= 1− = 1− = 0.625
TH 303.15 K
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SVNAS 8th Edition Annotated Solutions Chapter 5
T P
S = C p ln − R ln
T P
0 0
T2
Q = U = n Cv dT
t
T1
Q = U t = nCv T
Q 15000 J
T = = = 500 K
nCv 1.443 mol 2.5 8.31451J mol-1 K -1( )
T P 7 5
S = C p ln − R ln = R ln 2 − R ln 2 = R ln 2 = 1.733R = 14.4 J mol-1 K -1
T0 P0 2 2
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For an ideal gas with constant heat capacities, and for the changes T1 → T2 and P1 → P2, Eq. (5.14)
can be rewritten as:
V2 = V1, then
Whence,
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**********************
As an additional part of the problem, one could ask for the following proof, valid for constant heat
capacities. Return to the original equation and substitute dT/T = dP/P + dV/V:
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Whence, d ln TC = − d ln TH where ≡
For infinite time, TH =TC ≡T, and the answer of Part (a) becomes :
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For infinite time, TC = TH, and the boxed equation above becomes:
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Hence
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QC T 300
thermal = 1 − = 1− C = 1− = 0.5
QH TH 600
W QH T 300
= −1 = H −1 = −1 = 0.2
QC QC TC 250
T2 P
S = C p ln − R ln 2
T1 P1
7 T P
S = R ln 2 − ln 2 = 8.314 ( 3.5ln1.5 − ln 5 ) = −1.58 J mol-1 K -1
2 T1 P1
7 T P
S = R ln 2 − ln 2 = 8.314 ( 3.5ln1.667 − ln 5 ) =1.48 J mol-1 K -1
2 T1 P1
T2 P
S = C p ln − R ln 2
T1 P1
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5 T P
S = R ln 2 − ln 2 = 8.314 ( 2.5ln 0.667 − ln 0.2 ) = 4.96 J mol -1 K -1
P1
2 T1
T2 P
S = C p ln − R ln 2
T1 P1
9 T2 P
S = R ln − ln 2 = 8.314 ( 4.5 ln 0.75 − ln 0.2 ) = 2.62 J mol -1 K -1
2 T1 P1
T2 P
S = C p ln − R ln 2
T1 P1
T P
S = R 3ln 2 − ln 2 = 8.314 ( 4ln 0.6 − ln 0.2 ) = −3.61 J mol-1 K -1
T1 P1
This cycle is shown below. Assuming constant specific heats, the efficiency is given by:
Temperature T4 is not given and must be calculated. The following equations are used to derive
and expression for T4.
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SVNAS 8th Edition Annotated Solutions Chapter 5
Q= Ut = m CV T
A necessary condition for T to be zero when Q is non-zero is that m =∞. This is the reason that
natural bodies (air and water) that serve as heat reservoirs must be massive (oceans) or continually
renewed (rivers).
T P
Sad ,rev = C p ln rev − R ln 2 = 0
T1 P1
T P
C p ln rev = R ln 2
T1 P1
R
Trev P2 Cp
=
T1 P1
R 2
P Cp
7 7
T =T 2 = 298.15 = 426.46 K
1
rev
1
P 2
T P 471.4 7
S = C p ln 2 − R ln 2 = 7 / 2 * R ln − R ln = 0.3506R
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T1 P1 298.15 2
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SVNAS 8th Edition Annotated Solutions Chapter 5
T P
Sad ,rev = C p ln rev − R ln 2 = 0
T1 P1
T P T P
S − S ad ,rev = S = C p ln 2 − R ln 2 − C p ln rev − R ln 2
T1 P1 T1 P1
T T T
S = C p ln − C p ln
2
= C p ln
rev 2
T1 T1 Trev
If m1 = m2 = m,
Since
St is positive
Isentropic processes are not necessarily reversible and adiabatic. The term isentropic denotes a process
for which the system does not change in entropy. There are two causes for entropy changes in a
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SVNAS 8th Edition Annotated Solutions Chapter 5
system: The process may be internally irreversible, causing the entropy to increase; heat may be
transferred between system and surroundings, causing the entropy of the system to increase or decrease.
