S.A. Klein and G.F.

Nellis
Cambridge University Press, 2011

10.A-1 One of the first advanced equations was the Beattie-Bridgeman equation of state
originally proposed in 1928 which has the following form.

c
RT 1

v T3
b A a

P
v B0 1 20 1

2
v
v v v

A0, B0, a, b, and c, are substance-dependent coefficients. Values of these coefficients for
many gases can found in the literature. For carbon dioxide, the gas of interest in this
problem, the coefficients have the values provided in Table 10.A-1.
Table 10.A-1: Coefficients for the Beattie-Bridgeman equation of state for CO2 (from Cravalo and
Smith, Jr., Engineering Thermodynamics, Pitman, Boston, 1981

a
A0
b
B0
c

1.62129e3 [m3/kg]
262.07 [N-m4/kg2]
1.6444e3 [m3/kg]
2.3811e3 [m3/kg]
1.4997e4 [m3-K3/kg]

a.) Test the Beattie-Bridgeman equation's ability to accurately predict the specific
volume of carbon dioxide by comparing the specific volumes and compressibility
factors obtained from the equation of state with a reliable source for isotherms at 250
K, 304.1 K and 350 K and pressures ranging from atmospheric to 200 bar. What is
your assessment of the accuracy of the Beattie-Bridgeman equation of state for
carbon dioxide?
b.) It is difficult to accurately measure the critical volume, so there is some incentive to
obtain it from the equation of state. One way to do so is to plot the slope dP/dv along
the critical isotherm to determine the volume at which it is zero. Can you obtain an
accurate estimate of the critical volume from the Beattie-Bridgeman equation of
state?

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.A-2 The Benedict-Webb-Rubin (BWR) equation of state, originally proposed in 1940, has the
following form.
P

RT Bo RT Ao Co / T 2 b RT a a
c

6 3 2 1 2 exp 2
2
3
v
v
v
v
vT v
v

Ao, Bo, Co, a, b, c, and are substance-dependent coefficients. Values of these

coefficients can be found in the literature. For methane, the gas of interest in this
problem, the coefficients have the values indicated in Table 10.A-2 with P in Pa, v in
m3/kmol and T in K.
Table 10.A-2: Coefficients for the Benedict-Webb-Rubin equation of state for methane (Van Wylen,
G. and Sonntag, R., Fundamentals of Classical Thermodynamics, 3rd edition, Wiley, New York, 1986)

a = 5000
b = 0.003380
c = 2.578e8
=1.244e-4

Ao = 187.91E3
Bo = 0.04260
Co = 2.286e9
= 0.0060

a.) Determine the units of the eight coefficients

b.) Test the BWR equation's ability to accurately predict the specific volume of methane
in the superheated, subcooled and saturated regimes by comparing the specific
volumes obtained from the equation with a reliable source. Summarize your results
in a table and indicate the percentage error.
c.) It is much more difficult to accurately measure the critical volume than it is to
measure critical temperature and pressure. Assuming that the BWR constants
provided above are correct, determine the critical volume at which the critical
isotherm exhibits a slope of 0. How does your result compare to the accepted value?

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.A-3 One proposed solution to the environmental problems caused by transportation vehicles
is to use fuel cells powered by hydrogen fuel. In place of the gasoline tank, a pressurized
hydrogen tank would be needed. Tank pressures as high as 800 atm have been suggested.
Use the Guggenheim equation of state (Guggenheim, E.A., Molecular Physics, 9, pp.
199-200, 1965) to do your calculations and compare the results it provides with a reliable
source. The Guggenheim equation of state is given by:

