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Borgnakke Sonntag

Fundamentals of
Thermodynamics
SOLUTION MANUAL
CHAPTER 12

8e

Updated June 2013

Borgnakke and Sonntag

Fundamentals of Thermodynamics 8th Edition


Borgnakke and Sonntag
CONTENT CHAPTER 12
SUBSECTION
In-Text concept questions
Study guide problems
Clapeyron equation
Property Relations, Maxwell, and those for
Enthalpy, internal Energy and Entropy
Volume Expansivity and Compressibility
Equations of State
Generalized Charts
Mixtures
Helmholtz EOS
Review problems

PROB NO.
a-f
1-15
16-33
34-43
44-59
60-81
82-120
121-133
134-138
139-148

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The following table gives the values for the compressibility, enthalpy departure and the
entropy departure along the saturated liquid-vapor boundary. These are used for all the
problems using generalized charts as the figures are very difficult to read accurately
(consistently) along the saturated liquid line. It is suggested that the instructor hands out
copies of this page or let the students use the computer for homework solutions.

Tr

Pr

Zf

Zg

d(h/RT)f

d(h/RT)g

d(s/R)f

d(s/R)g

0.96

0.78

0.14

0.54

3.65

1.39

3.45

1.10

0.94

0.69

0.12

0.59

3.81

1.19

3.74

0.94

0.92

0.61

0.10

0.64

3.95

1.03

4.00

0.82

0.90

0.53

0.09

0.67

4.07

0.90

4.25

0.72

0.88

0.46

0.08

0.70

4.17

0.78

4.49

0.64

0.86

0.40

0.07

0.73

4.26

0.69

4.73

0.57

0.84

0.35

0.06

0.76

4.35

0.60

4.97

0.50

0.82

0.30

0.05

0.79

4.43

0.52

5.22

0.45

0.80

0.25

0.04

0.81

4.51

0.46

5.46

0.39

0.78

0.21

0.035

0.83

4.58

0.40

5.72

0.35

0.76

0.18

0.03

0.85

4.65

0.34

5.98

0.31

0.74

0.15

0.025

0.87

4.72

0.29

6.26

0.27

0.72

0.12

0.02

0.88

4.79

0.25

6.54

0.23

0.70

0.10

0.017

0.90

4.85

0.21

6.83

0.20

0.68

0.08

0.014

0.91

4.92

0.18

7.14

0.17

0.66

0.06

0.01

0.92

4.98

0.15

7.47

0.15

0.64

0.05

0.009

0.94

5.04

0.12

7.81

0.12

0.60

0.03

0.005

0.95

5.16

0.08

8.56

0.08

0.58

0.02

0.004

0.96

5.22

0.06

8.97

0.07

0.54

0.01

0.002

0.98

5.34

0.03

9.87

0.04

0.52

0.0007

0.0014

0.98

5.41

0.02

10.38

0.03

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In-Text Concept Questions

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12.a
Mention two uses of the Clapeyron equation.
If you have experimental information about saturation properties down to
a certain temperature Clapeyron equation will allow you to make an intelligent
curve extrapolation of the saturated pressure versus temperature function Psat(T)
for lower temperatures.
From Clapeyrons equation we can calculate a heat of evaporation, heat of
sublimation or heat of fusion based on measurable properties P, T and v. The
similar changes in entropy are also obtained since
hfg = Tsfg;

hif = Tsif;

hig = Tsig

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12.b
If I raise the temperature in a constant pressure process, does g go up or down?
From the definition and variation in Gibbs function, see Eq.12.15 and Maxwells
relation Eq.12.21 last one, we get
dg = s dT
so Gibbs function decreases as temperature increases.

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12.c
If I raise the pressure in an isentropic process, does h go up or down? Is that
independent upon the phase?
Tds = 0 = dh vdP , so h increases as P increases, for any phase. The
magnitude is proportional to v (i.e. large for vapor and small for liquid and
solid phases)

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12.d
If I raise the pressure in a solid at constant T, does s go up or down?
In Example 12.4, it is found that change in s with P at constant T is negatively
related to volume expansivity (a positive value for a solid),
dsT = - v P dPT
so raising P decreases s.

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12.e
What does it imply if the compressibility factor is larger than 1?
A compressibility factor that is greater than one comes from domination of
intermolecular forces of repulsion (short range) over forces of attraction (long
range) either high temperature or very high density. This implies that the density
is lower than what is predicted by the ideal gas law, the ideal gas law assumes the
molecules (atoms) can be pressed closer together.

12.f
What is the benefit of the generalized charts? Which properties must be known
besides the charts themselves?
The generalized charts allow for the approximate calculations of enthalpy
and entropy changes (and P,v,T behavior), for processes in cases where specific
data or equation of state are not known. They also allow for approximate phase
boundary determinations.
It is necessary to know the critical pressure and temperature, as well as
ideal-gas specific heat.

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Concept-Study Guide Problems

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12.1
The slope dP/dT of the vaporization line is finite as you approach the critical
point, yet hfg and vfg both approach zero. How can that be?
The slope is

hfg
dP
dT = Tv
sat
fg

Recall the math problem what is the limit of f(x)/g(x) when x goes
towards a point where both functions f and g goes towards zero. A finite limit for
the ratio is obtained if both first derivatives are different from zero so we have
dP/dT [dhfg /dT] / d(Tvfg)/dT as T Tc

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12.2
In view of Clapeyrons equation and Fig. 2.4, is there something special about ice
I versus the other forms of ice?
Yes. The slope of the phase boundary dP/dT is negative for ice I to liquid
whereas it is positive for all the other ice to liquid interphases. This also means
that these other forms of ice are all heavier than liquid water. The pressure must
be more than 200 MPa 2000 atm so even the deepest ocean cannot reach that
pressure (recall about 1 atm per 10 meters down).

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12.3
If we take a derivative as (P/T)v in the two-phase region, see Figs. 2.7 and 2.8,
does it matter what v is? How about T?
In the two-phase region, P is a function only of T, and not dependent on v.
The slope is the same at a given T regardless of v. The slope becomes
higher with higher T and generally is the highest near the critical point.
P
L

C.P.
V

T
S

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12.4
Sketch on a P-T diagram how a constant v line behaves in the compressed liquid
region, the two-phase L-V region and the superheated vapor region?
P
vsmall> vc

v < v Cr.P.
c
S

v
medium
v
large
T

v < vc

C.P.

v > vc
vmedium

S
V

large

v
The figures are for water where liquid is denser than solid.

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12.5
If I raise the pressure in an isothermal process does h go up or down for a liquid
or solid? What do you need to know if it is a gas phase?
Eq. 12.25:

(P)T = v T (T)P = v[1 - TP]

Liquid or solid, P is very small, h increases with P ;


For a gas, we need to know the equation of state.

12.6
The equation of state in Example 12.3 was used as explicit in v. Is it explicit in P?
Yes, the equation can be written explicitly in P.
RT
P=
C
v+ 3
T

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12.7
Over what range of states are the various coefficients in Section 12.5 most useful?
For solids or liquids, where the coefficients are essentially constant over a
wide range of Ps and Ts.

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12.8
For a liquid or a solid is v more sensitive to T or P? How about an ideal gas?
For a liquid or solid, v is much more sensitive to T than P.
For an ideal gas, v = RT/P , varies directly with T, inversely with P.

12.9
Most equations of state are developed to cover which range of states?
Most equations of state are developed to cover the gaseous phase, from
low to moderate densities. Many cover high-density regions as well, including
the compressed liquid region. To cover a wider region the EOS must be more
complex and usually has many terms so it is only useful on a computer.

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12.10
Is an equation of state valid in the two-phase regions?
No. In a two-phase region, P depends only on T. There is a discontinuity
at each phase boundary. It is actually difficult to determine the phase boundary
from the EOS.

12.11

As P 0, the specific volume v . For P , does v 0?


At very low P, the substance will be essentially an ideal gas, Pv = RT, so
that v becomes very large. However at very high P, the substance eventually must
become a solid, which cannot be compressed to a volume approaching zero.

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12.12
Must an equation of state satisfy the two conditions in Eqs. 12.49 and 12.50?
It has been observed from experimental measurements that substances do
behave in that manner. If an equation of state is to be accurate in the near-critical
region, it would have to satisfy these two conditions.
If the equation is simple it may be overly restrictive to impose these as it
may lead to larger inaccuracies in other regions.

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12.13
At which states are the departure terms for h and s small? What is Z there?
Departure terms for h and s are small at very low pressure or at very high
temperature. In both cases, Z is close to 1 and this is the ideal gas region.

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12.14
The departure functions for h and s as defined are always positive. What does that
imply for the real substance h and s values relative to ideal gas values?
Real-substance h and s are less than the corresponding ideal-gas values.
This is true for the range shown in the figures, Pr < 10. For higher P the isotherms
do bend down and negative values are possible.
Generally this means that there are slightly attractive forces between the
molecules leading to some binding energy that shows up as a negative potential
energy (thus smaller h and u) and it also give a little less chaos (smaller s) due to
the stronger binding as compared to ideal gas. When the pressure becomes large
the molecules are so close together that the attractive forces turns into repulsive
forces and the departure terms are negative.

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12.15
What is the benefit of Kays rule versus a mixture equation of state?
Kays rule for a mixture is not nearly as accurate as an equation of state
for the mixture, but it is very simple to use and it is general. For common
mixtures new mixture EOS are becoming available in which case they are
preferable for a greater accuracy in the calculation.

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Clapeyron Equation

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12.16
An approximation for the saturation pressure can be ln Psat = A B/T, where A
and B are constants. Which phase transition is that suitable for, and what kind of
property variations are assumed?
Clapeyron Equation expressed for the three phase transitions are shown in Eqs.
12.5-12.7. The last two leads to a natural log function if integrated and ideal gas
for the vapor is assumed.
dPsat
hevap
=
P
sat RT2
dT
where hevap is either hfg or hig. Separate the variables and integrate
-1

Psat dPsat = hevap R-1 T-2 dT


ln Psat = A B/T ;

B = hevap R-1

if we also assume hevap is constant and A is an integration constant. The function


then applies to the liquid-vapor and the solid-vapor interphases with different
values of A and B. As hevap is not excactly constant over a wide interval in T it
means that the equation cannot be used for the total domain.

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12.17
Verify that Clapeyrons equation is satisfied for R-410A at 10oC in Table B.4.

Clapeyron Eq.:

B.4:

dPsat dPg hfg


dT = dT = Tvfg

P = 1085.7 kPa,

hfg = 208.57 kJ/kg,

vfg = 0.02295 m3/kg

Slope around 10oC best approximated by cord from 5oC to 15oC


dPg 1255.4 933.9
= 32.15 kPa/K,
dT =
15 5
hfg
208.57
=
Tvfg 283.15 0.02295 = 32.096 kPa/K
This fits very well. Use CATT3 to do from 9 to 11oC for better approximation
as the saturated pressure is very non-linear in T.

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12.18
In a Carnot heat engine, the heat addition changes the working fluid from
saturated liquid to saturated vapor at T, P. The heat rejection process occurs at
lower temperature and pressure (T T), (P P). The cycle takes place in a
piston cylinder arrangement where the work is boundary work. Apply both the
first and second law with simple approximations for the integral equal to work.
Then show that the relation between P and T results in the Clapeyron equation
in the limit T dT.

T
T
T T

P- P

qH = Tsfg;

sfg at T

P- P

T- T

vfg at T

wnet = qH - qL = Tsfg

qL = (T-T)sfg ;

Pdv
The boundary movement work, w =
3

Pdv + (P - P)(v4 - v3) +


Pdv
wNET = P(v2-v1) +
2

Approximating,
3

P
Pdv (P - ) (v3 - v2);

2
2

P
Pdv (P - ) (v1 - v4)

2
1

v2+v3
v1+v4
wNET P[( 2 ) - ( 2 )]

Collecting terms:

(the smaller the P, the better the approximation)


sfg
P
1

1
T
(v + v ) (v + v )
2

In the limit as

T 0:

v3 v2 = vg ,

v4 v1 = vf

lim P dPsat sfg


& T0 = dT = v
T
fg

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12.19
Verify that Clapeyrons equation is satisfied for carbon dioxide at 6oC in Table
B.3.
dPsat dPg hfg
dT = dT = Tvfg

Clapeyron Eq.:

B.3:

P = 4072.0 kPa,

hfg = 211.59 kJ/kg,

vfg = 0.00732 m3/kg

Slope around 6oC best approximated by cord from 4oC to 8oC


dPg 4283.1 3868.8
= 103.575 kPa/K,
84
dT =
hfg
211.59
kJ/kg
=
Tvfg 279.15 0.00732 K m3/kg = 103.549 kPa/K
This fits very well.

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12.20
Use the approximation given in problem 12.16 and Table B.1 to determine A and
B for steam from properties at 25oC only. Use the equation to predict the
saturation pressure at 30oC and compare to table value.
dPsat
-2
dT = Psat (-B)(-T )
so we notice from Eq.12.7 and Table values from B.1.1 and A.5 that
hfg 2442.3 kJ/kg
B = R = 0.4615 kJ/kg-K = 5292 K
ln Psat = A B/T

Now the constant A comes from the saturation pressure as


5292
A = ln Psat + B/T = ln 3.169 + 273.15 + 25 = 18.9032
Use the equation to predict the saturation pressure at 30oC as
5292
ln Psat = A B/T = 18.9032 - 273.15 + 30 = 1.4462
Psat = 4.2469 kPa
compare this with the table value of Psat = 4.246 kPa and we have a very accurate
approximation.

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12.21
A certain refrigerant vapor enters a steady flow constant pressure condenser at
150 kPa, 70C, at a rate of 1.5 kg/s, and it exits as saturated liquid. Calculate the
rate of heat transfer from the condenser. It may be assumed that the vapor is an
ideal gas, and also that at saturation, vf << vg. The following quantities are known
for this refrigerant:
ln Pg = 8.15 - 1000/T ;

CP = 0.7 kJ/kg K

with pressure in kPa and temperature in K. The molecular mass is 100.


Solution:
Refrigerant: State 1 T1 = 70oC P1 = 150 kPa
State 2 P2 = 150 kPa x2 = 1.0
Energy Eq.:

State 3

P3 = 150 kPa x3 = 0.0

q = h3 - h1 = (h3 - h2) + (h2 - h1) = - hfg T3 + CP0(T2 - T1)

1 3

Get the saturation temperature at the given pressure


ln (150) = 8.15 - 1000/T2 => T2 = 318.5 K = 45.3oC = T3
Now get the enthalpy of evaporation hfg T3
dPg hfg
dT = Tvfg ,

dPg
d ln Pg
hfg
=
P
=
P
g dT
dT
RT2 g

RT
vfg vg = P ,
g

d ln Pg
2
2
dT = +1000/T = hfg/RT
hfg = 1000 R = 1000 8.3145/100 = 83.15 kJ/kg
Substitute into the energy equation
q = -83.15 + 0.7(45.3 - 70) = -100.44 kJ/kg
1 3
.
QCOND = 1.5(-100.44) = -150.6 kW

1
3

1
v

2
s

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12.22
Calculate the values hfg and sfg for nitrogen at 70 K and at 110 K from the
Clapeyron equation, using the necessary pressure and specific volume values
from Table B.6.1.
dPg hfg sfg
Clapeyron equation Eq.12.7:
dT = Tvfg = vfg
For N2 at 70 K, using values for Pg from Table B.6 at 75 K and 65 K, and also
vfg at 70 K,
Pg
76.1-17.41
hfg T(vg-vf)
= 70(0.525 015)
= 215.7 kJ/kg
75-65

sfg = hfg/T = 3.081 kJ/kg K

Table B.6.1:

hfg = 207.8 kJ/kg

and sfg = 2.97 kJ/kg K

Comparison not very close because Pg not linear function of T. Using 71 K &
69 K from the software, we can then get

(44.56-33.24
71-69 ) = 208.0 kJ/kg

hfg = 70(0.525 015)


At 110 K,

(1938.8-1084.2
115-105 ) = 134.82 kJ/kg

hfg 110(0.014 342)

134.82
sfg = hfg/T = 110 = 1.226 kJ/kg K
Table B.6.1: hfg = 134.17 kJ/kg and sfg = 1.22 kJ/kg K

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12.23
Find the saturation pressure for refrigerant R-410A at 80oC assuming it is higher
than the triple point temperature.
The lowest temperature in Table B.4 for R-410A is -60oC, so it must be extended
to -80oC using the Clapeyron Eq. 12.7 integrated as in example 12.1
Table B.4 at T1 = -60oC = 213.15 K:
P1 = 64.1 kPa, R = 0.1145 kJ/kg-K
P hfg (T - T1) 279.96 (193.15 - 213.15)
=
= -1.1878
ln P = R
T T1 0.1145 193.15 213.15
1
P = 64.1 exp(-1.1878) = 19.54 kPa

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12.24
Ammonia at 70oC is used in a special application at a quality of 50%. Assume
the only table available is B.2 that goes down to 50oC. To size a tank to hold 0.5
kg with x = 0.5, give your best estimate for the saturated pressure and the tank
volume.
To size the tank we need the volume and thus the specific volume. If we do not
have the table values for vf and vg we must estimate those at the lower T. We
therefore use Clapeyron equation to extrapolate from 50oC to 70oC to get the
saturation pressure and thus vg assuming ideal gas for the vapor.
The values for vf and hfg do not change significantly so we estimate
Between -50oC and 70oC:

hfg = 1430 kJ/kg

and at 70 C we get: vf = 0.001375 m3/kg


The integration of Eq.12.7 is the same as in Example 12.1 so we get
P2 hfg T2 - T1
1430
-70 + 50
= -1.2923
ln P = R ( T T ) = 0.4882
203.15 223.15
1
2 1
P2 = P1 exp(-1.2923) = 40.9 exp(-1.2923) = 11.2 kPa
0.4882 203.15
vg = RT2/P2 =
= 8.855 m3/kg
11.2
v2 = (1-x) vf + x vg = 0.5 0.001375 + 0.5 8.855 = 4.428 m3/kg
V2 = mv2 = 2.214 m3

A straight line extrapolation


will give a negative pressure.

T
-70 -50

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12.25
Use the approximation given in problem 12.16 and Table B.4 to determine A and
B for refrigerant R-410A from properties at 0oC only. Use the equation to predict
the saturation pressure at 5oC and compare to table value.
dPsat
-2
dT = Psat (-B)(-T )
so we notice from Eq.12.7 and Table values from B.4.1 and A.5 that
ln Psat = A B/T

hfg 221.37 kJ/kg


B = R = 0.1145 kJ/kg-K = 1933.4 K
Now the constant A comes from the saturation pressure as
A = ln Psat + B/T = ln 798.7 +

1933.4
273.15 = 13.7611

Use the equation to predict the saturation pressure at 5oC as


ln Psat = A B/T = 13.7611 -

1933.4
273.15 + 5 = 6.8102

Psat = 907 kPa


compare this with the table value of Psat = 933.9 kPa and we have an
approximation 3% low. Notice hfg decreases so we could have used a lower value
for the average in the interval.

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12.26
The triple point of CO2 is -56.4oC. Predict the saturation pressure at that point
using Table B.3.

The lowest temperature in Table B.3 for CO2 is -50oC, so it must be extended to
-56.4oC = 216.75 K using the Clapeyron Eq. 12.7 integrated as in Ex. 12.1
Table B.3:

at T1 = -50oC = 223.15 K,

Table A.5:

R = 0.1889 kJ/kg-K

P1 = 682.3 kPa, hfg = 339.73 kJ/kg

P hfg (T - T1) 339.73 (216.75 - 223.15)


ln P = R
=
= -0.23797
T T1 0.1889 216.75 223.15
1
P = 682.3 exp(-0.23797) = 537.8 kPa
Notice from Table 3.2: P = 520.8 kPa so we are 3% high. As hfg becomes larger
for lower Ts we could have estimated a more suitable value for the interval from
-50 to -56.4oC

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12.27

Helium boils at 4.22 K at atmospheric pressure, 101.3 kPa, with hfg = 83.3
kJ/kmol. By pumping a vacuum over liquid helium, the pressure can be lowered,
and it may then boil at a lower temperature. Estimate the necessary pressure to
produce a boiling temperature of 1 K and one of 0.5 K.
Solution:
Helium at 4.22 K: P1 = 0.1013 MPa,
dPSAT

hFG

dT = TvFG

hFGPSAT
RT2

hFG = 83.3 kJ/kmol


P2

hFG 1
1
ln P = R [T T ]
1
1
2

For T2 = 1.0 K:
P2
1
1
83.3
ln 101.3 = 8.3145[4.22 1.0]

=> P2 = 0.048 kPa = 48 Pa

For T2 = 0.5 K:
P2
1
1
83.3
ln 101.3 = 8.3145[4.22 0.5]
P2 = 2.160110-6 kPa = 2.1601 10-3 Pa

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12.28
Using the properties of water at the triple point, develop an equation for the
saturation pressure along the fusion line as a function of temperature.
Solution:
The fusion line is shown in Fig. 2.3 as the S-L interphase. From Eq.12.5 we have
dPfusion hif
dT = Tvif
Assume hif and vif are constant over a range of Ts. We do not have any simple
models for these as function of T other than curve fitting. Then we can integrate
the above equation from the triple point (T1, P1) to get the pressure P(T) as
hif
T
P P1 = v ln T
if
1
Now take the properties at the triple point from B.1.1 and B.1.5
P1 = 0.6113 kPa,

T1 = 273.16 K

vif = vf vi = 0.001 0.0010908 = - 9.08 105 m3/kg


hif = hf hi = 0.0 (-333.4) = 333.4 kJ/kg
The function that approximates the pressure becomes
T
P = 0.6113 3.672 106 ln
T1

[kPa]

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12.29
Using thermodynamic data for water from Tables B.1.1 and B.1.5, estimate the
freezing temperature of liquid water at a pressure of 30 MPa.
P
dPif hif
H2O dT = Tv const
if

30 MPa

T.P.

T
At the triple point,
vif = vf - vi = 0.001 000 - 0.001 090 8 = -0.000 090 8 m3/kg
hif = hf - hi = 0.01 - (-333.40) = 333.41 kJ/kg
dPif
333.41
dT = 273.16(-0.000 090 8) = -13 442 kPa/K
at P = 30 MPa,
(30 000-0.6)
T 0.01 + (-13 442) = -2.2 oC

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12.30
Ice (solid water) at 3C, 100 kPa, is compressed isothermally until it becomes
liquid. Find the required pressure.
Water, triple point T = 0.01oC , P = 0.6113 kPa
Table B.1.1: vf = 0.001 m3/kg, hf = 0.01 kJ/kg,
Tabel B.1.5:
Clapeyron

vi = 0.001 0908 m3/kg, hi = -333.4 kJ/kg


dPif
hf - hi
333.4
=
=
dT (vf - vi)T -0.0000908 273.16 = -13 442 kPa/K

dPif
P dT T = -13 442(-3 - 0.01) = 40 460 kPa
P = Ptp + P = 40 461 kPa

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12.31
From the phase diagram for carbon dioxide in Fig. 2.5 and 2.4 for water what can
you infer for the specific volume change during melting assuming the liquid has a
higher h than the solid phase for those two substances.

The saturated pressure versus temperature has a positive slope for carbon dioxide
and a negative slope for water.
Clapeyron

dPif
hf - hi
=
dT (vf - vi)T

So if we assume hf - hi > 0 then we notice that the volume change in the melting
gives
Water:
vf - vi < 0 so vf < vi
Carbon dioxide:

vf - vi > 0

so

vf > v i

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12.32
A container has a double wall where the wall cavity is filled with carbon dioxide
at room temperature and pressure. When the container is filled with a cryogenic
liquid at 100 K the carbon dioxide will freeze so that the wall cavity has a mixture
of solid and vapor carbon dioxide at the sublimation pressure. Assume that we do
not have data for CO2 at 100 K, but it is known that at 90C: Psat = 38.1 kPa,
hIG = 574.5 kJ/kg. Estimate the pressure in the wall cavity at 100 K.
Solution:
For CO2 space: at T1 = -90 oC = 183.2 K , P1 = 38.1 kPa, hIG = 574.5 kJ/kg
For T2 = TcO2 = 100 K: Clapeyron

dPSUB hIG hIGPSUB


dT = TvIG RT2

P2 hIG
1
1
574.5
1
1
ln P = R [183.2 100] = 0.188 92 [183.2 100] = 13.81
1
or P2 = P1 1.00510-6 P2 = 3.8310-5 kPa = 3.8310-2 Pa

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12.33
Small solid particles formed in combustion should be investigated. We would like
to know the sublimation pressure as a function of temperature. The only
information available is T, hFG for boiling at 101.3 kPa and T, hIF for melting at
101.3 kPa. Develop a procedure that will allow a determination of the sublimation
pressure, Psat(T).

TNBP = normal boiling pt T.

Solid

TNMP = normal melting pt T.

101.3 kPa
PTP

TTP = triple point T.

Liquid
Vap.

T
TTP TNMP T NBP

1) TTP TNMP
T
P

TP

hFG
2 dT
(1/P
)
dP

SAT
SAT

RT
TP

2)

0.1013 MPa

TNMP

Since hFG const hFG NBP the integral over temperature becomes
hFG NBP 1
PTP
1
ln 0.1013 R [T
-T ]
NBP
TP

get PTP

3) hIG at TP = hG - hI = (hG - hF) + (hF - hI) hFG NBP + hIF NMP


Assume hIG const. again we can evaluate the integral
PSUB

ln P
TP

hIG 1
hIG
1

=
(1/P
)
dP

dT

[
T]
2
SUB
SUB

R
T
RT
TP
SUB

PTP

TTP

or PSUB = fn(T)

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Property Relations

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12.34
Use Gibbs relation du = Tds Pdv and one of Maxwells relations to find an
expression for (u/P)T that only has properties P, v and T involved. What is the
value of that partial derivative if you have an ideal gas?
du = Tds Pdv

divide this by dP so we get

u
s
v
v
v
= T P = T P
PT
PT
PT
TP
PT
where we have used Maxwell Eq.12.19. Now for an ideal gas we get
RT
Ideal gas: Pv = RT v = P
then the derivatives are
R
v
v
and
=P
= RTP2
T
P

PT
and the derivative of u is
R
u
v
v
= T P = T P P( RTP2) = 0
PT
TP
PT
This confirms that u is not sensitive to P and only a function of T.

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12.35
The Joule-Thomson coefficient J is a measure of the direction and magnitude of
the temperature change with pressure in a throttling process. For any three
properties x,y,z use the mathematical relation
x y z
= 1
yz zx xy
to show the following relations for the Joule-Thomson coefficient:
v
T v
TP
RT2 Z
T
J = =
=
CP
PCP TP
P h
Let x = T, y = P and z = h and substitute into the relations as:
T

Ph

P h
= 1
h T TP

h
Then we have the definition of specific heat as CP = so solve for the first
TP
term

1 P
1 h
T
J = = C / = C
P h
P hT
P PT

The last derivative is substituted with Eq.12.25 so we get


v
T v
TP
T
J = =
CP
P h
If we use the compressibility factor then we get
ZR RT Z
v RT Z
v
Pv = ZRT

= P + P =T+ P
TP
TP
TP
so then
RT2 Z
RT2 Z
v
T v=v + P v= P
TP
TP
TP
and we have shown the last expression also.
v
T v
TP
RT2 Z
T
J = =
=
CP
PCP TP
P h

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12.36
Find the Joule-Thomson coefficient for an ideal gas from the expression given in
Problem 12.35
v
T v
TP
RT2 Z
T
J = =
=
CP
PCP TP
P h
For an ideal gas: v = RT/P so then the partial derivative
R
RT
v
v
T v= P v=vv=0
=P
TP
TP
For an ideal gas Z = 1 so the very last derivative of Z is also zero.

