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Thermodynamic Properties From Cubic Equations of State
Thermodynamic Properties From Cubic Equations of State
Thermodynamic Properties From Cubic Equations of State
by
PATRICK CHUNG-NIN M A K
in
February 1988
degree at the University of British Columbia, I agree that the Library shall make it
freely available for reference and study. I further agree that permission for extensive
copying of this thesis for scholarly purposes may be granted by the head of my
publication of this thesis for financial gain shall not be allowed without my written
permission.
Date /W - Z~ / f
ABSTRACT
that it can be applied over the entire PVT surface except along the critical
isotherm. The dimensionless T coordinate has been defined according to the two
T /T - 1
T = — for T < T
T /T - 1
c b
and
* T/T - 1
T = for T > T
V b T
" 1
where T c is the critical temperature and is the normal boiling point. The
a = 1 + p(T*) q
for T < T c
and
a = 1 - p(T ) q
for T > T
c
The two substance-dependent constants p and q are generated from the vapor
pressure data.
properties with known experimental data and with predictions from the
ii
is the most accurate equation of state for calculating vapor pressure, and
saturated vapor and liquid volumes. The Peng-Robinson equation is the best for
equation is the least accurate equation for pressure and volume predictions in the
single phase regions. F o r temperature prediction, all three equations of state give
similar results in the subcritical and supercritical regions. None of the three
Peng-Robinson equation and the proposed equation are very similar in accuracy
except in the region where the temperature is near the critical. That is, between
0.95 < T r ^ 1.05, the proposed equation gives rather poor results. F o r isobaric
are adequate. The Soave-Redlich-Kwong equation gives the lowest overall average
equation also provides the most reliable prediction for the J o u l e - T h o m s o n inversion
designed for the calculation of second virial coefficient has been included in this
work. The estimation from the proposed function gives equal, if not better,
iii
TABLE OF CONTENTS
ABSTRACT ii
LIST O F FIGURES vi
LIST OF TABLES x
ACKNOWLEDGEMENT xii
Chapter 1. INTRODUCTION 1
CONCLUSIONS 150
NOMENCLATURE 154
REFERENCES 157
APPENDIX A 164
1. Critical Compressibility F a c t o r 164
1.1. T h e Soave-Redlich-Kwong E q u a t i o n 169
1.2. T h e Peng-Robinson E q u a t i o n 169
1.3. T h i s Work 170
2. Constants A and B 170
2.1. T h e Soave-Redlich-Kwong E q u a t i o n 171
2.2. T h e Peng-Robinson Equation 171
2.3. T h i s W o r k 172
3. Compressibility Factor Equation 172
iv
3.1. T h e Soave-Redlich-Kwong E q u a t i o n 173
3.2. T h e Peng-Robinson Equation 173
3.3. This Work 173
4. F u g a c i t y Coefficient 173
4.1. T h e Soave-Redlich-Kwong Equation 176
4.2. T h e Peng-Robinson Equation 176
4.3. T h i s Work 177
5. E n t h a l p y Departure Function 177
5.1. T h e Soave-Redlich-Kwong Equation 179
5.2. T h e Peng-Robinson Equation 180
5.3. T h i s W o r k 181
6. Heat Capacity D e p a r t u r e Function 183
6.1. T h e Soave-Redlich-Kwong Equation 189
6.2. T h e Peng-Robinson Equation 190
6.3. This Work 190
7. Joule-Thomson Coefficient 191
7.1. T h e Soave-Redlich-Kwong Equation 191
7.2. T h e Peng-Robinson E q u a t i o n 192
7.3. T h i s W o r k 192
8. Inversion C u r v e 192
8.1. T h e Soave-Redlich-Kwong E q u a t i o n 195
8.2. T h e Peng-Robinson E q u a t i o n 195
8.3. T h i s W o r k 196
9. V i r i a l Coefficients 197
9.1. T h e Soave-Redlich-Kwong Equation 199
9.2. T h e Peng-Robinson Equation 199
9.3. T h i s W o r k 200
v
LIST OF FIGURES
and q 36
vi
Figure 4.16 Region II : Reduced Helmholtz departure functions of i-butane
(Pr=0.56) and water (Pr = 0.31) versus reduced temperature 85
Figure 4.24 Region III : Compressibility factors of n-octane (Pr = 4.03) and
ethanol ( P r = 1 . 6 3 ) versus reduced temperature 99
vn
Figure 4.33 Region III : Reduced Gibbs energy departure functions of
n-octane (Tr=1.76) and ethanol (Tr=1.95) versus reduced pressure 103
Figure 4.36 Region III : Fugacity coefficients of n-octane (Pr = 4.03) and
ethanol (Pr=1.63) versus reduced temperature 105
Vlll
Figure 4.49 Region I V : Reduced internal energy departure functions of
n-heptane (Tr = 0.67) and methanol (Tr = 0.70) versus reduced pressure. 121
Figure 4.53 Inversion curve of propane calculated from the S R K , PR, and
LM equations 129
Figure 4.54 Inversion curve of n-butane calculated from the S R K , PR, and
L M equations 130
Figure 4.55 Inversion curve of carbon monoxide calculated from the SRK,
P R , L M , and G C P equations 131
Figure 4.56 Inversion curve of carbon dioxide calculated from the S R K , PR,
and L M equations 132
Figure 4.57 Inversion curve of ethylene calculated from the SRK, PR, L M ,
and G C P equations 133
Figure 4.59 Inversion curve of ammonia calculated from the SRK, PR, and
L M equations 135
Figure 5.1 Second virial coefficients of n-butane and benzene versus reduced
temperature 148
Figure 5.2 Second virial coefficients of n-octane and argon versus reduced
temperature 149
ix
LIST OF TABLES
Table 3.3 Acentric Factor from the Proposed, Lee-Kesler, and Edmister
Correlations 43
Table 4.5 Overall Average Errors ( R M S % and A A D ) for the Four Regions
Table 4.13 Region II - Isobaric Heat Capacitj' : Average Absolute Deviation ...81
x
Table 4.18 Region III - Helmholtz and Gibbs Free Energy Departure
Functions : Average Absolute Deviation 96
Tbale 4.19 Region III - Internal Energy Departure Functions and Fugacity
Table 4.20 Region III - Isobaric Heat Capacity : Average Absolute Deviation .. 98
Table 4.27 Region IV - Isobaric Heat Capacity : Average Absolute Deviation 115
Table 5.1 Second Virial Coefficient : Average Absolute Deviation (cc/mole) 147
xi
ACKNOWLEDGEMENT
patience, and his support in carrying out this project and his assistance in the
Scholarship. Thanks are also due to the financial aid provided by the Natural
xn
CHAPTER 1. INTRODUCTION
essential part of engineering in the process industries. Many methods have been
proposed and used in past years. The older methods have usually relied on
charts or graphs. For the process engineer, the task has been time consuming
and tedious. Accuracy of the results were usually limited by the graph or chart
in minutes rather than hours. Hence, the demand for an accurate equation of
f(P,V,T,x) =0 ( L 1 )
finding an equation of state which is simple to use and yet accurate enough for
infancy stage, the semi-empirical approach is usually preferred and enjoys the
1
2
greatest success.
has a limited theoretical framework. This form of the equation is usually based
many cases, obtained from experimental data. There are two types of
cubic.
equation is usually reserved for highly accurate work. To define the constants,
vast amount of input data are needed for multiproperty regression routine. The
constants for hydrocarbons. However, no constants have yet been developed for
From here on Eq.(1.2) is known as the generalized cubic equation of state. With
for instance when u= 0 and w = 0, Eq.(1.2) becomes the van der Waals equation
[125]; with u=l and w = 0, Eq.(1.2) becomes the various versions of the
procedure. In many instances, the initial guess must be close to the solution in
order to have convergence. T h e cubic equation, on the other hand, can be solved
analytically, even though numerical techniques are often used. The constants
required are readily attainable from minimal input data. In many of the
well-accepted cubic equations only critical properties and the acentric factor are
polar substances poorly. Lielmezs and Merriman ( L M ) [64] realized this limitation
4
and proposed a modified PR equation. They claimed that their modification has
improved significantly vapor pressure prediction and slightly better saturated liquid
that it can be used for volume calculations in the subcritical region. The
experimental PVT data as the input data in order to determine the required
constants and therefore limited its application. Although improvements have been
made by Lielmezs and Merriman, their equation cannot be used in the region
The purpose of this work is, therefore, twofold: 1) to extend the capabilhVy
surface and 2) to test the modification for various property predictions. Since the
two equations along with the present work in property predictions that have
never been tested before. This work is limited to pure compound properties. It is
substances.
supercritical, and compressed. The subcritical region refers to the area above the
5
saturated vapor curve and beneath the critical isotherm. The supercritical region
is the area above the critical isotherm and the compressed liquid region is the
area under the the critical isotherm and above the saturated liquid curve. These
regions are shown in Figure 1.1. The properties included in the testing for the
saturation region are: vapor pressure, vapor and liquid volumes, and enthalpy
compressed liquid region, the properties are basically the same as those in the
subcritical and supercritical states except Joule-Thomson coefficient that has not
been included due to the lack of experimental data. In addition to the above
properties, the inversion curve and the second virial coefficient are also included
in this work.