1
a

RT v 1 y 4

where y

b
4v

a.) Determine the constants, a and b, for hydrogen by forcing the pressure-volume
isotherm to have a slope of zero and an inflection point at the critical point. Critical
property data for hydrogen are provided in EES.
b.) Determine the hydrogen storage volume required to provide a vehicle range
equivalent to 15 gallons of gasoline for storage pressures between 100 to 800 atm.
Note that the density of gasoline on a mass basis is 0.7 of the density of water at 300
K and 1 atm. The energy content of one kg of gasoline is about 44.4 MJ/kg whereas
the energy content of hydrogen is 119.95 MJ/kg.
c.) Compare the critical compressibility predicted by the Guggenheim equation with the
value determined from EES property functions or other reported critical point data.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.A-4 The two-parameter MMM equation of state proposed by Mohsen-Nia et al. (Mohsen-Nia,
M., Moddaress, H., and Mansoori, G.A., A Simple Cubic Equation of State for
Hydrocarbons and Other Compounds, SPE Paper #26667, Proceedings of the 1993
Annual Technical Conference and Exhibition of the Society of Petroleum Engineers,
Houston, TX.) is claimed to be more accurate than the Peng-Robinson and RedlichKwong-Soave equations. The MMM equation can be expressed in the following form.
z

v 1.319b
a

3/2
v b
RT v b

where z is the compressibility factor, T_r is the reduced temperature, Tc and Pc are the
critical temperature and pressure, respectively, and parameters a and b are determined
from by adjusting the parameters determined from critical point information as
follows:
ac 0.486989

R 2Tc2.5
Pc

1 1 / Tr
a ac
3
1 1

1 0.036139 0.14167

bc 0.064662

RTc
Pc

1 1 / Tr
b bc
3
1 1

1 0.0634 0.18769

where is the acentric factor.

a.) Test the MMM equation's ability to accurately predict the specific volume of carbon
dioxide in the superheated, subcooled and saturated regimes by plotting the 240 K,
280 K, and 320 K isotherms over a range of pressures between atmospheric and 275
bar. Compare your results with a reliable source and prepare a short summary of your
results indicating the accuracy of the equation in the different regimes.
b.) Apply the requirements that the equation of state must have zero first and second
derivatives of P with respect to v at the critical point and use this information to
determine parameters ac and bc. Compare your results with the values provided
above.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.A-5 The improved Patal-Teja equation of state (Patel, N.C., Improvements of the Patel-Teja
Equation of State, Int. Journal of Thermophysics, Vol. 17, No. 3, 1996) reportedly is
more accurate than the Redlich-Kwong-Soave and Peng-Robinson equations of state for
liquid density. The equation has the following form.
P

where

a a

RT
a(T )

v b v v b c v b

R 2Tc2
(T )
Pc

b b

(T ) 1 c1 Tr 1 c2

RTc
Pc

c c

RTc
Pc

Tr 1 c3 TrN 1

The values of the three dimensionless constants, a , b , and c , are established by

required that, at the critical point,
P

0
v crit

2P
2 0
v crit
Applying these criteria, the author notes that:
c 1 3 zc

zc

Pc vc
RTc

a 3 zc2 3 1 2 zc b b2 1 3 zc

b is obtained by solving for the smallest positive root of the following cubic equation
3b 2 3 zc b2 3 zc2 b zc3 0

The purpose of this problem is to test the Patel-Tejas equation's ability to accurately
predict PVT behavior in the superheated, subcooled and saturated regimes for carbon
dioxide. Patel provides the following constants for carbon dioxide.
c1 = 0.63199

c2 = 2.69935

c3 = 0

N=1

Plot pressure versus specific volume for isotherms at 340 K, 300 K, and 260 K. Overlay
the isotherms on a P-v property chart and comment on the agreement with the values
provided by EES.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.A-6 There have been literally hundreds of proposed equations of state for pure fluids.
Recently, Lin et al (Lin, H., Duan, Y., Zhang, T, and Huang, Z., Volumetric Property
Improvement for the Soave-Redlich-Kwong Equation of State, Ind. Eng. Chem Res, Vol. 45, pp.
1829-1839, 2006) have proposed an equation of state which can be summarized as follows.

RT
a (T )

v c - b v c v b c

where

a(T ) 0.42748

R 2Tc2

Pc

1/ 2 1 m 1- Tr1/ 2
b 0.08664

m 0.480 1.574 - 0.176 2

1
RT
c zc c f (T )
3
Pc

RTc
Pc

1 exp 1 Tr
for Tr 1
f (T )
for Tr 1
1 exp 0.5

3.7303exp 60.2833 zc 0.2334

3

In the above equations, Tr is the reduced temperature, is the acentric factor and zc is the
critical compressibility, i.e., the compressibility at the critical point.