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12.37
Start from Gibbs relation dh = Tds + vdP and use one of Maxwells equation to
get (h/v)T in terms of properties P, v and T. Then use Eq.12.24 to also find an
expression for (h/T)v.
Find

h
(hv)T and (T
)v

dh = Tds + vdP

and use Eq.12.18

(vh)T = T (vs )T + v(P


)
v T

=T

P
(T
)v + v(P
)
v T

Also for the second first derivative use Eq.12.24


h
P
P
(T
)v = T(Ts )v + v(T
)v = Cv + v(T
)v

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12.38
From Eqs. 12.23 and 12.24 and the knowledge that Cp > Cv what can you
conclude about the slopes of constant v and constant P curves in a T-s diagram?
Notice that we are looking at functions T(s, P or v given).
Solution:
The functions and their slopes are:
T
Constant v: T(s) at that v with slope
s v
T
Constant P: T(s) at that P with slope
s P
Slopes of these functions are now evaluated using Eq.12.23 and Eq.12.24 as
T
s -1 T
= = C
s P TP
p
-1
T
T s
= = C
T
s
v
v

v
Since we know Cp > Cv then it follows that T/Cv > T/Cp and therefore
T
T
>
s v
s P
which means that constant v-lines are steeper than constant P lines in a T-s
diagram.

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12.39
Derive expressions for (T/v)u and for (h/s)v that do not contain the properties
h, u, or s. Use Eq. 12.30 with du = 0.
P
P - T( )v
T
u
u
(T
)
(see Eqs. 12.33 and 12.34)
= - ( )T ( )v =
u
Cv
v
v
T

As dh = Tds + vdP => (

h
P
T
)
= T + v( )v = T - v( )s
v
s
s
v

But

s
s
(T
)
= - ( )T / ( )v = s
v
v
T

vT P
(h
)
= T + C ( )v
v
s
v T

P
)
T v
Cv

(Eq.12.20)

T(

(Eq.12.22)

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12.40
Evaluate the isothermal changes in the internal energy, the enthalpy and the
entropy for an ideal gas. Confirm the results in Chapters 3 and 6.
We need to evaluate duT, dhT and dsT for an ideal gas: P = RT/v.
From Eq.12.31 we get
duT = [ T

P
(T
)v P ] dvT = [ T ( Rv ) P ] dvT = [ P P] dvT = 0

From Eq.12.27 we get using v = RT/P


dhT = [ v T (

v
R
)
] dPT = [ v T ( P ) ] dPT = [ v v ] dPT = 0
P
T

These two equations confirms the statements in chapter 5 that u and h are
functions of T only for an ideal gas.
From Eq.12.32 or Eq.12.34 we get
v
P
dsT = ( )P dPT = ( )v dvT
T
T
R
R
= P dPT = v dvT
so the change in s can be integrated to find
P2
v2
s2 s1 = R ln P = R ln v
1

when T2 = T1

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12.41
Develop an expression for the variation in temperature with pressure in a constant
entropy process, (T/P)s, that only includes the properties PvT and the specific
heat, Cp. Follow the development for Eq.12.32.

(T
) =P s

s
(P
)T
s
(T
)P

v
)
T P T v
= - (C /T) = C ( )P
P
P T
-(

s
v
{(P
)T = -(T
)P, Maxwell relation Eq. 12.23 and the other is Eq.12.27}

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12.42
Use Eq. 12.34 to get an expression for the derivative (T/v)s. What is the general
shape of a constant s process curve in a T-v diagram? For an ideal gas can you say
a little more about the shape?
Equation 12.34 says

dT
P
ds = Cv T + ( )v dv
T
so then in a constant s process we have ds = 0 and we find
T P
(T
)
= C ( )v
s
v
v T
As T is higher the slope is steeper (but negative) unless the last term (P/T)v
counteracts. If we have an ideal gas this last term can be determined
P
(T
)v = Rv
P = RT/v

T R
P
(T
)
=
=

s
Cv v
Cv
v
and we see the slope is steeper for higher P and a little lower for higher T as Cv is
an increasing function of T.

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12.43
Show that the P-v-T relation as P(v b) = RT satisfies the mathematical relation
in Problem 12.35.
x y z
= 1
yz zx xy
Let (x, y, z ) be (P, v, T) so we have
P v T
= 1
vT TP Pv
The first derivative becomes, P = RT/(v b)
P
= RT (v b)-2 = P/(v b)
vT
The second derivative, v = b + RT/P
v
= R/P
TP
The third derivative, T = (P/R)(v b)
T
= (v b)/R
Pv
Substitute all three derivatives into the relation
RT
R vb
RT
1
P v T
P R = (v b) P = 1
=
2
vT TP Pv
(v b)
with the last one recognized as a rewrite of the original EOS.

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Volume Expansivity and Compressibility

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12.44

What are the volume expansivity p, the isothermal compressibility T, and the
adiabatic compressibility s for an ideal gas?
The volume expansivity from Eq.12.37 and ideal gas v = RT/P gives
1 R
1 v
1
p = v( )P = v ( P ) = T
T
The isothermal compressibility from Eq.12.38 and ideal gas gives
1 v
1
1
T = v( )T = v ( RT P2 ) =
P
P
The adiabatic compressibility s from Eq.12.40 and ideal gas
1 v
s = v( )s
P
From Eq.12.32 we get for constant s (ds = 0)
v
T v
T R
(T
)
= C ( )P = C P = C
s
P
p T
p
p
and from Eq.12.34 we get
C P
C
C
v
(T
)s = Tv (T
)v = Tv Rv = Pv
Finally we can form the desired derivative
Cv v
v
v
v
(P
)s = (T
)s (T
)
=

P Cp = kP
P s
1 v
1
1
v
1
s = v( )s = ( v) ( ) = kP = T
kP
k
P

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12.45
Assume a substance has uniform properties in all directions with V = LxLyLz and
show that volume expansivity p = 3T. Hint: differentiate with respect to T and
divide by V.
V = LxLyLz
From Eq.12.37
p =

LxLyLz
1 V
1
(
)
=
(
)P
V T P LxLyLz
T

LxLz Ly
LyLz Lx
LxLy Lz
=L L L (
)
+
(
)
+
( )
x y z T P LxLyLz T P LxLyLz T P
1
=L

1
1
x
y
z
(
)
+L (
)
+L (
)
P
P
x T
y T
z T P

= 3 T
This of course assumes isotropic properties (the same in all directions).

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12.46
Determine the volume expansivity, P, and the isothermal compressibility, T, for
water at 20C, 5 MPa and at 300C, and 15 MPa using the steam tables.
Water at 20oC, 5 MPa (compressed liquid)
1 v
1 v
P = v( )P v( )P ;
T
T

1 v
1 v
T = - v( )T - v( )T
P
P

Estimate by finite difference using values at 0oC, 20oC and 40oC,


1
0.001 0056 - 0.000 9977
P 0.000 9995
= 0.000 1976 oC-1
40 - 0
Using values at saturation, 5 MPa and 10 MPa,
1
0.000 9972 - 0.001 0022
= 0.000 50 MPa-1
T - 0.000 9995
10 - 0.0023
Water at 300oC, 15 MPa (compressed liquid)
1
0.001 4724 - 0.001 3084
P 0.001 377
= 0.002 977 oC-1
320 - 280
1
0.001 3596 - 0.001 3972
T - 0.001 377
= 0.002 731 MPa-1
20 - 10

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12.47
Use the CATT3 software to solve the previous problem.
The benefit of the software to solve for the partial derivatives is that we can
narrow the interval over which we determine the slope.
Water at 20oC, 5 MPa (compressed liquid)
1 v
1 v
P = v( )P v( )P ;
T
T

1 v
1 v
T = - v( )T - v( )T
P
P

Estimate by finite difference using values at 19oC, 20oC and 21oC,


1
0.000 9997 - 0.000 9993
P 0.000 9995
= 0.000 40 oC-1
21 - 19
Using values at saturation, 4.5 MPa and 5.5 MPa,
1
0.000 9993 - 0.000 9997
T - 0.000 9995
= 0.000 40 MPa-1
5.5 - 4.5
Water at 300oC, 15 MPa (compressed liquid)
1
0.001 385 - 0.001 369
= 0.011 619 oC-1
P 0.001 377
302 - 298
1
0.001 373 - 0.001 381
T - 0.001 377
= 0.002 905 MPa-1
16 - 14

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12.48
A cylinder fitted with a piston contains liquid methanol at 20C, 100 kPa and
volume 10 L. The piston is moved, compressing the methanol to 20 MPa at
constant temperature. Calculate the work required for this process. The isothermal
compressibility of liquid methanol at 20C is 1.22 10-9 m2/N.
2
2
v

w
=
Pdv
=
P
dP
=
1 2
vT PdPT
P T T

( )

For v constant & T constant the integral can be evaluated


1w2

vT 2 2
= - 2 P2 - P 1

For liquid methanol, from Table A.4: = 787 m3/kg


V1 = 10 L, m = 0.01 787 = 7.87 kg
1W2

0.011220
(20)2 - (0.1)2
2

] = 2440 J = 2.44 kJ

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12.49
For commercial copper at 25oC (see table A.3) the speed of sound is about 4800
m/s. What is the adiabatic compressibility s?
From Eq.12.41 and Eq.12.40
c2 =

P
(P
)
=
v
(
) =1
s
v s
2

1
1
=
s
v
-v

P s

( )

Then we get using density from Table A.3


s =

1
1
s2 m 3
1000
1
=
=
2
2
2
2
kPa
m
kg
c 4800 8300
4800 8300

= 5.23 109 kPa1

Cu

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12.50

Use Eq. 12.32 to solve for (T/P)s in terms of T, v, Cp and p. How large a
temperature change does 25oC water (p = 2.1 10-4 K-1) have, when
compressed from 100 kPa to 1000 kPa in an isentropic process?
From Eq.12.32 we get for constant s (ds = 0) and Eq.12.37

(T
) = T (v ) = CTp p v
P s Cp T P
Assuming the derivative is constant for the isentropic compression we estimate
with heat capacity from Table A.3 and v from B.1.1
T
T
Ts =
P
=
v Ps
P s s Cp p

( )

273.15 + 25
2.1 10-4 0.001003 (1000 100)
4.18

= 0.013 K

barely measurable.

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Borgnakke and Sonntag


12.51
Sound waves propagate through a media as pressure waves that cause the media
to go through isentropic compression and expansion processes. The speed of
sound c is defined by c 2 = (P/)s and it can be related to the adiabatic
compressibility, which for liquid ethanol at 20C is 9.4 10-10 m2/N. Find the
speed of sound at this temperature.

c2 =

P
(P
)
= v ( )s =
s

v
1

1
1
=
s
v
-v

s
P

From Table A.4 for ethanol,

c=

(940101

)
783

-12

( )

= 783 kg/m3
1/2

= 1166 m/s

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Borgnakke and Sonntag


12.52
Use Table B.3 to find the speed of sound for carbon dioxide at 2500 kPa near
100oC. Approximate the partial derivative numerically.
c2 =

(P
) = v (P
)
s
v s
2

We will use the 2000 kPa and 3000 kPa table entries. We need to find the change
in v between two states with the same s at those two pressures.
At 100oC, 2500 kPa:

s = (1.6843 + 1.5954)/2 = 1.63985 kJ/kg-K,


v = (0.03359 + 0.02182)/2 = 0.027705 m3/kg

2000 kPa, s = 1.63985 kJ/kg-K:


3000 kPa, s = 1.63985 kJ/kg-K:
c2 v2

(P
) = 0.027705
v
s

v = 0.031822 m3/kg
v = 0.0230556 m3/kg

3000 - 2000
kJ
J
0.0230556-0.031822 kg = 87 557.8 kg

c = 87 557.8 = 295.9 m/s

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12.53
Use the CATT3 software to solve the previous problem.
At 100oC, 2500 kPa:

s = 1.636 kJ/kg-K, v = 0.02653 m3/kg

101oC, s = 1.636 kJ/kg-K:


99oC, s = 1.636 kJ/kg-K:
c2 v2

(P
) = 0.02653
v
s

v = 0.02627 m3/kg, P = 2.531 MPa


v = 0.02679 m3/kg, P = 2.469 MPa
2

2531 - 2469
kJ
J
=
83
919.5
0.02627 - 0.02679 kg
kg

c = 83 919.5 = 289.7 m/s

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Borgnakke and Sonntag


12.54
Consider the speed of sound as defined in Eq. 12.41. Calculate the speed of sound
for liquid water at 20C, 2.5 MPa, and for water vapor at 200C, 300 kPa, using
the steam tables.
From Eq. 12.41:

c2 =

P
(P
)
=
-v
(
)
s
v s
2

Liquid water at 20oC, 2.5 MPa, assume


P
(P
)
( )
s
v
v

Using saturated liquid at 20oC and compressed liquid at 20oC, 5 MPa,


9995
5-0.0023
MJ
(0.001 002+0.000
) (0.000 9995-0.001
2
002) kg
2

c2 = -

J
kg
c = 1415 m/s

= 2.002106
=>

Superheated vapor water at 200oC, 300 kPa


v = 0.7163 m3/kg, s = 7.3115 kJ/kg K
At P = 200 kPa & s = 7.3115 kJ/kg K: T = 157oC,

v = 0.9766 m3/kg

At P = 400 kPa & s = 7.3115 kJ/kg K: T = 233.8oC, v = 0.5754 m3/kg


0.400-0.200
c2 = -(0.7163)2 0.5754-0.9766
=>
c = 506 m/s

) MJ
kg = 0.2558 10

m2/s2

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Borgnakke and Sonntag


12.55
Use the CATT3 software to solve the previous problem.

(P
) = -v (P
)
s
v s
P
P
Liquid water at 20 C, 2.5 MPa, assume ( )s ( )s
v
v
From Eq. 12.41:

c2 =

and CATT3: v = 0.001001 m3/kg, s = 0.2961 kJ/kg-K


Using liquid at 3 MPa and 2 MPa at the same s = 0.2961 kJ/kg-K,
c2 = - 0.0010012

-2
MJ
(0.001 -30.001
)
001 kg

J
kg
c = 1001 m/s

= 1.002106
=>

Superheated vapor water at 200oC, 300 kPa


CATT3:

v = 0.7163 m3/kg, s = 7.311 kJ/kg K

At P = 290 kPa & s = 7.311 kJ/kg K: T = 196.2oC, v = 0.7351 m3/kg


At P = 310 kPa & s = 7.311 kJ/kg K: T = 203.7oC, v = 0.6986 m3/kg
0.310 - 0.290
c2 = -(0.7163)2 0.6986 - 0.7351
=>
c = 530 m/s

) MJ
kg = 0.28114 10

m2/s2

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Borgnakke and Sonntag


12.56
Soft rubber is used as a part of a motor mounting. Its adiabatic bulk modulus is Bs
= 2.82 106 kPa, and the volume expansivity is p = 4.86 10-4 K-1. What is the
speed of sound vibrations through the rubber, and what is the relative volume
change for a pressure change of 1 MPa?
From Eq.12.41 and Eq.12.40
Bs
P
1
1
2 P
=
=
c =
= v
=
s
v s
s
1 v
-v

P s
2

( )

( )

( )

= 2.82 106 1000 Pa / 1100 kg/m3 = 2.564 106 m2/s2


c = 1601 m/s
If the volume change is fast it is isentropic and if it is slow it is isothermal. We
will assume it is isentropic
1 V
1
(
)
=

s
s
V P
Bs
then
V
P
1000
4
V = Bs = 2.82 106 = 3.55 10

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Borgnakke and Sonntag


12.57
Liquid methanol at 25oC has an adiabatic compressibility of 1.05 10-9 m2/N.
What is the speed of sound? If it is compressed from 100 kPa to 10 MPa in an
insulated piston/cylinder, what is the specific work?
From Eq.12.41 and Eq.12.40 and the density from table A.4
c2 =

P
1
1
(P
)
(
)
=
=
v
=
s
v s
1.05 10-9 787
2

= 1.210 106 m2/s2


c = 1100 m/s
The specific work becomes
2

w = P
P dP
dv =
P (-sv ) dP =
sv P dP = s v
1

= s v 0.5

2
2
(P2 P1)

0.5
= 1.05 10-9 m2/N 787 m3/kg (10 0002 1002) 10002 Pa2
= 66.7 J/kg

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12.58

Use Eq. 12.32 to solve for (T/P)s in terms of T, v, Cp and p. How much higher
does the temperature become for the compression of the methanol in Problem
12.57? Use p = 2.4 10-4 K-1 for methanol at 25oC.
From Eq.12.32 we get for constant s (ds = 0) and Eq.12.37

(T
) = T (v ) = CTp p v
P s Cp T P
Assuming the derivative is constant for the isentropic compression we estimate
with heat capacity and density (v = 1/) from Table A.4
T
T
Ts =
P =
v Ps
P s s Cp p

( )

298.15 K kg K
1 m3
-4 -1
= 2.55
kJ 2.4 10 K 787 kg (10 000 100) kPa
= 0.353 K

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Borgnakke and Sonntag


12.59
Find the speed of sound for air at 20C, 100 kPa using the definition in Eq. 12.41
and relations for polytropic processes in ideal gases.
From problem 12.41 :

c2 =

(P
) = -v (P
)
s
v s
2

For ideal gas and isentropic process, Pvk = constant


P
P = Cv-k
= -kCv-k-1 = -kPv-1
v
c2 = -v2(-kPv-1) = kPv = kRT
c = kRT = 1.40.287293.151000 = 343.2 m/s

For every 3
seconds after the
lightning the
sound travels
about 1 km.

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Borgnakke and Sonntag

Equations of State

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12.60
Use Table B3 and find the compressibility of carbon dioxide at the critical point.
Pv = Z RT
At the critical point from B.3:
P = 7377.3 kPa, T = 31C = 304.15 K, v = 0.002139 m3/kg
from A.5:

R = 0.1889 kJ/kg-K
Pv 7377.3 0.002139
Z = RT = 0.1889 304.15 = 0.27

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12.61
Use the equation of state as shown in Example 12.3 where changes in enthalpy
and entropy were found. Find the isothermal change in internal energy in a similar
fashion; do not compute it from enthalpy.
The equation of state is
Pv
P
RT = 1 C T4
and to integrate for changes in u from Eq.12.31 we make it explicit in P as
v
P = T4 ( R T3 + C )1
Now perform the partial derivative of P
P
(T
)v = 4 T3 ( Rv T3 + C )1 T4 ( Rv T3 + C )2 3 Rv T2
P P2 v
P
P Pv P
Pv
= 4 T 4 3 R T2 = 4 T 3 T RT = T [ 4 3 RT ]
T
Substitute into Eq.12.31
P
Pv
duT = [ T ( )v P ] dvT = [ P( 4 3
RT) P ] dvT
T
Pv
P
= 3 P ( 1 RT) dvT = 3 P C 4 dvT
T
The P must be eliminated in terms of v or the opposite, we do the latter as from
the equation of state
RT
RT
1

dvT = 2 dPT
v = P C R 3
P
T
so now
P2
1
duT = 3 C 4 dvT = 3 C R 3 dPT
T
T
and the integration becomes
u2 u1 = 3 C R T3 (P2 P1)

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Borgnakke and Sonntag


12.62
Use Table B.4 to find the compressibility of R-410A at 60oC and a) saturated
liquid b) saturated vapor and c) 3000 kPa.
Table A.2:
a)

R = 8.31451 / 72.585 = 0.1145 kJ/kg-K

Table B.4.1: P = 3836.9 kPa, v = 0.001227 m3/kg


Pv 3836.9 0.001227
Z = RT = 0.1145 333.15 = 0.1234

b)

Table B.4.1: P = 3836.9 kPa, v = 0.00497 m3/kg


Pv 3836.9 0.00497
Z = RT = 0.1145 333.15 = 0.5

c)

Table B.4.2: P = 3000 kPa, v = 0.00858 m3/kg


Pv 3000 0.00858
Z = RT = 0.1145 333.15 = 0.675

The R-410A is not an ideal gas at any of these states.

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12.63
Use a truncated virial EOS that includes the term with B for carbon dioxide at 20o
C, 1 MPa for which B = 0.128 m3/kmol and T(dB/dT) = 0.266 m3/kmol. Find
the difference between the ideal-gas value and the real-gas value of the internal
energy.
R BR RT dB
RT BRT
P
virial eq.:
P= v + 2 ;
(
)
=
+
+ 2 (dT )
T v v v2
v
v
v
u-u* = -

v
P
[ (T
) v - P]dv = [ RT
v

EA

(dB
dT)]dv
A

EA

RT
dB
= v T ( dT)
A

Solution of virial equation (quadratic formula):

RT 8.3145293.15
1 RT

v = 2 P 1 + 1 + 4BP/RT
where: P =
= 2.43737
1000
E

EA

EA

EA

[1 +

EA

1
v = 2 2.43737
A

1 + 4(-0.128)/2.43737

EA

] = 2.3018 m /kmol
A

Using the minus-sign root of the quadratic formula results in a compressibility


factor < 0.5, which is not consistent with such a truncated equation of state.
u u* =

-8.3145 293.15
0.266 / 44.01 = 6.4 kJ/kg
2.3018

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12.64
Solve the previous Problem with Table B.3 values and find the compressibility of
the carbon dioxide at that state.
B.3: v = 0.05236 m3/kg, u = 327.27 kJ/kg,
E

A5: R = 0.1889 kJ/kg-K

Pv 1000 0.05236
Z = RT = 0.1889 293.15 = 0.9455
A

close to ideal gas

To get u* let us look at the lowest pressure 400 kPa, 20oC: v = 0.13551 m3/kg
and u = 331.57 kJ/kg.
E

Z = Pv/RT = 400 0.13551/(0.1889 293.15) = 0.97883


It is not very close to ideal gas but this is the lowest P in the printed table.
u u* = 327.27 331.57 = 4.3 kJ/kg
E

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12.65
A gas is represented by the virial EOS with the first two terms, B and C. Find an
expression for the work in an isothermal expansion process in a piston-cylinder.

RT B(T) RT C(T) RT
P= v +
+
+ .
v2
v3

Virial EOS:

= RT[ v1 + B(T) v2 + C(T) v3 + .. ]


E

The work is

1
2
3
w=
[ v + B(T) v + C(T) v + .. ] dv
P dv = RT
A

EA

With just the first two terms we get


v2
1
1
1
2
2
w = RT [ ln v B(T) (v2 v1 ) 2 C(T) (v2 v1 ) ]
A

1
E

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12.66
Extend problem 12.63 to find the difference between the ideal-gas value and the
real-gas value of the entropy and compare to table B.3.
Calculate the difference in entropy of the ideal-gas value and the real-gas value
for carbon dioxide at the state 20C, 1 MPa, as determined using the virial
equation of state. Use numerical values given in Problem 12.63.
CO2 at T = 20oC, P = 1 MPa
E

RT/P*

RT/P*

*
sP*
A

P
- sP =
dv ;
T v
A

( )

ID Gas:

EA

R
P
- sP =
v dv = R ln *

*
sP*
A

EA

v(P)

v(P)
RT/P*
E

P
P
* + T v dv
P

Therefore, at P:

sP - sP = -R ln
A

( )

EA

v(P)

RT BRT
P
R BR RT dB
P= v + 2
and
= v + 2 + 2 dT
v
T
v
v
v
Integrating,
P
RT
dB
1 P*
*
sP - sP = -R ln * + R ln * + R B + T dT
v - RT
P
Pv
RT
dB 1
= R ln Pv + B + T dT v
virial:

( )

( )](
( )) ]

( )

Using values for CO2 from solution 12.63 and R = 0.1889 kJ/kgK
A

2.437 37
1
*
sP - sP = 0.1889 ln 2.3018 + -0.128 + 0.266 2.3018
= 0.02214 kJ/kg K

From Table B.3 take the ideal as the lowest P = 400 kPa:
*

sP - sP = 1.7904 1.6025 + 0.1889 ln(400/1000) = 0.0148 kJ/kgK


A

The lowest P = 400 kPa in B3 is not exactly ideal gas ( Z = Pv/RT = 0.9788)

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12.67
Two uninsulated tanks of equal volume are connected by a valve. One tank
contains a gas at a moderate pressure P1, and the other tank is evacuated. The
A

valve is opened and remains open for a long time. Is the final pressure P2 greater
A

than, equal to, or less than P1/2? Hint: Recall Fig. 12.5.
A

Assume the temperature stays constant then for an ideal gas the pressure will be
reduced to half the original pressure. For the real gas the compressibility factor
maybe different from 1 and then changes towards one as the pressure drops.
VA = VB V2 = 2V1, T2 = T1 = T
P2 V1 Z2 mRT
1 Z2
=
=
P1 V2 Z1 mRT
2 Z1
A

If T > TB, Z2 < Z1


A

Z
1T > T
B

1.0

1
P <2
1
A

P2

B
EVAC.

A
GAS

P2 1
If T < TB, Z2 > Z1 P > 2
1
A

2
2

P2

T < T
B
1
P1 P

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12.68
Show how to get the constants in Eq.12.52 for van der Waals EOS.
RT
a
2
vb v
The conditions at the critical point relate to these derivatives
RT
2a
6a
P
2P
(v)T = (v b)2 + v3
;
( 2)T = (v2RT
3 4
b)
v
v
van der Waals EOS:

P=

Set both derivatives to zero at the critical point

RTc
(vc b)

+
A

2a
3
vc
A

=0

2RTc

(1) ;

(vc b)

6a
4

vc

=0

(2)

we also have from the EOS


Pc =

RTc
a
2
vc b v

(3)

Now we need to solve theses three equations for vc, a and b. Solve the first
equation for a and substitute into the second equation to give
RTc
3RTc
2a
6a
=
=>
=
substitute into Eq.(2)
3
2
4
2
vc (vc b)
vc vc (vc b)
A

3RTc
vc (vc b)

2RTc

now solve to get

(vc b)3

vc = 3b

Substitute back into the first equation to get


RTc
27
3
2a=
2 vc = RTc 4 b
(vc b)
A

Now finally substitute a and vc into the EOS Eq.(3) to get b.


27

RTc
a RTc RTc 8 b
Pc =
2 = 2b
= RTc (0.5 3/8) /b
vc b v
9 b2
A

The result is as in Eq.12.52.