For processes that are internally irreversible, it is possible for heat to be transferred out of the system
in an amount such that the entropy changes from the two causes exactly compensate each other. One
can imagine irreversible processes for which the state of the system is the same at the end as at the
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SVNAS 8th Edition Annotated Solutions Chapter 5
beginning of the process. The process is then necessarily isentropic, but neither reversible nor adiabatic.
More generally, the system conditions may change in such a way that entropy changes resulting from
temperature and pressure changes compensate each other. Such a process is isentropic, but not
necessarily reversible. Expansion of gas in a piston/cylinder arrangement is a case in point. It may be
reversible and adiabatic, and hence isentropic. But the same change of state may be irreversible with
heat transfer to the surroundings. The process is still isentropic, but neither reversible nor adiabatic.
An isentropic process must be either reversible and adiabatic or irreversible and non-adiabatic.
By definition,
By inspection, one sees that for both T > T0 and T0 > T the numerators and denominators of the
above fractions have the same sign. Thus, for both cases <CP>H is positive. Similarly,
By inspection, one sees that for both T > T0 and T0 > T the numerators and denominators of the above
fractions have the same sign. Thus, for both cases <CP>S is positive. When T = T0, both the
numerators and denominators of the above fractions become zero, and the fractions are indeterminate.
Application of l’Hˆopital’s rule leads to the result: <CP>H = <CP>S = CP.
Step 1-2: Volume decreases at constant P. Heat flows out of the system. Work is done on the
system.
Step 2-3: Isothermal compression. Work is done on the system. Heat flows
out of the system.
Step 3-1: Expansion process that produces work. Heat flows into the system. Since the PT product
is constant,
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Moreover
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SVNAS 8th Edition Annotated Solutions Chapter 5
T
S = C p dT − R ln P
T0
T P0
T
S A D P
R
= + B + CT + 3 dT − ln
T
T0
T P0
S T
R T0
C
= Aln + B (T − T0 ) + T 2 − T02 −
2
D
2
( ) 0 ) − ln PP
0
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SVNAS 8th Edition Annotated Solutions Chapter 5
dT
S = C p
T
T0
T2
Q = H t = n C p dT
T1
T2
Q 800000 J Cp
= = 9622 K=
dT
nR 10 mol 8.314 J mol K -1 - R
1 473 K
( 2 1 ) ( 2 2
) ( 3 3
)
T2 T1
2 1 2 1
R 2 3
T1
1374.5 K
S
C p dT
=
R R T
473.15 K
2
T1 (K) T2 (K) A B (1/K) C (1/K2) D (K ) ICPS
473.15 1374.5 1.424 1.44E-02 -4.39E-06 0.00E+00 10.835
T2 T1
ICPS Cp
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SVNAS 8th Edition Annotated Solutions Chapter 5
RT T
dT 2 ( )
+ B C T2 −T2 − 2 2 11 )
= 1
T
(T2 − D 2 2
Aln
T1 ) +
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SVNAS 8th Edition Annotated Solutions Chapter 5
1374.5 K
S
C p dT
= = 10.835
R R T
473.15 K
T2
Q 2500000 J Cp
= = 20045 K=
dT
nR 15 mol 8.314 J mol-1 K - R
1 533.15 K
( 2 1 ) ( 2 2
) ( 3 3
)
T2 T1
2 1 2 1
R 2 3
T1
2
T1 (K) T2 (K) A B (1/K) C (1/K2) D (K ) ICPS
533.15 1413.7 1.967 3.16E-02 -9.87E-06 0.00E+00 21.307
T2
T2
RT dT = Aln T + B (T − T ) + 2 (T ) )
Cp C D
ICPS 2 1 2
2
− T12 − 2 1
1 2
T1
1413.7 K
S
C p dT
= = 21.307
R R T
533.15 K
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SVNAS 8th Edition Annotated Solutions Chapter 5
T2
Q 1000000 Btu Cp
= -1
= 1 2588 R = 69 93 K dT
nR R R
= 533.15 K
40 lbmol 1.986 Btu lbmol-1
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SVNAS 8th Edition Annotated Solutions Chapter 5
( 2 1 ) ( 2 2
) ( 3 3
)
T2 T1
2 1 2 1
R 2 3
T1
2
T1 (K) T2 (K) A B (1/K) C (1/K2) D (K ) ICPS
533.15 1202.7 1.424 1.44E-02 -4.39E-06 0.00E+00 8.244
T2
T
( ) )
Cp C 2 D