3.4620 exp 16.0813 zc 4.0957

a.) Using the Lin equation of state, calculate the specific volume of a hydrocarbon fluid
in the superheated, subcooled and saturated regimes. Compare the specific volumes
obtained from the equation data from EES for this fluid. In the superheat region, you
should select temperatures and pressures that cause the compressibility to
significantly differ from unity. Summarize your results in a table and indicate the
percentage error.
b.) Plot P vs v along at the critical temperature in the vicinity of the critical point. Use
the plot to determine the critical volume for the fluid and compare the result with an
accepted value.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.A-7 A heating plant for a building complex uses natural gas (methane) as a fuel. A concern
has been raised regarding an interruption in service. The plant manager has suggested
that they stockpile cylinders of methane to be used in an emergency. Each cylinder has a
volume of 2 ft3 and, when fully filled, the pressure is 3000 psia at a temperature of 70F.
When combusted in the plant equipment, methane provides 18,060 Btu/lbm.
a.) Estimate the number of cylinders of methane needed to supply a heating load of
500,000 Btu/hr for a 24 hour period using the Peng-Robinson equation of state.
b.) Compare the result in part a) with the value obtained using EES property data.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.A-8 The Carnahan-Starling-DeSantis (CSD) equation of state (Morrison, G and McLinden,

M.O., NBS Technical Note 1226, August, 1986) has the following form.
Z

1 y y 2 y3

1 y

a
RT v b

where y

b
4v

where Z is the compressibility factor. The claimed advantages of this equation are good
predictions of liquid density without the complex parameter fitting procedures of more
elaborate equations and the ability to be used in refrigerant mixture calculations. When
used for a pure fluid without additional data, the values of a and b must be determined by
requiring the critical isotherm to have a slope of zero and an inflection point at the critical
point.
Like most equations of state, the CSD equation is explicit in pressure but implicit in
specific volume. A numerical method (e.g., Newton's method) is needed to solve for
specific volume at specified temperature and pressure. For some conditions, there may
be three real solutions for the specific volume. In this case, the smallest and largest
solutions are the estimated specific volumes of saturated liquid and vapor, respectively.
The intermediate solution corresponds to an unstable state which is physically
unrealizable.
In this problem, we will test the CSD equation's ability to accurately predict PVT
behavior for R1234yf, which is a new refrigerant with properties similar to R134a.
Critical property data for R1234yf can be obtained with the P_crit, T_crit and v_crit
property routines in EES. EES also provides preliminary property data for this fluid so
that you can compare the results of the CSD equation of state with EES.
a.) Using the critical temperature, pressure, and volume provided by EES, calculate the
values of a and b (on a molar basis) for the CSD equation of state and determine the
critical compressibility.
b.) Use the CSD equation of state to determine the critical volume at the critical pressure
and temperature provided by EES. Note that the values of a and b are needed to
calculate the critical volume. These values should be obtained by repeating part a,
but use the critical volume obtained from the CSD equation of state in place of the
critical volume supplied by EES. Compare the values of a and b and the critical
compressibility with the values obtained in part a.
c.) Test the CSD equation of state by calculating the specific volume as a function of
pressure for pressures ranging from 1 bar to 50 bar at temperatures of 500 K, 400 K,
and 300 K. Compare the results with EES. (Note that at conditions below the critical
temperature, you need to select the correct root from the CSD equation. One way to
do this is to use the EES specific volume value as a guess for the CSD specific
volume.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.A-9 Properties are commonly formulated in terms of a reduced Helmholtz free energy
function, , which can be represented as

T , v

(u T s )
RT

The reduced Helmholtz equation is a complete equation of state so that all

thermodynamic properties can be determined from an equation in this form. The reduced
Helmholtz function is ordinarily represented as the sum of an ideal gas and residual
component (IG and res, respectively):