Tc
L Critical
VPoint
Region IV : / \ \ Region II :
\ /V
Compressed/* \ \ Subcritical
Liquid / *
Region I : \ \
Saturation Curve \ \
Volume
Ever since van der Waals [125] first proposed his equation of state more
than a centur\' ago, scores of modifications of his equation have been made.
Most of these equations have been empirical and arbitrary with parameters that
are adjustable to fit certain kinds of experimental data such as vapor pressure,
liquid or vapor volume. Literature on this subject has grown to large proportions.
A number of reviews have been published which addressed the merits and
Shah and Thodos [104] pointed out the advantages of cubic equations over
equation of state should possess. The following review will be confined to cubic
equation of state of the van der Waals type and is by no means exhaustive.
This review will focus on three areas: 1) what approaches have been adopted in
past j'ears for improving the van der Waals t3'pe equation, 2) what properties
and t3'pes of compounds have been tested and, 3) what are the limitations of
these modifications.
The van der Waals equation may be written as the sum of two terms:
P
" R
P + P
A (2.1)
all cubic equations of state of the semi-empirical t3'pe uses the van der Waals'
8
RT
P = (2.1a)
R
V-b
a(T)
(2.1b)
V*+ubV+wb 2
different temperature dependent function for a(T) and/or, 2) using different u and
w values. O n e of the most successful modification of the van der Waals equation
a(T)
(2.2)
V(V+b)
a(T) = fl a a (2.2a)
a = T -0.5 (2.2b)
r
b(T) = % — (2.2c)
9
The two constants Sl^ and fl^ at the critical point have numerical values of
After the work of Redlich and Kwong, Wilson [127,128] proposed that the
and 1.0. However his proposed equation did not gain much attention due to lack
substance-dependent constants Sl & and fl^, one set for the vapor phase and
another set for the liquid phase, which can be calculated from volumetric data.
The accuracy from the modified equation in estimating both vapor and liquid
volumetric properties has been increased, but the equation lacks internal
Chueh-Prausnitz equation by using only one set of constants which were fitted
with saturated liquid volume data. S i m i l a r to its predecessor, the equation is not
a generalized correlation. That is, experimental volumetric data are the necessary
for industrial application was due to the efforts of Soave [110] who proposed a
10
modified R K equation. This modified equation was generalized, simple to use and
its range of application exceeded all the other modifications. The necessary input
data for this modification are the critical pressure and temperature and acentric
factor, (j. Soave utilized Wilson's original idea by making the attraction constant
"a" temperature dependent. Vapor pressure data at T =0.7 and the critical point
fugacity criterion, that is the vapor phase fugacity is equal to the liquid phase
further in the next chapter. Instead of the a defined b}' Eq.(2.2b), Soave defined
a = [ 1 + m(l - T °' )
r
5
] 2
( 2. )
3
Eq.(2.3) and (2.3a) can only be applied to nonpolar and slightly polar compounds
[110]. However the accuracy in vapor pressure prediction had increased more
Chaudron [12], Simonet and Behar [107] generalized the Q & and 0^
constants with the acentric factor but without incorporating the equal fugacity
Peng and Robinson [87] furthered the work of Soave by fitting the
a-function with vapor pressure data from the normal boiling point to the critical
point. In other words, the a multiplier was used to optimize the vapor pressure
denominator of the attraction pressure term have also been changed to 2 and
-1, respectively. The repulsion pressure term P R remains the same as before but
a(T)
P a
V +2bV-b
2 2
^'^
2 4
The a-function has the same form as Eq.(2.3) but the coefficients of the constant
The two constants Q & and have values of 0.45724 and 0.07780 [87],
respectively. As the result of their modification, Peng and Robinsion claimed that
their equation is superior to the SRK equation for saturated liquid volume
predictions. It was shown by a number of studies that their claim was indeed
valid [66,67,84,129].
Graboski and Daubert [41,42] adopted the same approach as Peng and
12
Robinson by refitting the a-function of the SRK equation with the entire vapor
pressure curve instead of just two points as was done by Soave [110]. For
hydrocarbons and slightly polar compounds, the form of the a-function is the
same as the SRK equation (Eq.(2.3)) but the coefficients of the constant m
expressed as [42]:
a = 1.202exp(-0.30228T ) r ( .6)
2
generalized these two constants with acentric factors. Both vapor pressure and
saturated liquid volume data were used to obtain the two constants, a and b.
These studies have shown that saturated liquid volume predictions have improved
while vapor pressure predictions have remained approximately the same as those
for the SRK and PR equations. However, saturated vapor volume predictions
accuracy.
13
For polar compounds, none of the above equations of state are sufficiently
suitable for representing saturation properties. This is mainly due to the fact
that polar compounds do not follow the usual three-parameter corresponding states
the deviation of normal fluid behavior from simple fluid. Pitzer defined normal
fluid as the ones with zero or small dipole moment and he proposed that the
be this third parameter. In simple terms, the acentric factor accounts for the
effects of the size and shape of different molecules. In order to obtain the
third parameter is, - therefore, inadequate to account for the dipole moment found
have been proposed, for instance, by Halm and Stiel [46], O'Connell and
Prausnitz [81], and Tarakad and Danner [120]. Although each of the proposed
fourth parameter has correlated, with some degree of success, the thermodynamic
functions, however, none of them as yet has gained wide acceptance. It appears
constants with acentric factor are unlikely to provide good representation of state
This route was followed by Soave [111] who realized that his earlier
a = 1 + (1 - T )(m r + n/T )
r (2.8)
These two constants can be calculated from vapor pressure data. Lielmezs et al
(LHC) [63] modified the RK equation by defining a different a-function, also with
where
(2.9a)
These two constants can also be established from vapor pressure data. Similarly,
Lielmezs and Merriman (LM) [64] applied the same a-function to the PR
equation. The present forms of both the LHC and LM equations are incapable of
a = [ 1 + K<1 - T * ) ] r
0 5 2
( 2 1 0 )
(1 + T °' )(0.7 - T ) r
5
r (2 . 10a )
where »c is given by
0
+ 0.0196544w 3
(2.10b)
three constants, acentric factor, critical temperature and pressure are required.
Stryjek and Vera provided their own set of acentric factors and they claimed
their values are the most accurate and which should be used in conjuction with
their modification. In' other words, in order to achieve the accuracy claimed, four
constants instead of three are now necessary. Both polar and nonpolar compounds
have been tested and vapor pressure predictions have indeed been improved over
the original PR equation. Second virial coefficient calculation from EOS is also
part of their comparison and the performance is of the typical cubic equation of
16
state. More on this subject will be said in the chapter on second virial
coefficient. In the supercritical region, only the fugacity coefficient has been tested
against experimental data. The accurac}' from- the modification for this property
utilizing the volume-translation technique; the specific volume and the volume
correction constant b are corrected by c.The new volume and volume correction
V = V - c (2.11)
b" = b - c (2.12)
RT a(T)
P = - (o n i
V-b' (V'+c)(V'+b +2c)
, v
• ;
Peneloux and co-workers have shown that such translation does not alter the
vapor pressure predictions from the original SRK equation. In fact, this shift in
volume by the amount c changes the location of the isotherm and does not
established from saturated liquid volume at T = 0.7. r They claimed that at such
along the saturation curve. They generalized this constant c with the Rackett
This correction should be subtracted from the volume calculated by the SRK
equation. They tested the predictions from their modification for saturated liquid
volume with experimental data for 233 compounds. Both polar and nonpolar
compounds were included. The results from this correction are encouraging.
However, this correction can have adverse effects on vapor volume predictions
because the isotherm has shifted away from the experimental saturated vapor
Soave [112] used the same technique for the van der Waals equation and
obtained the constant c at the reduced normal boiling point instead of T = 0.7. r
Up to now, the two most popular cubic EOS, SRK and PR, have been
modification of the LHC [63] equation with the SRK and Lee-Kesler [59]
In the original work of Peng and Robinson [87], only the enthalpy departure
functions for five compounds were tested against experimental data. Mohanty et
SRK equation along with three other cubic equations for saturation property
fugacity coefficient and volumes of both vapor and liquid, enthalpy and entropy
SRK E O S , for saturated vapor and superheated gas phase density and fugacity
predictions for polar and nonpolar compounds. Probably the most comprehensive
cubic equations, both PR and S R K were included, for eight properties of straight
on cubic equations of state with experimental data is necessary. Thus, the effort
in modifying or improving the cubic equation of state. In the first part of this
properties for the region above the critical isotherm. In order to remove this
limitation, the equation must be modified and the second part of this chapter
region.
calculations and the conditions of phase equilibrium for a pure substance are
p l
' p V
(3.2)
G
" G
(3.3)
These conditions state that at equilibrium, temperature, pressure and Gibbs free
19
20
energy of the two phases, liquid and vapor, must be identical. Eq.(3.3) can
u
1 = Uv
(3.4)
u - u° = RTln (3.5)
f 1
= f v
(3.6)
these three conditions, Eq.(3.1), (3.2), and (3.6) must be incorporated into the
EOS. T h e following discussion will show how such a task can be accomplished.