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12.69
Show that the van der Waals equation can be written as a cubic equation in the
compressibility factor involving the reduced pressure and reduced temperature as
Pr
A

27 Pr2
27 Pr

+
Z
=0
64 T2
512 Tr 3
r

(8T + 1)

Z3

EA

Z2

AE

EA

RT a
P = v-b - 2
v

van der Waals equation, Eq.12.55:

2 2
27 R TC
a = 64 P
C
A

RTC
b = 8P
C

EA

EA

AE

AE

v2(v-b)
multiply equation by P
A

Get:

RT
a
ab
v3 - (b + P ) v2 + (P) v - P = 0
E

Multiply by

P3
Pv
3 3 and substitute Z = RT
R T

Get:

bP
aP
abP2
2
(RT + 1) Z + ( 2 2) Z ( 3 3) = 0
RT
R T

Z3
A

Substitute for a and b, get:


Pr
27 Pr2
27 Pr

Z3 (8T + 1) Z2 +
3=0
2 Z
512
T
r
6
4
T
r
r

EA

EA

AE

Where

P
Pr = P ,
c
A

EA

AE

T
Tr = T
c
A

EA

AE

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12.70
Evaluate changes in an isothermal process for u, h and s for a gas with an
equation of state as P (v b) = RT.
From Eq.12.31 we get
duT = [ T

P
(T
)v P ] dvT = [ T ( v R b ) P ] dvT = [ P P] dvT = 0
A

From Eq.12.27 we get using v = b + RT/P


dhT = [ v T (
A

v
R
)
] dPT = [ v T ( P ) ] dPT = b dPT
P
T
A

From Eq.12.32 or Eq.12.34 we get


v
P
dsT = ( )P dPT = ( )v dvT
T
T
A

R
R
= P dPT = v b dvT
A

Now the changes in u, h and s can be integrated to find


u2 u1 = 0
b dP = b(P2 P1)
h2 h1 =
A

EA

P2
v2 b
s2 s1 = R ln P = R ln v b
1

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12.71
Develop expressions for isothermal changes in internal energy, enthalpy and
entropy for a gas obeying the van der Waals equation of state.
RT a
P = v-b 2
v

van der Waals equation of state:

P
(T
)v = v-bR
P
RT RT a
(uv)T = T(T
)v - P = v-b
v-b +
v
A

P
a
1 1
(u2-u1)T = [T
dv = a(v v )
- P]dv =

2
v
T

v
1
2
A

( )

EA

EA

1 1
(h2-h1)T = (u2-u1)T + P2v2 - P1v1 = P2v2 P1v1 + a(v v )
1
2
A

v -b
P
R dv = R ln 2
(s2-s1)T =
dv
=

v1-b
v-b
T v
A

( )

EA

EA

( )
A

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12.72
Consider the following equation of state, expressed in terms of reduced pressure
2

and temperature: Z = 1 + (Pr/14Tr)[1 6Tr ]. What does this predict for the
reduced Boyle temperature?
A

Pr
Pv
6
Z = RT = 1 + 14 T (1 - 2)
Tr
r
A

1
6
Z
= 14P T (1 - 2)
P
T

Tr
c r
A

To find the Boyle temperature we must have


Lim Z
= 0 at Tboyle
P0 P T
A

The above derivative is then zero if:


(1 - T62) = 0 Tr = 6 = 2.45
r
A

EA

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12.73
Use the result of Problem 12.35 to find the reduced temperature at which the
Joule-Thomson coefficient is zero, for a gas that follows the EOS given in
Problem 12.72
Pr
Pv
6
Z = RT = 1 + 14 T (1 - 2)
Tr
r
From Problem 12.35
v
T v
TP
RT2 Z
T
J = =
=
CP
PCP TP
P h
A

AE

Pr -2
Pr
-2
-3
Z
= - 14T Tr (1 6 Tr ) + 14 T ( 12 Tr /Tc )
T P
c
r
A

Pr -2
-2
= 14T Tr ( 18 Tr - 1)
c
A

-2

So this is zero for 18 Tr = 1


A

or

Tr = 18
A

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12.74
RT a
What is the Boyle temperature for the following equation of state: P = v-b - 2
v T
where a and b are constants.
A

RT
a
P = v-b 2
vT
v-b
Multiplying by P gives:
Using for TBoyle:
A

RT a(1-b/v)
v b = P PvT

Z-1
1 lim
RT
lim Z
( ) = lim
= RT P0(v - P )
P0 P T
P0 P-0
A

a(1-0)
a
(v RT
)
=
b

=
b

= 0 at TBoyle
P
RTT
RT2

lim

P0
A

or

TBoyle =
A

a
Rb =
EA

2
27 R TC 1 8PC
64 PC R RTC =
E

EA

27
T
8 C
EA

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12.75
Determine the reduced Boyle temperature as predicted by an equation of state (the
experimentally observed value for most substances is about 2.5), using the van der
Waals equation and the RedlichKwong equation. Note: It is helpful to use Eqs.
12.47 and 12.48 in addition to Eq. 12.46
lim Z
The Boyle temp. is that T at which
( ) =0
P0 P T
A

1 lim
RT
lim Z
lim Z-1
(
)
=
=
(
v
P0 P T
P0 P-0
RT P0
P)
RT a
van der Waals:
P = v-b 2
v
v-b
multiply by P , get
RT a(v-b)
RT
a(1-b/v)
v-b = P or v - P = b Pv
2
Pv
But

a(1-0)
lim Z
& RT P0( )T = b RT = 0
P
a 27
or TBoyle = Rb = 8 TC = 3.375 TC
RT
a
Redlich-Kwong:
P = v-b
v(v+b)T1/2
as in the first part, get
RT
a(1-b/v)
v- P =b
Pv(1+b/v)T1/2
A

only at TBoyle

a(1-0)
lim Z
& RT P0( )T = b
=0
P
Pv(1+0)T1/2
A

or

3/2
TBoyle
A

only at TBoyle
A

2 5/2
PC
a 0.427 48 R TC
= Rb =

RPC
0.08 664 R TC
E

0.427 48 2/3
TBoyle = (0.086 64) TC = 2.9 TC
E

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12.76
One early attempt to improve on the van der Waals equation of state was an
expression of the form
RT a
P = v-b - 2
vT
A

Solve for the constants a, b, and vC using the same procedure as for the van der
Waals equation.
From the equation of state take the first two derivatives of P with v:
A

RT
2a
(P
) = - (v-b)
2+ 3
v T
vT

2P
2RT 6a
and ( 2 )T = v
(v-b)3 v4T
Since both these derivatives are zero at the critical point:
RT
2a
2RT 6a
and =0
2+ 3 =0
(v-b) v T
(v-b)3 v4T
RTC
a
Also,
PC = v -b 2
vC TC
C
A

solving these three equations:


3

vC = 3b,
A

2
27 R TC
a = 64 P ,
C
E

RTC
b = 8P
A

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12.77
Develop expressions for isothermal changes in internal energy, enthalpy and
entropy for a gas obeying Redlich-Kwong equation of state.
Redlich-Kwong equation of state:

P=

RT
a

v b v(v + b)T1/2
A

P
(T
)v = v R b + 2v(v +ab)T
A

3/2

From Eq.12.31
2

v2 + b
v1
3a
3a
(u2 u1)T =
dv
=
ln
[(
)
(
2v(v + b)T1/2
1/2
v2
v1 + b)]
2bT

AE

We find change in h from change in u, so we do not do the derivative in


Eq.12.27. This is due to the form of the EOS.
v2 + b
v1
3a
(h2 h1)T = P2v2 P1v1
1/2 ln
v2
v1 + b
2bT
A

[(

)(

)]

Entropy follows from Eq.12.35


2

R
a/2
(s2 s1)T =
+
3/2 dv
v b v(v + b)T
A

(vv bb) 2bTa


2

= R ln

3/2
A

[(v v+ b)(v v+ b)]

ln

2
E

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12.78
Determine the second virial coefficient B(T) using the van der Waals equation of
state. Also find its value at the critical temperature where the experimentally
observed value is about 0.34 RTc/Pc.
A

A
E

RT
where Eq. 12.44: = P v

lim
B(T) = - P0

From Eq.12.48:

From Eq. 12.51:


RT a
v-b
P = v-b - 2
which we can multiply by P , get
v
RT a(v-b)
RT
a(1-b/v)
v-b= P
or v P = b Pv
2
Pv

van der Waals:

Taking the limit for P -> 0 then (Pv -> RT and v -> ) we get :
RTC 1 27 TC
B(T) = b a/RT = P ( 8 64 T )
C
A

where a,b are from Eq.12.52. At T = TC then we have


RTC 19
RTC
B(TC) = P ( - 64) = 0.297 P
C
C
A

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12.79
Determine the second virial coefficient B(T) using the Redlich-Kwong equation
of state. Also find its value at the critical temperature where the experimentally
observed value is about 0.34 RTc/Pc.
A

A
E

RT
where Eq.12.44: = P v

lim
B(T) = - P0

From Eq.12.48:

For Redlich Kwong the result becomes


RT
a(1- b/v)
v P =b
Pv(1 + b/v) T1/2
A

Taking the limit for P -> 0 then (Pv -> RT and v -> ) we get :
a
=> B(T) = b
RT3/2
Now substitute Eqs. 12.54 and 12.55 for a and b,
RTC
TC3/2
B(T) = P
0.08664 - 0.42748 T

C
A

AE E

and evaluated at TC it becomes


RTC
RTC
B(TC) = P
0.08664 - 0.42748 = 0.341 P
C
C

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12.80
Oxygen in a rigid tank with 1 kg is at 160 K, 4 MPa. Find the volume of the tank
by iterations using the Redlich-Kwong EOS. Compare the result with the ideal
gas law.
For the ideal gas law:
Pv = RT
so v = RT/P
v = 0.2598 160 / 4000 = 0.0104 m3/kg ; V = mv = 0.0104 m3
E

For Redlich-Kwong, Eq.12.53 and oxygen


Pc = 5040 kPa;
Tc = 154.6 K;
R = 0.2598 kJ/kg K
RTc
0.2598 154.6
b = 0.08664 P = 0.08664
= 0.000 690 5 m3/kg
5040
c
A

5/2

R2Tc
0.25982 154.65/2
a = 0.427 48 P = 0.427 48
= 1.7013
5040
c
E

P=

RT
a

v b v(v + b)T1/2
A

trial and error to get v due to nonlinearity

v = 0.01 m3/kg
v = 0.008 m3/kg
v = 0.0075 m3/kg
v = 0.007 m3/kg

P = 4465.1 1279.9 = 3185.2 kPa too low


P = 5686.85 1968.1 = 3718.8 kPa too low
P = 6104.41 2227.43 = 3876.98 kPa
P = 6588.16 2541.70 = 4046.46 kPa

Now we interpolate between the last two entries and check


v = 0.00714 m3/kg P = 6445.15 2447.3 = 3997.8 kPa OK
V = mv = 0.00714 m3 (69% of the ideal gas value)
E

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12.81
A flow of oxygen at 230 K, 5 MPa is throttled to 100 kPa in a steady flow
process. Find the exit temperature and the specific entropy generation using
Redlich-Kwong equation of state and ideal gas heat capacity. Notice this becomes
iterative due to the non-linearity coupling h, P, v and T.
C.V. Throttle. Steady single flow, no heat transfer and no work.
Energy eq.:

h1 + 0 = h2 + 0
A

so constant h

Entropy Eq.: s1 + sgen = s2


A

so entropy generation
A
E

Find the change in h from Eq.12.26 assuming Cp is constant.


A

A
E

Redlich-Kwong equation of state:

RT
a

v b v(v + b)T1/2

P=
A

P
(T
)v = v R b + 2v(v +ab)T
A

3/2

From Eq.12.31
2

v2 + b
v1
3a
3a
(u2 u1)T =
dv
=
ln
[(
)
(

1/2
v2
v1 + b)]
2bT1/2
2v(v + b)T
A

AE

We find change in h from change in u, so we do not do the derivative in


Eq.12.27. This is due to the form of the EOS.
v2 + b
v1
3a
(h2 h1)T = P2v2 P1v1
ln
v2
v1 + b
2bT1/2
A

[(

)(

)]

Entropy follows from Eq.12.35


2

R
a/2
(s2 s1)T =
+
3/2 dv
v b v(v + b)T
A

(vv bb) 2bTa


2

= R ln

3/2
A

[(v v+ b)(v v+ b)]


2

ln

2
E

Tc = 154.6 K;
R = 0.2598 kJ/kg K
Pc = 5040 kPa;
RTc
0.2598 154.6
b = 0.08664 P = 0.08664
= 0.000 690 5 m3/kg
5040
c
A

A
E

5/2

R2Tc
0.25982 154.65/2
a = 0.427 48 P = 0.427 48
= 1.7013
5040
c
E

We need to find T2 so the energy equation is satisfied


A

A
E

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h2 h1 = h2 hx + hx h1 = Cp(T2 T1) + (h2 h1)T = 0
A

and we will evaluate it similar to Fig. 12.4, where the first term is done from state
x to 2 and the second term is done from state 1 to state x (at T1 = 230 K). We do
this as we assume state 2 is close to ideal gas, but we do not know T2.
We first need to find v1 from the EOS, so guess v and find P
A

A
E

A
E

A
E

P = 5796.0 872.35 = 4924

v1 = 0.011 m /kg
A

too low

v1 = 0.01082 m /kg P = 5899.0 900.7 = 4998.3 OK


Now evaluate the change in h along the 230 K from state 1 to state x, that requires
a value for vx. Guess ideal gas at Tx = 230 K,
3

vx = RTx/P2 = 0.2598 230/100 = 0.59754 m3/kg


From the EOS:
P2 = 100.1157 0.3138 = 99.802 kPa (close)
A few more guesses and adjustments gives
vx = 0.59635 m3/kg; P2 = 100.3157 0.3151 = 100.0006 kPa OK
E

A
E

3a
ln
2bT1/2

(hx h1)T = Pxvx P1v1


A

[(v v+ b)(v v+ b)]


x

0.59704 0.01082
= 59.635 5000 0.01082 243.694 ln [

]
0.59635 0.01151
= 59.635 54.1 + 14.78335 = 20.318 kJ/kg
A

From energy eq.: T2 = T1 (hx h1)T/Cp = 230 20.318 / 0.922 = 208 K


Now the change in s is done in a similar fashion,
A

sgen = s2 s1 = (sx s1)T + s2 sx


A

(vv bb) 2bTa

= R ln

3/2
A

[(v v+ b)(v v+ b)] + C

ln

x
E

p
A

T2
ln T
A

0.59566
208
= 0.2598 ln(0.0101295) 0.35318 ln (0.94114) + 0.922 ln(230)
A

= 1.05848 + 0.021425 0.092699


= 0.987 kJ/kg K

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Generalized Charts

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12.82
How low should the pressure be so that nitrous oxide (N2O) gas at 278.6 K can be
treated as an ideal gas with 5% accuracy or better?
A

A
E

From Table A.2:

Tc = 309.6 K,
A

A
E

278.6
Pc = 7.24 MPa => Tr1 = 309.6 = 0.9
A

Look in Fig. D.1 following the curve Tr1 = 0.9 to the point where Z = 0.95
A

Pr1 = 0.125
A

so
P < 0.125 7.24 MPa = 0.9 MPA = 900 kPa

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12.83
Nitrous oxide (N2O) at 278.6 K is at a pressure so that it can be in a two-phase
state. Find the generalized enthalpy departure for the two saturated states of liquid
and vapor.
A

A
E

From Table A.2:

278.6
Pc = 7.24 MPa => Tr1 = 309.6 = 0.9

Tc = 309.6 K,
A

From Fig. D.2:


Saturated liquid:
Saturated vapor:

(h*- hf)/RTc = 4.08;


E

(h - hg)/RTc = 0.875
A

A
E

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12.84
Find the heat of evaporation, hfg, for R-134a at 0C from the generalized charts
and compare to the value in Table B.5.
A

From Table A.2:

273.15
Pc = 4.06 MPa => Tr1 = 374.2 = 0.73

Tc = 374.2 K,
A

From Fig. D.2:


(h*- hf)/RTc = 4.7;

Saturated liquid:

(h - hg)/RTc = 0.3
hfg = hg - hf = RTc [-0.3 (-4.7)] = 4.4 RTc
Saturated vapor:
A

A
E

A
E

= 4.4 0.08149 374.2 = 134.2 kJ/kg


Table B.5.1: hfg = 198.36 kJ/kg
A

The approximation is not very good and can be improved by using the
accentric factor.

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12.85
A 200-L rigid tank contains propane at 9 MPa, 280C. The propane is then
allowed to cool to 50C as heat is transferred with the surroundings. Determine
the quality at the final state and the mass of liquid in the tank, using the
generalized compressibility chart, Fig. D.1.
Propane C3H8: V = 0.2 m3, P1 = 9 MPa, T1 = 280oC = 553.2 K
E

cool to T2 = 50 oC = 323.2 K
E

From Table A.2:

Tc = 369.8 K,
A

Pc = 4.25 MPa

A
E

9
553.2
Pr1 = 4.25 = 2.118, Tr1 = 369.8 = 1.496
A

v2 = v1 =
A

Z1RT1
P1
A

From Fig. D.1: Z1 = 0.825

0.8250.188 55553.2
= 0.00956 m3/kg
9 000

From Fig. D.1 at Tr2 = 0.874,


A

PG2 = 0.45 4250 = 1912 kPa


A

vG2 = 0.71 0.188 55 323.2/1912 = 0.02263 m3/kg


E

vF2 = 0.075 0.188 55 323.2/1912 = 0.00239 m3/kg


E

0.00956 = 0.002 39 + x2(0.02263 - 0.00239) =>


A

x2 = 0.354
A

mLIQ 2 = (1-0.354)0.2/0.00956 = 13.51 kg


A

These tanks
contain liquid
propane.

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12.86
A rigid tank contains 5 kg of ethylene at 3 MPa, 30C. It is cooled until the
ethylene reaches the saturated vapor curve. What is the final temperature?
V = const m = 5 kg
P1 = 3 MPa T1 = 30 oC = 303.2 K

C2 H4

cool to x2 = 1.0
3
Pr1 = 5.04 = 0.595,
A

Final state: x = 1, v2 = v1
A

Fig. D.1:

303.2
Tr1 = 282.4 = 1.074
A

Z1 = 0.82
A

Pv = ZRT so take the ratio between the two states


Z2Tr2
ZG2Tr2
Pr2 = Pr1 Z T = 0.595
= 0.6756 ZG2Tr2
0.821.074
1 r1
A

Trial & error, Table D.4 may be easier to use than Fig. D.1:
Tr2
A

0.866

ZG2
A

0.72

Pr2
A

0.42

Pr2 CALC
A

0.421

~ OK

=> T2 = 244.6 K
A

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12.87
The new refrigerant R-152a is used in a refrigerator with an evaporator
temperature of 20oC and a condensing temperature of 30oC. What are the high
and low pressures in this cycle?
E

Since we do not have the printed tables for R-152a we will use generalized charts.
The critical properties are: Tc = 386.4 K, Pc = 4.52 MPa.
A

A
E

Evaporator:
Tr1 = T/Tc = (273.15 20)/386.4 = 0.655
A

A
E

PG T1 = Pr1 sat Pc = 0.06 4.52 = 0.271 MPa

Fig. D.1:

Condenser:
Tr2 = T/Tc = (273.15 + 30)/386.4 = 0.785
A

A
E

Fig. D.1:

PG T2 = Pr2 sat Pc = 0.22 4.52 = 0.994 MPa


A

A
E

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12.88
A 4-m3 storage tank contains ethane gas at 10 MPa, 100oC. Use Lee-Kesler EOS
and find the mass of the ethane.
E

The Lee-Kesler EOS is shown as the generalized charts.


Table A.2: Tc = 305.4 K, Pc = 4.88 MPa,
The reduced properties are:
A

10
Pr1 = 4.88 = 2.05,
A

373.15
Tr1 = 305.4 = 1.22

PV
m = ZRT =

Table A.5: R = 0.2765 kJ/kg-K

Fig. D.1: Z = 0.56

10 000 4
= 692.3 kg
0.56 0.2765 373.15
A

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12.89
The ethane gas in the storage tank from the previous problem is cooled to 0oC.
Find the new pressure.
E

273.15
Tr2 = 305.4 = 0.8944
Since Z and P are unknown this becomes trial and error solution.
The new final state is given by: (T2, v2 = v1)
A

P2 / Z2 = mRT2 /V = 692.3 0.2765 273.15 /4 = 13071.7 kPa


A

A
E

Assume it is saturated

Pr2 = 0.53 (see Fig. D.1), Zg = 0.67, Zf = 0.09


A

P2 = 0.53 4880 = 2586 kPa and


A

Z2 = P2 / 13071.7 = 0.198 (two phase OK)


A

Ans.: P2 = 2586 kPa


A

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12.90
Use CATT3 to solve the previous two problems when the acentric factor is used
to improve the accuracy.
Problem 12.88:
The Lee-Kesler EOS is shown as the generalized charts.
Table A.2: Tc = 305.4 K, Pc = 4.88 MPa, Table A.5: R = 0.2765 kJ/kg-K
Table D.4: = 0.099
The reduced properties are:
A

10
Pr1 = 4.88 = 2.05,
A

373.15
Tr1 = 305.4 = 1.22

PV
m = ZRT =
A

CATT3: Z = 0.605

10 000 4
= 640.8 kg
0.605 0.2765 373.15
A

Problem 12.89:
273.15
Tr2 = 305.4 = 0.8944
Since Z and P are unknown this becomes trial and error solution.
The new final state is given by: (T2, v2 = v1)
A

P2 / Z2 = mRT2 /V = 640.8 0.2765 273.15 /4 = 12099.3 kPa


A

A
E

Assume it is saturated vapor

Pr2 = 0.483 (CATT3), Zg = 0.69, Zf = 0.078


A

P2 = 0.483 4880 = 2357 kPa and


A

Z2 = P2 / 12 099.3 = 0.1948 (two phase OK)


A

Ans.: P2 = 2357 kPa


A

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12.91
A geothermal power plant uses butane as saturated vapor 80oC into the turbine
and the condenser operates at 30oC. Find the reversible specific turbine work.
E

C4H10 cycle

.
WT

Turbine

T1 = 80 oC, x1 = 1.0 ; T3 = 30oC, x3 = 0.0


353.2
Tr1 = 425.2 = 0.831
From D.1, D.2 and D.3:
P1 = 0.325 3800 = 1235 kPa
E

Ht.
Exch

.
QH

*
(h1-h1) = 0.143 04425.20.56 = 34.1
*
(s1-s1) = 0.143 040.475 = 0.0680

Cond

.
-WP

303.2
Tr3 = 425.2 = 0.713
A

From D.1, D.2 and D.3: P3 = 0.1133800 = 429 kPa


A

sat. liq.: (h*- hf) = RTc4.81 = 292.5 ;

(s*- sf) = R6.64 = 0.950

sat. vap.: (h*- hg) = RTc0.235 = 14.3 ;

(s*- sg) = R0.22 = 0.031

Because of the combination of properties of C4H10 (particularly the large CP0/R),


A

s1 is larger than sg at T3. To demonstrate,


A

353.2
1235
* *
(s1-sg3) = 1.7164 ln 303.2 - 0.143 04 ln 429 = 0.1107
A

(s1-sg3) = -0.0680 + 0.1107 + 0.031 = +0.0737 kJ/kg K


A

A
E

T
1

so that T2S will be > T3, as shown in the T-s


diagram. A number of other heavy hydrocarbons
also exhibit this behavior.
A

2s 2

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Solution 12.91 Continued.
Assume T2S = 315 K,

=> Tr2S = 315 / 425.2 = 0.741

From D.2 and D.3:


*

(h2S - h2S) = RTc0.21 = 12.8

and

(s2S - s2S) = R0.19 = 0.027

353.2
1235
*
*
(s1 - s2S) = 1.7164 ln 315 - 0.143 04 ln 429 = +0.0453
(s1 - s2S) = -0.0680 + 0.0453 + 0.027 0
T2S = 315 K
*

(h1 - h2S) = 1.7164(353.2-315) = 65.6


wST = h1 - h2S = -34.1 + 65.6 + 12.8 = 44.3 kJ/kg

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12.92
Consider the following EOS, expressed in terms of reduced pressure and
temperature:
Pr
6
Z = 1 + 14 T (1 - 2 )
Tr
r
What does this equation predict for enthalpy departure from the ideal gas value at
the state Pr = 0.4, Tr = 0.9 ? What is it from the generalized charts?
Pr
Pv
6
Z = RT = 1 + 14 T (1 - 2)
Tr
r
3

6Tc2
RT RTc
v = P + 14P (1 - 2 ) ;
T
c

R 12RTc
v
=P+
Tp
14PcT3
3

RTc 18RTc
v
v - T = 14P 2
Tp
c 14PcT
Now Eq.12.27 is integrated with limits similar to Eq.12.62
P
RTc
18
v
h h* = [v T ] dP = 14 (1 2) Pr = 0.606 RTc

Tp
Tr
0

Evaluate at Pr = 0.4, Tr = 0.9 from Fig. D2 to get


h h* = (h* h) 0.6 RTc
This result matched with in the accuracy the figure can be read.