T , v IG T , v res T , v
This problem illustrates that a pressure explicit equation of state can be converted into
the reduced Helmholtz form.
a.) Show that

res T , v

1
RT

RT

P dv
v
T
v
v

(1)

b.) Using the Peng-Robinson equation of state to show that

v 1 2 b
a
v

ln

v b 2 RT 2 b v 1 2 b

res T , v ln

(2)

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-1 The isentropic index, k, is defined as the coefficient relating pressure and volume such
that during an isentropic process, Pvk=Constant. For an ideal gas, k is the ratio of the
specific heat capacities, cp/cv. Derive a relation for k that is applicable for non-ideal gas
behavior. Your relation should involve only the specific heat ratio and expressions
involving pressure, volume, and temperature.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-2 The specific heat of a gas is 825 J/kg-K at 800 K. The molar mass of the gas is 30
kg/kmol. The gas is known to obey the Berthelot equation of state at 800 K for pressures
ranging from atmospheric to 100 MPa. The Berthelot equation is

RT
a
2
vb T v

where a=21420 N-m4-K/kg2 and b=0.00126 m3/kg. Prepare a plot of the constant volume
and constant pressure specific heat capacities as a function of pressure for pressures
between atmospheric and 100 MPa.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-3 The change in internal energy of ideal gas is identically zero if it is compressed
isothermally. Determine the values of U and S if one kmol of ammonia vapor is
isothermally compressed from 22.4 liters to 10 liters at 0C, assuming that the gas
behavior can be described by the Berthelot equation of state.

a
P
v b R T
T v2

a = 1.725E8 [K-Pa-m6/kmol2]
b = 0.03737 m3/kmol

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-4 Consider a piece of rubber as a thermodynamic system. The differential work on the
rubber is given by

W F dl
where F is the force exerted on the rubber when it is extended to a length of l.
a.) Assuming a reversible process, show that the fundamental property relation for this
system is dU TdS Fdl .
b.) Develop an expression for the differential change in entropy of the system dS in terms
of independent variables T and l. Your result should involve only T, F, l, and Cl,
U
where Cl, is the heat capacity at constant length, defined as: Cl
.
T l
c.) Derive an equation that will determine the temperature (T) as a function of length (l)
for reversible adiabatic stretching process, given the following equation of state for
the rubber.
F bT l lo

where
b is a positive-valued constant
lo is the unstretched length at temperature To.
Assume Cl to be constant.
d.) Use your relation in c) to determine whether the temperature of the rubber increases
or decreased when it is adiabatically stretched.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-5 Find an expression for the following derivatives involving only P, T, v, cP and cv
a.)
T

v u
b.)
h
v
s
c.)

h u

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-6 Propane at 50 atm is heated at constant pressure from 500 K to 600 K. Determine the
heat transfer and entropy change for this process per mole of propane. Assume that the
constant pressure specific heat of propane is c op = 125 J/gmol-K and that propane obeys
the following equation of state.

RT
a
2
v b v

where
a = 9.255 liters2 atm/gmol2
b = 0.09033 liters/gmol

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-7 The purpose of this problem is to determine the specific volume, enthalpy, and entropy
of carbon dioxide using the Beattie-Bridgeman equation of state equation of state
equation of state described in problem 10.A-1. The ideal gas specific heat capacity in
units of kJ/kmol-K is
c op 3.7357 30.529 0.5 4.1034 0.024198 2

where T [ K ] /100 . Write a program to calculate and plot the compressibility,

specific enthalpy, and specific entropy of carbon dioxide as a function of pressure for
100 Pa < P < 10e7 Pa for isotherms of 310 K and 350 K. Refer your values of h and s to
reference values of 9.211 [kJ/kg] and 0.03123 [kJ/kg-K], respectively at 310 K and 101.3
kPa, which will result in your values having the same reference states as used in EES.
Compare your results with values from EES. At what conditions do significant errors
occur and what is the major cause of these errors?

