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Borgnakke and Sonntag Fundamentals of Thermodynamics Solutions

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Anda di halaman 1dari 218

Fundamentals of

Thermodynamics

SOLUTION MANUAL

CHAPTER 12

8e

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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testing or instructional purposes only to students enrolled in courses for which this textbook has been

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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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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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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:

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

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

ln Psat = A B/T ;

B = hevap R-1

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:

dT = dT = Tvfg

P = 1085.7 kPa,

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

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:

sfg

P

1

1

T

(v + v ) (v + v )

2

In the limit as

T 0:

v3 v2 = vg ,

v4 v1 = vf

& 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,

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

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

Solution:

Refrigerant: State 1 T1 = 70oC P1 = 150 kPa

State 2 P2 = 150 kPa x2 = 1.0

Energy Eq.:

State 3

1 3

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

Table B.6.1:

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

At 110 K,

(1938.8-1084.2

115-105 ) = 134.82 kJ/kg

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:

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

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

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

ln Psat = A B/T = 13.7611 -

1933.4

273.15 + 5 = 6.8102

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

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

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]

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

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

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

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).

Solid

101.3 kPa

PTP

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

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

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

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

)

v T

=T

P

(T

)v + v(P

)

v T

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

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

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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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

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

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

( )

1w2

vT 2 2

= - 2 P2 - P 1

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

( )

s =

1

1

s2 m 3

1000

1

=

=

2

2

2

2

kPa

m

kg

c 4800 8300

4800 8300

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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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

c=

(940101

)

783

-12

( )

= 783 kg/m3

1/2

= 1166 m/s

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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:

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

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

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12.53

Use the CATT3 software to solve the previous problem.

At 100oC, 2500 kPa:

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

c2 v2

(P

) = 0.02653

v

s

v = 0.02679 m3/kg, P = 2.469 MPa

2

2531 - 2469

kJ

J

=

83

919.5

0.02627 - 0.02679 kg

kg

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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

P

(P

)

( )

s

v

v

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

=>

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

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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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 =

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

=>

CATT3:

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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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

( )

( )

( )

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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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

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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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

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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Equations of State

testing or instructional purposes only to students enrolled in courses for which this textbook has been

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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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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)

Pv 3836.9 0.001227

Z = RT = 0.1145 333.15 = 0.1234

b)

Pv 3836.9 0.00497

Z = RT = 0.1145 333.15 = 0.5

c)

Pv 3000 0.00858

Z = RT = 0.1145 333.15 = 0.675

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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

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

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

Pv 1000 0.05236

Z = RT = 0.1889 293.15 = 0.9455

A

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

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:

E

The work is

1

2

3

w=

[ v + B(T) v + C(T) v + .. ] dv

P dv = RT

A

EA

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:

*

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

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=

RTc

(vc b)

+

A

2a

3

vc

A

=0

2RTc

(1) ;

(vc b)

6a

4

vc

=0

(2)

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

(vc b)3

vc = 3b

RTc

27

3

2a=

2 vc = RTc 4 b

(vc b)

A

27

RTc

a RTc RTc 8 b

Pc =

2 = 2b

= RTc (0.5 3/8) /b

vc b v

9 b2

A

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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

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

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

dhT = [ v T (

A

v

R

)

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

P

T

A

v

P

dsT = ( )P dPT = ( )v dvT

T

T

A

R

R

= P dPT = v b dvT

A

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

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

Lim Z

= 0 at Tboyle

P0 P T

A

(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

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

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

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

[(

)(

)]

2

R

a/2

(s2 s1)T =

+

3/2 dv

v b v(v + b)T

A

2

= R ln

3/2

A

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:

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

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

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:

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

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

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

v = 0.01 m3/kg

v = 0.008 m3/kg

v = 0.0075 m3/kg

v = 0.007 m3/kg

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

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

A

so entropy generation

A

E

A

A

E

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

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

[(

)(

)]

2

R

a/2

(s2 s1)T =

+

3/2 dv

v b v(v + b)T

A

2

= R ln

3/2

A

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

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

v1 = 0.011 m /kg

A

too low

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

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

A

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

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

A

A

= R ln

3/2

A

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

= 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

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

278.6

Pc = 7.24 MPa => Tr1 = 309.6 = 0.9

Tc = 309.6 K,

A

Saturated liquid:

Saturated vapor:

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

273.15

Pc = 4.06 MPa => Tr1 = 374.2 = 0.73

Tc = 374.2 K,

A

(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

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

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

0.8250.188 55553.2

= 0.00956 m3/kg

9 000

A

A

E

E

A

x2 = 0.354

A

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

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

Fig. D.1:

Condenser:

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

A

A

E

Fig. D.1:

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

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 =

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

A

A

E

Assume it is saturated

A

A

A

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

A

A

E

A

A

A

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

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

A

A

A

353.2

1235

* *

(s1-sg3) = 1.7164 ln 303.2 - 0.143 04 ln 429 = 0.1107

A

A

A

E

T

1

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,

*

and

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

*

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

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

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

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:

(h*- h)1 = 0.22 RTc ,

*

*

= -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,

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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

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

= 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

= 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

Z1 = 0.68

From Fig. D.2:

*

8.3145425.2

(-0.90 + 1.30) = -58.8 kJ/kg

58.124

U2 - U1 = m(h2 - h1) - P2V2 + P1V1

h2 - h1 = -83.1 +

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

x1 = 0.0

P1 = PG T1 = 0.254.25 = 1.063 MPa,

Z1 = 0.04

P1V1

m1 = Z RT =

1

1063510-6

= 0.00238 kg

0.040.188 55296.2

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

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

M = 44.094, Tc = 369.8 K, Pc = 4.25 MPa

R = 0.188 55, CP0 = 1.6794

1

v

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=

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

A

*

(h2-h2)

A

A

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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

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

A

A

E

E

E

A

A

E

= 271.5 kJ/kg

CATT3:

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

E

A

Z1 = 0.85

A

A

E

A

*

(h2-h2)

A

Z2 = 0.17 ,

A

A

A

E

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

A

A

1w2

A

A

E

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.:

A

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

A

A

A

E

A

Substituting :

E

*

(h2-h2)

A

Substituting :

T2 = -6.0 oC

E

E

A

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

353.2

Tr1 = 425.2 = 0.831

.

WT

Turbine

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

A

*

E

A

A

* *

(s1-sg3)

A

353.2

1005

= 1.716 ln 303.2 - 0.1430 ln 282.8 = 0.0806

A

A

A

E

T

1

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,

From CATT3:

*

and

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,

*

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

*

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

260.2

1.536

Tr1 = 282.4 = 0.921 Pr1 = Pr2 = 5.04 = 0.305

*

v1 =

Z1RT1

P1

0.850.29637260.2

= 0.042675

1536

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

*

v2 =

Z2RT2

P2

0.050.29637232.7

= 0.002245 m3/kg

1536

*

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

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,

Entropy Eq.:

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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

re

(s*-s)re/R = 4.74

= - 0.188 92304.10.01 + 0.8418(278.2-243)

+ 0.188 92304.14.5 = 287.6 kJ/kg

*

* *

= - 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

si = 2.015 kJ/kg-K

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

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

*

*

0.584

306.2

*

*

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

*

= 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

*

From Fig. D.2:,

*

Turbine:

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

Pump:

vF3 =

= 0.00225

P3 =

584

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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.:

*

*

From D.2:

Check first law (he- hi) = -0.4 -20.3 + 20.1 0 OK => Te = 208 K

From D.3,

*

and

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,

Pr1 = Pr sat = 0.25,

From D.1:

P1V1

m = Z RT =

11500.010

= 0.471 kg

0.42250.197 58292.2

V1 = 10 L

Q = m(u2-u1) + 1W2

1 2

2

1 2

Q = TdS = Tm(s2-s1)

1 2

*

*

The ideal gas change in h and s are

*

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

*

*

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

*

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

*

= -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

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:

TC = 304.1 K,

6

Pri = 7.38 = 0.813,

PC = 7.38 MPa

373.2

Tri = 304.1 = 1.227

~

h = 0.70

~

*

(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;

*

~

~

= 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

Zi = 0.99

*

*

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

*

*

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

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

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,

x2 = 0.889

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

Energy Eq.:

1Q2

*

(h*2 h2)f

= 4.51 RTC ,

52.2 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,

353.2

500

Tr1 = 425.2 = 0.831, Pr1 = 3800 = 0.132

Z1 = 0.92,

v1 =

Z1RT1

P1

0.920.143353.2

= 0.09296 m3/kg

500

State 2:

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

sat. vap.: ZG = 0.775,

Therefore

vF =

0.050.143353.2

= 0.00205 m3/kg

1235

vG =

0.7750.143353.2

= 0.0317 m3/kg

1235

*

= 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:

TC = 568.8 K,

3

Pri = 2.49 = 1.205,

PC = 2.49 MPa

673.2

Tri = 568.8 = 1.184

~

*

(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)

*

*

and

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:

303.2

Tr3 = 386.4 = 0.785

2

3

4

Sat.liq.:

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

*

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:

303.2

Tr3 = 386.4 = 0.785

2

3

1

Sat.liq.:

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

*

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,

*

*

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

=>

m = v = 0.0073 = 32.26 kg/s

e

*

*

*

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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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,

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,

*

Fig. D.2:

*

State 4: T4 = T1 = 246.7 K,

h4 = h3

*

qL = h1 - h3 = (h1 h1)

*

h4 = h3

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

*

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

*

.

Q = -1.0 kW,

.

m = 0.1 kg/s

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 Pi = 2 MPa, Ti = 100 oC, Flow in to T2 = T0 = 20oC

VLIQ 2 = VVAP 2 = 50 L

Continuity: mi = m2 ; Energy:

*

293.2

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

sat. liq.:

sat. vap.:

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

*

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

= -10 343 kJ

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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

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

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

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

Fig. D.1:

1.2

Pr2 = 4.70 = 0.255,

Reduced properties 1:

*

h2 h2

Fig. D.1:

393.15

Tr2 = 345.25 = 1.139

1q2

A

A

A

A

E

= 88.55 kJ/kg mix

Table B.4.2:

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 =

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 =

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

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:

6

Pr2 =

= 1.095,

5.48

Reduced properties 2:

Tr2 =

*

h2 h2

Fig. D.1:

400

= 1.366

292.8

A

1q2

A

A

A

A

E

= 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

A

Mixture at 2 :

PC2 = 0.8 5.04 + 0.2 7.38 = 5.508 MPa

A

A

A

D.1 :

Z2 = 0.32

A

P2V

10 0000.05

- = 0.328.3145298.2 = 0.6302 kmol

Z2RT2

n2 =

A

A

A

298.2

Tr1 = 304.1 = 0.981

A

n1ZB1RT1

Pr1 =

A

PCBV

A

73800.05

A

= 0.8466 ZB1

A

A

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

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

h2 = 0.08

= -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 ,

h3 = 0.15

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

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

.

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

EA

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

E

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

E

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

EA

b) van der waal's equation

For CO2 : b = R Tc/8Pc = 8.3145 304.1/8 7380 = 0.04282

E

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

For C2H6 :

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

A

EA

EA

8.3145*308.2 456.384

- - 700 = 0

v- - 0.05393

v 2

A

E

8.3145*308.2 456.384

- 5500 = 0

v- - 0.05393

v- 2

A

E

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

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

v

P

dsT = ( )P dPT = ( )v dvT

T

T

A

R

R

= P dPT = v b dvT

A

(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

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

4C

(h2 h1)T = 3 (P2 P1)T

T

P2

3C

(s2 s1)T = R ln P 4 (P2 P1)T

1T T

A

(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

A

A

From D.2:

A

E

A

From D.3,

*

A

T3

100

* *

(s3-s2) = 1.766 ln 611 - 0.2765 ln 2440

A

A

A

E

at Pr3 = 0.020

A

A

E

* *

A

From D.3,

*

A

A

A

E

Therefore, T3 = 368 K

A

A

E

From D.2,

*

A

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

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

E

*

*

*

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

A

A

A

*

*

*

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

A

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

Tcmix = yiTci = 248 K,

A

A

E

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.:

u- = h - PvE

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

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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

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

473.2

293.2

Tr1 = 500 = 0.946 , Tr3 = 500 = 0.586

Cond

P

4

.

-WP

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

A

A

vF3 =

A

= 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

*

A

*

(h3-h3)

A

A

A

A

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*

A

*

A

293.2

115

* *

(s2-s1) = 0.80 ln 473.2 - 0.103 93 ln 3600 = -0.0250

A

Substituting,

*

A

A

*

(h2-h2)

A

*

(h2-hF2)

- x2hFG2

A

=> x2 = 0.922

A

hFG2 = 0.10393 500 (5.2-0.07) = 266.6

A

A

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

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

A

= 55.3

Energy Eq.:

A

E

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

A

E

Let h1 = 0 then

A

A

A

A

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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

.

.

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

E

C4H10 cycle

Turbine

.