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12.93
Consider the following equation of state, expressed in terms of reduced pressure
and temperature:
Pr
6
Z = 1 + 14 T (1 - 2 )
Tr
r
What does this equation predict for entropy departure from the ideal gas value at
the state Pr = 0.4, Tr = 0.9 ?
The entropy departure is the change in s for a real gas minus the change in s
for an ideal gas, so from Eq.12.32 and eq.6.14 we get
d(s - s*) = Cp

dT v
dT R
R v
dP
[
C
dP
]
=
[

p
T T p
T P
P T p] dP

Solve now for v from the compressibility factor ( Z = Pv/RT) to get


Pr
Pv
6
Z = RT = 1 + 14 T (1 2)
Tr
r
6Tc2
RT RTc
v = P + 14P (1 2 ) ;
T
c

R 12RTc
v
=P+
T p
14PcT3
3

P
12RTc
R v
6 Pr
s - s* = [ P - ] dP = [
]
dP
=

7 R T3

T p
14PcT3
P
0

Evaluate at Pr = 0.4, Tr = 0.9 to get


s - s* = 0.4703 R

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12.94
A very low temperature refrigerator uses neon. From the compressor the neon at
1.5 MPa, 80 K goes through the condenser and comes out at saturated liquid 40 K.
Find the specific heat transfer using generalized charts.
80
1.5
State 1: 80 K, 1.5 MPa : Tr1 = 44.4 = 1.802, Pr1 = 2.76 = 0.543
State 2: 40 K, x = 0:

Tr2 = 0.90, Pr2 = 0.532

The enthalpy departure chart Fig. D.2:


(h*- h)1 = 0.22 RTc ,
*

(h*- h)2 = 4.10 RTc

h2 - h1 = 1.03 (40 - 80) = -41.2 kJ/kg


*

h2 - h1 = h2 - h1 - (h*- h)2 + (h*- h)1


= -41.2 + 0.412 44.4 (-4.10 + 0.22) = -112.2 kJ/kg
q = h2 - h1 = -112.2 kJ/kg

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12.95
Repeat the previous problem using CATT3 software for the neon properties.
From CATT3:

h1 = 138.3 kJ/kg,

h2 = 30.24 kJ/kg (P = 1.46 MPa)

q = h2 - h1 = 30.24 138.3 = -108.1 kJ/kg

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12.96
A piston/cylinder contains 5 kg of butane gas at 500 K, 5 MPa. The butane
expands in a reversible polytropic process to 3 MPa, 460 K. Determine the
polytropic exponent n and the work done during the process.
C4H10 m = 5 kg T1 = 500 K P1 = 5 MPa
Rev. polytropic process:

P1V1 = P2V2

500
5
Tr1 = 425.2 = 1.176, Pr1 = 3.8 = 1.316

From Fig. D.1:

3
460
=
1.082,
P
=
= 0.789 From Fig. D.1:
r2 3.8
425.2
mZRT 5 0.68 0.1430 500
V1 = P =
= 0.0486 m3
5000
Tr2 =

Z1 = 0.68
Z2 = 0.74

mZRT 5 0.74 0.1430 460


= 0.0811 m3
3000
P =
Solve for the polytropic exponent, n, as
5
0.0811
n = ln(P1/P2) / ln(V2/V1) = ln ( ) / ln (0.0486) = 0.9976
3
V2 =

W = PdV =
1 2
1

P2V2 - P1V1 30000.0811 - 50000.0486


= 125 kJ
=
1-n
1 - 0.9976

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12.97
Calculate the heat transfer during the process described in Problem 12.96.
From solution 12.96,
V1 = 0.0486 m3, V2 = 0.0811 m3,

W2 = 125 kJ

500
5
Tr1 = 425.2 = 1.176, Pr1 = 3.8 = 1.316

From Fig. D.1:

Z1 = 0.68

Tr2 = 1.082, Pr2 = 0.789, T2 = 460 K


From Fig. D.2:
*

(h*- h)1 = 1.30 RTC ,

(h*- h)2 = 0.90 RTC

h2 - h1 = 1.716(460 - 500) = -83.1 kJ/kg


8.3145425.2
(-0.90 + 1.30) = -58.8 kJ/kg
58.124
U2 - U1 = m(h2 - h1) - P2V2 + P1V1
h2 - h1 = -83.1 +

= 5(-58.8) 3000 0.0811 + 5000 0.0486 = -288.3 kJ


Q = U2 - U1 + 1W2 = -174.3 kJ
1 2

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12.98
An ordinary lighter is nearly full of liquid propane with a small amount of vapor,
the volume is 5 cm3, and temperature is 23C. The propane is now discharged
slowly such that heat transfer keeps the propane and valve flow at 23C. Find the
initial pressure and mass of propane and the total heat transfer to empty the
lighter.
Propane C3H8

T1 = 23oC = 296.2 K = constant,

V1 = 5 cm3 = 510-6 m3,

x1 = 0.0

Tr1 = 296.2/369.8 = 0.804

From Figs. D.1 and D.2,


P1 = PG T1 = 0.254.25 = 1.063 MPa,

Z1 = 0.04

(h1-h1) = 0.188 55369.84.51 = 314.5


P1V1
m1 = Z RT =
1

1063510-6
= 0.00238 kg
0.040.188 55296.2

State 2: Assume vapor at 100 kPa, 23oC ideal gas so no corrections


Therefore, m2 much smaller than m1 ( 9.0 10-6 kg)
QCV = m2u2 m1u1 + mehe
= m2h2 m1h1 (P2P1)V + (m1m2)he
= m2(h2he) + m1(heh1) (P2P1)V
(he h1) = 0 + 0 + 314.5
QCV = 0 + 0.00238(314.5) (100 1063)510-6 = 0.753 kJ

Actual lighters use


butane and some
propane.

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12.99
250-L tank contains propane at 30C, 90% quality. The tank is heated to 300C.
Calculate the heat transfer during the process.
V = 250 L = 0.25 m3
T1 = 30 oC = 303.2 K, x1 = 0.90

C3 H8
T

Heat to T2 = 300 oC = 573.2 K


M = 44.094, Tc = 369.8 K, Pc = 4.25 MPa
R = 0.188 55, CP0 = 1.6794

1
v

Tr1 = 0.82 Fig. D.1:


Z1 = (1- x1) Zf1 + x1 Zg1 = 0.1 0.05 + 0.9 0.785 = 0.711
*

h1-h1

EA

Fig D.2:
SAT
A

AE

SAT

= 0.30 P1
A

m=

RTc = 0.1 4.43 + 0.9 0.52 = 0.911

Pr

A
E

= 1.275 MPa

12750.25
= 7.842 kg
0.7110.188 55303.2
A

7.842Z20.188 55573.2

Pr2 =

Z2
= 1.254

0.254250
at Tr2 = 1.55 Trial and error on Pr2
A

Pr2 = 0.743 => P2 = 3.158 MPa, Z2 = 0.94 , (h*- h)2 = 0.35 RTC
E

(h2-h1) = 1.6794(300-30)
A

= 453.4 kJ/kg

(h1-h1) = 0.9110.188 55369.8 = 63.5 kJ/kg


A

*
(h2-h2)
A

= 0.350.188 55369.8 = 24.4 kJ/kg

Q12 = m(h2-h1) - (P2-P1)V = 7.842(-24.4+453.4+63.5) - (3158-1275)0.25


A

= +3862 - 471 = 3391 kJ

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12.100
Find the heat of evaporation, hfg, for isobutane (Tc = 408.2 K, Pc = 3.65 MPa, M
= 58.124) at 12.6C from the generalized charts and compare to the values in the
CATT3 computerized tables.
A

To read the charts we need the reduced temperature


Tr1 = T/Tc = (12.6 + 273.15)/408.2 = 0.70
A

A
E

(h* h)g = 0.2 RTc ; (h* h)f = 4.85 RTc


E

hfg = hg hf = (h* h)g (h* h)f = (0.2 + 4.85) RTc


E

= 4.65 RTc = 4.65 (8.3145/58.124) 408.2


A

A
E

= 271.5 kJ/kg
CATT3:

hfg = -25.62 + 368.7 = 343 kJ/kg


A

The generalized charts are not super accurate, some improvement can be done
using the accentric factor.

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12.101
A cylinder contains ethylene, C2H4, at 1.536 MPa, 13C. It is now compressed
isothermally in a reversible process to 5.12 MPa. Find the specific work and heat
transfer.
A

A
E

Ethylene C2H4 P1 = 1.536 MPa , T2 = T1 = -13oC = 260.2 K


E

Tr2 = Tr1 = 260.2 / 282.4 = 0.921 , Pr1 = 1.536 / 5.04 = 0.305


A

From D.1, D.2 and D.3:

Z1 = 0.85
A

A
E

(h1-h1) = 0.2964282.40.40 = 33.5 and


A

From D.1, D.2 and D.3:


*
(h2-h2)
A

Z2 = 0.17 ,
A

(s1-s1) = 0.29640.30 = 0.0889


A

Pr2 = 5.12/5.04 = 1.016 (comp. liquid)

A
E

= 0.2964282.44.0 = 334.8 and

(s2-s2) = 0.29643.6 = 1.067


A

A
E

5.12
= -0.3568
1.536
1q2 = T(s2-s1) = 260.2(-1.067 - 0.3568 + 0.0889) = -347.3 kJ/kg
*

Ideal gas:

(h2-h1) = 0
A

* *

and

(s2-s1) = 0 - 0.2964 ln
A

(h2 - h1) = -334.8 + 0 + 33.5 = -301.3 kJ/kg


A

(u2 - u1) = (h2-h1) - RT(Z2-Z1) = -301.3 - 0.2964260.2(0.17-0.85) = -248.9


A

1w2
A

A
E

= 1q2 - (u2 - u1) = -347.3 + 248.9 = -98.4 kJ/kg


A

A
E

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12.102
Saturated vapor R-410A at 30C is throttled to 200 kPa in a steady flow process.
Calculate the exit temperature assuming no changes in the kinetic energy, using
the generalized charts, Fig. D.2 and the R-410A tables, Table B.4.
R-410A throttling process
*

Energy Eq.:

h2 - h1 = 0 = (h2 - h2) + (h2 - h1) + (h1 - h1)


A

Generalized Chart, Fig. D.2, R = 8.31451/72.585 = 0.11455 kJ/kg-K


303.2
*
Tr1 = 344.5 = 0.88 => (h1-h1) = 0.11455 344.5 (0.85) = 33.54 kJ/kg
For CP0, use h values from Table B.4 at low pressure.
A

CP0 (330.83 - 314.40) / (40 - 20) = 0.8215 kJ/kg K


A

Substituting: (h2-h2) + 0.8215 (T2-30) + 33.54 = 0


A

at Pr2 = 200/4900 = 0.041


A

Assume T2 = -10oC => Tr2 = 263.2/344.5 = 0.764


E

(h2-h2) = RT 0.1 = 0.11455 344.5 (0.1) = 3.95


A

Substituting :

-3.95 + 0.8215 (-10 - 30) + 33.54 = -3.27

Assume T2 = -5oC => Tr2 = 268.2/344.5 = 0.778


E

*
(h2-h2)
A

= RT 0.1 = 0.11455 344.5 (0.1) = 3.95

Substituting :

-3.95 + 0.8215 (-5 - 30) + 33.54 = 0.84

T2 = -6.0 oC
E

R-410A tables, B.4: at T1 = 30oC, x1 = 1.0


E

=> h1 = 284.16 kJ/kg


A

h2 = h1 = 284.16 , P2 = 0.2 MPa => T2 = -13.4 oC


E

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12.103
Repeat Problem 12.91 using CATT3 and include the acentric factor for butane to
improve the accuracy.
C4H10 cycle

T1 = 80 oC, x1 = 1.0 ; T3 = 30oC, x3 = 0.0


353.2
Tr1 = 425.2 = 0.831

.
WT

Turbine

From CATT3 with = 0.199:


P1 = 0.2646 3800 = 1005 kPa

Cond

*
(h1-h1) = 0.1430 425.20.5685 =
*
(s1-s1) = 0.1430 0.4996 = 0.0714

P
4

Ht.
Exch

.
QH

34.6

.
-WP

303.2
Tr3 = 425.2 = 0.713
A

From CATT3 with = 0.199: P3 = 0.07443 3800 = 282.8 kPa


A

sat. liq.: (h - hf) = RTc6.048 = 367.74 ;

(s*- sf) = R8.399 = 1.201

sat. vap.: (h*- hg) = RTc0.202 = 12.28 ;

(s*- sg) = R0.201 = 0.0287

*
E

Because of the combination of properties of C4H10 (particularly the large CP0/R),


A

s1 is larger than sg at T3. To demonstrate,


A

* *
(s1-sg3)
A

353.2
1005
= 1.716 ln 303.2 - 0.1430 ln 282.8 = 0.0806
A

(s1-sg3) = -0.0714 + 0.0806 + 0.0287 = +0.0379 kJ/kg K


A

A
E

T
1

so that T2S will be > T3, as shown in the T-s


diagram. A number of other heavy hydrocarbons
also exhibit this behavior.
A

2s 2

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Solution 12.103 continued.
Assume T2S = 315 K,

=> Tr2S = 315 / 425.2 = 0.741

From CATT3:
*

(h2S - h2S) = RTc0.183 = 11.13

and

(s2S - s2S) = R0.1746 = 0.025

353.2
1005
*
*
(s1 - s2S) = 1.716 ln 315 - 0.1430 ln 282.8 = +0.01509
(s1 - s2S) = -0.0714 + 0.01509 + 0.025 = -0.031
Repeat at T2S = 310 K to get Tr2S = 0.729,
*

(h2S - h2S) = RTc0.1907 = 11.595 and (s2S - s2S) = R0.1853 = 0.0265


353.2
1005
*
*
(s1 - s2S) = 1.716 ln 310 - 0.1430 ln 282.8 = +0.04255
(s1 - s2S) = -0.0714 + 0.04255 + 0.0265 = -0.0023 very close to 0, OK
T2S = 310 K
*

(h1 - h2S) = 1.716 (353.2 - 310) = 74.13


wST = h1 - h2S = -34.6 + 74.13 + 11.6 = 51.1 kJ/kg

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12.104
A cylinder contains ethylene, C2H4, at 1.536 MPa, 13C. It is now compressed
in a reversible isobaric (constant P) process to saturated liquid. Find the specific
work and heat transfer.
Ethylene C2H4 ; P1 = 1.536 MPa = P2 ,

T1 = -13oC = 260.2 K

State 2: saturated liquid, x2 = 0.0


260.2
1.536
Tr1 = 282.4 = 0.921 Pr1 = Pr2 = 5.04 = 0.305
*

From Figs. D.1, D.2: Z1 = 0.85 , (h1 - h1)/RTc = 0.40


v1 =

Z1RT1
P1

0.850.29637260.2
= 0.042675
1536

(h1 - h1) = 0.296 37 282.4 0.40 = 33.5


From Figs. D.1, D.2: T2 = 0.824282.4 = 232.7 K
*

Z2 = 0.05 , (h2 - h2)/RTc = 4.42


v2 =

Z2RT2
P2

0.050.29637232.7
= 0.002245 m3/kg
1536

(h2 - h2) = 0.296 37 282.4 4.42 = 369.9


*

(h2 - h1) = CP0(T2 - T1) = 1.5482(232.7 - 260.2) = -42.6


3
w12 =
Pdv = P(v2 - v1) = 1536 kPa (0.002 245 - 0.042 675) m /kg

q12

= -62.1 kJ/kg
= (u2 - u1) + w12 = (h2 - h1) = -369.9 - 42.6 + 33.5
= -379 kJ/kg

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12.105
Refrigerant-123, dichlorotrifluoroethane, which is currently under development as
a potential replacement for environmentally hazardous refrigerants, undergoes an
isothermal steady flow process in which the R-123 enters a heat exchanger as
saturated liquid at 40C and exits at 100 kPa. Calculate the heat transfer per
kilogram of R-123, using the generalized charts, Fig. D.2
R-123: M = 152.93, TC = 456.9 K, PC = 3.67 MPa

T1 = T2 = 40 oC, x1 = 0
P2 = 100 kPa
1

2
Heat

Tr1 = Tr2 = 313.2/456.9 = 0.685,

Pr2 = 0.1/3.67 = 0.027

From Fig. D.2: Pr1 = 0.084, (h* h)1/RTC = 4.9


From D.1: saturated P1 = 0.0843670 = 308 kPa
P2 < P1 with no work done, so process is irreversibel.
Energy Eq.:

q + h 1 = h 2,

From Fig. D.2:

Entropy Eq.:

s1 + dq/T + sgen = s2, sgen > 0

(h*- h)2/RTC = 0.056

q = h2 - h1 = 8.3145 456.9 [-0.056 + 0 + 4.90]/152.93 = 120.4 kJ/kg

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12.106
Carbon dioxide collected from a fermentation process at 5C, 100 kPa should be
brought to 243 K, 4 MPa in a steady flow process. Find the minimum amount of
work required and the heat transfer. What devices are needed to accomplish this
change of state?
278.2
100
Tri = 304.1 = 0.915, Pri = 7380 = 0.0136
From D.2 and D.3 : (h*-h) /RTC = 0.02, (s*-s)ri/R = 0.01
ri

243
Tre = 304.1 = 0.80,
From D.2 and D.3:
*

4
Pre = 7.38 = 0.542

(h*-h) /RTC = 4.5 ,


re

(s*-s)re/R = 4.74

(hi-he) = - (hi -hi) + (hi -he ) + (he -he)


= - 0.188 92304.10.01 + 0.8418(278.2-243)
+ 0.188 92304.14.5 = 287.6 kJ/kg
*

* *

(si-se) = - (si -si) + (si -se ) + (se -se)


= - 0.188 920.01 + 0.8418 ln(278.2/243)
- 0.188 92 ln(0.1/4) + 0.188 924.74 = 1.7044 kJ/kg K
wrev = (hi-he) -T0(si-se) = 287.6 - 278.2(1.7044) = -186.6 kJ/kg
qrev = (he-hi) + wrev = -287.6 -186.6 = -474.2 kJ/kg
We need a compressor to bring the pressure up and a cooler to bring the
temperature down. Cooling it before compression and intercooling between
stages in the compressor lowers the compressor work. In an actual set-up we
require more work than the above reversible limit.

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12.107
Determine how accurate the generalized chart is for the carbon dioxide process in
Problem 12.106 by using the CATT3 software for the carbon dioxide properties.
From the CATT3 software:
Inlet superheated vapor

hi = 376.1 kJ/kg and

si = 2.015 kJ/kg-K

Exit compressed liquid

he = 20.21 kJ/kg and

se = 0.07349 kJ/kg-K

wrev = (hi he) T0(si se) = 376.1 20.21 278.2 (2.015 0.07349)
= -184.1 kJ/kg
q

rev

= (he hi) + wrev = (20.21 376.1) 184.1 = -540 kJ/kg

The work is very accurate but the heat transfer a little less so. The enthalpy and
entropy differences are both under-estimated by the generalized charts.

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12.108
A geothermal power plant on the Raft River uses isobutane as the working fluid.
The fluid enters the reversible adiabatic turbine at 160C, 5.475 MPa, and the
condenser exit condition is saturated liquid at 33C. Isobutane has the properties
Tc= 408.14 K, Pc= 3.65 MPa, CP0= 1.664 kJ/kg K and ratio of specific heats k =
1.094 with a molecular weight as 58.124. Find the specific turbine work and the
specific pump work.
Turbine inlet: T1 = 160oC , P1 = 5.475 MPa
Condenser exit: T3 = 33oC , x3 = 0.0, Tr3 = 306.2 / 408.1 = 0.75
From Fig. D.1:
Pr3 = 0.16, Z3 = 0.03

=> P2 = P3 = 0.16 3.65 = 0.584 MPa

Tr1 = 433.2 / 408.1 = 1.061,

Pr1 = 5.475 / 3.65 = 1.50

From Fig. D.2 & D.3:


*

(h1 - h1) = 0.143 05408.12.84 = 165.8


*

(s1 - s1) = 0.143 052.15 = 0.3076


0.584
306.2
*
*
(s2 - s1) = 1.664 ln 433.2 - 0.143 05 ln 5.475 = -0.2572
*

(s2 - s2) = (s2 - sF2) - x2 sFG2


= 0.143 056.12 - x20.143 05(6.12-0.29) = 0.8755 - x20.8340
(s2 - s1) = 0 = -0.8755 + x20.8340 - 0.2572 + 0.3076 => x2 = 0.99
*

(h2 - h1) = CP0(T2 - T1) = 1.664(306.2 - 433.2) = -211.3


From Fig. D.2:,
*

(h2 - h2) = (h2 - hF2) - x2hFG2 = 0.143 05408.1[4.69-0.99(4.69-0.32)]


Turbine:

= 273.8 0.99 255.1 = 21.3


wT = (h1 - h2) = -165.8 + 211.3 + 21.3 = 66.8 kJ/kg

Pump:

vF3 =

ZF3RT3 0.030.143 05306.2


= 0.00225
P3 =
584

wP = - v dP vF3(P4 - P3) = -0.00225 (5475-584) = -11.0 kJ/kg

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12.109
A flow of oxygen at 230 K, 5 MPa is throttled to 100 kPa in a steady flow
process. Find the exit temperature and the entropy generation.
Process: Throttling
.
Small surface area: Q = 0;
.
No shaft:
W=0
.
Irreversible:
Sgen > 0
We will solve the problem using generalized charts.
230
5
0.1
Tri = 154.6 = 1.488, Pri = 5.04 = 0.992, Pre = 5.04 = 0.02
From D.2:
Energy Eq.:

(hi -hi) = RTc h = 0.2598 154.6 0.50 = 20.1 kJ/kg


*

(he- hi) = 0 = - (he -he) + (he -hi ) + (hi -hi)

Assume Te = 208 K , Tre = 1.345:


*

(he -hi ) = Cp (Te Ti) = 0.922 (208 - 230) = -20.3 kJ/kg


From D.2:

(he -he) = RTc h = 0.2598 154.6 0.01 = 0.4

Check first law (he- hi) = -0.4 -20.3 + 20.1 0 OK => Te = 208 K
From D.3,
*

(si -si) = 0.25980.25 = 0.0649

and

(se -se) = 0.25980.01 = 0.0026

0.1
208
* *
(se -si ) = 0.9216 ln 230 - 0.2598 ln 5 = 0.9238 kJ/kg K
sgen = (se- si) = -0.0026 + 0.9238 + 0.0649 = 0.9861 kJ/kg K

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12.110
An uninsulated piston/cylinder contains propene, C3H6, at ambient temperature,
19C, with a quality of 50% and a volume of 10 L. The propene now expands
very slowly until the pressure in the cylinder drops to 460 kPa. Calculate the mass
of propene, the work, and heat transfer for this process.
T1 = 19oC = 292.2 K,

Propene C3H6:

x1 = 0.50,

Tr1 = 292.2/364.9 = 0.80,

From Fig. D.1:


Pr1 = Pr sat = 0.25,

P1 = 0.25 4.6 = 1.15 MPa

From D.1:

Z1 = 0.5 0.04 + 0.5 0.805 = 0.4225

P1V1
m = Z RT =

11500.010
= 0.471 kg
0.42250.197 58292.2

V1 = 10 L

Assume reversible and isothermal process (slow, no friction, not insulated)


Q = m(u2-u1) + 1W2
1 2
2

W = PdV (cannot integrate);


1 2

Q = TdS = Tm(s2-s1)
1 2

From Figs. D.2 and D.3:


*

h1 - h1 = 0.19758 364.9(0.5 4.51 + 0.5 0.46) = 179.2 kJ/kg


*

(s1 - s1) = 0.197 58 (0.5 5.46 + 0.5 0.39) = 0.5779 kJ/kg K


The ideal gas change in h and s are
*

(h2 - h1) = 0 and

460
*
*
(s2 - s1) = 0 - 0.197 58 ln 1161 = + 0.1829 kJ/kg K

At Tr2 = 0.80, Pr2 = 0.10, from D.1, D.2 and D.3, Z2 = 0.93
*

(h2 - h2) = 0.197 58 364.9 0.16 = 11.5 kJ/kg


*

(s2 - s2) = 0.197 58 0.13 = 0.0257 kJ/kg K


Now we can do the change in s and h from state 1 to state 2
*

(s2 - s1) = -(s2 - s2) + (s2 - s1) + (s1 - s1)


= -0.0257 + 0.1829 + 0.5779 = 0.7351 kJ/kg K
*

(h2 - h1) = - (h2 - h2) + (h2 - h1) + h1 - h1


= -11.5 + 0 + 179.2 = 167.7 kJ/kg

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Solution 12.110 continued.
The heat transfer is found from the second law
q = 292.2 0.7351 = 214.8 kJ/kg

1 2

=>

Q = m 1q2 = 101.2 kJ

1 2

We need the internal energy in the energy equation


u2 - u1 = (h2 - h1) + RT(Z1 - Z2) = 167.7 + 0.197 58 292.2 (0.4225 - 0.93)
= 138.4 kJ/kg
w = 1q2 - (u2 - u1) = 214.8 - 138.4 = 76.4 kJ/kg

1 2
1

W2 = m 1w2 = 36.0 kJ

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12.111
An alternative energy power plant has carbon dioxide at 6 MPa, 100oC flowing
into a turbine with an exit as saturated vapor at 1 MPa. Find the specific turbine
work using generalized charts and repeat using Table B.3.
From Table A.5:

R = 0.1889 kJ/kgK, CP = 0.842 kJ/kg

From Table A.2:

TC = 304.1 K,

6
Pri = 7.38 = 0.813,

PC = 7.38 MPa

373.2
Tri = 304.1 = 1.227

~
h = 0.70

From D.2 and D.3,


~
*
(hi - hi) = RTC h = 0.1889 304.1 0.70 = 46.8 kJ/kg;
1
Pre = 7.38 = 0.1355, x = 1 so Tre = 0.73, Te = 0.73 304.1 = 222 K
From D.2 and D.3,
~
*
(he - he) = RTC h = 0.1889 304.1 0.25 = 46.8 kJ/kg;
*

w = hi he = hi he (hi - hi) + (he - he)


~
~
= CP( hi he) RTC ( hi he)
= 0.842 (373.15 222) 0.1889 0304.1 (0.7 0.25)
= 101.45 kJ/kg
From Table B.3
w = hi he = 421.69 322.39 = 99.3 kJ/kg

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12.112
A distributor of bottled propane, C3H8, needs to bring propane from 350 K, 100 kPa
to saturated liquid at 290 K in a steady flow process. If this should be accomplished
in a reversible setup given the surroundings at 300 K, find the ratio of the volume
. .
flow rates Vin/Vout, the heat transfer and the work involved in the process.
350
From Table A.2: Tri = 369.8 = 0.946 ,

0.1
Pri = 4.25 = 0.024

From D.1, D.2 and D.3,


Zi = 0.99
*

(hi -hi) = 0.1886 369.8 0.03 = 2.1 kJ/kg


*

(si -si) = 0.1886 0.02 = 0.0038 kJ/kg K


290
369.8 = 0.784, and x = 0
From D.1, D.2 and D.3,
Pre = 0.22 , Pe = 0.22 4.25 = 0.935 MPa and
Tre =

Ze = 0.036

(he -he) = 0.1886 369.8 4.57 = 318.6 kJ/kg


*

(se -se) = 0.1886 5.66 = 1.0672 kJ/kg K


*

(he -hi ) = 1.679(290 - 350) = -100.8 kJ/kg


0.935
290
* *
(se -si ) = 1.679 ln 350 - 0.1886 ln 0.1 = -0.7373 kJ/kg K
(he-hi) = -318.6 - 100.8 + 2.1 = -417.3 kJ/kg
(se-si) = -1.0672 - 0.7373 + 0.0038 = -1.8007 kJ/kg K
.
Vin
.
Vout

ZiTi/Pi
0.99 350 0.935
= Z T /P = 0.036 290 0.1 = 310.3
e e e

wrev = (hi-he) -T0(si-se) = 417.3 - 300(1.8007) = -122.9 kJ/kg


qrev = (he-hi) + wrev = -417.3 122.9 = -540.2 kJ/kg

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12.113
An insulated cylinder fitted with a frictionless piston contains saturated-vapor
carbon dioxide at 0oC, at which point the cylinder volume is 20 L. The external
force on the piston is now slowly decreased, allowing the carbon dioxide to
expand until the temperature reaches - 30oC. Calculate the work done by the
CO2 during this process.
CO2: TC = 304.1 K, Pc = 7.38 MPa, Cp = 0.842 kJ/kg-K, R = 0.1889 kJ/kg K
State 1: T1 = 0oC, sat. vap., x1 = 1.0, V1 = 20 L
Tr1 = 0.9, P1 = Pr1PC = 0.53 7380 = 3911 kPa, Z1 = Zg = 0.67

(h*1 h1)g

P1V1
*
= 0.9 RTC, (s1 s1)g/R = 0.72, m = Z RT = 2.262 kg
1
1

State 2: T2 = -30oC
Tr2 = 0.8, P2 = Pr2Pc = 0.25 7380 = 1845 kPa
Entropy Eq.:
Sgen = m(s2 s1) 1Q2/T ;
1Q2 = 0,
*

s2 - s1 = (s2 s2)

Sgen = 0

+ (s*2 s*1) + (s*1 s1) = 0

T2
P2
*
*
*
s2 s1 = CP ln T R ln P = 0.044 kJ/kg-K, s1 s1 = 0.136 kJ/kg-K
1
1
*

s2 - s2 = 0.180 kJ/kg K,

(s*2 s2)f = 5.46 R, (s*2 s2)g = 0.39 R

(s*2 s2) = (1-x2)(s*2 s2)f + x2 (s*2 s2)g

x2 = 0.889

= m(u2 u1) + 1W2 ; 1Q2 = 0, u = h - Pv


Z2 = (1 - x2)Zf + x2Zg = 0.111 0.04 + 0.889 0.81 = 0.725;