Gibbs free energy is the sum of the Helmholtz free energy, A and the
G = A + PV (3.7)
Since condition (3.3) requires that the Gibbs free energy be equal for the two
phases, or
G 1
- G V
= 0 (3.3a)
A 1
- A V
+ P V - P V
1 1 V V
=0 (3.8)
3A
A 1
-A V
=/ dv (3.9)
av
3A
= -P (3.10)
3V
JT
By combining Eq.(3.2), (3.8), (3.9), and (3.10), condition (3.3) can now be
J , PdV + P ( V - V ) = 0 1 v
(3.11)
V 1
The first term of Eq.(3.11) gives the area underneath the isotherm or
22
V v
and the second term represents the area bound by the isobar P and the isochors
V (=V ) and V
1
7
V
(=V ) or
6
P(V V
- v ) = area 1-3-5-6-7-1
1
( 3 1 3 )
But
incorporate the Maxwell-rule into the equation of state. The most commonly used
with vapor pressure data. The reason is that by fitting the constant "a" with
23
experimental vapor pressure data, it is possible to adjust the two areas such
that their sum equals zero. From the Gibbs phase rule:
F = m + 2 - (3.16)
and 7r is the number of phases, it is clear that there is one degree of freedom
the constant a. The algorithm used is given in a later section of this chapter.
also be considered. These two criteria are 1) an equation of state should reduce
PV
lim — = 1 (3.17)
P—>0 RT
and 2) the EOS should satisfy the thermodynamic stability criteria at the critical
point. From Figure 1.1, it is clear that the critical point is not only an
inflection point, but it is also a point which has zero slope. In other words, at
the critical point, the first and second derivatives of pressure with respect to
3P
= 0 (3.18)
3V
24
9P 2
= 0
(3.19)
av JT 2
is the functional dependence of the constants. When the generalized cubic equation
a 1 uab
Z = 1+ b — + b 2
+
RT V RT
(w-u )ab2 2
1
b 3
+ (3.20)
RT V 3
B C D
Z = 1 + - + — + — + (3.21)
V V 2 y3
where B, C, D etc are the second, third, and fourth virial coefficients.
Comparing the coefficients of Eq.(3.20) and (3.21), the virial coefficients in terms
B = b- (3.22)
RT
uab
C = b + 2
(3.23)
RT
25
(w-u )ab 2 2
D = b 3
+ (3.24)
RT
The above criteria are not restricted to cubic equations of state but are
by defining a new a term of Eq.(2.2a) but retaining the same u and w values
* _ T
c / T
' 1
where T , T^, T are the critical temperature, normal boiling point temperature,
*
and the state temperature, respectively. This T coordinate system have been
self-diffusion coefficient [61], thermal conductivity [49], and surface tension [65]
26
correlations.
*
The a term was written in terms of the proposed T as
o(T*) = 1 + p(T*)3 ( 2 9 )
where p and q were characteristic constants of the given pure substance. One
that quantum or polar effects are absorbed by the two constants and the
a-function with the least-squares routine. For the sake of completeness, the
studied in this work along with the fitted p and q values are given in Table
3.1. Some of the p and q values are different than the ones given previously
by Lielmezs and Merriman [64]. This is due to the fact that different data sets
have been evaluated. These included the Lee-Kesler (LK) [59], Riedel [94],
(GNT) [95] equations. These are all generalized equations and only critical
temperature and pressure, normal boiling point temperature, acentric factor, and
27
molecular weight of the compound are needed as input data. To evaluate these
five equations, they were used to predict vapor pressure of 36 compounds studied
in this work. The predicted results are compared with the experimental data
used to obtain the p and q constants. The comparison is based on root mean
I (% e r r o r ) 2
where
Experimental - Calculated
% Error = X 100
Experimental
Of the five equations studied, the GNT and FKT equations seem to give
the most reliable results for both polar and nonpolar compounds. However,
pressure explicit equation and is simpler to solve. Therefore, the GNT equation is
parameter, s [28,77,94] :
28
T, ln(P /P")
s = -£= (3.26)
l-T.br
which is the negative of the slope between the critical point and normal boiling
lnP = s r 1 - (3.27)
expressed in atm and P° is one atmosphere. Miller [77] suggested that this
Riedel factor a Q [96], the critical compressibility Z , c and the acentric factor o.
AH , = sRT
vb c (3.28)
u =
1 1^ 5
~ 1 , 0 ( 3
- 2 9 )
their vapor pressure equations and later Campbell and Thodos [9] used it in
their saturated liquid density correlation. Since the constants p and q are so
closely related to vapor pressure, a relation might exist between the constants p
divided into three groups according to the nature of the compounds: nonpolar
(Group 1), polar and slightly polar (Group 2), and inert and quantum (Group 3):
Carbon dioxide and acetylene do not have normal boiling points because their
triple point pressures are above one atmosphere, therefore they are not included.
But if they were included, both of them would belong to Group 1. From Table
3.1, one can see that all the q values are relatively constant within each group.
In light of this fact, the constant q of the compound is taken to be the average
value for the group. For Group 1, the average value of q is 0.83, for Group 2,
For the constant p, values vary from 0.01582 to 0.47769. These p values
for the three groups have been plotted against both the parameter s and the
acentric factor o> in Figure 3.3. Also least squares fits have been used to
Group 1 :
(3.30)
variance = 0.00004469
30
variance = 0.00004475
Group 2
variance = 0.00024869
variance= 0.00023931
Group 3 :
variance = 0.00003188
variance = 0.00041294
the same variance. For Group 3, the variance produced by fitting p with s is
ten times smaller than for the fit of p with a). This indicates that the
correlation of p with s is stronger than with a). The advantage is more revealing
as is shown in Figure 3.3. Not only does p correlates better with s, the
determination of s is simpler than is o>. Only T , T^, and P c are needed for
point. This kind of treatment can lead to a wide range of results. For example,
in the case of methane, five different values have been reported. Reid et al gave
a value of 0.008 in 1977 [94] and 0.011 in 1987 [95]. Stryjek and Vera [117]
report a value of 0.01045 and which is supposedly based on the most accurate
vapor pressure data available. Passut and Danner [83] tabulate the acentric
factors for 192 hydrocarbons, and for methane, the value of 0.0072 is given.
Edmister and Lee [29] report a value of 0.0115. These different values of
acentric factors are mainly caused by the uncertaintj' in determining the vapor
pressure at T = 0.7.
r On the other hand, the boiling point temperature, critical
[28], it might be possible to improve his correlation. The plots of p=f(s) look
similar to that of p = f(u) for all groups, therefore the correlation of acentric
factor with s is again divided into the same three groups. The results of the
Group 1 :
variance = 0.00000867
Group 2 :
(3.37)
variance = 0.00001785
32
Group 3 :
variance = 0.00000316
Neon has not been included in Group 3 for the curve-fit because the acentric
factor value, 0.0 given by Reid et al [94] in their 1977 version is substantial^'
different than the value, -0.029 given in their 1987 version [95]. By visual
inspection of Figure 3.4, the value, -0.029 is definitely the more reasonable one.