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

A

A

A

353.2

1235

* *

(s1-sG3) = 1.7164 ln 303.2 - 0.143 04 ln 429 = 0.1107

A

A

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T

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:

*

A

and

A

353.2

1235

* *

(s1-s2S) = 1.7164 ln 315 - 0.143 04 ln 429 = +0.0453

A

A

T2S = 315 K

A

A

A

A

At state 3,

0.0190.143 04303.2

v3 =

= 0.001 92 m3/kg

429

E

A

-wP =

A

SP

A

-wSP

1.55

= 0.8 = 1.94 kJ/kg

A

A

.

.

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

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

(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 = (

u = h - Pv

u2 - u1 = (h2 - h1) - (P2v2 - P1v1) = -122.2 kJ/kg

1Q2

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b) Entropy Eq.:

*

s2 - s1 = (s2 s2)

To = 0oC = 273.15 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,

*

*

Assume T2S = 253 K, Tr2S = 0.832

From D.2 and D.3:

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

*

wS = (h1 - h2S) = -29.9 + 101.2 + 11.5 = 82.8 kJ/kg

*

Assume T2 = 275 K, Tr2 = 0.904

*

From D.2 and D.3,

*

Substituting,

w = -29.9 + 82.7 + 9.8 = 62.7 62.1

T2 = 275 K

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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 =

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

*

] = 431.1

*

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*

(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,

uF1 = -178.47

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

*

s-0 = 200 kJ/kmol K

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 ,

*

s-0 CH4 = s-LIQ 0 P + (s-*-s-LIQ)at P - R ln (P0/PG)

G

*

s-0 MIX = 0.5141.36 + 0.5200 - 8.3145(0.5 ln 0.5 + 0.5 ln 0.5) = 176.44

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

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

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

D.1 :

n2 =

Z2 = 0.32

P2V

10 0000.05

- = 0.328.3145298.2 = 0.6302 kmol

Z2RT2

nB2 = n1 = 0.2 n2 = 0.1260 kmol CO2

298.2

Tr1 = 304.1 = 0.981 and

4560

Pr1 = 7380 = 0.618

- -*

- -*

- -*

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

*

*

*

*

*

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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Borgnakke Sonntag

Fundamentals of

Thermodynamics

SOLUTION MANUAL

CHAPTER 12

English Units

8e

UPDATED JULY 2013

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,

dT = dT = Tvfg

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

=

= -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.

T

dPif

143.34

778.2

2

=

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,

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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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

( )

=>

vT 2 2

w

=

1 2

2 P2 - P1

V1 = 1.0 ft3,

W =

1 2

(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

( )

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

Assume

(P

) (P

)

v s

v

(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 = 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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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

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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Equations of State

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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)

Pv 556.488 0.01966 144

= 0.1234

Z = RT =

21.29 599.7

b)

Pv 556.488 0.0796 144

= 0.5

Z = RT =

21.29 599.7

c)

Pv 400 0.1574 144

Z = RT = 21.29 599.7 = 0.71

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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:

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

( )

-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

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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Generalized Charts

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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

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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:

Saturated vapor:

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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.

Tc = 673.6 R,

489.7

Pc = 589 psia => Tr1 = 673.6 = 0.727

From Fig. D.2:

Saturated liquid:

Saturated vapor:

= 4.4 0.01946 673.6 = 57.67 Btu/lbm

Table F. 10:

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

accentric factor.

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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

= 0.1554 ft3/lbm

1300 144

From D.1 at Tr2 = 0.871, saturated => PG2 = 0.43 616 = 265 lbf/in.2

vG2 =

= 0.3808 ft3/lbm

265 144

vF2 =

= 0.0399 ft3/lbm

265 144

=>

x2 = 0.3388

7.0

mLIQ 2 = (1 - 0.3388) 0.1554 = 29.8 lbm

These tanks

contain liquid

propane.

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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

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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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

900

750

Tr1 = 765.4 = 1.176, Pr1 = 551 = 1.361

V1 = mZRT/P =

n

P1V1

n

P2V2

Z1 = 0.67

= 1.484 ft3

750 144

750

V2 = 1.484 450

( )

1

1.05

= 2.414 ft3

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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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

( )

= 0.95

h2 - h1 = -34.3 +

26.58765.4

(-0.95 + 1.36) = -23.6 Btu/lbm

778

= 10(-23.6) -

4501442.414 7501441.484

+

= -231.1 Btu

778

778

1 2

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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:

Fig. D.1:

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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 ,

v1 =

Z1RT1

P1

h -h

(RT

)

C

= 0.40

= 0.683

222.6 144

From D.1 and D.2:

Z2 = 0.05 ,

v2 =

Z2RT2

P2

h*-h

RTC

( )

=

= 4.42

= 0.035 89 ft3/lbm

222.6 144

*

2

144

Pdv = P(v2-v1) = 222.6(0.035 89 - 0.683)

w =

778 = -26.7 Btu/lbm

1 2

1 2

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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.:

Generalized charts,

From D.2:

539.7

Tr1 = 620.1 = 0.87

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

30

at Pr2 = 711 = 0.042

469.7

Assume T2 = 10 F = 469.7 R => Tr2 = 620.1 = 0.757

*

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

*

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

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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:

= 4.65 RTc = 4.65 0.03417 Btu/lbm-R 735.8 R

= 116.9 kJ/kg

CATT3:

The generalized charts are not super accurate, some improvement can be

done using the accentric factor.

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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

M = 44.094, TC = 665.6 R

PC = 616 lbf/in.2

Tr1 = 0.826 Figs. D.1 and D.2

h1-h1

SAT

Pr

= 0.31 ;

PV

m = ZRT =

Pr2 =

SAT

P1

191 144 10

= 20.2 lbm

0.707 35.04 549.7

616 144 10

Pr2 = 0.79

Trial & error:

Z2 = 0.94

*

Z2

= 1.183

at Tr2 = 1.592

*

h2-h2

and RT = 0.36

c

*

*

From the energy equation

Q12 = m(h2-h1) - (P2-P1)V

= 20.2 (-10.8 + 207.6 + 28.0) - (490 - 191)

144 10

778

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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

438

Tre = 547.4 = 0.80,

From D.2 and D.3:

*

590

Pre = 1070 = 0.551

*

se-se = 4.70 R

= - 0.045 12 547.4 0.02 + 0.203(500 - 438) + 0.045 12 547.4 4.50

= 123.2 Btu/lbm

*

* *

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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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 ,

T2 = T1 = 8 F = 467.7 R

467.7

Tr2 = Tr1 = 508.3 = 0.920;

222.6

Pr1 = 731 = 0.305

*

Z1 = 0.85 ,

h -h

(RT

)

C

= 0.40

*

= 0.0212 Btu/lbm R

742

Pr2 = 731 = 1.015 (comp. liquid)

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

Z2 = 0.17

*

*

(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

(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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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 ;

From D.1 :

From D.2 and D.3,

*

*

88.6

550.7

* *

(s2-s1) = 0.3974 ln 779.7 - 0.034 166 ln 805 = -0.0628 Btu/lbm R

*

= 0.2090 - x2 0.1992

(s2-s1) = 0 = -0.2090 + x2 0.1992-0.0628 + 0.0735

*

=> x2 = 0.9955

From D.2,

*

= 117.7 0.9955 109.7 = 8.5 Btu/lbm

Turbine:

Pump

vF3 =

ZF3RT3

P3

= 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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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

440

1209.7

Pri = 361 = 1.219, Tri = 1023.8 = 1.182

From D.2 and D.3:

*

*

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:

*

*

and

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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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.

.

630

14.7

Tri = 665.6 = 0.947 Pri = 616 = 0.024

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

Zi = 0.99

*

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

*

*

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

= Z T /P = 0.035 520 14.7 = 300.7

e e e

qrev = (he - hi) + wrev = -181.2 - 52.4 = -233.6 Btu/lbm

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Mixtures

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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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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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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.

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:

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

Fig. D.1:

Reduced properties 2:

Fig. D.1:

Tr1 =

Pr2 =

200

681.5 = 0.293,

739.67

Tr2 = 621.45 = 1.19

1q2

= 41.9 Btu/lbm mix

Table F.9.2:

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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Review Problem

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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

Pr3 = 0.025, P3 = 19 lbf/in.2 = P2,

vf3 = Zf3RT3/P3 =

Zf3 = 0.0045

= 0.0168 ft3/lbm

19 144 80

wP = -

vdP vf3(P4 -P3) = -0.0168 (570 - 19)

3

144

= -1.71 Btu/lbm

778

From D.2,

*

*

*

(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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*

From D.3,

*

530

19

*

*

(s2 - s1) = 0.20 ln 860 - 0.024 82 ln 570 = -0.0124 Btu/lbm R

Substituting,

*

0.0139 = 0.024 82 8.77 - x2 0.024 82 (8.77 - 0.075)

=> x2 = 0.9444

*

From D.2,

hfg2 = 0.024 82 900 (5.2 0.07) = 114.6 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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