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-8 A closed system contains two pounds of a gas mixture of unknown composition that is
compressed isothermally from 240 to 320 psia at 300F. Experimental P, v, T data are
provided in Table 10.B-8. Using these data, estimate the heat, the work and the change
in entropy of the gas, assuming the process to be reversible. If these data are insufficient
to do the calculation, indicate what other data are required and how you would use the
additional data to do the calculation.
Table 10.B-8: Values of specifc volume [ft3/lbm]
P [psia] 285F
290F 295F 300F 305F 310F 315F
230
0.491
0.497
0.503
0.509
0.515
0.521
0.527
240
0.465
0.471
0.477
0.483
0.489
0.495
0.500
250
0.441
0.447
0.453
0.459
0.465
0.470
0.476
260
0.419
0.425
0.431
0.437
0.442
0.448
0.453
270
0.398
0.404
0.410
0.416
0.421
0.427
0.432
280
0.379
0.385
0.391
0.396
0.402
0.407
0.413
290
0.361
0.367
0.373
0.378
0.384
0.389
0.395
300
0.344
0.350
0.356
0.361
0.367
0.372
0.377
310
0.328
0.334
0.340
0.345
0.351
0.356
0.361
320
0.313
0.319
0.325
0.330
0.336
0.341
0.346
330
0.299
0.305
0.310
0.316
0.321
0.327
0.332

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-9 Write a program to determine the specific volume, enthalpy, and entropy of isobutane
using the Lin et al (2006) equation of state described in problem 10.A-6. Critical
constants for isobutane are available in EES. The ideal gas specific heat of isobutane can
be approximated as
c 0p 6.772 0.34147 T 1.0271E 4 T 2 3.6849 E 8 T 3 2.0429 E 11 T 4
where c 0p is in units of kJ/kmol-K and T is in Kelvin. Refer your values of h and s to
reference values of 598.9 [kJ/kg] and 2.513 [kJ/kg-K], respectively at 298.15 K and
101.3 kPa. Use your program to plot the specific volume, enthalpy and entropy of
isobutane as a function of pressure at 420 K, 450 K and 500 K for pressures ranging
between 0.10 and 10 MPa. Compare your results with values from EES and comment on
the differences.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-10 A gas storage tank with a volume of 3 m3 contains a gas at 900 kPa and 25 C, the
temperature of the surroundings. Compressibility data for this gas at 25C, 50C and
75C are provided in Figure 10.C-10. A valve on this tank leaks slightly so that, after a
considerable time, the tank pressure drops to 300 kPa.
a.) Estimate the heat transfer between the tank contents and the surroundings for this
process.
b.) What would the heat transfer be if the gas obeyed the ideal gas law?
c.) Estimate the change in specific entropy of the gas that remains in the tank.
1
0.95
0.9

50C
0.85

25C
0.8

0C
0.75
0.7
0

200

400

600

800

1000

P [kPa]

Figure 10.C-10: Compressibility factor versus pressure at 0, 25 and 50C

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-11 A superheated organic vapor flowing through an insulated pipeline passes through a
restriction. Upstream of the restriction, the pressure is 35 bar and the temperature is
230C. Downstream of the restriction, the pressure is 31.5 bar and the temperature is
225.5C. Pressure, volume, temperature data for this substance are provided in Table
10.B-11.
Table 10.B-11: property data for a superheated organic vapor

Pressure
(bars)

Specific volume
(m3/kg)
220C
230C
240C
30
0.02302 0.02431 0.0255
35
0.01839 0.01971 0.02089
40
0.01466 0.01611 0.01733
a.) Estimate an average value for the constant pressure specific heat capacity at the
conditions encountered at the pipeline restriction.
b.) Estimate the change in specific entropy of the vapor as it passes through the
restriction.
c.) It has been reported that in some sections of the pipeline, the temperature increases
as it passes through a restriction. Is this possible? Would the entropy change be
positive in this case? Explain.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-12 A thermodynamic system consists of a solid paramagnetic substance having a magnetic

moment per unit volume, M ([=] amp/m). The substance is subjected to a magnetic field
of intensity F ([=] amp/m) and is reversibly magnetized. The work done on the
substance is:
W oV F dM
where

o is the magnetic permeability of free space (4x107 N/amp2)

V is the volume of the material in m3.