Energy Eq.:

1Q2

(h2 - h1) = (h2 h2)


*

+ (h*2 h*1) + (h*1 h1)

h2 h1 = Cp(T2 - T1) = -25.3 kJ/kg, (h1 h1) = 51.7 kJ/kg

(h*2 h2)f

= 4.51 RTC ,

(h*2 h2)g = 0.46 RTC

(h*2 h2) = (1 - x2)(h*2 h2)f + x2 (h*2 h2)g =

52.2 kJ/kg

h2 - h1 = -52.2 25.3 + 51.7 = -25.8 kJ/kg


u2 - u1 = (h2 - h1) - Z2RT2 + Z1RT1 = -25.8 0.725 0.18892 243.2
+ 0.67 0.18892 273.2 = -24.5 kJ/kg
1W2 = 55.4 kJ

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12.114
A control mass of 10 kg butane gas initially at 80C, 500 kPa, is compressed in a
reversible isothermal process to one-fifth of its initial volume. What is the heat
transfer in the process?
Butane C4H10: m = 10 kg,

T1 = 80 oC, P1 = 500 kPa

Compressed, reversible T = const, to V2 = V1/5


353.2
500
Tr1 = 425.2 = 0.831, Pr1 = 3800 = 0.132
Z1 = 0.92,

From D.1 and D.3:


v1 =

Z1RT1
P1

(s1- s1) = 0.1430.16 = 0.0230

0.920.143353.2
= 0.09296 m3/kg
500

v2 = v1/5 = 0.01859 m3/kg;

State 2:

Tr2 = Tr1 = 0.831

From D.1: PG = 0.3253800 = 1235 kPa


(s*-sF) = R5.08 = 0.7266

sat. liq.: ZF = 0.05,


sat. vap.: ZG = 0.775,

(s*-sG) = R0.475 = 0.0680

Therefore
vF =

0.050.143353.2
= 0.00205 m3/kg
1235

vG =

0.7750.143353.2
= 0.0317 m3/kg
1235

Since vF < v2 < vG x2 = (v2-vF)/(vG-vF) = 0.5578


*

(s2 - s2) = (1 - x2)(s2 - sF2) + x2(s2 - sG2)


= 0.4422 0.7266 + 0.5578 0.0680 = 0.3592 kJ/kg K
1235
*
*
(s2 - s1) = CP0 ln (T2/T1) - R ln (P2/P1) = 0 - 0.143 ln 500 = -0.1293
(s2 - s1) = -0.3592 - 0.1293 + 0.0230 = -0.4655 kJ/kg K
Q = Tm(s2 - s1) = 353.2 10 (-0.4655) = -1644 kJ

1 2

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12.115
A line with a steady supply of octane, C8H18, is at 400C, 3 MPa. What is your
best estimate for the availability in a steady flow setup where changes in potential
and kinetic energies may be neglected?
Ti = 400 oC, Pi = 3 MPa

Availability of Octane at
From Table A.5:

R = 0.07279 kJ/kgK, CP = 1.711 kJ/kg

From Table A.2:

TC = 568.8 K,

3
Pri = 2.49 = 1.205,

PC = 2.49 MPa

673.2
Tri = 568.8 = 1.184

From D.2 and D.3,


~
*
(hi - hi) = RTC h = 0.072 79 568.8 1.13 = 46.8 kJ/kg;
*
~
(si - si) = R s = 0.072 79 0.69 = 0.05 kJ/kgK

This is relative to the dead ambient state, assume T0 = 298.2 K, P0 = 100 kPa
298.2
Tr0 = 568.8 = 0.524 ,

0.1
Pr0 = 2.49 = 0.040

From D.2 and D.3, The s correction is outside chart (extrapolate or use CATT3)
*

(h0 - h0) = RTC 5.4 = 223.6


*

and

(s0 - s0) = R 9 = 0.655 kJ/kgK

(hi - h0) = CP(Ti T0) = 1.711 (673.2 298.2) = 641.7 kJ/kg


673.2
3
*
*
(si - s0) = 1.711 ln 298.2 0.072 79 ln 0.1 = 1.1459 kJ/kgK
(hi - h0) = -46.8 + 641.7 + 223.6 = 818.5 kJ/kg
(si - s0) = -0.05 + 1.1459 + 0.655 = 1.7509 kJ/kgK
i = wrev = (hi - h0) - T0(si - s0) = 818.5 298.2(1.7509) = 296.5 kJ/kg

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12.116
The environmentally safe refrigerant R-152a is to be evaluated as the working
fluid for a heat pump system that will heat a house. It uses an evaporator
temperature of 20oC and a condensing temperature of 30oC. Assume all
processes are ideal and R-152a has a heat capacity of Cp = 0.996 kJ/kg K.
Determine the cycle coefficient of performance.
Ideal Heat Pump TH = 30 oC
From A.2:

M = 66.05, R = 0.125 88, TC = 386.4 K, PC = 4.52 MPa


303.2
Tr3 = 386.4 = 0.785

2
3
4

Pr3 = Pr2 = 0.22


Sat.liq.:

=> P3 = P2 = 994 kPa

h3 - h3 = 4.56RTC = 221.8

v
T1 = -20 oC = 253.2 K, Tr1 = 0.655, Pr1 = 0.058 P1 = 262 kPa
*

h1 - h1 = 0.14RTC = 6.8

and

s1 - s1 = 0.14R = 0.0176

Assume T2 = 307 K, Tr2 = 0.795 given Pr2 = 0.22


*

From D.2, D.3: s2 - s2 = 0.34R = 0.0428 ;

h2 - h2 = 0.40RTc = 19.5

307
994
*
*
s2 - s1 = 0.996 ln 253.2 - 0.125 88 ln 262 = 0.0241
s2 - s1 = -0.0428 + 0.0241 + 0.0176 = -0.001 0 OK
h2 - h1 = -19.5 + 0.996(307-253.2) + 6.8 = 40.9
h2 - h3 = -19.5 + 0.996(307-303.2) + 221.8 = 206.1
qH h2 - h3 206.1
= w = h - h = 40.9 = 5.04
IN
2
1

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12.117
Rework the previous problem using an evaporator temperature of 0oC.
Ideal Heat Pump TH = 30 oC
From A.2:

M = 66.05, R = 0.125 88, TC = 386.4 K, PC = 4.52 MPa


303.2
Tr3 = 386.4 = 0.785

2
3
1

Pr3 = Pr2 = 0.22


Sat.liq.:

=> P3 = P2 = 994 kPa

h3 - h3 = 4.56RTC = 221.8

v
T1 = 0 oC = 273.2 K, Tr1 = 0.707 => Pr1 = 0.106, P1 = 479 kPa
*

h1 - h1 = 0.22RTC = 10.7

and

s1 - s1 = 0.21R = 0.0264

Assume T2 = 305 K, Tr2 = 0.789


*

s2 - s2 = 0.35R = 0.0441

and

h2 - h2 = 0.38RTC = 18.5

305.0
994
*
*
s2 - s1 = 0.996 ln 273.2 - 0.125 88 ln 479 = 0.0178
s2 - s1 = -0.0441 + 0.0178 + 0.0264 = 0.0001 0 OK
h2 - h1 = -18.5 + 0.996(305.0-273.2) + 10.7 = 23.9
h2 - h3 = -18.5 + 0.996(305.0-303.2) + 221.8 = 205.1
h2 - h3 205.1
= h - h = 23.9 = 8.58
2

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12.118
An uninsulated compressor delivers ethylene, C2H4, to a pipe, D = 10 cm, at 10.24
MPa, 94C and velocity 30 m/s. The ethylene enters the compressor at 6.4 MPa,
20.5C and the work input required is 300 kJ/kg. Find the mass flow rate, the total
heat transfer and entropy generation, assuming the surroundings are at 25C.
293.7
6.4
Tri = 282.4 = 1.040 , Pri = 5.04 = 1.270
From D.2 and D.3,
*

(hi -hi) = 0.296 37 282.4 2.65 = 221.8 kJ/kg


*

(si -si) = 0.296 37 2.08 = 0.6164 kJ/kg K


367.2
10.24
Tre = 282.4 = 1.30 , Pre = 5.04 = 2.032 => From D.1:
ve =
Ae =

ZeRTe
Pe

Ze = 0.69

0.690.296 37367.2
= 0.0073 m3/kg
10 240

2
D = 0.007 85 m2
4 e

=>

. AeVe 0.007 8530


m = v = 0.0073 = 32.26 kg/s
e

From D.2 and D.3,


*

(he -he) = 0.296 37 282.4 1.6 = 133.9 kJ/kg


*

(se -se) = 0.296 37 0.90 = 0.2667 kJ/kg K


*

(he -hi ) = 1.5482(367.2-293.7) = 113.8


10.24
367.2
* *
(se -si ) = 1.5482 ln 293.7 - 0.296 37 ln 6.4 = 0.2065
(he-hi) = -133.9 + 113.8 + 221.8 = 201.7 kJ/kg
(se-si) = -0.2667 + 0.2065 + 0.6164 = 0.5562 kJ/kg K
Energy Eq.:
q = (he-hi) + KEe + w = 201.7 +

302
- 300 = -97.9 kJ/kg
21000

.
.
Qcv = mq = 32.26(-97.9) = -3158 kW
.
Qcv .
.
3158
Sgen = T + m(se - si) = + 298.2 + 32.26(0.5562) = 28.53 kW/K
o

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Borgnakke and Sonntag


12.119
The new refrigerant fluid R-123 (see Table A.2) is used in a refrigeration system
that operates in the ideal refrigeration cycle, except the compressor is neither
reversible nor adiabatic. Saturated vapor at -26.5C enters the compressor and
superheated vapor exits at 65C. Heat is rejected from the compressor as 1 kW,
and the R-123 flow rate is 0.1 kg/s. Saturated liquid exits the condenser at 37.5C.
Specific heat for R-123 is CP = 0.6 kJ/kg. Find the coefficient of performance.
R-123: Tc = 456.9 K, Pc = 3.67 MPa, M = 152.93 kg/kmol, R = 0.05438 kJ/kg K
State 1: T1 = -26.5oC = 246.7 K, sat vap., x1 = 1.0
Tr1 = 0.54, Fig D.1, Pr1 = 0.01, P1 = Pr1Pc = 37 kPa
Fig. D.2,

h1-h1 = 0.03 RTC = 0.8 kJ/kg

State 2: T2 = 65oC = 338.2 K


State 3: T3 = 37.5oC = 310.7 K, sat. liq., x3 = 0
Tr3 = 0.68, Fig. D.1: Pr3 = 0.08, P3 = Pr3Pc = 294 kPa
P2 = P3 = 294 kPa, Pr2 = 0.080, Tr2 = 0.74,
*

h2-h2 = 0.25 RTC = 6.2 kJ/kg

Fig. D.2:
*

h3-h3 = 4.92 RTC = 122.2 kJ/kg


State 4: T4 = T1 = 246.7 K,

h4 = h3

Energy Eq. Evaporator: qL + h4 = h1 + w; w = 0,


*

qL = h1 - h3 = (h1 h1)
*

h4 = h3

+ (h*1 h*3) + (h*3 h3)

h1 h3 = CP(T1 - T3) = -38.4 kJ/kg, qL = -0.8 38.4 + 122.2 = 83.0 kJ/kg


Energy Eq. Compressor: q + h1 = h2 + wc;
*

wc = h1 - h2 + q; h1 - h2 = (h1 h1)
*

.
Q = -1.0 kW,

.
m = 0.1 kg/s

+ (h*1 h*2) + (h*2 h2)

h1 h2 = CP(T1 - T2) = -54.9 kJ/kg,


wc = -0.8 54.9 + 6.2 10.0 = -59.5 kJ/kg
= qL/wc = 83.0/59.5 = 1.395

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12.120
An evacuated 100-L rigid tank is connected to a line flowing R-142b gas,
chlorodifluoroethane, at 2 MPa, 100C. The valve is opened, allowing the gas to
flow into the tank for a period of time, and then it is closed. Eventually, the tank
cools to ambient temperature, 20C, at which point it contains 50% liquid, 50%
vapor, by volume. Calculate the quality at the final state and the heat transfer for
the process. The ideal-gas specific heat of R-142b is Cp = 0.787 kJ/kg K.
Rigid tank V = 100 L, m1 = 0

Line: R-142b CH3CClF2

M = 100.495, TC = 410.3 K, PC = 4.25 MPa,

CP0 = 0.787 kJ/kg K

R = R/M = 8.31451 / 100.495 = 0.082 73 kJ/kg K


Line Pi = 2 MPa, Ti = 100 oC, Flow in to T2 = T0 = 20oC
VLIQ 2 = VVAP 2 = 50 L
Continuity: mi = m2 ; Energy:

QCV + mihi = m2u2 = m2h2 - P2V

From D.2 at i: Pri = 2 / 4.25 = 0.471,

Tri = 373.15 / 410.3 = 0.91

(hi -hi) = 0.082 73410.30.72 = 24.4


*

(h2-hi ) = CP0(T2-Ti) = 0.787(20-100) = -63.0


293.2
From D.2: Tr2 = 410.3 = 0.715 => P2 = 0.1154250 = 489 kPa
sat. liq.:

ZF = 0.02, (h*-hF) = RTC4.85 = 164.6

sat. vap.:

ZG = 0.88, (h*-hG) = RTC0.25 = 8.5

P2VLIQ 2
4890.050
= 50.4 kg
mLIQ 2 = Z RT =
0.020.082 73293.2
F
2
P2VVAP 2
mVAP 2 = Z RT = 1.15 kg,
G
2

m2 = 51.55 kg

x2 = mVAP 2/m2 = 0.0223


*

(h2-h2) = (1-x2)(h2-hF2) + x2(h2-hG2) = 0.9777 164.6 + 0.0223 8.5 = 161.1


QCV = m2(h2 - hi) - P2V = 51.55(-161.1 - 63.0 + 24.4) 489 0.10
= -10 343 kJ

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Borgnakke and Sonntag

Mixtures

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12.121
A 2 kg mixture of 50% argon and 50% nitrogen by mole is in a tank at 2 MPa,
180 K. How large is the volume using a model of (a) ideal gas and (b) Kays
rule with generalized compressibility charts.
a) Ideal gas mixture
Eq.11.5:
Mmix = yi Mi = 0.5 39.948 + 0.5 28.013 = 33.981

mRT 2 8.3145 180


V=M P=
= 0.044 m3
33.981 2000
mix
b) Kays rule Eq.12.84
Pc mix = 0.5 4.87 + 0.5 3.39 = 4.13 MPa
Tc mix = 0.5 150.8 + 0.5 126.2 = 138.5 K
2
180
Reduced properties:
Pr = 4.13 = 0.484, Tr = 138.5 = 1.30
Fig. D.1: Z = 0.925

mRT
V = Z M P = 0.925 0.044 = 0.0407 m3
mix

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12.122
A 2 kg mixture of 50% argon and 50% nitrogen by mass is in a tank at 2 MPa,
180 K. How large is the volume using a model of (a) ideal gas and (b) van der
Waals equation of state with a, b for a mixture?
a) Ideal gas mixture
Eq.11.15: Rmix = ci Ri = 0.5 0.2081 + 0.5 0.2968 = 0.25245 kJ/kg K
mRmixT 2 0.25245 180
V=
=
= 0.0454 m3
P
2000
b) van der Waals equation of state. before we can do the parameters a, b for the
mixture we need the individual component parameters.
2

2
27 R Tc 27 (0.2081 150.8)2
aAr = 64 P = 64
= 0.08531
4870
c
A

2
27 R Tc 27 (0.2968 126.2)2
aN2 = 64 P = 64
= 0.17459
3390
c
RTc 0.2081 150.8
bAr = 8P =
= 0.000 805
8 4870
c
RTc 0.2968 126.2
bN2 = 8P =
= 0.001 381
8 3390
c
Now the mixture parameters are from Eq.12.84
AE

1/22

amix =
ci ai = (0.5 0.08531 + 0.5 0.17459)2 = 0.126
bmix = ci bi = 0.5 0.000 805 + 0.5 0.001 381 = 0.001 093
RT
a
Using now Eq.12.52:
P=
2
vb v
0.25245 180 0.126
2000 =
2
v 0.001 093
v
By trial and error we find the specific volume, v = 0.02097 m3/kg
V = mv = 0.04194 m3
A

E AE

EA

EA

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12.123
R-410A is a 1:1 mass ratio mixture of R-32 and R-125. Find the specific volume
at 20oC, 1200 kPa using Kays rule and the generalized charts and compare to
Table B.4
E

Kays rule Eq.12.83


Pc mix = 0.5 5.78 + 0.5 3.62 = 4.70 MPa
Tc mix = 0.5 351.3 + 0.5 339.2 = 345.25 K
1.2
293.15
Reduced properties: Pr = 4.70 = 0.255, Tr = 345.25 = 0.849
Table A.5: R = 0.1145 kJ/kg-K or compute from mix
Fig. D.1: Z = 0.85
v = ZRT/P = 0.85 0.1145 293.15 / 1200 = 0.0238 m3/kg
Table B.4: v = 0.02260 m3/kg
A

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12.124
The R-410A in Problem 12.123 is flowing through a heat exchanger with an
exit at 120oC, 1200 kPa. Find the specific heat transfer using Kays rule and the
generalized charts and compare to solution using Table B.4
E

Rmix = 0.5 0.1598 + 0.5 0.06927 = 0.1145 kJ/kg-K,


CP mix = ci CP i = 0.5 0.822 + 0.5 0.791 = 0.8065 kJ/kg K
Kays rule Eq.12.84
Pc mix = 0.5 5.78 + 0.5 3.62 = 4.70 MPa
Tc mix = 0.5 351.3 + 0.5 339.2 = 345.25 K
1.2
293.15
Reduced properties 1:
Pr1 = 4.70 = 0.255, Tr1 = 345.25 = 0.849
A

(h*1 h1) = 0.4 RTc = 0.4 0.1145 345.25 = 15.81 kJ/kg

Fig. D.1:

1.2
Pr2 = 4.70 = 0.255,

Reduced properties 1:

*
h2 h2

Fig. D.1:

) = 0.2 RTc = 0.2 0.1145 345.25 = 7.906 kJ/kg

393.15
Tr2 = 345.25 = 1.139

The energy equation gives


1q2
A

= (h2 - h1) = (h2 h2)


A

+ (h*2 h*1) + (h*1 h1)


A

A
E

= -7.906 + 0.8065 (120 20) + 15.81


= 88.55 kJ/kg mix
Table B.4.2:

q = h2 h1 = 393.13 290.51 = 102.62 kJ/kg


A

A
E

The main difference is in the value of specific heat, about 1 kJ/kg-K at the avg.
T, whereas it is 0.8 kJ/kg-K at 25oC.
E

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12.125
A 2 kg mixture of 50% argon and 50% nitrogen by mass is in a tank at 2 MPa,
180 K. How large is the volume using a model of (a) ideal gas and (b) Redlich
Kwong equation of state with a, b for a mixture.
a) Ideal gas mixture
Eq.11.15: Rmix = ci Ri = 0.5 0.2081 + 0.5 0.2968 = 0.25245 kJ/kg K
mRmixT 2 0.25245 180
V=
=
= 0.0454 m3
P
2000
b) Redlich Kwong equation of state. Before we can do the parameters a, b for the
mixture we need the individual component parameters, Eq.12.54, 13.55.
E

5/2

R2Tc
0.20812 150.82.5
aAr = 0.42748 P
= 0.42748
= 1.06154
4870
c
AE

5/2

R2Tc
0.29682 126.22.5
aN2 = 0.42748 P
= 0.42748
= 1.98743
3390
c
RTc
0.2081 150.8
bAr = 0.08664 P = 0.08664
= 0.000 558
4870
c
RTc
0.2968 126.2
bN2 = 0.08664 P = 0.08664
= 0.000 957
3390
c
Now the mixture parameters are from Eq.12.84
AE

1/22

amix =
ci ai = (0.5 1.06154 + 0.5 1.98743)2 = 1.4885
bmix = ci bi = 0.5 0.000 558 + 0.5 0.000 957 = 0.000 758
RT
a
Using now Eq.12.53:
P=

v b v(v + b)T1/2
0.25245 180
1.4885
2000 =

v 0.000 758 v(v + 0.000 758) 1801/2


By trial and error we find the specific volume, v = 0.02102 m3/kg
V = mv = 0.04204 m3
A

E AE

EA

EA

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12.126
A modern jet engine operates so that the fuel is sprayed into air at a P, T higher
than the fuel critical point. Assume we have a rich mixture of 50% n-octane and
50% air by mole at 500 K and 3.5 MPa near the nozzle exit. Do I need to treat this
as a real gas mixture or is an ideal gas assumption reasonable? To answer find Z
and the enthalpy departure for the mixture assuming Kays rule and the
generalized charts.
The mole fractions are:
yC8H18 = 0.5, yN2 = 0.5 0.79 = 0.395, yO2 = 0.5 0.21 = 0.105
Eq.11.5:
Mmix = yi Mi = 0.5 114.232 + 0.395 28.013 + 0.105 31.999
= 71.541
Kays rule Eq.12.84
Pc mix = 0.5 2.49 + 0.395 3.39 + 0.105 5.04 = 3.113 MPa
Tc mix = 0.5 568.8 + 0.395 126.2 + 0.105 154.6 = 350.5 K
3.5
500
Reduced properties:
Pr = 3.113 = 1.124, Tr = 350.5 = 1.427
Fig. D.1: Z = 0.87
I must treat it as a real gas mixture.
8.3145
Fig. D.2 h* h = 0.70 RTc = 0.70 71.541 350.5 = 28.51 kJ/kg
A

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12.127
A mixture of 60% ethylene and 40% acetylene by moles is at 6 MPa, 300 K. The
mixture flows through a preheater where it is heated to 400 K at constant P. Using
the Redlich Kwong equation of state with a, b for a mixture find the inlet specific
volume. Repeat using Kays rule and the generalized charts.
To do the EOS we need the gas constant, so from Eq.11.5 we get
Mmix = yi Mi = 0.6 28.054 + 0.4 26.068 = 27.26
Rmix = 8.3145/27.26 = 0.305 kJ/kg K
Redlich Kwong EOS the individual component parameters, Eq.12.54, 12.55.
5/2

R2Tc
0.29642 282.42.5
aC2H4 = 0.42748 P
= 0.42748
= 9.9863
5040
c
AE

5/2

R2Tc
0.31932 308.32.5
aC2H2 = 0.42748 P
= 0.42748
= 11.8462
6140
c
RTc
0.2964 282.4
bC2H4 = 0.08664 P = 0.08664
= 0.001 439
5040
c
RTc
0.3193 308.3
bC2H2 = 0.08664 P = 0.08664
= 0.001 389
6140
c
Now the mixture parameters are from Eq.12.84 so we need the mass fractions
y M 0.6 28.054
cC2H4 = M
=
= 0.6175,
cC2H4 = 1 - cC2H4 = 0.3825
27.26
mix
AE

1/22

amix =
ci ai = (0.6175 9.9863 + 0.3825 11.8462)2 = 10.679
bmix = ci bi = 0.6175 0.001 439 + 0.3825 0.001 389 = 0.001 42
RT
a
Using now Eq.12.53:
P=

v b v(v + b)T1/2
0.305 300
10.679
6000 =

v 0.001 42 v(v + 0.001 42) 3001/2


By trial and error we find the specific volume, v = 0.006683 m3/kg
Kays rule Eq.12.84
Pc mix = 0.6 5.04 + 0.4 6.14 = 5.48 MPa
Tc mix = 0.6 282.4 + 0.4 308.3 = 292.8 K
6
300
Reduced properties: Pr = 5.48 = 1.095, Tr = 292.8 = 1.025
Fig. D.1: Z = 0.4 (difficult to read)
v = ZRT/P = 0.4 0.305 300 / 6000 = 0.0061 m3/kg
A

E AE

EA

EA

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12.128
For the previous problem, find the specific heat transfer using Kays rule and the
generalized charts.
To do the EOS we need the gas constant, so from Eq.11.5 we get
Mmix = yi Mi = 0.6 28.054 + 0.4 26.068 = 27.26
Rmix = 8.3145/27.26 = 0.305 kJ/kg K
y M 0.6 28.054
cC2H4 = M
=
= 0.6175,
cC2H4 = 1 - cC2H4 = 0.3825
27.26
mix
A

CP mix = ci CP i = 0.6175 1.548 + 0.3825 1.699 = 1.606 kJ/kg K


Kays rule Eq.12.84
Pc mix = 0.6 5.04 + 0.4 6.14 = 5.48 MPa
Tc mix = 0.6 282.4 + 0.4 308.3 = 292.8 K
6
300
Reduced properties 1:
Pr1 = 5.48 = 1.095, Tr1 = 292.8 = 1.025
A

*
h1 h1

Fig. D.1:

) = 2.1 RTc = 2.1 0.305 292.8 = 187.5 kJ/kg

6
Pr2 =
= 1.095,
5.48

Reduced properties 2:

Tr2 =

*
h2 h2

Fig. D.1:

) = 0.7 RTc = 0.7 0.305 292.8 = 62.5 kJ/kg

400
= 1.366
292.8
A

The energy equation gives


1q2
A

= (h2 - h1) = (h2 h2)


A

+ (h*2 h*1) + (h*1 h1)


A

A
E

= -62.5 + 1.606 (400 300) + 187.5


= 285.6 kJ/kg mix

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12.129
A gas mixture of a known composition is frequently required for different
purposes, e.g., in the calibration of gas analyzers. It is desired to prepare a gas
mixture of 80% ethylene and 20% carbon dioxide (mole basis) at 10 MPa, 25C
in an uninsulated, rigid 50-L tank. The tank is initially to contain CO2 at 25C
and some pressure P1. The valve to a line flowing C2H4 at 25C, 10 MPa, is now
opened slightly, and remains open until the tank reaches 10 MPa, at which point
the temperature can be assumed to be 25C. Assume that the gas mixture so
prepared can be represented by Kays rule and the generalized charts. Given the
desired final state, what is the initial pressure of the carbon dioxide, P1?
A = C2H4, B = CO2
A

Pi =10 MPaA
o
Ti = 25 C

T1 = 25 oC
E

P2 = 10 MPa, T2 = 25 oC
E

V=0.05 3
m B

yA2 = 0.8, yB2 = 0.2


A

Mixture at 2 :
PC2 = 0.8 5.04 + 0.2 7.38 = 5.508 MPa
A

TC2 = 0.8 282.4 + 0.2 304.1 = 286.7 K


A

Tr2 = 298.15/286.7 = 1.040; Pr2 = 10/5.508 = 1.816


A

D.1 :