For the sake of comparison, the predictions from the proposed correlations,
Eq.(3.36) to (3.38), were compared with that of the Lee-Kesler equation [59], and
the Edmister correlation, Eq.(3.29). The results from the correlations are shown
in Table 3.3. The proposed correlations are the best in estimating the acentric
factors for all three types of compounds. This shows that the characterization
Before the work of Lielmezs and Merriman [64], the proposed a-function,
Eq.(2.9) had also been applied to two other equations of state: van der Waals
and Redlich-Kwong, by Law and Lielmezs (LL) [58], and Lielmezs, Howell and
Campbell (LHC) [63]. Recently this a-function has also been applied to the
Martin equation (CLI) [11]. All four modifications, LL, LHC, LM, and CLI give
excellent results in the saturation region. However all suffer the same
shortcoming, that is, they cannot be applied, without modification, to the region
33
above the critical isotherm or the supercritical region. F o r temperatures above the
*
the present form. Additional constants will only complicate the equation and
positive in all regions. To do so, two ways have been considered. One is to let
by the first modification is slighty lower than the second modification. For
methane, the R M S % errors from the first and second modifications are 4.95
and 6.53, respectively, and for water, 3.21 and 3.06. Therefore, the first
*
T/T c - 1
and
a = 1 - p(T*) q
(3.40)
The proposed modification of the a-function has kept the simplicity of the
original L M equation and yet it is applicable to the entire PVT surface for
modification is applicable to all regions except along the critical isotherm. The
reason is that such derivative function is undefined at T , that is, at the critical
c
practical point of view, this is not a problem because most processes do not
operate near the critical point. Process designers trj' to avoid such conditions
because near the critical, it is extremely difficult to have stable processes; fluids
that are near their critical points exhibit exceptional physical and thermodynamic
behavior. Therefore the inadequacy of the present proposed equation does not
INPUT 7
\ INPUT /
\ T t P/
CALCULATE
T
ASSUME
a
CALCULATE
A & B
ADJUST
a
SOLVE
Z -(1-B)Z +(A-3B -2B)Z-(AB-B -B')=0
J 1 1 1
FOR Z & Z V
CALCULATE
fV
& f 1
NO
YES
NO
CURVEFIT ^
a = 1 + p(T ) q
OUTPUT"\
p & q 7
8.0
10.0
3 -0.1
e.o
p q
Compound Fitted p = f(s) p = f(u) Fitted Avg. s u Group
CO
T a b l e 3.1 Cont'l nued
p q
Compound Fitted p = f(s) p = f(u) Fitted Avg. s u Group
1^-
o
Table 3.2 Vapor Pressure RMS % Error
Methane 0. 660 0 .787 0,.431 0. 749 0., 565 ' 0.,586--o .990 29
Ethane 0. 542 0 . 569 0,.442 0. 202 0,. 185 0..604--o .999 23
Propane 0. 542 0 .498 0,. 750 0. 059 0.. 148 0., 625-
-0 .991 30
n-Butane 0. 330 0 . 267 0..733 0. 194 0 . 282 0..641--0 . 998 32
i-Butane 0. 357 0 .312 0,.731 0. 186 O.. 345 0.,640--0 .998 30
n-Pentane 0. 678 0 . 565 0,,500 0. 184 0., 236 0,,658--0 .999 27
i-Pentane 0. 501 0 .404 0.,526 0. 164 0,, 146 0,,654--0 .999 27
Neopentane 0. 203 0 . 140 0..741 0. 246 0.,426 0.,652--0 .999 25
n-Hexane 1 .464 1.. 136 0.,403 0. 573 0.,445 0.,538--0..995 43
n-Heptane 1 .583 1.. 128 0.,351 0. 455 0., 241 0.,545--0..987 30
n-Octane 1 .841 0 .894 0.,601 0. 543 0., 751 0.,488--0..976 27
Benzene 1 .008 0,.896 0.,745 0. 495 0.,636 0.,553--0..997 47
Carbon Monoxide 0. 730 0..699 1. 254 0. 925 1 .. 188 0. 513--0 .981 24
Carbon Dioxide 16.99 17.28 18.79 17.83 16.84 0. 712--0.,995 32
Carbon Disulfide 3. 836 3..841 2. 482 3. 310 3 .761 0. 500--0..976 26
Hydrogen Sulfide 1 .580 1 ,593
. 1 .767 1 .378 1 .814 0. 565--o.,997 30
Sulfur Dioxide 1 .921 1 ,723
, 0. 806 1 .1 16 4 .404 0. 593--0..992 35
Methanol 5. 409 4 ,618
. 3. 211 4 .654 1 .477 0. 532--0,,996 44
Ethanol 3. 595 2 .761
. 2. 940 3. 378 0. 684 0. 543--0.,979 29
1-Propano1 5. 667 6..876 7 .565 6. 800 2 .488 0. 555--0. 993 13
Tertiary Butanol 1 .121 1 .295
. 1 .832 1 .709 2. 945 0. 701--0. 993 12
Acetylene 2. 391 2.,423 3. 067 2 .668 2 .479 0. 623--0.,989 20
Ethy 1ene 0. 924 0. 951 0. 914 0. 923 0. 815 0. 599--0. 981 19
T a b l e 3.2 Continued
Propylene 0. 688 0..651 0,,707 0.. 139 0,, 168 0,.618--o. .989 26
1-Butene 0..972 0.,886 0,,876 0.,450 0,.531 0 .651- -o .979 26
Water 7 .389 6..574 2,, 1 16 7 . 154 1 .715
, 0,.422--0,.995 43
n-Deuter i urn 0,.897 1 .647
. 2 ,878
, 2., 134 2 .824
. 0,,488--o. ,991 21
n-Hydrogen 0,.251 0.,665 1 ,, 135 1 .469 0,.613 0,.615--0,.964 13
p-Hydrogen 0,.097 0.,533 1 ,010
, 1 ,. 384 3 .023
, 0,.615--0,.970 13
Ni trogen 0..695 0,,787 0,.586 0, 578 0,.449 0,.614--0,.991 18
Ammon i a 2..053 1..853 1 ,664
, 1 ,335
. 0,.811 0,.602--0,.986 29
Oxygen 0..248 0..408 0,.493 0., 194 0,, 303 0,.583--0,.986 24
Neon 0..539 0.,797 0,,545 0. 753 0,,294 0,. 563-
-0,.968 19
Argon 0,.224 0..442 0,,244 0. 293 0,, 155 0,,555--o. .994 15
Krypton 0,. 183 0. 245 0..469 0. 243 0,.490 0.. 573-
-0,.984 20
Xenon 0,.225 0.,417 0,,492 0. 138 0,,338 0,.569--0..932 12
Table 3.3 Acentric Factor from the Proposed, Lee-Kesler, and Edmister Correlations
This chapter is divided into five parts. The first four parts are discussions
of various property predictions from the three cubic equations of state: S R K , PR,
1.1: saturation, subcritical, supercritical, and compressed. The last part is devoted
to the inversion curve estimation. A l l the equations derived from the generalized
cubic equation of state for calculating different properties are shown in the
Appendix A. The physical constants required as input data have been tabulated
s. For carbon dioxide and acetylene, their triple point pressures are above one
atmosphere. Therefore these two compounds do not have normal boiling points.
The normal boiling points of carbon dioxide and acetylene shown in Table 4.1
have been used in all of the calculations found in this work. Although small
use various sources of experimental data; even though the ideal is to use a
single source. Often, the so called experimental data found in the literature are
not data measured from experiments but data calculated from an empirical
equation with its constants fitted with experimental data. Since different data
sources use different sets of units, to be consistent, all data are converted to the
45
46
Pressure - atm
Volume - cm /g-mole
3
Temperature - K
Energy - calorie
The following conversion constants are used and are taken from [30,102,126]:
1 ft /lb = 0.062428 cm /g
3 3
atm cm 3
cal
Gas constants, R = 82.05606 = 1.9872
g-mole K g-mole K
Properties tested in this region included vapor pressure, liquid and vapor
volumes, and enthalpy and entropy of vaporization. The experimental data sources
are given in Table 4.2. In order to ensure internal consistency, all the properties
of a compound were taken from the same source. The algorithm for calculating
these properties from an EOS is given in Figure 4.1. The results from this
work (LM(1), LM(2)) together with those of the SRK and PR are reported in
Tables 4.2-4.4. The LM(1) equation refers to the L M equation with the two
constants, p and q, fitted with experimental vapor pressure data. The LM(2)
equation refers to the L M equation with the constants p correlated with the
parameter s (Eq.(3.30), (3.32) and (3.34)) and the constant q calculated as the
47
average value of the group. In this region, a total of 36 compounds are tested
1. Nonpolar
2. Polar and slightly polar
3. Inert and quantum
the same predictions for the Group 1 compounds. The PR equation gives slightty
lower RMS % errors for hydrocarbons. The LM(2) equation does not give
satisfactory predictions for all compounds. This is due to the fact that LM(2)
only gives approximate p and q values and vapor pressure is extremely sensitive
to these two constants, especially p. For Groups 2 and 3, the LM(1) equation is
the best among the three equations. This is the strength of any correlation
which uses individual constants instead of generalized ones such as the SRK or
PR equation. The SRK and PR equations were designed not for Groups 2 and 3
types of compounds. Therefore it is not surprising to find that they both give
The % errors of vapor pressure, liquid, and vapor volumes are plotted
against the reduced temperature, T r in Figures 4.2 to 4.5 for four compounds
selected from the three groups (group 1: n-Pentane; group 2: 1-Propanol; group
3: Methane and Argon). These figures show that the L M (LM refers to the
LM(1) equation) equation gives vapor pressure errors that are evenly distributed
along the temperature range studied whereas the SRK and PR either over
predict in one compound and under predict in another. Near the lower end of
the temperature range, the errors from all three equations seem to increase
48
rapidly. This behavior suggests that all the equations considered here should not
be used for extrapolation purposes; they should be used within the temperature
For the saturated liquid and vapor volume predictions, the P R and L M ( 1 )
equations give almost identical results. The LM(1) equation gives slightly lower
errors near the critical point. In terms of R M S % error, the S R K equation gives
be seen that the S R K equation tends to over predict liquid volumes along the
entire saturation curve for all three groups of compounds. F o r the P R and L M ( 1 )
It is interesting to note that the shape of the error distribution curves for
the three equations are almost identical. The only difference between them is
how much they have shifted away from the others. There is evidence in the
literature [129] that this shift may be directly connected to the two constants u
they have the same u and w values, and their error distribution curves are
indeed on top of each other and are shown in Figures 4.2 to 4.5. From the
evidence presented up to this point, one may conclude that altering the a-function
Table 4.4 contains the results of the enthalpy and entropy of vaporization
49
from the four equations. Usually entropy of vaporization is not tabulated in the
AH
AS„ = — * (4.1)
v T
Enthalpj' of vaporization is just the difference between the vapor and liquid
phase enthalpy:
AH v = (H - H ° ) v
- (H - H ) 0 1
(4.2)
where H° is the enthalpy at zero pressure. Some data sources did not specify
their reference state or the value of the reference state. Therefore, instead of
comparing the departure function with that predicted from an EOS, the difference
as the basis of comparison. It should be pointed out that Table 4.4 gives
I |Deviation|
=
~ ' (4.3)
where
and not RMS % error. Figures 4.6 to 4.9 have the plots of reduced enthalpy
of AAD both PR and LM(1) give similar results, Figures 4.6-4.9 reveal the
strength of each. For both enthalpy and entropy of vaporization calculations, the
PR equation gives better predictions for the lower temperature region and the
T = 0.7. The SRK equation gives similar results as the LM(1) equation at the
r
lower end and similar to the PR equation at the higher end. The limitation of
the LM(1) equation is that it is not applicable at the critical point. The LM(2)
equation gives reasonable predictions for all compounds and in some cases, it
gives the lowest AAD. When no p and q values are available, LM(2) is
recommended.