The equilibrium relationship for a paramagnetic solid can be expressed by the Curie
equation as follows:

VMT
mC

where
m is the mass of the solid [kg]
T is the absolute temperature [K]
C is the Curie constant, a characteristic of the material with units of m3-K/kg
a.) Assuming that the only work interaction is that due to the magnetization of the
substance, show that:

dU TdS o V F dM
b.) Develop an expression for dS in terms of independent variables T and M. (Your
result should involve only T, V, o , M, m, C, and Cm, the specific heat of the
substance at constant magnetic moment.
c.) Determine an expression for T as a function of M for a reversible adiabatic process.
Does the temperature increase or decrease when the substance is demagnetized?

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-13 When a pressure disturbance occurs in a compressible fluid, the disturbance travels with
a velocity that depends on the state of the fluid. A sound wave is a very small pressure
disturbance which can be approximated as an isentropic process. The speed of sound, c,
is an easily measured thermodynamic quantity defined by:
P
c

s
where P is pressure, is the fluid density, and s is specific entropy.

Derive an equation for the speed of sound through a fluid that is described by the MMM
equation of state proposed by Mohsen-Nia et al. which is described in Problem 10.A-4.
Your equation should involve only of P, v, T, cp/cv and derivatives involving these
properties. Use your equation to calculate and plot the speed of sound through carbon
dioxide at 350, 300, and 250 K as a function of reduced pressures between 0.1 and 1.0.
Use the EES value of cp/cv in your evaluations. Compare your results with the
SoundSpeed function results provided by EES. Provide an explanation for differences
between your results and the accepted values.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-14 A large sphere with a pinhole provide a good approximation of a black (i.e., perfect
absorber) surface. Energy exchange between the inner surface of the sphere occurs by
thermal radiation. Experiments show that if the volume of the sphere (V) is increased
with the temperature (T) held constant, the rate of radiation exchange is increased but the
energy density e(T) (i.e., the energy per unit volume) remains constant. Thus, the
internal energy of the surface of the sphere can be expressed as U = V e(T). Experiments
also show that radiation exerts a pressure P=1/3 e(T) on the walls of the surface. Using
these experimental facts, derive an equation for e(T) in terms of the temperature T, a
reference temperature, To and a constant eo=e(To).

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-15 A gas obeys the equation of state

RT
a

v b
T v2
where a=1.426e4 kJ-m3 K1/2/kmol2 and b =0.0211 m3/kmol. The ideal gas constant
volume specific heat capacity of this gas is 30 kJ/kmol-K. The specific volume of the
gas is 0.423 m3/kmol at 400 K. The gas is heated at constant volume to 800 K.
a.) Determine the initial and final pressures
b.) Determine the change in internal energy per kmol of gas.
P

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-16 The specific heat capacity ratio, k, is needed to calculate the speed of sound and for other
thermodynamic processes. This problem investigates the use of CSD equation of state
described in problem 10.A-8 for calculating the specific heat ratio of refrigerant
R1234yf.
c
a.) Derive a general relation for v
v T
b.) In the temperature range between 300 K and 500 K, the constant volume specific
heat of R1234yf at ideal gas conditions in J/kmol-K can be represented by:

cvo 6816.44 368.528 T 0.234306 T 2

Specialize the general relation found in part a.) to allow evaluation of cv for
R1234yf at a specified temperature and pressure using the CSD equation of state.
c.) Use the relation for cv determined in part b and the general relation between cp and
cv to determine the specific heat ratio. Calculate and plot the specific heat ratio as
a function of pressure for pressures between 1 bar and 50 bar at 400 K and 500 K.
Compare the result with EES and comment on the agreement.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-17 High accuracy equations of state for many substances have recently been formulated by
representing the reduced Helmholtz Free energy function as the sum of ideal gas and
residual parts, i.e.,
a
,
IG , res ,
(1)
RT

where

crit

(2)

Tcrit
(3)
T
a is the specific Helmholtz free energy and superscripts IG and res refer to the ideal gas
and residual components. For R134a, the ideal gas and residual components have been
correlated as:

IG , ln a1 a2 a3 ln ai n

(4)

i4

res , ai d t ai d t exp e
8

21

i 1

i 9

(5)

Coefficients needed in Eqs. (4) and (5) for R134a are provided in the table 10.B-17 and
in EES Lookfile FEQR134a.lkt.
a.) Derive expressions for the pressure, specific internal energy, and specific entropy as
functions of and .
b) Using your results from part a.), calculate values of pressure, specific enthalpy, and
specific entropy at 300 K as a function of specific volume ranging from 1 m3/kg to
0.03 m3/kg. Compare your results with values from EES. Note that EES uses the
ASHRAE reference for h and s whereas the Tillner-Roth equation of state uses the
IIR reference state. Include the following directive in your program to change the
reference state in EES.
Table 10.B-17: Coefficients for Eqs. (4) and (5) for R134a from
Tillner-Roth, R., Fundamental Equations of State, Shaker Verlag, Aachen, 1998.

1
2
3
4
5
6
7
8
9
10
11
12

aio
-1.019535
9.047135
-1.629789
-9.723916
-3.927170
0

ni

0
0
0
-0.5
-0.75
0

ai

0.49822300
0.02458698
0.00085701
0.00047886
-1.80080800
0.26716410
-0.04781652
0.05586817
0.33240620
-0.00748591
0.01423987
0.20571440

ei

0
0
0
0
0
0
0
0
1
1
1
2

ti

0
0
0
1.5
1.5
2
2
-0.5
3
5
1
6

di

1
3
6
6
1
1
2
2
2
2
5
1

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

13
14
15
16
17
18
19
20
21

-0.51845670
-0.08692288
0.00010173
0.00046033
-0.00500046
-0.00349784
0.00699504
-0.01452184
-0.00012855

2
2
2
2
2
3
3
3
4

5
5
1
10
10
10
18
22
50

1
4
4
4
2
1
5
3
10

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.B-18 Calculate plot the change in enthalpy and entropy as a function of initial pressure using
the Peng-Robinson equation of state for carbon dioxide undergoing an isothermal change
in pressure from 10,000 to 100 kPa at 310 K. You may use the Peng-Robinson library
functions provided in EES. Compare your result with accepted values.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.C-1 A 180 lbm person is planing to ice skate on hollow ground blades that have a total area in
contact with the ice of 0.012 in2. The ice temperature is 28F. Will the ice melt under
the blades? Data for water at its triple point are provided in Table 10.C-1.
Table 10.C-1

Triple point data for water

Pressure
Temperature
liquid specific volume
solid specific volume
liquid specific enthalpy
solid specific enthlapy

611.7 Pa
273.16 K
0.001000 m3/kg
0.001091 m3/kg
23.26 J/kg
-333,316 J/kg

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.C-2 The critical temperature and pressure of n-butane are 425.2 K and 3796 kPa, respectively.
Its molar mass is 58.12 kg/kmol. In the temperature range between 300 K and 400 K, the
vapor pressure of n-butane is represented by
ln( Psat ) 21.54 2722.08 / T
where Psat is in Pa and T is in K. The specific volume of liquid n-butane in this
temperature range is approximately
vliq 0.00535 0.00002577T 4.608E-8T 2
where vliq is in units of m3/kg. Using these data, estimate the enthalpy of vaporization of
n-butane liquid at 340 K with
a.) The Clausius-Clapeyron equation
b.) The Clapeyron equation
c.) Compare the results to each other and to the value obtained from EES.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.C-3 Shown in Figure 10.C-3 is a plot of pressure versus specific volume along an isotherm of
90C for R134a calculated with the Peng-Robinson equation of state. Using only this
plot, estimate the vapor pressure of R134a at 90C. Compare your result with the vapor
pressure provided by EES.
40

Peng-Robinson Equation of State for R134a

P [bar]

35

T=90C
30

25
0.001

0.002

0.003

0.004

0.005

0.006

0.007

0.008

v [m /kg]

Figure 10.C-3 Pressure versus volume at 90C for R134a determined with the Peng Robinson EOS