Z2 = 0.32
A

P2V

10 0000.05
- = 0.328.3145298.2 = 0.6302 kmol
Z2RT2

n2 =
A

nA2 = ni = 0.8 n2 = 0.5042 kmol C2H4


A

nB2 = n1 = 0.2 n2 = 0.1260 kmol CO2


A

298.2
Tr1 = 304.1 = 0.981
A

n1ZB1RT1

0.126 ZB1 8.3145298.2

Pr1 =
A

PCBV
A

73800.05
A

= 0.8466 ZB1
A

By trial & error: Pr1 = 0.618 & ZB1 = 0.73


A

P1 = 0.618 7.38 = 4.56 MPa


A

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12.130
One kmol/s of saturated liquid methane, CH4, at 1 MPa and 2 kmol/s of ethane,
C2H6, at 250C, 1 MPa are fed to a mixing chamber with the resultant mixture
exiting at 50C, 1 MPa. Assume that Kays rule applies to the mixture and
determine the heat transfer in the process.
Control volume the mixing chamber, inlet CH4 is 1, inlet C2H6 is 2 and the
exit state is 3. Energy equation is
.
. . . QCV = n3 h3 - n1 h1 - n2 h2
E

Select the ideal gas reference temperature to be T3 and use the


generalized charts for all three states.
Pr1 = Prsat = 1/4.60 = 0.2174 =>
Trsat = 0.783,
T1 = 0.783 190.4 = 149.1 K,

h1 = 4.57

Pr2 = 1/4.88 = 0.205, Tr2 = 523/305.4 = 1.713,

h2 = 0.08

h1 = C1(T1 - T3) - h1 RTc = 36.15(149.1 - 323.2) - 4.57 8.3145 190.4


= -13528 kJ/kmol
h2 = C2(T2 - T3) - h2 RTc = 53.11(250 - 50) - 0.08 8.3145 305.4
E

= 10 419 kJ/kmol
Kays rule Eq.12.84
Tcmix = (1 190.4 + 2 305.4)/3 = 267.1 K
Pcmix = (1 4.60 + 2 4.88)/3 = 4.79 MPa
Tr3 = 323.2/267.1 = 1.21 ,

Pr3 = 1/4.79 = 0.21,

h3 = 0.15

h3 = 0 - 0.15 267.1 8.3145 = - 333 kJ/kmol


E

.
QCV = 3(-333) - 1(-13528) - 2(10 419) = - 8309 kW
E

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12.131
Saturated-liquid ethane at T1 = 14C is throttled into a steady flow mixing
chamber at the rate of 0.25 kmol/s. Argon gas at T2 = 25C, P2 = 800 kPa, enters
the chamber at the rate of 0.75 kmol/s. Heat is transferred to the chamber from a
heat source at a constant temperature of 150oC at a rate such that a gas mixture
exits the chamber at T3 = 120oC, P3 = 800 kPa. Find the rate of heat transfer and
the rate of entropy generation.
.
Argon, Ta2 = 25oC, P2 = 800 kPa, n2 = 0.75 kmol/s
A

A
E

A
E

Tca = 150 K, Pca = 4.87 MPa, Ma = 39.948 kg/kmol, Cpa = 0.52 kJ/kg K
ha3 - ha2 = MaCpa(T3 - Ta2) = 1973.4 kJ/kmol
.
Inlet: Ethane, Tb1 = 14oC, sat. liq., xb1 = 0, n1 = 0.25 kmol/s
Tcb = 305.4 K, Pcb = 4.88 MPa, Mb = 30.07 kg/kmol, Cpb = 1.766 kJ/kg-K
Tr1 = 0.94, Pb1 = Pr1Pcb = 0.69 4880 = 3367 kPa

hb1 hb1 = 3.81 RTcb = 9674.5 kJ/kmol, s-b1 s-b1 = 3.74 R = 31.1
E


hb3 - h b1 = MbCpb(T3 - Tb1) = 5629.6 kJ/kmol
Exit: Mix, T3 = 120oC, P3 = 800 kPa consider this an ideal gas mixture.
. . . . . . Energy Eq.: n1hb1 + n2ha2 +Q = n3h3 = n1hb3 + n2ha3
E

. . . Q = n1(hb3 - hb1) + n2(ha3 - ha2) = 0.25 (5629.6 + 9674.5) + 0.75(1973.4)


E

= 5306 kW
.
.
.
.
Entropy Eq.: Sgen = n1(s-b3 s-b1) + n2(s-a3 s-a2) - Q/TH ;
E

TH = 150oC

. .
ya = n2/ntot = 0.75;

. .
yb = n1/ntot = 0.25
T3 yaP3
s-a3 s-a2 = MaCpalnT - R ln P = 8.14 kJ/kmol-K
a2
a2
E

T3 ybP3
s-b3 s-b1 = MbCpblnT - R ln P + s-b1 s-b1 =
E

b1

b1

= 40.172 + 31.1 = 71.27 kJ/kmol K


.
Sgen = 0.25 71.27 + 0.75 8.14 - 5306 / 423 = 11.38 kW/K

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12.132
A cylinder/piston contains a gas mixture, 50% CO2 and 50% C2H6 (mole basis)
at 700 kPa, 35C, at which point the cylinder volume is 5 L. The mixture is now
compressed to 5.5 MPa in a reversible isothermal process. Calculate the heat
transfer and work for the process, using the following model for the gas mixture:
a. Ideal gas mixture.
b. Kays rule and the generalized charts.
a) Ideal gas mixture
U2 - U1 = mCv mix(T2 - T1) = 0
A

Q12 = W12 = P dV = P1V1 ln(V2/V1) = - P1V1 ln(P2/P1)

EA

= - 700 0.005 ln(5500/700) = -7.71 kJ


b) Kay's rule
Tcmix = 0.5 304.1 + 0.5 305.4 = 304.75 K
Pcmix = 0.5 7.38 + 0.5 4.88 = 6.13 MPa
Tr1 = 308.15/304.75 = 1.011, Pr1 = 0.7/6.13 = 0.1142
Z1 = 0.96, h1 = 0.12, s1 = 0.08
700*0.005
n = P1V1/Z1R T1 = 0.962*8.3145*308.15 = 0.00142 kmol
Tr2 = Tr1 , Pr2 = 5.5/6.13 = 0.897,
E

h2 = 1.35,

Z2 = 0.58,

s2 = 1.0

- - h2 - h1 = (h2 - h1) - R Tc(h2 - h1)


E

= 0 - 8.3145 304.75(1.35 - 0.12) = - 3117


- u-2 - u-1 = h2 - h1 + RT(Z1 - Z2) = - 3117
E

+ 8.3145 308.15(0.96 - 0.58) = -2143 kJ/kmol


Q12 = nT(s-2 - s-1)T = 0.00142 308.15 8.3145[ 0 - ln(5.5/0.7) -1.0
E

W12 = Q12

+ 0.08 ] = - 10.85 kJ
- n(u- - u- ) = -10.85 - 0.00142(-2143) = - 7.81 kJ
E

2
A

1
A

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12.133
A cylinder/piston contains a gas mixture, 50% CO2 and 50% C2H6 (mole basis) at
700 kPa, 35C, at which point the cylinder volume is 5 L. The mixture is now
compressed to 5.5 MPa in a reversible isothermal process. Calculate the heat
transfer and work for the process, using the following model for the gas mixture:
a. Ideal gas mixture. b. The van der Waals equation of state.
a) Ideal gas mixture
U2 - U1 = mCv mix(T2 - T1) = 0
A

Q12 = W12 = P dV = P1V1 ln(V2/V1) = - P1V1 ln(P2/P1)

EA

= - 700 0.005 ln(5500/700) = -7.71 kJ


b) van der waal's equation
For CO2 : b = R Tc/8Pc = 8.3145 304.1/8 7380 = 0.04282
E

a = 27 Pc b2 = 27 7380 0.042822 = 365.45


b = R Tc/8Pc = 8.3145 305.4/8 4880 = 0.06504

For C2H6 :

a = 27 Pc b2 = 27 4880 0.065042 = 557.41


amix = (0.5 365.45 + 0.5 557.41)2 = 456.384
A

EA

EA

bmix = 0.5 0.04282 + 0.5 0.06504 = 0.05393


8.3145*308.2 456.384
- - 700 = 0
v- - 0.05393
v 2
A

By trial and error: v-1 = 3.5329 m3/kmol


E

8.3145*308.2 456.384
- 5500 = 0
v- - 0.05393
v- 2
A

By trial and error: v-2 = 0.2815 m3/kmol


E

n = V1/v-1 = 0.005/3.5329 = 0.00142


v-2 - b
Q12 = nT(s-2 - s-1)T = n R T ln
v-1 - b
E

0.2815 - 0.05392
= 0.00142 8.3145 308.2 ln 3.5329 - 0.05392 = - 9.93 kJ
A

U2 - U1 = 0.00142 456.39(3.5329-1 - 0.2815-1) = -2.12 kJ


Q12 = U2 - U1 + W12 => W12 = -9.93 -(-2.12) = -7.81 kJ

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Helmholtz EOS

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12.134
Verify that the ideal gas part of Helmholtz function substituted in Eq.12.89
does lead to the ideal gas law as in note after Eq.12.97.
The ideal gas Helmholtz function is from its definition, see Eq.12.12,
a* = u* Ts* = h* RT T s*
We have
E

h* = ho +
CPo dT
E

* CPo
T
s* = so + T dT R ln

oTo
a*
Now from Eq.12.89 we need to look at so following 12.92
T
*
h
a*
s*
RT
=
T
T T T
T
T

= 0 0 + TR ln
oToT
= RT /
So then
a*
2 = P = RT
Ideal gas OK
T
E

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12.135
Gases like argon and neon have constant specific heats. Develop an expression
for the ideal gas contribution to Helmholtz function in Eq.12.92 for these cases.
The ideal gas Helmholtz function is from its definition, see Eq.12.92,
a* = u* Ts* = h* RT T s*
We have
E

h* = ho +
CPo dT = ho + CPo(T To)
E

* CPo
T
s* = so + T dT R ln

oTo
*
T
= so + CPo ln(T /To) R ln

oTo
So now we get
E

a* = ho + CPo(T To) RT T s*
E

T
*
*
T
= ho T so + CPo(T To) CPoT ln ( T ) RT + RT ln

o
oTo
T

= Co + C1 T C2 T ln ( T ) + RT ln
o
o
A

where
*

Co = ho CPoTo ;
A

C1 = CPo R so ;
A

C2 = CPo R

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12.136
Find an expression for the change in Helmholtz function for a gas with an EOS as
P(v b) = RT.
From Eq.12.31 we get
duT = [ T

P
(T
)v P ] dvT = [ T ( v R b ) P ] dvT = [ P P] dvT = 0
A

From Eq.12.32 or Eq.12.34 we get


v
P
dsT = ( )P dPT = ( )v dvT
T
T
A

R
R
= P dPT = v b dvT
A

Now the changes in u and s can be integrated to find


(u2 u1)T = 0
P2
v2 b
(s2 s1)T = R ln P = R ln b
v1
1
to this we now need to add the variation due to T. For this we get
2
2

(u2 u1)v =
Cv dT

and

Cv
(s2 s1)v = T dT

Finally since the Helmholtz function contains the product Ts we need the absolute
value of the entropy so
1

v1 b
Cv
s1 = so + T dT + R ln b
vo

Then the change in Helmholtz function becomes


a2 a1 = u2 u1 T2s2 + T1s1 = u2 u1 T2(s2 s1) + (T1 T2) s1
2
2

v2 b
Cv

=
C
dT

T
[
dT
+
R
ln
v
2

v1 b ] + (T1 T2) s1
T
1

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12.137
Use the equation of state in Example 12.3 and find an expression for isothermal
changes in Helmholtz function between two states.
The EOS is
A

Pv
P
=
1

C
RT
T4
A

RT C
v= P 3
T

or
A

and we use the isothermal changes found in Ex.14.3 as


4C
(h2 h1)T = 3 (P2 P1)T
T
P2
3C
(s2 s1)T = R ln P 4 (P2 P1)T
1T T
A

As Helmholtz function is: a = u Ts; we get


(a2 a1)T = (u2 u1)T T(s2 s1)T
= (h2 h1)T (P2v2 P1v1) T(s2 s1)T
4C
C
= 3 (P2 P1)T [RT2 RT1 3(P2 P1)T ]
T
T
P2
3C
+ RT ln P + 3 (P2 P1)T
1T T
A

P2
4C
C
3C
= 3 (P2 P1)T + 3(P2 P1)T + RT ln P + 3 (P2 P1)T
T
T
1T T
This now reduces to the final answer
P2
(a2 a1)T = RT ln P
1T
A

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12.138
Assume a Helmholtz equation as

a* = Co + C1 T C2 T ln ( T ) + RT ln ( )
E

where Co, C1, C2 are constants and To and o reference values for temperature
and density, see Eqs. 12.92 - 95. Find the properties P, u and s from this
expression. Is anything assumed for this particular form.
Given Helmholtz function we can find the pressure and entropy from Eq. 12.21
and then u from the definition: a = u Ts.
T
v
a* = Co + C1 T C2 T ln ( T ) RT ln ( v )
o
o
E

a*
= RT ln ( v ) = RT / v
v
v T
o
*
a

P = = RT / v
i.e. Ideal gas.
v T
A

T
v
a*
s = = C1 + C2 ln ( T ) + C2 + R ln ( v )
T v
o
o
Notice how it looks like Eq.6.17.
T
v
u = a + Ts = Co + C1 T C2 T ln ( T ) RT ln ( v )
o
o
T
v
C1T + C2T ln ( T ) + C2T + RT ln ( v )
o
o
= Co + C2 T
We find that u is linear in T.
A

Not only is it ideal gas but it also has constant specific heats.

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Review Problems

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12.139
Saturated liquid ethane at 2.44 MPa enters a heat exchanger and is brought to 611
K at constant pressure, after which it enters a reversible adiabatic turbine where it
expands to 100 kPa. Find the heat transfer in the heat exchanger, the turbine exit
temperature and turbine work.
From D.2,
Pr1 = 2.44/4.88 = 0.50 , Tr1 = 0.89, T1 = 0.89305.4 = 271.8 K
A

*
(h1-h1)
A

= 0.2765305.44.12 = 347.9

(h2-h1) = 1.766 (611 - 271.8) = 599.0


A

Pr2 = 0.50 , Tr2 = 611/305.4 = 2.00


A

(h2-h2) = RTc 0.14 = 0.2765305.40.14 = 11.8

From D.2:

A
E

q = (h2-h1) = -11.8 + 599.0 + 347.9 = 935.1 kJ/kg


A

From D.3,
*

(s2-s2) = 0.27650.05 = 0.0138


A

T3
100
* *
(s3-s2) = 1.766 ln 611 - 0.2765 ln 2440
A

Assume T3 = 368 K , Tr3 = 1.205


A

A
E

at Pr3 = 0.020
A

A
E

* *

(s3-s2) = -0.8954 + 0.8833 = -0.0121


A

From D.3,
*

(s3-s3) = 0.27650.01 = 0.0028


A

(s3-s2) = -0.0028 - 0.0121 + 0.0138 0


A

A
E

Therefore, T3 = 368 K
A

A
E

From D.2,
*

(h3-h3) = 0.2765305.40.01 = 0.8


A

w = (h2-h3) = -11.8 + 1.766 (611 - 368) + 0.8 = 418.1 kJ/kg


A

A
E

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12.140
A piston/cylinder initially contains propane at T = -7C, quality 50%, and volume
10L. A valve connecting the cylinder to a line flowing nitrogen gas at T = 20C, P
= 1 MPa is opened and nitrogen flows in. When the valve is closed, the cylinder
contains a gas mixture of 50% nitrogen, 50% propane on a mole basis at T =
20C, P = 500 kPa. What is the cylinder volume at the final state, and how much
heat transfer took place?
State 1: Propane, T = -7oC, x = 0.5, V = 10 L
A

A
E

Tc = 369.8 K, Pc = 4.25 kPa, CP = 1.679 kJ/kg-K, M = 44.097 kg/kmol


Tr1 = 0.72, Pr1 = 0.12, P1 = Pr1Pc = 510 kPa
Zf1 = 0.020, Zg1 = 0.88, Z1 = (1 - x1)Zf1 + x1Zg1 = 0.45

Fig. D.1:

A
E

Fig. D.1:

A
E

n1 = P1V1/(Z1RT1) = 510 0.01/(0.45 8.3145 266.2) = 0.00512 kmol


E

*
*
*
h1 = h 1o + CP(T1 - To) + (h 1 - h 1 ) ; h1o = 0,
A

(h 1-h 1)f /RTc = 4.79,


A

(h1-h 1)g /RTc = 0.25


A

*
*
*
h 1 - h 1 = (1 - x1) (h 1 - h 1)f + x1 (h 1 - h 1)g = 7748 kJ/kmol
A

h 1 = 0 + 1.679 44.094(-7 - 20) - 7748 = -9747 kJ/kmol


Inlet: Nitrogen, Ti = 20oC, Pi = 1.0 MPa,
Tc = 126.2 K, Pc = 3.39 MPa, Cpn = 1.042 kJ/kg-K, M = 28.013 kg/kmol
*
Tri = 2.323, Pri = 0.295, h i -h i = 0.06 8.3145 126.2 = 62.96 kJ/kmol
*
*
*
h i = hio + CPn(Ti - To) + (hi - h i ) ; hio = 0, Ti - To = 0
A

State 2: 50% Propane, 50% Nitrogen by mol, T2 = 20oC, P2 = 500 kPa


Tcmix = yiTci = 248 K,
A

A
E

Pcmix = yiPci = 3.82 MPa


A

*
Tr2 = 1.182, Pr2 = 0.131, Z2 = 0.97, (h 2 - h2)/RTc = 0.06
*
*
*
h2 = h 2o + CPmix(T2 - To) + (h 2 - h 2 ) ; h2o = 0, T2 - To = 0
A

A
E

a) ni = n1 => n2 = n1 + ni = 0.1024,

V2 = n2Z2RT2/P2 = 0.0484 m3

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b) Energy Eq.:

Qcv + nihi = n2u-2 - n21u-21 + Wcv;

u- = h - PvE

Wcv = (P1 + P2)(V2 - V1)/2 = 19.88 kJ


Qcv = n2h2 - n1h1 - nihi - P2V2 + P1V1 + Wcv

h i = -62.96 kJ/kmol, h2 = -123.7 kJ/kmol, Qcv = 50.03 kJ

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12.141
A newly developed compound is being considered for use as the working fluid in
a small Rankine-cycle power plant driven by a supply of waste heat. Assume the
cycle is ideal, with saturated vapor at 200C entering the turbine and saturated
liquid at 20C exiting the condenser. The only properties known for this
compound are molecular weight of 80 kg/kmol, ideal gas heat capacity CPO= 0.80
A

kJ/kg K and TC = 500 K, PC = 5 MPa. Calculate the work input, per kilogram, to
A

the pump and the cycle thermal efficiency.


T1 = 200oC = 473.2 K, x1 = 1.0

.
WT

Turbine
.
QH

T3 = 20 C = 293.2 K, x3 = 0.0
A

Properties known:
M = 80, CPO = 0.8 kJ/kg K
A

Ht.
Exch

TC = 500 K, PC = 5.0 MPa


473.2
293.2
Tr1 = 500 = 0.946 , Tr3 = 500 = 0.586

Cond

P
4

.
-WP

R = R/M = 8.31451/80 = 0.10393 kJ/kg K

From Fig. D.1,


Pr1 = 0.72, P1 = 0.72 5 = 3.6 MPa = P4
A

Pr3 = 0.023, P3 = 0.115 MPa = P2 , ZF3 = 0.004


A

vF3 =
A

ZF3RT3 0.004 0.10393 293.2


= 0.00106 m3/kg
P3 =
115
E

wP = -
vdP vF3(P4 -P3) = -0.00106(3600-115) = -3.7 kJ/kg
A

EA

qH + h4 = h1 , but h3 = h4 + wP
A

=>

qH = (h1-h3) + wP
A

From Fig. D.2:


*

(h1-h1) = RTC 1.25 = 0.103 93 500 1.25 = 64.9 kJ/kg


A

*
(h3-h3)
A

= 0.103 93 500 5.2 = 270.2 kJ/kg

(h1-h3) = CP0(T1-T3) = 0.80(200-20) = 144.0 kJ/kg


A

(h1-h3) = -64.9 + 144.0 + 270.2 = 349.3 kJ/kg


A

qH = 349.3 + (-3.7) = 345.6 kJ/kg


A

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*

Turbine, (s2 - s1) = 0 = -(s2 - s2)+(s2 - s1) + (s1 - s1)


A

From Fig. D.3,


*

(s1-s1) = 0.103930.99 = 0.1029 kJ/kg K


A

293.2
115
* *
(s2-s1) = 0.80 ln 473.2 - 0.103 93 ln 3600 = -0.0250
A

Substituting,
*

s2-s2 = +0.1029 - 0.0250 = 0.0779 = (s2-sF2) - x2sFG2


A

0.0779 = 0.103 938.85 - x20.103 93(8.85-0.06)


A

*
(h2-h2)
A

*
(h2-hF2)

- x2hFG2
A

=> x2 = 0.922
A

From Fig. D.2,


hFG2 = 0.10393 500 (5.2-0.07) = 266.6
A

(h2-h2) = 270.2 -0.922 266.6 = 25.0


A

wT = (h1-h2) = -64.9 + 144.0 + 25.0 = 104.1 kJ/kg


A

TH =
A

wNET
qH
A

104.1-3.7
345.6 = 0.29
A

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12.142
A 200-L rigid tank contains propane at 400 K, 3.5 MPa. A valve is opened, and
propane flows out until half the initial mass has escaped, at which point the valve
is closed. During this process the mass remaining inside the tank expands
according to the relation Pv1.4 = constant. Calculate the heat transfer to the tank
during the process.
C3H8: V = 200 L, T1 = 400 K, P1 = 3.5 MPa
E

1.4

Flow out to m2 = m1/2 ; Pv


A

= const inside

400
3.5
Tr1 = 369.8 = 1.082, Pr1 = 4.25 = 0.824 Fig D.1: Z1 = 0.74
A

A
E

0.740.188 55400
= 0.01594, v2 = 2v1 = 0.03188
3500
0.2
1
m1 = 0.015 94 = 12.55 kg, m2 = 2 m1 = 6.275 kg,
v1 =
A

v1
P2 = P1 v
2

A
E

1.4

3500
= 1326 kPa
21.4
Trial & error: saturated with
1.326
T = 0.826369.8 = 305.5 K &
Pr2 = 4.25 = 0.312
2

Z = 13260.03188 = 0.734
P2v2 = Z2RT2
2 0.188 55305.5
Z2 = ZF2 + x2(ZG2 - ZF2) = 0.734 = 0.05 + x2(0.78-0.05) => x2 = 0.937
A

( )

*
(h1-h1)
* *
(h2-h1)
A

A
E

= 1.6794(305.5-400) = -158.7

= 0.188 55369.8(0.9) = 62.8

(h2-h2) = (h2-hF2) - x2hFG2 = 0.188 55369.8 4.41 - 0.937(4.41-0.55)


A

= 55.3
Energy Eq.:

A
E

h1 = 0 + (h1-h1) = -62.8

A
E

QCV = m2h2 - m1h1 + (P1-P2)V + mehe AVE

Let h1 = 0 then
A

h2 = h1 + (h2-h1) + (h2-h2) = 0 - 158.7 55.3 = -214.0


A

he AVE = (h1+h2)/2 = -138.4


A

QCV = 6.275(-214.0) - 12.55(-62.8)


A

+ (3500-1326)0.2 + 6.275(-138.4) = -981.4 kJ

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12.143
One kilogram per second water enters a solar collector at 40C and exits at 190C,
as shown in Fig. P12.143. The hot water is sprayed into a direct-contact heat
exchanger (no mixing of the two fluids) used to boil the liquid butane. Pure
saturated-vapor butane exits at the top at 80C and is fed to the turbine. If the
butane condenser temperature is 30C and the turbine and pump isentropic
efficiencies are each 80%, determine the net power output of the cycle.
H2O cycle: solar energy input raises 1 kg/s of liquid H2O from 40oC to 190oC.
E

Therefore, corresponding heat input to the butane in the heat exchanger is


.
.
QH = m(hF 190 C-hF 40 C)H2O = 1(807.62-167.57) = 640.05 kW
E

C4H10 cycle

Turbine

T1 = 80 oC, x1 = 1.0 ; T3 = 30 oC, x3 = 0.0

.
WT

ST = SP = 0.80
353.2
Tr1 = 425.2 = 0.831
From D.1, D.2 and D.3:
P1 = 0.3253800 = 1235 kPa
A

Ht.
Exch

.
QH

Cond

*
(h1-h1) = 0.143 04425.20.56 = 34.1
*
(s1-s1) = 0.143 040.475 = 0.0680

.
-WP

303.2
Tr3 = 425.2 = 0.713
A

From D.1, D.2 and D.3: P3 = 0.1133800 = 429 kPa


A

sat. liq.: (h*-hF) = RTC4.81 = 292.5 ;

(s*-sF) = R6.64 = 0.950

sat. vap.: (h -hG) = RTC0.235 = 14.3 ;

(s -sG) = R0.22 = 0.031

Because of the combination of properties of C4H10 (particularly the large CP0


A

/R), s1 is larger than sG at T3. To demonstrate,


A

353.2
1235
* *
(s1-sG3) = 1.7164 ln 303.2 - 0.143 04 ln 429 = 0.1107
A

(s1-sG3) = -0.0680 + 0.1107 + 0.031 = +0.0737 kJ/kg K


A

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T

so that T2S will be > T3, as shown in the T-s


diagram. A number of other heavy hydrocarbons
also exhibit this behavior.
Assume T2S = 315 K, Tr2S = 0.741
A

2s 2

s
From D.2 and D.3:
*

(h2S-h2S) = RTC0.21 = 12.8


A

and

(s2S-s2S) = R0.19 = 0.027


A

353.2
1235
* *
(s1-s2S) = 1.7164 ln 315 - 0.143 04 ln 429 = +0.0453
A

(s1-s2S) = -0.0680 + 0.0453 + 0.027 0


A

T2S = 315 K
A

(h1-h2S) = 1.7164(353.2-315) = 65.6


A

wST = h1-h2S = -34.1 + 65.6 + 12.8= 44.3 kJ/kg


A

wT = SwST = 0.8044.3 = 35.4 kJ/kg


A

At state 3,
0.0190.143 04303.2
v3 =
= 0.001 92 m3/kg
429
E

-wSP v3(P4-P3) = 0.001 92(1235-429) = 1.55 kJ/kg


A

-wP =
A

SP
A

-wSP

1.55
= 0.8 = 1.94 kJ/kg
A

wNET = wT + wP = 35.4 - 1.94= 33.46 kJ/kg


A

For the heat exchanger,


.
.
QH = 640.05 = mC4H10(h1-h4)
E

But

h1-h4 = h1-h3+wP
A

*
(h1-h1)

h1-h3 =
A

* *
(h1-h3)
E

+ (h3-h3)
A

= -34.1 + 1.716(80 - 30) + 292.5 = 344.2 kJ/kg


Therefore,
640.05
.
mC4H10 = 344.2-1.94 = 1.87 kg/s
.
.
WNET = mC4H10wNET = 1.87 33.46 = 62.57 kW
E

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12.144
A piston/cylinder contains ethane gas, initially at 500 kPa, 100 L, and at ambient
temperature, 0C. The piston is now moved, compressing the ethane until it is at
20C, with a quality of 50%. The work required is 25% more than would have
been required for a reversible polytropic process between the same initial and
final states. Calculate the heat transfer and the entropy generation for the process.
Ethane: Tc = 305.4 K, Pc = 4.88 MPa,
R = 0.2765 kJ/kg-K, Cp = 1.766 kJ/kg K
Tr1 = 0.895, Pr1 = 0.102 Z1 = 0.95
v1 = Z1RT1/P1 = 0.1435 m3/kg, m1 = V1/v1 = 0.697 kg

