Chapter 5

5.1.
Shown to the right is a P V 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 rst 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.
5.2.

Given:
QH= 250 kJ/s
TH= 525 + 273.15 = 798.15 K
TC= 50 + 273.15 = 323.15 K
Required: power developed and QC
Soln: by Eq. 5.8
= 1= 1= 0.5951

5.3.

Work = QH
= (0.5951)(250 kJ/s)
Work = 148.7816 kW
|
QC = | | |
= 250 148.7816
QC = 101.2148 kJ/s

Given:
TH = 750 K
TC = 300 K
W = 95,000 W
Required: QC and QH
a. = 1
= 1 = 0.6
QH =

|
QC =| | |
= 158,333 95000
QC = 63, 333.33 kW
b. = 0.35
QH =

QC = |
5.4.

QC = 176428.57 kW

Given:
TC = 303.15K
TH = 623.15 K

b. = 0.35
Carnot =

=
= 0.6364

a. = 1
= 1 = 0.5135
Carnot = (0.55) = 0.2824

TH =

arnot

0 6364

TH = 833.6625K

5.5. The energy balance for the over-all process is written:

Q = U t + EK + EP
Assuming the egg is not scrambled in the process, its internal-energy change after it returns
to its initial temperature is zero. So too is its change in kinetic energy. The potential-energy change,
however, is negative, and by the preceding equation, so is Q. Thus heat is transferred to the
surroundings.
The total entropy change of the process is:
Just as Ut for the egg is zero, so is St. Therefore,
=

Since Q is negative, Stotal is positive, and the process is irreversible.

5.6.

By. Eq. (5.8) the thermal efficiency of a Car/not engine is:

Since TC /TH is less unity, the efficiency changes more rapidly with TC than with TH . So in theory it
is more effective to decrease TC . In practice, however, TC is xed by the environment, and is not
subject to control. The practical way to increase is to increase TH . Of course, there are limits to this
too.
5.7.

Given:
V = 9000 m3/s
T = 25 + 273.15 = 298.15 K
TH = 30 + 273.15 = 303.15 K
TC = 113.7 K

mol wt = 17 g/mol
P = 1.0133 bar

Required: Work and QH

QC = 512 kJ/kg mLNG
MLNG = (mol wt)
=

(
(

)(
)(

= 6254 kg/s

)
)

(17)

QC = 512(6254.3854)
= 3202245 kW

W = QC( T

= 5335285 kW = 5.34 x 106 kW

5.8.

QH= QC + Work
= 8537258 kW = 8.54 x 106 kW

Given:
T1 = 273.15 K
T2 = 373.15 K
CpH2O 4.184 kJ/kg K

Reqd: SH2O, Sres, Stotal

Solution:
SH2O = Cp ln (T2/ T1)
= 4.184 ln (373.15/273.15)
= 1.3052 kJ/ kg K

Q = Cp ln (T2 T1)
= 418.4

Sres = -Q/T2
=
= -1.1213 kJ/ kg K

Stotal = SH2O + Sres

= 1.3052 + (-1.1213)
= 0.1839 kJ/ kg K

b. Stotal
Sres =
(
)+(
= -1.208 kJ/ kg K

Stotal = SH2O + Sres

= 1.305 1.208
= 0.097 kJ/ kg K

c. The reversible heating of the water requires an infinite number of heat reservoirs covering the
range of temperatures from 273.15 to 373.15 K, each one exchanging an infinitesimal quantity of
heat with the water and raising its temperature by a differential increment.
5.9.

Given:
P = 1 bar
Q = 15,000 J
T1 = 500 K

Cv = 5/2 R
V = 0.06 m3

a. n = PV/ RT = 1.443 mol

T 2 = T1 +
= 500 +

( (

))

= 1000.1208 K
S = nCv ln T2/ T1
= 1.443 (5/2(8.314)) ln
= 20.7894 J/K
b. The entropy change of the gas is the same as in (a). The entropy change of the
surroundings is zero.

S = 20.7894 J/K
5.10.

Given:
Cp = 7/2 R
T2 = 190 + 273.15 = 463.15 K
T1 = 70 + 273.15 = 343.15 K
a. SA = Cp ln (T2/T1)
= 7/2 (8.314) ln (
)
= 8.726 J/ mol K
SB = Cp ln (T2/T1)
= 7/2 (8.314) ln (
= -6.577 J/ mol K

b. Stotal = SA + SB
= 2.149 J/ mol K

c. SA = Cp ln (T2/T1)
= 7/2 (8.314) ln (
= 8.726 J/ mol K

SB = Cp ln (T2/T1)
= 7/2 (8.314) ln (
= -8.512 J/ mol K

Stotal = SA + SB
= 0.214 J/ mol K

5.11. For an ideal gas with constant heat capacities, and for the changes T1 T2 and P1 P2 ,
Eq. (5.14) can be rewritten as:
ln
(a) If P2= P1,

ln

Whence,

ln

ln

If V2 = V1,
ln

ln

Since CP > CV, this demonstrates that SP > SV.