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.C-4 The saturation pressure, liquid density and vapor density of a refrigerant have been
measured as a function of temperature. These data are reported in Table 10.C-4.
Table 10.C-4: Measured saturation data for a refrigerant

T
(C)
50
55
60
65
70
75
80
85
90
95
100

P
(bar)
2.346
2.707
3.11
3.557
4.05
4.594
5.191
5.844
6.556
7.332
8.174

liquid density
(kg/m3)
1414
1402
1389
1375
1362
1348
1334
1320
1306
1291
1276

Vapor density
(kg/m3)
12.88
14.75
16.82
19.11
21.64
24.42
27.48
30.84
34.52
38.54
42.94

a.) Calculate and plot the specific enthalpy change of vaporization and the specific
entropy change of vaporization as a function of temperature.
b.) Estimate the normal boiling point for this refrigerant.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.C-5 Data for an organic substance that is used in an industrial process are reported in Table
10.C-5.
Table 10.C-5: Physical property data for an organic substance

Molecular weight
Normal melting point
Heat of fusion at 1 atm
Vapor pressure at the normal melting point
Vapor pressure at 100C
Density of solid at the normal melting point
Density of liquid at the normal melting point

127.6 kg/kmol
72.5C
19.674E6 J/kmol
5.0 mm Hg
20.0 mm Hg
1.429 g/cm3
1.150 g/cm3

Using these data and appropriate assumptions,

a.) estimate the heat of vaporization of the liquid at 1 atm
b.) esimate the heat of sublimation of the solid at 1 atm
c.) estimate the melting point of the solid at 100 atm
d.) estimate the boiling point of the liquid at 1 atm.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.C-6 Liquid benzene is pumped to a vaporizer as a saturated liquid at a 2200 kPa. Benzene
vapor exits the vaporizer as a wet vapor with 92% quality and essentially the same
pressure as it entered. Estimate the heat load on the vaporizer per kg of benzene. Data
for benzene are provided in Table 10.C-6.
Table 10.C-6: Property Information for Benzene

T
Psat
liq
[C]
[kPa]
[kg/m3]
220
1958.7
622.2
225
2107.8
612.8
230
2265.2
602.9
235
2431.2
592.5
240
2606.0
581.6
245
2790.2
570.1
Critical Temperature = 562.0 K
Critical Pressure = 4.894 Mpa
Acentric factor =0.2092
Molar mass = 78.108 kg/kmol

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.C-7 Refrigerant R134a at 300 K is isothermally compressed from as initial pressure of 100
kPa until it reaches a condition of saturation. Use the Peng Robinson equation of state to
determine the following quantities for this process:
a.) the saturation pressure at 300 K by equating the fugacities of the liquid and vapor
b.) the change in specific volume
c.) the change in specific enthalpy
d.) the change in specifi entropy
You are welcome to use the Peng-Robinson library in EES. Compare your values with
the R134a property data.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.C-8 The vapor pressure of water can be represented by the equation:

5301
ln P 32.99
1.2236 ln(T )
T
where P is the saturation pressure in Pa and T is in K.
a.) Using only the information given above, prepare a plot of the enthalpy of
vaporization of water as a function of temperature for temperatures between 300 K
and 635 K. Compare the results with the steam table data.
b.) Use the specific volume data provided in the steam tables to obtain a more correct
result.

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.C-9 The vapor pressure of carbon tetrachloride (CCl4, MW=153.82) at several temperatures
is shown in Table 10.C-9. Using these data, estimate the enthalpy of vaporization of
carbon tetrachloride in this temperature range.
Table 10.C-9: Vapor pressure versus temperature for carbon tetrachloride

T [C]
P [atm]

25
0.15

35
0.229

45
0.341

55
0.492

 S.A. Klein and G.F. Nellis

Cambridge University Press, 2011

10.C-10 Using the Peng Robinson equation of state, estimate the saturation vapor pressure of
carbon dioxide at 250 K and the corresponding specific volumes of saturated liquid and
vapor by:
a.) using the Fundamental property relation involving Gibbs free energy, and by
b.) equating the fugacities of saturated liquid and vapor.
Compare these estimates with values from a respected source.