Table 4.5 has the overall average errors of the five properties tested in
this region. Among the three equations, the LM(1) equation is the most accurate
in estimating vapor pressure and saturated liquid and vapor volumes. The PR
equation gives the lowest deviations for the two derivative properties, namely,
+ P h y s i c a l p r o p e r t i e s that are not given i n the original data source are taken
from r e f e r e n c e 94.
t C a l c u l a t e d from Tb, t c , and Pc.
Table 4 . 2 Region I - Vapor Pressure RMS % Error
CO
Table 4.2 Continued
t Vapor p r e s s u r e , l i q u i d and vapor volumes, enthalpy and entropy of v a p o r i z a t i o n data are taken from
the same source.
Table 4.3 Region I - Liquid and Vapor Volume RMS % E r r o r s
Methane 48.9 30.8 30.6 36.3 0..333 0.. 183 0,.210 0.278
Ethane 97. 1 82. 1 56.8 51.9 0.. 356 0., 283 0,.228 0.202
Propane 87.3 66 .0 71 .9 48.3 0., 283 0. 205 0.. 252 0. 176
n-Butane 129.7 131.7 94 .0 43.7 0.. 321 0. 330 0.. 260 0. 127
1-Butane 69.0 63.7 40. 1 83.8 0. 181 0. 167 0.. 130 0.233
n-Pentane 167.3 139.8 95. 1 60.7 0..406 0. 327 0..257 O. 168
1-Pentane 141.6 124.3 52.6 75.6 0.. 337 0. 289 0.. 142 0. 196
Neopentane 164.0 142.4 112.9 78 .9 0. 415 0. 348 0.,302 0. 239
n-Hexane 1 16.6 102.2 84.4 144.6 0. 287 0. 262 0. 250 0.442
n-Heptane 127 .0 93.0 100. 3 123 .0 0. 309 0. 224 0. 277 0.344
n-Octane 113.2 141.5 159 .5 194 .7 0. 236 0. 369 0, 457 0.548
Benzene 130.4 121.2 74 . 3 105 . 1 0. 296 0. 285 0. 200 0. 232
Carbon Monoxide 22.4 26.9 16.0 35. 1 0. 226 0. 312 O. 193 0.432
Carbon D i o x i d e 57.9 41.3 59.8 0. 231 0. 162 0. 236
Carbon D i s u l f i d e 224.4 146.7 241 .3 325. 3 0. 587 0. 362 0. 606 0.949
Hydrogen Su1f i de 107 .5 136.5 145 .8 183 .0 0. 301 0. 435 0. 468 0.587
Sulfur Dioxide 99.2 77.7 118.8 262 . 1 0. 187 0. 141 0. 359 0.793
Methano1 563.3 433.8 402 . 1 406 .0 1.643 1 .250 1 .166 1 .235
Ethanol 236.2 87 . 2 281 .6 283.5 0. 703 0. 250 0. 856 0. 781
1-Propanol 275. 1 365.9 309.7 363. 1 0.620 0. 942 0. 844 0.915
T e r t i a r y Butanol 246.8 195.0 298 .7 473.9 0. 574 0. 437 0. 705 1 .056
Acetylene 1 10.2 97.5 49.9 0. 441 0. 397 0. 213
E thy1ene 52.9 27.4 36.9 25.8 0. 239 0. 145 0. 201 0. 153
T a b l e 4.4 Continued
Propylene 82.7 48.8 47 .0 41.1 0.. 268 0. 174 0.. 158 0. 138
1-Butene 84.6 67.5 98 . 7 72.3 0. 241 0. 184 0,.301 0.217
Water 426.8 284.5 349.5 462.8 1 ,, 144 0. 729 0,.894 1 .378
n-Deuterlum 27.0 18.9 13.4 13.9 1 ,057
. 0. 719 0.,467 0.539
n-Hydrogen 9. 10 5.20 5.20 6.70 0..386 0. 203 0..220 0.281
p-Hydrogen 9.20 6 . 70 4.40 7 .00 0,, 380 0. 252 0.. 180 0. 281
Nltrogen 28.3 28 .8 26.4 31.5 0..250 0. 254 0,, 247 0.326
Ammonia 209.8 174.5 220.5 213.2 0,,434 0. 326 0..489 0.443
Oxygen 39.4 23.8 25. 1 25.6 0., 330 0. 181 0.,221 0.215
Neon 26.5 20. 4 3.50 6.80 0. 851 0. 648 0. 1 18 0. 229
Argon 32.4 17 . 1 24.9 23.2 0., 291 0. 122 0. 239 0.221
Krypton 42.0 30.4 38.3 30.0 0. 260 0. 171 0. 241 0. 175
Xenon 39 .9 25 .6 38 .0 34 .6 0., 192 0. 118 0. 186 0. 156
Table 4.5 Overall Average Errors (RMS % and AAD) for the Four
Regions (NC = number of compounds ; N = number of data points)
Region I : Saturation
Region II : Subcritical
Property SRK PR LM NC N
Property SRK PR LM NC N
R e g i o n I V : Compressed L i q u i d
Property SRK PR LM NC N
ASSUME
P
CALCULATE
a, A, B
ADJUST
P
SOLVE FOR Z 1
& Z V
CALCULATE
fV
& f 1
NO
CALCULATE AH & AS
CALCULATE ERRORS
CALCULATE AAE &
RMS % ERROR
NO YES
/OUTPUT Z , Z , P\
1 V
y A H , AS, ERRORSy
o EXPT LM SRK PR
o i 1 1 1 1 1 1 1 1 1 1 1 1 1 1
0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
10
vapor curve and the critical isotherm (Figure 1.1). In this region, predictions of
PVT, five departure functions which include enthalpy (H-H°), entropy (S-S°),
Helmholtz free energy (A-A°), Gibbs free energy (G-G°), and internal energy
(U-U°); fugacity coefficient (f/P), isobaric heat capacity (Cp), and Joule-Thomson
coefficient (u) from the SRK, PR, and L M equations have been tested against
experimental data. The data sources of the 22 compounds are given in Table
4.8. Since the LM(2) equation does not show any real advantages over the
Data taken from reference [122] are in departure function form and some
equation. Only PVT, enthalpy and entropy departure functions data were taken
H° = A + BT + CT 2
+ DT 3
(4>8 )
and
S° = E + FT + GT 2
+ HT 3
( A q-i
polynomials are tabulated in Tables 4.6 and 4.7. The data, H and S, are
The enthalpy departure function and fugacity coefficient equations derived from
Tables 4.8 and 4.9. All three equations are very similar in accuracy for
water are plotted against reduced temperature in Figure 4.10 and against
reduced pressure in Figure 4.11. These two figures show that the predictions of
72
the PR and L M equations are almost identical for both nonpolar (i-butane) and
polar (water) compounds. From Figure 4.10, it is evident that the SRK equation
is more accurate near the critical isotherm whereas the PR and LM equations
the compressibility factors for the entire temperature range considered. The PR
and LM equations underpredict in the region above T = 0.95 r and overpredict for
the rest. Although only one isobar has been plotted for each of the two
compounds, the above observation is true in general for other isobars and
compounds. Figure 4.11 shows that as the pressure increases, the prediction from
the SRK equation deviates more and more from the experimental data. The PR
and L M equations are practically identical along the entire pressure range. Table
4.5 shows that for this region, the PR equation is the most accurate in volume
energy, and internal energy, and fugacity coefficient are tabulated in Tables 4.10
to 4.12. Note that the errors are not in RMS % but AAD. The reason is that
departure functions can take on both positive and negative values or even zero.