(b) If T2= T1, ST= -Rln (P2/P1)

If V2=V1, T2/T1 =P2/P1

Whence, SV= CP ln (P2/P1)- R ln(P2/P1)= Cv ln (P2/P1)

This demonstrates that the signs for ST and SV are opposite.
5.12.

Start with the equation just preceding Eq. (5.14) on p. 170:

For an ideal gas PV=Rt, and ln P + ln V =ln R + lnT. Therefore,

or
Whence,
(
Because (

, this reduces to:

Integration yields:
5.13.

As indicated in the problem statement the basic differential equations are:

dW-dQH-dQC =0

(A)
(B)

Where QC and QH refer to the reservoirs.

(a) With dQH = CHdTH and dQC = CCdTC, Eq. (B) becomes:

Whence,

d ln TC =- d ln TH

where

Integration from TH0 andTC0 to TH and TC yields:

(

(b) With dQH = CHdTH and dQC = CCdTC, Eq. (A) becomes:
dW = CHdTH + CCdTC
Integration yields:

W=CH (TH-TH0) + CC(TC-TC0)

(c)For infinite time, TH=TC T,

T=
From which:

T-+ = T C0 (
T =(TC0)

)-

= TC0(

/(+ )(TH0)/(+ )

and

(TC0)

/(+ )(TH0)/(+ )-1

Because /(+1)-1= -1(+1), then:

(

5.14.

/(+ )

and

) =(

) /(+

)-1

As indicated in the problem statement the basic differential equations are:

dW -dQH- dQC =0

(A)
(B)

Where QC and QH refer to the reservoirs.

(a) With dQC = CCdTC , Eq. (B) becomes:

Integrate from TC0 to TC:

W=-CC TH ln

+ CC (TC-TC0)

(b) For infinite time, TC = TH, the equation above becomes

W=CC (TH ln
5.15.

+ TH-TC0 )

Write Eqs. (5.8) and (5.1) in rate form and combine to eliminate | |:
| |
= 1| | | |

With |

or

| |

| |

| | where r

) , this becomes:

| |(

| |(

Differentiate, nothing that the quantity in square brackets is constant:

=*

| |
(

+ *(

| |
(

+ *(

Equating this equation to zero, leads immediately to: 4r=3 or r=0.75.

5.16.

Given:
T1 = 600 K
T2 = 400 K

T = 300 K
Cp= 7/2 R

Solution:
Q = Cp (T2 T1)
= 7/2 (8.314) (400-600)
= -5819.8 J/mol

Work = Q - T S
= -5819.8 (300)(-11.7986)
= -2280.22 J/ mol

S = Cp ln

|
Q = | | |
= 5819.8 2280.22
= 3539.58 J/ mol

= 7/2 ln
= -11.7986 J/ mol K
Sres =

=
= 11.7986 J/ mol K
S + Sres = 0
Process is reversible.

5.17.

Given:
TH1 = 600 K
TH2 = 300 K
Tc1 = 300 K
Tc2 = 250 K
| |
|
|

| |
|
|
5.18.

a. Given:
T1 = 300 K
P1 = 1.2 bar
T2 = 450 K

P2 = 6 bar
Cp = 7/2 R

H = Cp (T2 T1)
= 7/2 (8.314)(450-300)
= 4362.85 J/mol

S =
)
= (
= -1.5822 J/mol K

b. Given:
T1 = 300 K
P1 = 1.2 bar
T2 = 500 K

P2 = 6 bar
Cp = 7/2 R

H = Cp (T2 T1)
= 7/2 (8.314)(500 -300)
= 5819.8 J/mol
S =
)
= (
= 1.4836 J/mol K
c. Given:
T1 = 450 K
P1 = 10 bar
T2 = 300 K
H = Cp (T2 T1)
= 5/2 (8.314)(300 -400)
= -3117.75 J/mol

P2 = 2 bar
Cp = 5/2 R

S =

= (

= 4.9533 J/mol K

d. Given:
T1 = 400 K
P1 = 6 bar
T2 = 300 K

P2 = 1.2 bar
Cp = 9/2 R

H = Cp (T2 T1)
= 9/2 (8.314)(300 -400)
= -3741.3J/mol
S =
)
= (
= 2.6178 J/mol K
e. Given:
T1 = 500 K
P1 = 6 bar
T2 = 300 K

P2 = 1.2 bar
Cp = 4 R

H = Cp (T2 T1)
= 4 (8.314)(300 -400)
= -6651.2 J/mol
S =
)
= (
= -3.6072 J/mol K

5.19.