State 1:

(h*1 h1) = 0.13RTc = 11.0 kJ/kg, (s*1 s1) = 0.09 R = 0.025 kJ/kg K
State 2: T2 = 20oC, x2 = 0.5, 1W2 = 1.25Wrev
Tr2 = 0.96, Pr2 = 0.78, P2 = Pr2Pc = 3806 kPa
Zf2 = 0.14, Zg2 = 0.54, Z2 = (1 - x2)Zf + x2Zg = 0.34

(h*2 h2) = (1 - x2) 3.65 RTc + x2 (1.39 RTc) = 212.8 kJ/kg


(s*2 s2) = (1 - x2) 3.45 R + x2 1.10 R = 0.629 kJ/kg K
v2 = Z2RT2/P2 = 0.0072 m3/kg,

V2 = mv2 = 0.005 m3

Polytropic process
n

P1V1 = P2V2 ,

P2
V1
ln P = n ln V
1

n = 0.6783

P2V2 - P1V1
= -96.3 kJ,
1-n
1W2 = 1.25Wrev = -120.4 kJ

Wrev = P dV =

a) Energy Eq.:

1Q2
*
h 2 h2

h2 - h1 = (

= m(u2 - u1) + 1W2;

u = h - Pv

) + (h*2 h*1) + (h*1 h1)

= -212.8 + 1.766(20 0) + 11.0 = -166.5 kJ/kg


u2 - u1 = (h2 - h1) - (P2v2 - P1v1) = -122.2 kJ/kg
1Q2

= 0.697 kg (-122.2) kJ/kg - 120.4 kJ = -205.6 kJ

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b) Entropy Eq.:

Sgen = m(s2 - s1) - 1Q2 /To;


*

s2 - s1 = (s2 s2)

To = 0oC = 273.15 K

+ (s*2 s*1) + (s*1 s1)

(s*2 s*1) = Cp ln(T2 / T1) R ln(P2 / P1) = -0.436 kJ/kg K,


205.6
Sgen = 0.697(-0.629 - 0.436 + 0.025) + 273.15 = 0.028 kJ/K

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12.145
Carbon dioxide gas enters a turbine at 5 MPa, 100C, and exits at 1 MPa. If the
isentropic efficiency of the turbine is 75%, determine the exit temperature and the
second-law efficiency using the generalized charts.
CO2 turbine: S = w/wS = 0.75
inlet: T1 = 100oC, P1 = 5 MPa, exhaust: P2 = 1 MPa
5
373.2
1
a) Pr1 = 7.38 = 0.678, Tr1 = 304.1 = 1.227, Pr2 = 7.38 = 0.136
From D.2 and D.3,
*

(h1 - h1) = 0.188 92304.10.52 = 29.9


*

(s1 - s1) = 0.188 920.30 = 0.0567


Assume T2S = 253 K, Tr2S = 0.832
From D.2 and D.3:

(h2S-h2S) = RTC0.20 = 11.5

(s2S - s2S) = R0.17 = 0.0321


253
1
*
*
(s2S - s1) = 0.8418 ln 373.2 - 0.188 92 ln 5 = -0.0232
(s2S - s1) = -0.0321 - 0.0232 + 0.0567 0
T2S = 253 K
*

(h2S - h1) = 0.8418(253-373.2) = -101.2


wS = (h1 - h2S) = -29.9 + 101.2 + 11.5 = 82.8 kJ/kg
*

w = SwS = 0.7582.8 = 62.1 kJ/kg = (h1-h1) + (h1-h2) + (h2-h2)


Assume T2 = 275 K, Tr2 = 0.904
*

(h1 - h2) = 0.8418 (373.2 - 275) = 82.7


From D.2 and D.3,
*

(h2 - h2) = RTC0.17 = 9.8 ;

(s2 - s2) = R0.13 = 0.0245

Substituting,
w = -29.9 + 82.7 + 9.8 = 62.7 62.1

T2 = 275 K

For the exergies we need the entropy changes


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275
1
*
*
(s2 - s1) = 0.8418 ln 373.2 - 0.188 92 ln 5 = +0.0470
(s2 - s1) = -0.0245 + 0.0470 + 0.0567 = +0.0792
Assuming T0 = 25 oC,
(1 - 2) = (h1 - h2) - T0(s1 - s2) = 62.1 + 298.2(0.0792) = 85.7 kJ/kg
2nd Law =

w
62.1
=
= 0.725
1-2 85.7

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12.146
A 10- m3 storage tank contains methane at low temperature. The pressure inside is
700 kPa, and the tank contains 25% liquid and 75% vapor, on a volume basis. The
tank warms very slowly because heat is transferred from the ambient.
a. What is the temperature of the methane when the pressure reaches 10 MPa?
b. Calculate the heat transferred in the process, using the generalized charts.
c. Repeat parts (a) and (b), using the methane tables, Table B.7. Discuss the
differences in the results.
CH4: V = 10 m3, P1 = 700 kPa
VLIQ 1 = 2.5 m3, VVAP 1 = 7.5 m3
0.70
10
a) Pr1 = 4.60 = 0.152, Pr2 = 4.60 = 2.174
From D.1: ZF1 = 0.025, ZG1 = 0.87 &
T1 = 0.74 190.4 = 140.9 K
vF1 =

0.0250.5183140.9
= 0.00261
700

0.870.5183140.9
= 0.0908
700
2.5
7.5
mLIQ 1 = 0.00261 = 957.9 kg, mVAP 1 = 0.0908 = 82.6 kg
Total m = 1040.3 kg
Z20.5183190.4Tr2
V
10
v2 = v1 = m = 1040.5 = 0.00961 =
10 000
vG1 =

or Z2Tr2 = 0.9737 at Pr2 = 2.174


By trial and error
Tr2 = 1.334 & Z2 = 0.73,

T2 = 1.334190.4 = 254.0 K

b) Energy Eq.:
Q12 = m(u2-u1) = m(h2-h1) - V(P2-P1)
82.6
Using D.2 & x1 = 1040.5 = 0.0794
*

(h1-h1) = (h1-hf1) - x1hfg1

] = 431.1

= 0.518 35190.4 4.72-0.0794(4.72-0.29)


*

(h2 - h1) = CP (T2 T1) = 2.254 (254.0 - 140.9) = 254.9


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*

(h2 - h2) = 0.5183 190.4(1.47) = 145.1


(h2 - h1) = -145.1 + 254.9 + 431.1 = 540.9 kJ/kg
Q12 = 1040.5 kg (540.9) kJ/kg 10 m3 (10 000-700) kPa
= 469 806 kJ
c) Using Table B.7 for CH4
T1 = TSAT 1 = 141.7 K,

vF1 = 0.002 675,

uF1 = -178.47

vG1 = 0.090 45 , uG1 = 199.84


2.5
mLIQ 1 = 0.002 675 = 934.6,
Total mass

7.5
mVAP 1 = 0.090 45 = 82.9

m = 1017.5 kg and

10
v2 = 1017.5 = 0.009 828 m3/kg

T2 = 259.1 K
At v2 & P2 = 10 MPa u = 296.11
2
Q12 = m(u2-u1) = 1017.5296.11 - 934.6(-178.47) - 82.9(199.84)
= 451 523 kJ

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12.147
Consider the following reference state conditions: the entropy of real saturated
liquid methane at 100C is to be taken as 100 kJ/kmol K, and the entropy of
hypothetical ideal gas ethane at 100C is to be taken as 200 kJ/kmol K.
Calculate the entropy per kmol of a real gas mixture of 50% methane, 50% ethane
(mole basis) at 20C, 4 MPa, in terms of the specified reference state values, and
assuming Kays rule for the real mixture behavior.
CH : T = -100 oC, s= 100 kJ/kmol K
4

LIQ 0

C2H6: T0 = -100 oC, P0 = 1 MPa,

*
s-0 = 200 kJ/kmol K

Also for CH4: TC = 190.4 K, PC = 4.60 MPa


For a 50% mixture Kays rule Eq.12.84:
Tcmix = 0.5 190.4 + 0.5 305.4 = 247.9 K
Pcmix = 0.5 4.60 + 0.5 4.88 = 4.74 MPa
IG MIX at T0(=-100 oC), P0(=1 MPa):
CH4: Tr0 = 0.91 ,

PG = 0.57 4.60 = 2.622 MPa

*
s-0 CH4 = s-LIQ 0 P + (s-*-s-LIQ)at P - R ln (P0/PG)
G

= 100 + 4.018.3145 - 8.3145 ln (1/2.622) = 141.36


*
s-0 MIX = 0.5141.36 + 0.5200 - 8.3145(0.5 ln 0.5 + 0.5 ln 0.5) = 176.44

CP0 MIX = 0.516.042.254 + 0.530.071.766 = 44.629


293.2
4
*
s-TP MIX = 176.44 + 44.629 ln 173.2 - 8.3145 ln 1 = 188.41 kJ/kmol K
For the mixture at T, P: Tr = 1.183,
Entropy departure

Pr = 0.844

*
s-TP MIX - s-TP MIX = 0.43638.3145 = 3.63 kJ/kmol K

Therefore,
s-TP MIX = 188.41 - 3.63 = 184.78 kJ/kmol K

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An alternative is to form the ideal gas mixture at T, P instead of at T0, P0 :
T P
*
s-TP CH4 = s-LIQ 0 + (s-*-s-LIQ) + CP0 CH4 ln T - R ln P
0

P ,T
G 0

at P , T
G 0

293.2
4
= 100 + 33.34 + 16.042.254 ln 173.2 - 8.3145 ln 2.6
= 100 + 33.34 + 19.03 - 3.53 = 148.84 kJ/kmol K
293.2
4
*
s-TP C2H6 = 200 + 30.071.766 ln 173.2 - 8.3145 ln 1
= 200 + 27.96 - 11.53 = 216.43 kJ/kmol K
*
s= 0.5148.84 + 0.5216.43
TP MIX

- 8.3145(0.5 ln 0.5 + 0.5 ln 0.5) = 188.41 kJ/kmol K


s-TP MIX = 188.41 - 3.63 = 184.78 kJ/kmol K

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12.148
Determine the heat transfer and the net entropy change in problem 12.129. Use
the initial pressure of the carbon dioxide to be 4.56 MPa before the ethylene is
flowing into the tank.
A gas mixture of a known composition is frequently required for different
purposes, e.g., in the calibration of gas analyzers. It is desired to prepare a gas
mixture of 80% ethylene and 20% carbon dioxide (mole basis) at 10 MPa, 25C
in an uninsulated, rigid 50-L tank. The tank is initially to contain CO2 at 25C
and some pressure P1. The valve to a line flowing C2H4 at 25C, 10 MPa, is now
opened slightly, and remains open until the tank reaches 10 MPa, at which point
the temperature can be assumed to be 25C. Assume that the gas mixture so
prepared can be represented by Kays rule and the generalized charts. Given the
desired final state, what is the initial pressure of the carbon dioxide, P1?
A = C2H4, B = CO2

Pi =10 MPaA
o
Ti = 25 C

T1 = 25 oC
P2 = 10 MPa, T2 = 25 oC

V=0.05 3
m B

yA2 = 0.8, yB2 = 0.2


Mixture at 2 :
PC2 = 0.8 5.04 + 0.2 7.38 = 5.508 MPa
TC2 = 0.8 282.4 + 0.2 304.1 = 286.7 K

Tr2 = 298.15/286.7 = 1.040; Pr2 = 10/5.508 = 1.816


D.1 :
n2 =

Z2 = 0.32
P2V

10 0000.05
- = 0.328.3145298.2 = 0.6302 kmol
Z2RT2

nA2 = ni = 0.8 n2 = 0.5042 kmol C2H4


nB2 = n1 = 0.2 n2 = 0.1260 kmol CO2
298.2
Tr1 = 304.1 = 0.981 and

4560
Pr1 = 7380 = 0.618

Energy Eq.: QCV + nihi = n2u-2 - n1u-1 = n2h2 - n1h1 - (P2-P1)V


- -*
- -*
- -*
or QCV = n2(h2-h2) - n1(h1-h1) - ni(hi-hi ) - (P2-P1)V
-* -* -*
(since Ti = T1 = T2, hi = h1 = h2)
-* (h1-h1) = 0.83 8.3145 304.1 = 2099 kJ/kmol
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-* (h2-h2) = 3.40 8.3145 286.7 = 8105 kJ/kmol
298.2
10
Tri = 282.4 = 1.056, Pri = 5.04 = 1.984
-* (hi -hi) = 3.358.3145282.4 = 7866 kJ/kmol
QCV = 0.6302(-8105) - 0.126(-2099) - 0.5042(-7866) - (10 000-4560)0.05
= -1149 kJ
SCV = n2s-2 - n1s-1 , SSURR = - QCV/T0 - nis-i
Sgen = n2s-2 - n1s-1 - QCV/T0 - nis-i
*
*
Let s-A0 = s-B0 = 0 at T0 = 25 oC, P0 = 0.1 MPa
*

Then s-MIX 0 = -8.3145 (0.8 ln 0.8 + 0.2 ln 0.2) = 4.161 kJ/kmol K


*
*
*
*
s-1 = s-B0 + (s-P1 T1-s-P0 T0)B + (s-1-s-P1 T1)B

4.56
= 0 + (0-8.3145 ln 0.1 ) - 0.60 8.3145 = -36.75 kJ/kmol K
*
*
*
*
s-i = s-A0 + (s-Pi Ti-s-P0 T0)A + (s-i-s-Pi Ti)A
10
= 0 + (0-8.3145 ln 0.1) - 2.448.3145 = -58.58 kJ/kmol K
*
*
*
*
s-2 = s-MIX 0 + (s-P2 T2-s-P0 T0)MIX + (s-2-s-P2 T2)MIX

10
= 4.161 + (0-8.3145 ln 0.1) - 2.5518.3145 = -55.34 kJ/kmol K
Sgen = 0.6302(-55.33) - 0.126(-36.75) - 0.5042(-58.58) + 1149/298.2
= +3.15 kJ/K

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Fundamentals of
Thermodynamics
SOLUTION MANUAL
CHAPTER 12
English Units

8e
UPDATED JULY 2013

Borgnakke and Sonntag

CHAPTER 12

CONTENT CHAPTER 12
SUBSECTION

PROB NO.

Clapeyron equation
Volume Expansivity and Compressibility
Equations of State
Generalized Charts
Mixtures
Review problem

149-153
154-160
161-162
163-178
179-181
182

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Clapeyron Equation

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12.149E
Verify that Clapeyrons equation is satisfied for R-410A at 30 F in Table F.9.

Clapeyron Eq.:

F.9:

P = 111.796 psia,

dPsat dPg hfg


dT = dT = Tvfg

hfg = 95.75 Btu/lbm,

vfg = 0.5289 ft3/lbm

Slope around 30 F best approximated by cord from 20 F to 40 F


dPg 133.163 93.128
= 2.00 psia/R,
dT =
40 20
hfg
778
95.75
=
Tvfg 489.7 0.5289 144 = 1.997 psia/R
This fits very well.

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12.150E
Use the approximation given in Problem 12.16 and Table F.7 to determine A and
B for steam from properties at 70 F only. Use the equation to predict the
saturation pressure at 80 F and compare to table value.
dPsat
-2
dT = Psat (-B)(-T )
so we notice from Eq.12.7 and Table values from F.7.1 and F.4 that
hfg
1053.95
B = R = 85.76 / 778 = 9561.3 R
Now the constant A comes from the saturation pressure as
9561.3
A = ln Psat + B/T = ln 0.363 + 459.67 + 70 = 17.038
Use the equation to predict the saturation pressure at 80 F as
9561.3
ln Psat = A B/T = 17.038 - 459.67 + 80 = -0.6789
Psat = 0.5071 psia
compare this with the table value of Psat = 0.507 psia and we have a very accurate
approximation.
ln Psat = A B/T

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12.151E
Find the saturation pressure for refrigerant R-410A at 100 F assuming it is higher
than the triple point temperature.
The lowest temperature in Table F.9 for R-410A is -80 F, so it must be
extended to -100 F using the Clapeyron Eq. 12.7 integrated as in example 12.1
At T1 = -80 F = 379.7 R ,
P1 = 8.196 lbf/in.2

and

1.9859
R = 72.585 = 0.027 36 Btu/lbm R

P hfg (T-T1) 121.14 (359.7-379.7)


=
= -0.6484
ln P = R
T T1 0.027 36 359.7 379.7
1
P = P1 exp(-0.6484) = 4.286 lbf/in.2

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12.152E
Using thermodynamic data for water from Tables F.7.1 and F.7.3, estimate the
freezing temperature of liquid water at a pressure of 5000 lbf/in.2.
P

5000 psia

dPif hif
H2O dT = Tv constant
if
At the triple point,

T.P.

vif = vf - vi = 0.016 022 - 0.017 473


T

= -0.001 451 ft3/lbm

hif = hf - hi = 0.0 - (-143.34) = 143.34 Btu/lbm


dPif
143.34
778.2
2
=

dT 491.69(-0.001 451) 144 = -1085.8 lbf/in. R

at P = 5000 lbf/in2,

(5000-0.09)
T 32.02 + (-1085.8) = 27.4 F

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12.153E
Ice (solid water) at 27 F, 1 atm is compressed isothermally until it becomes liquid.
Find the required pressure.
Water, triple point T = 32.02 F = 491.69 R,
vf = 0.016 022 ft3/lbm,

vi = 0.017 473 ft3/lbm

hf = 0.00 Btu/lbm
Clapeyron

P = 0.088 67 lbf/in.2

hi = -143.34 Btu/lbm

dPif
hf - hi
143.34778.2
=
=
dT (vf - vi)T -0.001 451491.69144 = -1085.8 psia/R
dPif
P dT T = -1085.8 (27 - 32.02) = 5450.7 lbf/in.2
P = Ptp + P = 5451 lbf/in.2

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Volume Expansivity and Compressibility

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12.154E
Determine the volume expansivity, P, and the isothermal compressibility, T, for
water at 50 F, 500 lbf/in.2 and at 400 F, 1500 lbf/in.2 using the steam tables.
Water at 50 F, 500 lbf/in.2 (compressed liquid)
1 v
1 v
P = v( )P v( )P
T
T
Using values at 32 F, 50 F and 100 F
1
0.016 1 - 0.015 99
P 0.015 99
= 0.000 101 F-1
100 - 32
1 v
1 v
T = - v( )T - v( )T
P
P
Using values at saturation, 500 and 1000 lbf/in.2
1
0.015 99 - 0.016 02
T - 0.015 99
= 0.000 0019 in.2/lbf
1000 - 0.178
Water at 400 F, 1500 lbf/in.2 (compressed liquid)
1
0.019 25 - 0.017 85
= 0.000 76 F-1
P 0.018 45
450 - 350
1
0.0184 - 0.0185
T - 0.018 45 2000 - 1000 = 0.000 0054 in.2/lbf

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12.155E
Use the CATT3 software to solve the previous problem.
The benefit of the software to solve for the partial derivatives is that we can
narrow the interval over which we determine the slope.
Water at 50 F, 500 lbf/in.2 (compressed liquid)
1 v
1 v
1 v
1 v
P = v( )P v( )P ; T = - v( )T - v( )T
T
T
P
P
Estimate by finite difference using values at 40 F, 50 F and 60 F,
1
0.01601 - 0.01599
= 0.000 0625 F-1
P 0.01600
60 - 40
Using values at saturation, 500 psia and 1000 psia,
1 0.01597 - 0.01602
T - 0.0160 1000 - 0.178 = 0.000 0031 psi-1
Water at 400 F, 1500 lbf/in.2 (compressed liquid)
Estimate by finite difference using values at 350 F, 400 F and 450 F,
1
0.019 26 - 0.017 86
P 0.01 849
= 0.000 757 F-1
450 - 350
Using values at 1000 psia, 1500 psia and 2000 psia,
1
0.01 844 - 0.01 855
T - 0.018 49
= 0.000 0059 psi-1
2000 - 1000

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12.156E
A cylinder fitted with a piston contains liquid methanol at 70 F, 15 lbf/in.2 and
volume 1 ft3. The piston is moved, compressing the methanol to 3000 lbf/in.2 at
constant temperature. Calculate the work required for this process. The isothermal
compressibility of liquid methanol at 70 F is 8.3 106 in.2/lbf.
2
2
v

w
=
Pdv
=
P
dP
=
v PdPT
1 2
T
P T T

( )

For v const & T const.

=>

vT 2 2
w
=
1 2
2 P2 - P1

For liquid methanol, from Table F.3 : = 49.1 lbm/ft3


V1 = 1.0 ft3,
W =
1 2

m = 1.0 49.1 = 49.1 lbm

1.0 8.3 106


(3000)2 - (15)2 144 = 5378.4 ft lbf = 6.9 Btu
2

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12.157E
Sound waves propagate through a media as pressure waves that causes the media
to go through isentropic compression and expansion processes. The speed of
sound c is defined by c2 = (P/)s and it can be related to the adiabatic
compressibility, which for liquid ethanol at 70 F is 6.4 10-6 in.2/lbf. Find the
speed of sound at this temperature.
c2 =

P
(P
)
=
-v
(
)=
s
v s 1

1
1
=
s
v
-v

P s

( )

From Table F.3 for ethanol,


c=

32.174144
(6.410
)
48.9
-6

1/2

= 48.9 lbm/ft3
= 3848 ft/s

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12.158E
Consider the speed of sound as defined in Eq. 12.42. Calculate the speed of sound
for liquid water at 50 F, 250 lbf/in.2 and for water vapor at 400 F, 80 lbf/in.2 using
the steam tables.
From Eq 12.42 :

c2 =

P
(P
)
=
-v
(
)
s
v s
2

Liquid water at 50 F, 250 lbf/in.2


Assume

(P
) (P
)
v s
v

Using saturated liquid at 50 F and compressed liquid at 50 F, 500 lbf/in.2,

(0.016024+0.015998
) ((500-0.18)14432.174
2
0.015998-0.016024 ) = 22.83210
2

c2 = -

c = 4778 ft/s
Superheated vapor water at 400 F, 80 lbf/in.2
v = 6.217 ft3/lbm,

s = 1.6790 Btu/lbm R

At P = 60 lbf/in.2 & s = 1.6790: T = 343.8 F, v = 7.7471 ft3/lbm


At P = 100 lbf/in.2 & s = 1.6790: T = 446.2 F, v = 5.2394 ft3/lbm
c2 = -(6.217)2

((100-60)14432.174
) = 2.856 10
5.2394-7.7471

c = 1690 ft/s

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Borgnakke and Sonntag

12.159E
Liquid methanol at 77 F has an adiabatic compressibility of 7.1 10-6 in2/lbf.
What is the speed of sound? If it is compressed from 15 psia to 1500 psia in an
insulated piston/cylinder, what is the specific work?
From Eq.12.41 and Eq.12.42 and the density from table F.3
c2 =

(P
) = v (P
) = 1 = 7.1 101-6 49.1 144 32.174 ft2/s2
s
v s
2

= 13.290 106 ft2/s2


c = 3645 ft/s
The specific work becomes
2

w = P
dv =
P dP
P (-sv ) dP =
sv P dP = s v
1

= s v 0.5

2
(P2

2
P1)

0.5
= 7.1 10-6 in2/lbf 49.1 ft3/lbm (15002 152) psi2
= 0.163 (ft-lbf/lbm) (ft/in)2 = 23.4 ft-lbf/lbm = -0.03 Btu/lbm

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Borgnakke and Sonntag

Equations of State

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Borgnakke and Sonntag

12.160E
Use Table F.9 to find the compressibility of R-410A at 140 F and a) saturated
liquid b) saturated vapor and c) 400 psia
.
Table F.1:
a)

R = 1545.36 / 72.585 = 21.29 lbf-ft/lbm-R

Table F.9.1: P = 556.488 psia, v = 0.01966 ft3/lbm


Pv 556.488 0.01966 144
= 0.1234
Z = RT =
21.29 599.7

b)

Table F.9.1: P = 556.488 psia, v = 0.0796 ft3/lbm


Pv 556.488 0.0796 144
= 0.5
Z = RT =
21.29 599.7

c)

Table F.9.2: P = 400 psia, v = 0.1574 ft3/lbm


Pv 400 0.1574 144
Z = RT = 21.29 599.7 = 0.71

The R-410A is not an ideal gas at any of these states.

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Borgnakke and Sonntag

12.161E
Calculate the difference in internal energy of the ideal-gas value and the real-gas
value for carbon dioxide at the state 70 F, 150 lbf/in.2, as determined using the
virial EOS. At this state B = -2.036 ft3/lb mol, T(dB/dT) = 4.236 ft3/lb mol.

Solution:
virial:

CO2 at 70 F, 150 lbf/in2


P
RT dB
(T
)v = Rv + BR
+
( )
v dT
v

RT BRT
P= v + 2 ;
v

RT2 dB

P
RT2 dB
u-u = - T
dv = - v dT
- P dv = -
2
T v
v
v v dT
*

[( ) ]

B = -2.036 ft3/lbmol

( )

dB
T dT = 4.236 ft3/lbmol

( )

Solution of virial equation (quadratic formula):


-v = 1 RT 1 +
2 P

But

1+4BP/RT

RT 1545529.7
P = 150144 = 37.8883

] = 35.7294 ft /lbmol

v- = 0.537.8883 1 + 1+4(-2.036)/37.8883

Using the minus-sign root of the quadratic formula results in a compressibility


factor < 0.5, which is not consistent with such a truncated equation of state.
RT dB -1.9859529.7
u- - u-* = - v T dT =
4.236 = -123.9 Btu/lbmol
35.7294

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Borgnakke and Sonntag

Generalized Charts

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Borgnakke and Sonntag

12.162E
How low should the pressure be so that nitrous oxide (N2O) gas at 501.6 R can be
treated as an ideal gas with 5% accuracy or better?
From Table F.1:

Tc = 557.3 R,

Pc = 1050 psi

501.6
=> Tr1 = 557.3 = 0.9
Look in Fig. D.1 following the curve Tr1 = 0.9 to the point where Z = 0.95
Pr1 = 0.125

so

P < 0.125 1050 psi = 131 psi

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Borgnakke and Sonntag

12.163E
Nitrous oxide (N2O) at 501.6 R is at a pressure so that it can be in a two-phase
state. Find the generalized enthalpy departure for the two saturated states of liquid
and vapor.
From Table F.1:

Tc = 557.3 R,

Pc = 1050 psi

501.6
=> Tr1 = 557.3 = 0.9
From Fig. D.2:
Saturated liquid:

(h*- hf)/RTc = 4.08;

Saturated vapor:

(h*- hg)/RTc = 0.875

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Borgnakke and Sonntag

12.164E
Find the heat of evaporation, hfg, for R-134a at 30 F from the generalized charts
and compare to the value in Table F.10.