Therefore deviation from experimental data is chosen over % error as the basis
of comparison. These tables show that there are very small differences among
the three equations in accuracy. Figures 4.12 to 4.23 have the plots of the five
departure functions and fugacity coefficient of i-butane and water versus reduced
temperature and pressure. For the enthalpy, entropy, and internal energy
departure functions, the L M equation behaves rather radically in the region above
T = 0.95
r and below this temperature, the predictions are very similar to the
73
SRK and PR equations as can be seen in Figures 4.12, 4.14, and 4.20. This
radical behavior of the L M equation is due to the fact that the derivative of the
critical temperature. This causes the three departure functions rise rapidly. This
behavior, however, does not appear in the Helmholtz free energy and Gibbs free
energy departure functions, and fugacity coefficient because these three functions
involve both the enthalpy and entropy and the subtraction of these two functions
cancels out the effect near the critical region. Thus, these three functions are
well-behaved even near the critical temperature. Although this behavior of the
L M equation is so different than the PR and SRK equations, the overall average
deviations from the L M equation for the enthalpy, entrop3 , and internal energy
7
departure function predictions are the lowest among the three equations. For
Helmholtz and Gibbs free energy departure functions, the predictions from the
three equations are very similar. Figures 4.16, 4.17, 4.18, and 4.19 show that
the three curves are practically on top of each other. Figures 4.22 and 4.23
have the plots of fugacity coefficients versus reduced temperature and pressure.
Again, these two figures show that almost no differences are observed between
The isobaric heat capacity data taken from reference [122] are given in
the departure function form, (C -C °). To convert these data to heat capacity C , p
the ideal gas heat capacity is calculated from correlations given by Reid et al
[94]. Table 4.13 has the results from the three equations. The results show that
the PR and SRK equations are practically identical in estimating this property.
74
The higher errors found in the L M equation are again due to the points near
the critical isotherm. For the region away from T = 0.95, the predictions of the
r
difficult to make a general statement about the predictive accuracy of the three
equations at this stage. However, for the six compounds studied here, the RMS
% errors from the SRK and PR equations are almost the same. The LM
equation gives the highest % errors among the three equations. The results are
From the above discussion, it is clear that very small differences are
observed among the three equations. No one equation exhibits clear advantage
over the others in all property estimations. For the region below T = 0.95, the r
here. Both of these equations give lower errors than the SRK equations. One
predictions.
Table 4 . 6 Coefficients of Ideal Gas Enthalpy Polynomial
Compound E F(10 )
!
G(10') H(10") Temp. Range Variance
Methane 0 . 565 2 . 759 3,. 258 0,.629- -0 .986 0 .022- -0 .895 51 122
E thane 1 .227 1 . 535 2,,095 0,.655- -0 .982 0 .021- -0,.892 26 31
Propane 1 .298 1 . 1 18 1 ,, 369 0,.649- -0 .995 0 .024- -0 .952 40 122
n-Butane 0 .802 1 .034 1 ,, 138 0,.659- -0 .988 0 .027- -0,. 747 35 18
i-Butane 2 . 779 0 .998 1 ., 1 15 0,.662- -0,.999 0 .028- -0,.972 59 19
n-Pentane 1 .740 0 .589 0,,708 0,.660- -0,.980 0 .030- -0,.842 31 20
i-Pentane 3 .279 1 .058 0.,659 0.,673- -0..988 0 .030- -0,, 899 37 21
Neopentane 1 . 197 1 .211 1 .455 0,,669- -o,,991 0 .032- -o,.919 28 22
n-Hexane 3 . 224 1 . 154 0.,840 0.. 722--o.,995 0 .033- -0,,910 40 10
n-Heptane 0 .432 1 .425 1.,729 0..703- -0..963 0 .037- -0,. 731 35 122
n-Octane 0 .739 1 .778 2, 065 0..703- -0..985 0,.041- -0..806 37 122
Benzene 0 . 335 0..816 0. 990 i'O..658- -0,.978 0,.021- -0. 811 51 122
Carbon Dioxide 3 .904 2..381 2. 388 0. 730- -0. 986 0,.014- -0. 888 33 10
Sulfur Dioxide 1 .453
. 1 .. 140 1 .500 0. 645- -0. 993 0..013- -o. 918 56 10
Methanol 1 .644
. 2..501 2. 795 0. 702- -o. 974 0.,013- -o. 628 51 122
Ethanol 0..784 1 ,650
. 1 .871 0. 701- -o. 973 0.,017- -o. 652 43 122
1-Propanol 0.,602 1 ,318
. 1 .321 0. 708- O. 968 0. 020- -o. 590 40 122
Acetylene 6 . 196 2 ,961
, 2 .326 o. 97 1--o. 998 0..016- -0. 971 43 10
Propylene 2 . 101 1 ,, 256 1 .266 0. 822- -0. 989 0, 022- -0. 895 37 10
1-Butene 0.. 283 0. 678 0. 737 0. 667- -0. 953 0.,025- -o. 498 33 122
Water 2 , 157 1 .199 o. 840 0. 652- -0. 995 0. O05--0. 935 93 10
Ammon i a 3 .081
. 1 .354 1. 196 0. 630- -0. 986 0. 009- -0. 856 48 10
t PVT, departure f u n c t i o n , and fugacity coefficient data are taken from the same source.
T a b l e 4.9 Region II - Pressure and Temperature RMS % E r r o r s
Pressure Temperature
Compound SRK PR LM SRK PR LM
oo
Table 4.11 Region II - Helmholtz and Gibbs Free Energy Departure Functions : Average Absolute Deviation
00
o
Table 4.13 Region II - Isobar1c Heat Capacity : Average Absolute Deviation (cal/mole-K)
E thane 1 . 8 1 .7
. 2 .4 0..655-0 .982 0 .021-0 .892 26 122
Propane 1 ..4 1 .3 3 .8 0..649-0..995 0 .024-0,,952 40 122
n-Butane 1 .. 1 1 .1 1 .9
. 0.,659-0,.988 0,.027-0..747 35 122
i-Butane 2 .6
. 2 .6 3 .3 0..662-0..980 0..028-0..861 30 122
n-Heptane 0,,3 0..3 0 .4 0..703-0..963 0..037-0.. 731 35 122
n-Octane 0.,2 0..3 0 .8 0..703-0..985 0..041-0..806 37 122
Methanol 0..3 0. 3 0,6 0..702-0.. 974 0..013-0.. 628 51 122
Ethanol 0..2 0. 2 0..6 0,,701-0,.973 0..017-0..652 43 122
1-Propanol 0. 2 0. 2 0.. 3 .968
0., 708-0, 0..020-0., 590 40 122
1-Butene 0..3 0. 4 0,,4 0. 667-0,.953 0..025-0.,498 33 122
0.60 0.90
0.88
0.88 -
N 0.84
0.80
0.66
0.64
Figure 4.10 Region II : Compressibilitj' factors of i-butane (Pr = 0.56) and water
(Pr = 0.31) versus reduced temperature.
1.0
0.9 -
o.e
IS
tSJ
0.7
0.6
0 85
0.4
Figure 4.11 Region II : Compressibility factors of i-butane (Tr = 0.98) and water
(Tr=0.96) versus reduced pressure.
83
3.10 4.4
i-Butane
Data
3 05
— SRK
— PR
LM
3.00
2 95
<
i
<
Z.B5
2 80 i . i . i
0.90 0.92 0.94 0.96 0.98 1.00 1.02
Tr
0.85 0.55
i-Butane
0.80 • Data
SRK
PR
0.75
LM
CH
0.70
I
0.65
0.60
0.55
0.25
0.90 0.92 0.94 0.96 0.98 1.00 1.02
Tr
0.7
0.84 0.90
0.82
0.88 -
0.80
0 86
0.78 a,
0.84
0.78 -
0.82 -
0.74
0.72 0.80
Figure 4.22 Region II : Fugacity coefficients of i-butane (Pr = 0.56) and water
(Pr = 0.31) versus reduced temperature.
1.05 1.05
Water
1.00 1.00 • Data
SRK
PR
LM
0 90 0 90
OH
0.85 0.85
0.80 0.80
0.75 0.75
0.70 0.70
0.85
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Pr
Figure 4.23 Region II : Fugacity coefficients of i-butane (Tr = 0.98) and water
(Tr = 0.96) versus reduced pressure.