3
Cp = 7/2 R
Cv = 5/2 R
Required:
T4 =?

T1 = 200C
T2 = 1000C
T3 = 1700C
1-2 Reversible Adiabatic Compression
T1V1-1 = T2V2-1

2-3 Isobaric

T3V3-1 = T4V4-1
4-1
3-4 Reversible Adiabatic Expansion

V 4 = V1

From 3-4
Eq. 5 T4= T3V3-1/ V4-1
From 1-4
Eq.6 V4 = V1-1 = T2V2-1/ T1
Eq. 5 & 6
T4 = (T3V3-1/ T2V2-1) T1
Ideal gas

T4 =

V3 = RT3/P3

&

V2 = RT2/P2

( ) -1 = 837.7588K

Q2-3= Cp(T3 T2)

= 1+ (

) = 1+

= 0.5912
5.20.

Because W = 0, Eq. (2.3) here becomes:

Q=Ut = mCVT

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).
5.21.

Given:
Cv = CpR
P1 = 2 bar
P2 = 7 bar
T1 = 298.15 K
= Cp/ Cv
= 7/2 5/2
= 1.4

W= 1.35
= 1.35

[( )
(

[( )

= 3600.4711 J/mol
Q =0 and W = U = v (T2 T1)
T 2 = T1 +
= 298.15 +

= 471.3744 K
S = p ln
= (

ln
) ln (

ln( )

= 2.9135 J/mol K
5.22. Amn appropriate energy balance here is: Q=Ht = 0
Applied to the process described, with T as the final temperature, this becomes:
m1CP(T-T1)+ m2CP (T-T2)=0

whence

(1)

If m1=m2, T= (T1+T2)/2
The total entropy change as a result of temperature changes of the two masses of water:
St= mCP ln
Because T=(T1+T2)/2 >

or St= 2mCP ln

, St is positive.

5.23. 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 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 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.
5.24.

By definition,

(CP)H=

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,

(CP)S=

5.25.

T=800

Given: P=4

Step 1-2: Volume decreases at constant P.

Het flows out of the system. Work is done on the system.
]
[ (
W12= [ (
)]
Step 2-3: Isothermal compession. Work is done on the system. Heat flows out of the system.
W23= R T2 ln (P3/P2) =RT2 ln(P3/P1)
Step 3-1: Expansion process that produces work. Heat flows into the system. Since the PT product is
constant,
PdT + TdP =0
T =-dT
(A)
PV = RT
PdV + V dP = R dT
P dV =R dT V dP = R dT RT
In combination with (A) this becomes
PdV = R dT + RdT =2R dT
CP =7/2 R
T1 = 700K
T2 = 350 K

P1= 1.5 bar

P3= P1 T1/ T2

W12= -R(T2-T1)
= 2.91 x 103 J/mol

W31 = -2R(T1-T2)
= -5.82 x 103 J/mol

W23 = RT2 ln(P3/P1)

= 2.017 x 103 J/mol

Q31 =(Cp +R) (T1-T2)

= 1.309 x 104 J/mol
|

Example 6.4
Find the values for the residual enthalpy HR and the residual entropy SR for n- butane gas at 500 K
and 50 bar as given by the Van der Waals equation.
Given:
n- butane @ T = 500 K
P = 50 bar
TC = 435.1 K

PC = 37.96 bar
TR =
PR =
Parameters for VDW:
( )

(
(

( )
(

Solving for z
(

)(

)*

( )

( )

= 0.2118
Solving for HR
*

= 0.6610 -1 + *

+(2.8694)(0.2118)

HR = 0.6610 -1 + *
HR = -3935.2894 J/mol
ln(

*ln (

+(2.8694)(0.2118)[(

)+ (

6.30 Superheated Steam

Given:
P1= 500 kPa
T1= 300 = 573.15 K
P2 = 50 kPa
S- constant

; ( )=1

)(

)]

Required: Final Enthalpy

S1= 7.4614 kJ/kg K
HL = 340.564
SL = 1.0912
7.4614 =S2 = S1 = SL + X(SV-SL)
XV = 0.9795
H2= HL + xV +(HV-HL)
= 340.564 + (0.9795)(2646-340.564)
H2= 2598.7386

HG= 2464
SG = 7.5947