ICPS dT = Aln 2 + B (T2 − T1 ) + T2 − T12 − 2 1
RT 1
T 2 2
T1
1202.7 K
S
C p dT
= = 8.244
R R T
533.15 K
248.15 K
298.15 K 1 bar
5 bar 348.15 K
1 bar
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SVNAS 8th Edition Annotated Solutions Chapter 5
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The process involves three heat reservoirs: the house, a heat source; the tank, a heat source; and the
surroundings, a heat sink. Notation is as follows:
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Shown to the right is a scheme designed to accomplish this result. A Carnot heat engine operates
with the furnace as heat source and the house as heat sink. The work produced by the engine drives a
Carnot refrigerator (reverse Carnot engine) which extracts heat from the surroundings and discharges heat
to the house. Thus the heat rejected by the Carnot engine (|Q1|) and by the Carnot refrigerator (|Q2|)
together provide the heat |Q| for the house. The energy balances for the engine and refrigerator are:
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The process involves three heat reservoirs: the house, a heat source; the tank, a heat source; and the
surroundings, a heat sink. Notation is as follows:
Shown below is a scheme designed to accomplish this result. A Carnot heat engine operates with the tank
as heat source and the surroundings as heat sink. The work produced by the engine drives a Carnot
refrigerator (reverse Carnot engine) which extracts heat |Q_| from the house and discharges heat to the
surroundings. The energy balances for the engine and refrigerator are:
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SVNAS 8th Edition Annotated Solutions Chapter 5
Q
− = Sg
T
−135 J s −1
Sg = − = 0.45 J K -1 s-1
300 K
Q
− = Sg
T
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SVNAS 8th Edition Annotated Solutions Chapter 5
−2500 J s −1
Sg = − = 8.33 J K-1 s-1
300 K
For a closed system the first term of Eq. (5.16) is zero, and it becomes:
Where j is here redefined to refer to the system rather than to the surroundings. Nevertheless, the second
term accounts for the entropy changes of the surroundings, and can be written simply as dSt surr/dt:
(a) : For a single stream flowing within the pipe and with a single heat
source in the surroundings, this becomes:
(b)
(c)
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SVNAS 8th Edition Annotated Solutions Chapter 5
(d)
(e)
(f)
(g)
T2 P
S = C p ln − R ln 2
T1 P1
7 T P
S = R ln 2 − ln 2 = 8.314 ( 3.5ln 0.742 − ln 0.2 ) = 4.698 J mol -1 K -1
2 T1 P1
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SVNAS 8th Edition Annotated Solutions Chapter 5
Qj
S − = Sg
j Tj
Wlost = T S g
T2 P
S = C p ln − R ln 2
T1 P1
T P
S = R 4ln 2 − ln 2 = 8.314 ( 4ln 0.8356 − ln 0.4 ) =1.643 J mol -1 K -1
T1 P1
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SVNAS 8th Edition Annotated Solutions Chapter 5
Qj
S − = Sg
j Tj
Wlost = T S g
T2 P
S = C p ln − R ln 2
T1 P1
11 T P 11
S = R ln 2 − ln 2 = 8.314 ln 0.8724 − ln 0.3 = 3.767 J mol-1 K-1
2 T1 P1 2
Qj
S − = Sg
j Tj
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SVNAS 8th Edition Annotated Solutions Chapter 5
Wlost = T S g
T2 P
S = C p ln − R ln 2
T1 P1
9 T2 P
S = R ln − ln 2 = 8.314 ( 4.5 ln 0.7832 − ln 0.2143) = 3.663 J mol -1 K -1
2 T
1 P1
Qj
S − = Sg
j Tj
Wlost = T S g
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SVNAS 8th Edition Annotated Solutions Chapter 5
T2 P
S = C p ln − R ln 2
T1 P1
5 T2 P
S = R ln − ln 2 = 8.314 ( 2.5ln 0.7327 − ln 0.3) = 3.546 J mol -1 K -1
2 T1
P1
Qj
S − = Sg
j Tj
Wlost = T S g
The figure below indicates the direct, irreversible transfer of heat |Q| from a reservoir at T1
to a reservoir at T2. The figure on the right depicts a completely reversible process to accomplish the
same changes in the heat reservoirs at T1 and T2.