89
functions which include the enthalpy, entropy, Helmholtz free energy, Gibbs free
energy, and internal energy; fugacit3' coefficient, isobaric heat capacity, and
have been tested against experimental data. The data sources of the 22
The results of the PVT predictions from the three EOS are tabulated in
Tables 4.15 and 4.16. The overall average errors for this region are summarized
in Table 4.5. For pressure prediction, the PR and L M equations are very similar
in accuracy. The overall average RMS % error from the SRK equation is about
equations are about the same in accuracy where the PR produces the smallest
overall average RMS % error while the L M produces the largest. For volume
prediction, The PR and L M equations are again almost identical in accuracy for
most compounds. However, in terms of the overall average RMS % error, the
PR equation gives the lowest. In many cases, the error from the SRK equation
is almost twice that of the PR or L M equation. This observation also has been
found earlier in the saturation region. Figures 4.24 and 4.25 present the plots of
n-octane and ethanol. These two figures clearly indicate that all three equations
are poor for polar compounds and reasonable for nonpolar compounds. These
figures once again reinforce the fact that the PR and L M equations are indeed
90
very similar in accuracy for volume prediction and the SRK is the least accurate
The results for the five departure functions and fugacity coefficient are
4.5), the SRK and PR equations are very similar for enthalpy, entropy, and
internal energy departure function predictions. The L M equation is poor near the
Hence, these three departure functions, enthalpy, entropy, and internal energy,
predictions from the L M equation are very similar to those of SRK and PR
equations. This observation can be seen in Figures 4.26, 4.27, and 4.34. For
Helmholtz and Gibbs free energy departure functions, error cancellation near the
critical points resulted in similar accuracy for all three equations in this region.
Figures 4.30 and 4.31 represent the plots of the Helmholtz free energy versus
reduced temperature and pressure for n-octane and ethanol. Figures 4.32 and
4.33 are the plots of Gibbs free energy versus reduced temperature and pressure
for the same compounds. For fugacity coefficient calculation, the L M equation is
inferior to the PR equation. The SRK equation exhibits the highest overall
average deviation among the three equations. Fugacity coefficients of n-octane and
ethanol are plotted against reduced temperature in Figure 4.36 and against
The average absolute deviations of the isobaric heat capacity for ten
91
compounds are tabulated in Table 4.20 along with the experimental data sources.
It should be noted that, in general, the isobaric heat capacity data are not
accurate near the critical region where the heat capacity changes rapidly with
temperature and pressure. In many cases, all three equations give similar
ethane, propane, n-butane, and i-butane, may be due to the inabilitj' of the EOS
to predict this property in the critical region or may be due to the low accuracy
EOS have been tested against experimental data for five compounds. The results
are summarized in Table 4.21. The SRK equation gives the lowest RMS % error
for four of the five compounds. In terms of overall average RMS % error shown
in Table 4.5, The SRK is also the lowest among the three equations. Again, the
this time.
Out of the eleven properties studied in this region, the PR equation gives
the lowest overall average RMS % errors for pressure, volume, and temperature
predictions and also the lowest overall average deviations for Helmholtz free
note that the PR and L M a-functions, Eq.(2.3) and (3.39), are so different, and
yet, the accuracy of the two equations is similar for a number of properties.
One important point that is observed in Table 4.5 is that between Region H and
III, the accuracy of the three equations decrease substantially. The departure
92
function deviations of Region HI, in many cases, are double that of Region II.
For pressure, temperature, and heat capacity predictions, the accuracy reduces at
t PVT, departure f u n c t i o n , fugacity coefficient data are taken from the same source.
Table 4.18 Region I I I - Pressure and Temperature RMS % E r r o r s
Pressure Temperature
Compound SRK PR LM SRK PR LM
CO
Table 4.19 Region III - Internal Energy Departure Function and Fugacity Coefficient Average Absolute
Devi at Ion
to
Table 4.20 Region III - Isobaric Heat Capacity : Average Absolute Deviation (cal/mole-K)
E thane 4 .6
. 4 ,8 4 .. 4 1 .048-1 . 768 0..021-10.37 90 31
Propane 7 .. 1 7.
.2 6.6 1 .027-1 .892 0..024-16.66 162 122
n-Butane 9., 1 9 .3 9 .8 1 . 129- 1 .411 0 .027-18.68 32 122
i-Butane 9.. 5 9..7 8 .9 1 .029-1 .715 0..028- 11.11 149 122
n-Heptane 0. 8 0,.7 1 .4
. 1 .037-1 .851 0 .037-18.28 156 122
n-Octane 1 .. 1 1 .0
. 3..4 1 .020-1 .758 0..041-20.14 143 122
Methano1 0.. 7 0..6 2.3 1 .013-1 .949 0..013-6.907 208 122
Ethanol 0. 8 0..7 2 .. 7 1 .012-1 .946 0.,017-8.147 182 122
1-Propanol 0. 9 0. 8 0..5 1 .043-1 .862 0.,020-9.828 169 122
1-Butene 0. 3 0. 3 0. 3 1 .049-2 . 383 0. 025-12.44 195 122
1.1
1.0
0.9
0.9 h
tSl 0.8
0.5
0.7
0.3
0.5
1.0 1.2 1.4 1.6 l.B Z.O
Tr
1.9 1.30
n-Octane Ethanol
O Data 1.25 h O Data
SRK SRK
PR 1.20 PR
1.15 h
tsi
1.10
O
1.06
1.00
0.95 _1_
0.0 2.0 4.0 6.0 6.0 10.0
Pr
10.0
9.0 10.0
8.0 - 9.0 -
7.0 8.0
Ir-
CC
6.0 - 7.0 -
< <
I i
<
5.0 n-Octane 6 0 Ethanol
O Data O Data
SRK SRK
PR 5.0 PR
LM LM
1
- • i — - J • ._i . 1 1 ,
3.0 4.0
1.0 12 1.6 1.0 1.2 1.4 1.8 1.8 2.0
Tr Tr
12.0 14 0
12.0
10.0
10.0
8.0
6.0
<
I
<
4.0
n-Octane Ethanol
) O Data O Data
) SRK SRK
20 , )> PR PR
> LM LM
0.0 ©• 1 . 1
0.0®— 1- ) —. i i-
0.0 5.0 10.0 15 0 20.0 25.0 0.0 2.0 4.0 6.0 8.0 10.0
Pr Pr
9.0 10.0
9.0 I--
8.0 h
8.0
o
E- E-
K 7.0
6.0
a O
i I 6.0
o O
n-Octane Ethanol
5.0
O Data O Data
SRK SRK
4.0 PR
PR 4.0
- LM LM
1
3.0 I , I i i
3.0
1.0 1.2 1.6 1.8 1.0 1.2 1.4 1.6 1.8 2.0
Tr Tr
Figure 4.32 Region III : Reduced Gibbs energy departure functions of n-octane
(Pr = 4.03) and ethanol (Pr=1.63) versus reduced temperature.
12.0 14.0
12.0
10.0
10.0
8.0
o
E-
8.0
6.0
O o
I i 6.0 -X
O o
4.0 Ethanol
O Data
I SRK
2.0 1
) PR
< ) LM
Figure 4.33 Region III : Reduced Gibbs energy departure functions of n-octane
(Tr=1.76) and ethanol (Tr=1.95) versus reduced pressure.
104
Figure 4.34 Region III : Reduced internal energy departure functions of n-octane
(Pr=4.03) and ethanol (Pr=1.63) versus reduced temperature.
Figure 4.35 Region III : Reduced internal energy departure functions of n-octane
(Tr=1.76) and ethanol (Tr=1.95) versus reduced pressure.
105
106
studied are limited due to the lack of available experimental data, especially data
include the enthalpy, entropy, Helmholtz free energy, Gibbs free energy, and
internal energy; fugacity coefficient, and isobaric heat capacity obtained from the
SRK, PR, and L M equations have been compared with experimental data. The
Joule-Thomson coefficient is not part of this study because data are not
The RMS % errors from the three EOS for PVT calculations are
tabulated in Tables 4.22 and 4.23. The overall average RMS % errors are
summarized in Table 4.5. For pressure prediction, all three equations give
enormously high errors. Each of the three equations gives more than 100 %
RMS error for all compounds considered. For temperature estimation, the
magnitude of the errors from the PR and L M equations is the same in all
cases while the SRK equation gives substantially higher errors than the PR or
errors from the PR and L M equations are about half that of the SRK equation.
A very similar conclusion can also be drawn for the volume prediction. Both PR
and L M equations are much more accurate than the SRK equation. Overall
average RMS % error of the SRK equation shown in Table 4.5 is twice that of
the PR or L M equation. Figures 4.38 and 4.39 further illustrate this observation.
Figure 4.38 shows the plots of compressibility factor against reduced temperature
107
for n-heptane and methanol and Figure 4.39 shows the plots of compressibility
factor against reduced pressure for the same two compounds. Both of these plots
extremely scarce in this region. The TRC data book [122] contains enthalpy and
which have been selected for comparison with the predictions from the three EOS
for calculating enthalpy departure function of compressed liquid. They claim that
Therefore, in addition to the seven compounds from the TRC data book, thirteen
other compounds have been added to this study. However, only enthalpy and
internal energy departure functions are tested for these additional compounds. The
(o ) (i)
H - H" H - H° H - H"
+ 0)
(4.12)
RT RT.
where
(o)
H - H"
= A + AJPJ. + A P *
0 2 R
(4.13)
RT,
(i)
H - H°
= B 0 + BjP r + B P = 2 r
(4.14)
RT.
108
The quantities Aj and Bj are functions of T r and are given by the following:
(4.13a)
(4.13b)
(4.13c)
(4.14a)
(4.14b)
(4.14c)
This correlation is applicable in the region where 0.5<T ^0.8 and 0.2<T<9.0.
r r
The results of the comparison for the five departure functions and fugacity
coefficient are summarized in Tables 4.24 to 4.26. The overall average errors are
listed in Table 4.5. Figures 4.40 through 4.49 are plots of the five departure
functions against reduced temperature and pressure for n-heptane and methanol.