From Table F.1:

Tc = 673.6 R,

489.7
Pc = 589 psia => Tr1 = 673.6 = 0.727

R = 1.98589/102.03 = 0.01946 Btu/lbm-R


From Fig. D.2:
Saturated liquid:

(h*- hf)/RTc = 4.7;

Saturated vapor:

(h*- hg)/RTc = 0.3

hfg = hg - hf = RTc [-0.3 (-4.7)] = 4.4 RTc


= 4.4 0.01946 673.6 = 57.67 Btu/lbm
Table F. 10:

hfg = 85.63 Btu/lbm

The approximation is not very good and can be improved by using the
accentric factor.

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Borgnakke and Sonntag

12.165E
A 7-ft3 rigid tank contains propane at 1300 lbf/in.2, 540 F. The propane is then
allowed to cool to 120 F as heat is transferred with the surroundings. Determine
the quality at the final state and the mass of liquid in the tank, using the
generalized compressibility charts.
Propane C3H8:
V = 7.0 ft3, P1 = 1300 lbf/in.2, T1 = 540 F = 1000 R
cool to T2 = 120 F = 580 R
From Table F.1 : TC = 665.6 R, PC = 616 lbf/in.2
1300
1000
Pr1 = 616 = 2.110, Tr1 = 665.6 = 1.502
From D.1: Z1 = 0.83
v2 = v1 =

Z1RT1
P1

0.83 35.04 1000


= 0.1554 ft3/lbm
1300 144

From D.1 at Tr2 = 0.871, saturated => PG2 = 0.43 616 = 265 lbf/in.2
vG2 =

0.715 35.04 580


= 0.3808 ft3/lbm
265 144

vF2 =

0.075 35.04 580


= 0.0399 ft3/lbm
265 144

0.1554 = 0.0399 + x2(0.3781-0.0399)

=>

x2 = 0.3388

7.0
mLIQ 2 = (1 - 0.3388) 0.1554 = 29.8 lbm

These tanks
contain liquid
propane.

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Borgnakke and Sonntag

12.166E
A rigid tank contains 5 lbm of ethylene at 450 lbf/in.2, 90 F. It is cooled until the
ethylene reaches the saturated vapor curve. What is the final temperature?
C2H4 m = 5 lbm

C2 H4

P1 = 450 lbf/in2, T1 = 90 F = 249.7 R

T
1

450
Pr1 = 731 = 0.616,
2

Fig. D.1

549.7
Tr1 = 508.3 = 1.082

Z1 = 0.82

v
Z2Tr2

ZG2Tr2
Pr2 = Pr1 Z T = 0.616
= 0.6943 ZG2Tr2
0.82 1.082
1 r1
Trial & error to match a saturated Pr2, Tr2 and the ZG2 so Eq. is satisfied.
Guess a Tr2 and find the rest and compare with computed Pr2 from Eq.
Tr2

ZG2

0.871 0.715

Pr2

Pr2 CALC

0.43

0.432

~ OK

=> T2 = 442.7 R

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Borgnakke and Sonntag

12.167E
A piston/cylinder contains 10 lbm of butane gas at 900 R, 750 lbf/in.2. The butane
expands in a reversible polytropic process with polytropic exponent, n = 1.05,
until the final pressure is 450 lbf/in.2. Determine the final temperature and the
work done during the process.
C4H10 ,

m = 10 lbm , T1 = 900 R ,

P1 = 750 lbf/in.2

Rev. polytropic process (n = 1.05), P2 = 450 lbf/in.2


900
750
Tr1 = 765.4 = 1.176, Pr1 = 551 = 1.361
V1 = mZRT/P =
n
P1V1

n
P2V2

=> From Fig. D.1 :

Z1 = 0.67

10 0.67 26.58 900


= 1.484 ft3
750 144

750
V2 = 1.484 450

( )

1
1.05

= 2.414 ft3

P2V2 450 144 2.414


Z2Tr2 = mRT =
= 0.7688
C 10 26.58 765.4
at Pr2 = 450/551 = 0.817
Trial & error:
2

W = PdV =
1 2
1

Tr2 = 1.068,
P2V2 - P1V1
1-n

Z2 = 0.72

=>

T2 = 817.4 R

- 750 1.484
(450 2.414
) 144
778 = 98.8 Btu
1 - 1.05

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Borgnakke and Sonntag

12.168E
Calculate the heat transfer during the process described in Problem 12.167E.
From solution 12.167,
V1 = 1.473 ft3,

V2 = 2.396 ft3,

Tr1 = 1.176,

Pr1 = 1.361,

From D.1:

h*-h
RTC

( )

= 1.36,

W2 = 98.8 Btu

Tr2 = 1.068,
h*-h
RTC

( )

Pr2 = 0.817, T2 = 817.4 R


= 0.95

h2 - h1 = 0.415 (817.4 - 900) = -34.3 Btu/lbm


h2 - h1 = -34.3 +

26.58765.4
(-0.95 + 1.36) = -23.6 Btu/lbm
778

U2 - U1 = m(h2 - h1) - P2V2 + P1V1


= 10(-23.6) -

4501442.414 7501441.484
+
= -231.1 Btu
778
778

Q = U2 - U1 + 1W2 = -132.3 Btu

1 2

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Borgnakke and Sonntag

12.169E
The new refrigerant R-152a is used in a refrigerator with an evaporator
temperature of -10 F and a condensing temperature of 90 F. What are the high and
low pressures in this cycle?
Since we do not have the printed tables for R-152a we will use generalized charts.
The critical properties are: Tc = 695.5 R, Pc = 656 psi.
Tr1 = T/Tc = (459.67 10)/ 695.5 = 0.646
Fig. D.1:

PG T1 = Pr1 sat Pc = 0.06 656 = 39.4 psi

Tr2 = T/Tc = (459.67 + 90)/ 695.5 = 0.79


Fig. D.1:

PG T2 = Pr2 sat Pc = 0.25 656 = 164 psi

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Borgnakke and Sonntag

12.170E
A cylinder contains ethylene, C2H4, at 222.6 lbf/in.2, 8 F. It is now compressed in
a reversible isobaric (constant P) process to saturated liquid. Find the specific
work and heat transfer.
Ethylene C2H4 P1 = 222.6 lbf/in.2 = P2, T1 = 8 F = 467.7 R
State 2: saturated liquid, x2 = 0.0
R = 55.07 ft lbf/lbm R = 0.070 78 Btu/lbm R
467.7
222.6
Tr1 = 508.3 = 0.920 Pr1 = Pr2 = 731 = 0.305
*

Z1 = 0.85 ,

From D.1 and D.2:

v1 =

Z1RT1
P1

h -h
(RT
)
C

= 0.40

0.85 55.07 467.7


= 0.683
222.6 144

(h1-h1) = 0.070 78 508.3 0.40 = 14.4


From D.1 and D.2:
Z2 = 0.05 ,
v2 =

Z2RT2
P2

h*-h
RTC

T2 = 0.822 508.3 = 417.8 R

( )
=

= 4.42

0.05 55.07 417.8


= 0.035 89 ft3/lbm
222.6 144

(h2-h2) = 0.070 78 508.3 4.42 = 159.0 Btu/lbm


*

(h2-h1) = CP0(T2-T1) = 0.411(417.8 - 467.7) = -20.5 Btu/lbm


2

144
Pdv = P(v2-v1) = 222.6(0.035 89 - 0.683)
w =
778 = -26.7 Btu/lbm

1 2

q = (u2 - u1) + 1w2 = (h2-h1) = -159.0 - 20.5 + 14.4 = -165.1 Btu/lbm

1 2

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Borgnakke and Sonntag

12.171E
Saturated vapor R-410A at 80 F is throttled to 30 lbf/in.2 in a steady flow process.
Find the exit temperature, neglecting kinetic energy, using the generalized charts,
Fig. D.2 and repeat using Table F.9.
R-410A throttling process, R = 1.98589/72.585 = 0.02736 Btu/lbm-R
T1 = 80 F, x1 = 1.00, P2 = 30 lbf/in.2,
*

Energy Eq.:

h2-h1 = (h2-h2) + (h2-h1) + (h1-h1) = 0

Generalized charts,
From D.2:

539.7
Tr1 = 620.1 = 0.87

(h1-h1) = 0.02736 620.1 0.75 = 12.72 Btu/lbm

To get CP0, use h values from Table F.9 at low pressure (5 psia).
CP0

137.6-133.75
= 0.1925 Btu/lbm R
80-60

Substituting into energy Eq.:

(h2-h2) + 0.1925 (T2 - 30) + 12.72 = 0

30
at Pr2 = 711 = 0.042
469.7
Assume T2 = 10 F = 469.7 R => Tr2 = 620.1 = 0.757
*

(h2-h2) = 0.02736 620.1 0.07 = 1.19


Substituting,
-1.19 + 0.1925(10 - 80) + 12.72 = -1.945
479.7
Guess T2 = 20 F = 479.7 R => Tr2 = 620.1 = 0.774
*

(h2-h2) = 0.02736 620.1 0.07 = 1.19


Substituting,
-1.19 + 0.1925(20 - 80) + 12.72 = -0.02 nearly OK
T2 = 20 F (maybe re-estimate CP0 at avg T)
R-410A tables, F.9:

T1 = 80 F, x1 = 1.0

=> h1 = 122.14 Btu/lbm

h2 = h1 = 122.14 Btu/lbm, P2 = 30 lbf/in.2 => T2 = 8.15 F


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Borgnakke and Sonntag

12.172E
Find the heat of evaporation, hfg, for isobutane (Tc = 735.8 R, Pc = 529.4
psia, M = 58.124) at 54.7 F from the generalized charts and compare to the values
in the CATT3 computerized tables.
To read the charts we need the reduced temperature
Tr1 = T/Tc = (54.7 + 459.7)/735.8 = 0.70
R = 1.98589 / 58.124 = 0.03417 Btu/lbm-R
From Fig. D.2:

(h* h)g = 0.2 RTc ; (h* h)f = 4.85 RTc

hfg = hg hf = (h* h)g (h* h)f = (0.2 + 4.85) RTc


= 4.65 RTc = 4.65 0.03417 Btu/lbm-R 735.8 R
= 116.9 kJ/kg
CATT3:

hfg = 11.01 (158.5) = 147.5 Btu/lbm

The generalized charts are not super accurate, some improvement can be
done using the accentric factor.

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Borgnakke and Sonntag

12.173E
A 10-ft3 tank contains propane at 90 F, 90% quality. The tank is heated to 600 F.
Calculate the heat transfer during the process.
P
V = 10 ft3
T1 = 90 F = 549.7 R, x1 = 0.90

Heat to T2 = 600 F = 1059.7 R


M = 44.094, TC = 665.6 R

PC = 616 lbf/in.2

R = 35.04, CP0 = 0.407 Btu/lbm R


Tr1 = 0.826 Figs. D.1 and D.2

Z1 = 0.1 0.053 + 0.9 0.78 = 0.707,

h1-h1

RTc = 0.1 4.4 + 0.9 0.55 = 0.935


SAT

Pr

= 0.31 ;

PV
m = ZRT =
Pr2 =

SAT

P1

= 0.31 616 = 191 lbf/in.2

191 144 10
= 20.2 lbm
0.707 35.04 549.7

20.2 Z2 35.04 1059.7


616 144 10

Pr2 = 0.79
Trial & error:
Z2 = 0.94
*

Z2
= 1.183

at Tr2 = 1.592

and P2 = 490 lbf/in.2


*

h2-h2

and RT = 0.36
c

(h2-h1) = 0.407(600-90) = 207.6 Btu/lbm


*

(h1-h1) = 0.935 35.04 665.9/ 778 = 28.0


*

(h2-h2) = 0.36 35.04 665.9/ 778 = 10.8


From the energy equation
Q12 = m(h2-h1) - (P2-P1)V
= 20.2 (-10.8 + 207.6 + 28.0) - (490 - 191)

144 10
778

= +4541 - 553 = 3988 Btu

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Borgnakke and Sonntag

12.174E
Carbon dioxide collected from a fermentation process at 40 F, 15 lbf/in.2 should
be brought to 438 R, 590 lbf/in.2 in a steady flow process. Find the minimum
amount of work required and the heat transfer. What devices are needed to
accomplish this change of state?
35.1
R = 778 = 0.045 12 Btu/lbm R
500
Tri = 547.4 = 0.913 ,

15
Pri = 1070 = 0.014
*

h -h
(RT
) = 0.02, (sR-s) = 0.01 R

From D.2 and D.3:

438
Tre = 547.4 = 0.80,
From D.2 and D.3:
*

590
Pre = 1070 = 0.551

he-he = 4.50 RTc,


*

se-se = 4.70 R

(hi-he) = - (hi -hi) + (hi -he) + (he-he)


= - 0.045 12 547.4 0.02 + 0.203(500 - 438) + 0.045 12 547.4 4.50
= 123.2 Btu/lbm
*

* *

(si-se) = - (si -si) + (si -se) + (se-se)


500
15
= - 0.045 120.01 + 0.203 ln 438 - 0.045 12 ln 590 + 0.045 124.70
= 0.4042 Btu/lbm R
wrev = (hi-he) -T0(si-se) = 123.2 - 500(0.4042) = -78.4 Btu/lbm
qrev = (he-hi) + wrev = -123.2 - 78.9 = -202.1 Btu/lbm

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Borgnakke and Sonntag

12.175E
A cylinder contains ethylene, C2H4, at 222.6 lbf/in.2, 8 F. It is now compressed
isothermally in a reversible process to 742 lbf/in.2. Find the specific work and
heat transfer.
Ethylene C2H4 ,

R = 55.07 ft lbf/lbm R = 0.070 78 Btu/lbm R

State 1: P1 = 222.6 lbf/in.2,

T2 = T1 = 8 F = 467.7 R

State 2: P2 = 742 lbf/in.2


467.7
Tr2 = Tr1 = 508.3 = 0.920;

222.6
Pr1 = 731 = 0.305
*

From D.1, D.2 and D.3:

Z1 = 0.85 ,

h -h
(RT
)
C

= 0.40

(h1-h1) = 0.070 78 508.3 0.40 = 14.4 Btu/lbm


*

(s1-s1) = 0.070 78 0.30

= 0.0212 Btu/lbm R

742
Pr2 = 731 = 1.015 (comp. liquid)
From D.1, D.2 and D.3:

Z2 = 0.17

(h2-h2) = 0.070 78 508.3 4.0 = 143.9


*

(s2-s2) = 0.070 78 3.6 = 0.2548


*

(h2-h1) = 0
742
* *
(s2-s1) = 0 - 0.070 78 ln 222.6 = -0.0852
q = T(s2-s1) = 467.7(-0.2548 - 0.0852 + 0.0212) = -149.1 Btu/lbm

1 2

(h2-h1) = -143.9 + 0 + 14.4 = -129.5


(u2-u1) = (h2-h1) - RT(Z2-Z1)
= -129.5 - 0.070 78 467.7 (0.17 - 0.85) = -107.0
w = 1q2 - (u2-u1) = -149.1 + 107.0 = -42.1 Btu/lbm

1 2

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Borgnakke and Sonntag

12.176E
A geothermal power plant on the Raft river uses isobutane as the working fluid.
The fluid enters the reversible adiabatic turbine at 320 F, 805 lbf/in.2 and the
condenser exit condition is saturated liquid at 91 F. Isobutane has the properties
Tc = 734.65 R, Pc = 537 lbf/in.2, Cpo = 0.3974 Btu/lbm R and ratio of specific
heats k = 1.094 with a molecular weight as 58.124. Find the specific turbine work
and the specific pump work.
R = 26.58 ft lbf/lbm R = 0.034 166 Btu/lbm R
Turbine inlet: Tr1 = 779.7 / 734.7 = 1.061,
Condenser exit: T3 = 91 F , x3 = 0.0 ;

Pr1 = 805 / 537 = 1.499

Tr3 = 550.7 / 734.7 = 0.75

Pr3 = 0.165, Z3 = 0.0275

From D.1 :

P2 = P3 = 0.165 537 = 88.6 lbf/in.2


From D.2 and D.3,
*

(h1-h1) = 0.034 166 734.7 2.85 = 71.5 Btu/lbm


*

(s1-s1) = 0.034 166 2.15 = 0.0735 Btu/lbm R


88.6
550.7
* *
(s2-s1) = 0.3974 ln 779.7 - 0.034 166 ln 805 = -0.0628 Btu/lbm R
*

(s2-s2) = (s2-sF2) - x2sFG2 = 0.034 166 6.12 - x2 0.034 166(6.12 - 0.29)


= 0.2090 - x2 0.1992
(s2-s1) = 0 = -0.2090 + x2 0.1992-0.0628 + 0.0735
*

=> x2 = 0.9955

(h2-h1) = CP0(T2-T1) = 0.3974(550.7-779.7) = -91.0 Btu/lbm


From D.2,
*

(h2-h2) = (h2-hF2) - x2hFG2 = 0.034 166734.7[4.69 - 0.9955(4.69 - 0.32)]


= 117.7 0.9955 109.7 = 8.5 Btu/lbm
Turbine:
Pump

wT = (h1-h2) = -71.5 + 91.0 + 8.5 = 28.0 Btu/lbm


vF3 =

ZF3RT3
P3

0.0275 26.58 550.7


= 0.031 55 ft3/lbm
88.6 144

144
vdP vF3(P4 -P3) = -0.031 55(805-88.6)
wP = -
778 = -4.2 Btu/lbm
3

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Borgnakke and Sonntag

12.177E
A line with a steady supply of octane, C8H18, is at 750 F, 440 lbf/in.2. What is
your best estimate for the availability in an steady flow setup where changes in
potential and kinetic energies may be neglected?
Availability of Octane at

Ti = 750 F, Pi = 440 lbf/in.2

R = 13.53 ft lbf/lbm-R = 0.017 39 Btu/lbm-R


440
1209.7
Pri = 361 = 1.219, Tri = 1023.8 = 1.182
From D.2 and D.3:
*

(h1-h1) = 0.017 39 1023.8 1.15 = 20.5 Btu/lbm


*

(s1-s1) = 0.017 39 0.71 = 0.0123 Btu/lbm R


Exit state in equilibrium with the surroundings
Assume T0 = 77 F, P0 = 14.7 lbf/in.2
536.7
14.7
Tr0 = 1023.8 = 0.524 , Pr0 = 361 = 0.041
From D.2 and D.3:
*

(h0-h0) = RTC 5.41 = 96.3


*

and

(s0-s0) = R 10.38 = 0.1805

(hi -h0) = 0.409(1209.7 - 536.7) = 275.3 Btu/lbm


1209.7
440
* *
(si -s0) = 0.409 ln 536.7 - 0.017 39 ln 14.7 = 0.2733 Btu/lbm R
(hi-h0) = -20.5 + 275.3 + 96.3 = 351.1 Btu/lbm
(si-s0) = -0.0123 + 0.2733 + 0.1805 = 0.4415 Btu/lbm R
i = wrev = (hi-h0) - T0(si-s0) = 351.1 - 536.7 (0.4415) = 114.1 Btu/lbm

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Borgnakke and Sonntag

12.178E
A distributor of bottled propane, C3H8, needs to bring propane from 630 R, 14.7
lbf/in.2 to saturated liquid at 520 R in a steady flow process. If this should be
accomplished in a reversible setup given the surroundings at 540 R, find the ratio
of the volume flow rates Vin /Vout, the heat transfer and the work involved in the
process.
.

R = 35.04/778 = 0.045 04 Btu/lbm R


630
14.7
Tri = 665.6 = 0.947 Pri = 616 = 0.024
From D.1, D.2 and D.3 :

Zi = 0.99

(hi -hi) = 0.045 04 665.6 0.03 = 0.9 Btu/lbm


*

(si -si) = 0.045 04 0.02 = 0.0009 Btu/lbm R


Tre = 520/665.6 = 0.781,
From D.1, D.2 and D.3 :
Pre = = 0.21 , Pe = 0.21 616 = 129 lbf/in.2 ,

Ze = 0.035

(he-he) = 0.045 04 665.6 4.58 = 137.3 Btu/lbm


*

(se-se) = 0.045 04 5.72 = 0.2576 Btu/lbm R


*

(he-hi ) = 0.407 (520 - 630) = -44.8 Btu/lbm


520
132
* *
(se-si ) = 0.407 ln 630 - 0.045 04 ln 14.7 = -0.1770 Btu/lbm R
(he-hi) = -137.3 - 44.8 + 0.9 = -181.2 Btu/lbm
(se-si) = -0.2576 - 0.1759 + 0.0009 = -0.4326 Btu/lbm R
.
Vin
.
Vout

ZiTi/Pi 0.99 630 129


= Z T /P = 0.035 520 14.7 = 300.7
e e e

wrev = (hi - he) - T0(si - se) = 181.2 - 540(0.4326) = -52.4 Btu/lbm


qrev = (he - hi) + wrev = -181.2 - 52.4 = -233.6 Btu/lbm

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Borgnakke and Sonntag

Mixtures

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Borgnakke and Sonntag

12.179E
A 4 lbm mixture of 50% argon and 50% nitrogen by mole is in a tank at 300 psia,
320 R. How large is the volume using a model of (a) ideal gas and (b) Kays
rule with generalized compressibility charts.
a) Ideal gas mixture
Eq.11.5:
Mmix = yi Mi = 0.5 39.948 + 0.5 28.013 = 33.981
R = 1545.36 / 33.981 = 45.477 lbf-ft/lbm-R
mRT 4 45.477 320
lbf-ft
V= P =
= 1.347 ft3
300 144
psi in2/ft2
b) Kays rule Eq.12.84
Pc mix = 0.5 706 + 0.5 492 = 599 psia
Tc mix = 0.5 271.4 + 0.5 227.2 = 249.3 R
300
320
Reduced properties:
Pr = 599 = 0.50, Tr = 249.3 = 1.284
Fig. D.1: Z = 0.92

mRT
V = Z M P = Z VID gas = 0.92 1.347 = 1.24 ft3
mix

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Borgnakke and Sonntag

12.180E
R-410A is a 1:1 mass ratio mixture of R-32 and R-125. Find the specific volume
at 80 F, 200 psia using Kays rule and the generalized charts and compare to Table
F.9
Kays rule Eq.12.84
Pc mix = 0.5 838 + 0.5 525 = 681.5 psia
Tc mix = 0.5 632.3 + 0.5 610.6 = 621.45 R
200
539.67
Reduced properties: Pr = 681.5 = 0.293, Tr = 621.45 = 0.868
Table F.1: R = 1545.36 / 72.585 = 21.29 lbf-ft/lbm-R
Fig. D.1: Z = 0.82
ZRT 0.82 21.29 539.67 lbf-ft/lbm
= 0.327 ft3/lbm
v= P =
200 144
psi in2/ft2
Table F.9:

v = 0.3174 ft3/lbm

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Borgnakke and Sonntag

12.181E
The R-410A in Problem 12.180E flows through a heat exchanger and exits at 280
F, 200 psia. Find the specific heat transfer using Kays rule and the generalized
charts and compare this to solution found using Table F.9.

Kays rule Eq.12.84


Pc mix = 0.5 838 + 0.5 525 = 681.5 psia
Tc mix = 0.5 632.3 + 0.5 610.6 = 621.45 R
Table F.1:

R = 1545.36 / 72.585 = 21.29 lbf-ft/lbm-R = 0.02736 Btu/lbm-R


CP mix = ci CP i = 0.5 0.196 + 0.5 0.189 = 0.1925 Btu/lbm-R

200
Reduced properties 1: Pr1 = 681.5 = 0.293,

539.67
621.45 = 0.868

(h*1 h1) = 0.45 RTc = 0.45 0.02736 621.45 = 7.65 Btu/lbm

Fig. D.1:

Reduced properties 2:
Fig. D.1:

Tr1 =

Pr2 =

200
681.5 = 0.293,

739.67
Tr2 = 621.45 = 1.19

(h*2 h2) = 0.25 RTc = 0.25 0.02736 621.45 = 4.25 Btu/lbm

The energy equation gives


1q2

= (h2 - h1) = (h2 h2)

+ (h*2 h*1) + (h*1 h1)

= -4.25 + 0.1925 (280 80) + 7.65


= 41.9 Btu/lbm mix
Table F.9.2:

q = h2 h1 = 176.26 126.34 = 49.92 Btu/lbm

The main difference is in the value of specific heat, about 0.25 Btu/lbm-R at
the avg. T, whereas it is 0.1925 Btu/lbm-R at 77 F.

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Borgnakke and Sonntag

Review Problem

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Borgnakke and Sonntag

12.182E
A new compound is used in an ideal Rankine cycle where saturated vapor at 400
F enters the turbine and saturated liquid at 70 F exits the condenser. The only
properties known for this compound are a molecular mass of 80 lbm/lbmol, an
ideal gas heat capacity of Cpo = 0.20 Btu/lbm-R and Tc = 900 R, Pc = 750 psia.
Find the specific work input to the pump and the cycle thermal efficiency using
the generalized charts.
T1 = 400 F = 860 R

1
.
WT

Turbine
.
QH

Ht.
Exch

T3 = 70 F = 530 R

2
Cond
P
4

.
-W P

x1 = 1.0
x3 = 0.0
Properties known:
M = 80, CPO = 0.2 Btu/lbm R
TC = 900 R, PC = 750 lbf/in.2
860
530
Tr1 = 900 = 0.956, Tr3 = 900 = 0.589

From D.1: Pr1 = 0.76, P1 = 0.76 750 = 570 lbf/in.2 = P4


Pr3 = 0.025, P3 = 19 lbf/in.2 = P2,
vf3 = Zf3RT3/P3 =

Zf3 = 0.0045

0.0045 1545 530


= 0.0168 ft3/lbm
19 144 80

wP = -
vdP vf3(P4 -P3) = -0.0168 (570 - 19)
3

144
= -1.71 Btu/lbm
778

qH + h4 = h1 , but h3 = h4 + wP => qH = (h1 - h3) + wP


From D.2,
*

(h1 - h1) = (1.9859/80) 900 1.34 = 30.0 Btu/lbm


*

(h3 - h3) = (1.9859/80) 900 5.2 = 116.1 Btu/lbm


*

(h1 - h3) = CP0(T1-T3) = 0.2(400-70) = 66.0 Btu/lbm


(h1 - h3) = -30.0 + 66.0 + 116.1 = 152.1 Btu/lbm
qH = 152.1 + (-1.71) = 150.4 Btu/lbm
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Borgnakke and Sonntag


*

Turbine, (s2 -s1) = 0 = -(s2 - s2) + (s2 - s1) + (s1 - s1)


From D.3,
*

(s1 - s1) = (1.9859/80) 1.06 = 0.0263 Btu/lbm R


530
19
*
*
(s2 - s1) = 0.20 ln 860 - 0.024 82 ln 570 = -0.0124 Btu/lbm R
Substituting,
*

(s2-s2) = - 0.0124 + 0.0263 = 0.0139 = (s2-sf2) - x2sfg2


0.0139 = 0.024 82 8.77 - x2 0.024 82 (8.77 - 0.075)
=> x2 = 0.9444
*

(h2-h2) = (h2-hf2) - x2hfg2


From D.2,
hfg2 = 0.024 82 900 (5.2 0.07) = 114.6 Btu/lbm
*

(h2-h2) = 116.1 - 0.9444 114.6 = 7.9 Btu/lbm


wT = (h1-h2) = -30.0 + 66.0 + 7.9 = 43.9 Btu/lbm
TH =

wNET
qH

43.9 - 1.7
150.4 = 0.281

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