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SVNAS 8th Edition Annotated Solutions Chapter 5
For the completely reversibl e process the net work produced is Wideal:
This is the work that is lost, Wlost, in the direct, irreversible transfer of heat |Q|. Therefore,
Note that a Carnot engine operating between T1 and T2 would not give the correct Wideal or Wlost, because
the heat it transfers to the reservoir at T2 is not Q.
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SVNAS 8th Edition Annotated Solutions Chapter 5
QH QC 1 0.55
Sg = − − =− + = −6.7 10−5 kJ/K
TH TC 523.15 298.15
W T 293.15
= =1− C =1− = 0.5016
QH TH 588.15
Equation (5.14) can be written for both the reversible and irreversible processes:
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SVNAS 8th Edition Annotated Solutions Chapter 5
Since Sirrev must be greater than zero, Tirrev must be greater than Trev.
=−+−+−−− ( 2 1 ) ( 2 2
) ( 3 3
)
R 2
2 1
3
2 1
T1 T2 T1
T2
Cp B C 1 1
ICPH dT AT T T T T T D
=−+−+−−− ( 2 1 ) ( 2 2
) ( 3 3
)
R 2
2 1
3
2 1
T1 T2 T1
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SVNAS 8th Edition Annotated Solutions Chapter 5
ICPS =+−+−d−T− Aln 2
B (T2 T1 ) (
T2 T2
2 1
) (
T2 2
T1 2
)
T
RT T1 2 2
1
ICPS =+−+−d−T− Aln 2
T
B (T2 T1 ) (
T2 T2
2 1
) (T 2
2
T1 2
)
T
RT 1 2 2
1
pV 1*100000
n= = = 258.6 lbmol hr −1
RT 0.7302*529.67
T2
1 1
(T ) (T )
Cp
dT = A (T − T0 ) +
B C
ICPH( T ,T;A,B,C,D ) 2
−T 2 + 3
−T3 − D −
0 0 0
T1
R 2 3 T T0
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SVNAS 8th Edition Annotated Solutions Chapter 5
T
Cp T D T − T
2 2
ICPS ( T ,T;A,B,C,D )
0
dT = Aln + B (T − T0 ) + C +
0
RT T0 T 2T02 2
T0
pV 101325*3000
n= = = 122629 mol hr −1 = 34.06 mol s −1
RT 8.314* 298.15
T2
T0 (K) T (K) A
2
B (1/K) C (1/K ) D (K2) ICPS Sig (J/(mol K))
298.15 265.15 3.355 5.75E-04 0 -1.60E+03 -0.410 -3.4099
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SVNAS 8th Edition Annotated Solutions Chapter 5
Calculate the rate of entropy generation in the boiler. This is the sum of the entropy generation of
the steam and the gas.
(b)
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Calculate the rate of entropy generation in the boiler. This is the sum of the entropy generation of
the steam and the gas.
(b)
Now place a heat engine between the ethylene and the surroundings. This would constitute a
reversible process, therefore, the total entropy generated must be zero. calculate the heat released
to the surroundings for ΔStotal = 0.
Now apply an energy balance around the heat engine to find the work produced. Note that the
heat gained by the heat engine is the heat lost by the ethylene.
The lost work is exactly equal to the work that could be produced by the heat engine.
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