These plots provide some information on how accurate the three equations are in
predicting various departure functions. In general, all three equations are very
similar in accuracy and none of these equations has clear advantage over the
others. The accuracy of each of these EOS for this region are lower comparing
to the other regions. In fact, the overall average deviation shown in Table 4.5
indicate that this region has the highest deviation comparing to the subcritical
and supercritical regions for the same five departure functions and fugacity
coefficient. For fugacity coefficient prediction, all three equations behave quite
similarly. Figures 4.50 and 4.51 show that the difference among the three
The results from the three EOS for predicting the isobaric heat capacity
are summarized in Table 4.27. Also in Table 4.27 are the data source references
and temperature and pressure ranges. Alike to the subcritical and supercritical
regions, the SRK and PR equations are again very similar iri accuracy for
predicting the isobaric heat capacity. The LM equation gives the highest
deviations for all cases. Overall average deviation shown in Table 4.5 also shows
It follows that none of the above three EOS are adequate for predicting
the PR and L M equations are similar for temperature and volume prediction. For
pressure prediction, all three are poor. For departure functions and fugacity
differences are observed. In predicting isobaric heat capacitj', the SRK and PR
error, this region is the highest among the single phase regions in each of the
property studied.
T a b l e 4.22 Region IV - Volume RMS % Error
t PVT, departure function, and fugacity coefficient data are taken from the same source
Table 4.23 Region IV - Pressure and Temperature RMS % Errors
Pressure Temperature
Compound SRK PR LM SRK PR LM
0.14 0.105
n-Heptane
eS DaU
0.13
0.095
0 12
0.09 0.065 -i 1 1
0.5 0.6 0.7 0.8 0.9 1.0 0.65 0.70 0.75 0.80 0.85 0.90
Tr Tr
0.14 0.10
Methanol
0.12 - Q Data
0.08 SRK
PR
o.io LM
0.06
0.08
0.06
0.04
0.02
0.00
0.0 0.2 0.4 0.6 0.8
Pr
7.45 9.6
9.4
es 0 0
7.40 00 ra 0
9.2
Methanol
O
0 Data
9.0 -
cS 7
35 OS SRK
PR
ad 8.8 LM
I I
£ 7.30 PC
I
8.6
n-Heptane
Q Data 8.4 -
7.25 —SRK
PR 8.2
LM
• i . i i .
7.20 ' i — i i 8.0 • 1
0.0 0.2 0.4 0 6 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Pr Pr
10 0
0.5 0.6 0.7 0.8 0.9 1.0 0.65 0.70 0.75 0.80 0.85 0.90
Tr Tr
15.5
Methanol
0 Data
15.0
11.0 SRK
PR
LM
14.5 h-
10.9 \
CO CO 0 0 0
I 00 I 14.0 h
CO CO
Y 10 8 V
13.5
10.7
13.0 -
10.6
0.0 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Pr
0.51 1.28
n-Heptanc
0 Data
0.49 — SRK
1.26 -
PR
0 0
L M
0.47
O
E— 0 o 1.24 - ro
OS E—
\ OS
0 0
°< <
I . I 0
< < 1.22
0.43 -
Methanol 0
0 Data
1.20 SRK
0 41
PR
LM
I . I . I .
0.39 1.18 • * • • - • - • - •
0.0 0.2 0.4 0.6 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Pr Pr
3.0 3.0
2.5 -
2.0 -
2.0
O o
E- 1.0 E-
QJ
\
O G~* 1.5
I O
o o.o - I
O
10
n-Heptane Methanol
0 Data • Data
-1.0 —SRK SRK
0.5
PR PR
LM LM
-2.0
1
0.0
1
1 , i . 1...
0.5 0.6 0.7 0.8 0.9 1.0 0.65 0.70 0.75 0.60 0.85 0.90
Tr Tr
Figure 4.46 Region I V : Reduced Gibbs energy departure functions of n-heptane
(Pr = 0.73) and methanol (Pr = 0.63) versus reduced temperature.
-0.10 0.65
0
-0.15 0.60
O
E-
\ 0
-0.20 0.55 0 0
o O
i I
o O
Methanol
-0.25 0 Data
—SRK
PR
LM
-0.30 0.45 -I 1 L_ ^ 1 .__L . 1 .
0.0 0.2 0.4 0.6 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Pr Pr
6.85 8.8
0 0 0 Q
8.6
6.80 -
Methanol
8.4 •
0 Data
O
es O SRK
0 0 PR
\ 8.2
LM
C
ZD
I 8.0
2- 6.70 I
I
n—Heptane 7.8
0 Data
6.65
SRK
PR
LM
6.60 1 , L_ 1 I 1 I [ I 1 1
0.0 0.2 0.4 0.6 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Pr Pr
0.7 0.5
n-Heptane Methanol
0.6 • Data es eS Data
SRK 0.4 SRK
PR PR
0.5 LM LM
0.4 0.3
0.3
0.2
0.2
0.1
0.1
0.25 0.7
Methanol
- eS Data
0.20 SRK
PR
0.5 LM
0.15
0.4 \
0.3 \
o.io V
0.2
0.05
t 1
0.0
0.0 0.2 0.4 0.6 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Pr Pr
u = (4.15)
9P JH
is positive, cooling occurs and when negative, heating results. The condition at
which the crossover from cooling to heating occurs, is called the inversion
" = 0
(4.16)
and the corresponding pressure is the inversion pressure. For each isenthalpic
curve on a T-P diagram, there is one inversion point. These points form a
unique line and this locus of points is called the inversion curve. The object of
this section is to compare the inversion curve calculated from the three equations
of state: SRK, PR, and L M with experimental data. A total of nine compounds
are studied. The experimental data sources have been tabulated in Table 4.28.
Along with the experimental data, the predictions from the three EOS are also
compared with the generalized inversion correlation proposed by Gunn, Chueh, and
points of fluids with acentric factors that are close to zero. These fluids include
argon, xenon, nitrogen, carbon monoxide, methane, and ethylene. The GCP
124
- 1.6721T * r + 0.091167T r
5
( 4 1 ? )
The three inversion curve equations derived from the SRK, PR, and L M
equations are given in Appendix A. For ease of reference, the inversion equation
derived from the generalized cubic equation of state, Eq.(1.2) is given below:
C^r+uS+w) 2
+ C $(2$+u)(£-l)
2
2
+ c ($-l) ($ +u$+w) = 0
3
2 2
(4.18)
where
Ci = % T r (4.18a)
° 2 =
" a
fl a
(4.18b)
C 3 = 0.0
a* (4.18c)
S = V/b (4.18d)
o _ RT r 1
aa 1
p
r " ~ 7777 TT7 77777777 (4.19)
(5-1) 0^ ($ +u$+w) 2
The results of the nine compounds tested are summarized in Table 4.28.
Since the GCP correlation is only applicable for simple compounds, that is
compounds with small acentric factor, no estimations are given for propane,
RMS % error. From Table 4.28, it is clear that the SRK equation is more
reliable than the PR or L M equation. The SRK equation gives the lowest RMS
% error for most compounds. The large RMS % errors for carbon monoxide
reported for the PR and SRK equations are due to the points that are near the
high temperature ideal gas region at which the inversion pressure is close to
zero but both the PR and SRK equations give large negative inversion pressures.
There are two points on the inversion curve which can be used to
characterize any fluid. These are the maximum inversion pressure and the
approximation for locating these two points. For compounds which follow the
temperature is about 5 times the critical temperature and the maximum inversion
pressure is about 11.75 times the critical pressure at the reduced temperature of
2.25. The values of the maximum reduced inversion pressure, P (max), and
r
state have been tabulated in Table 4.29. On the average, the maximum reduced
inversion pressure from the SRK equation is 12.05, PR is 13.40, and from L M
is 14.25. The maximum reduced inversion temperature is 4.22 for the SRK
equation, 5.25 for the PR equation, and 5.80 for the L M equation. Therefore, in
general, the SRK equation tends to give the closest maximum inversion pressure
126
and the PR equation gives the closest maximum inversion temperature. The LM
equation overpredicts both the maximum inversion pressure and temperature for
Figures 4.52 to 4.60 show the inversion curves of the nine compounds
calculated from the three EOS. In the case of fluid which has small acentric
factor, the curve calculated from the GCP correlation is also included in the plot.
For the low temperature region, all equations give similar predictions. None of
appears on all the graphs at T = 1.0. It is safe to say that the behavior of the
r
three equations is identical at reduced temperature below 1.5. The SRK equation
is probably the most accurate among the three EOS right up to the maximum
inversion pressure. This observation is consistent with the findings of Dilay and
Heidemann [24]. The PR and LM equations are not recommended for inversion
SRK PR LM
Compound Pr(max) Tr Tr(max) Pr(max) Tr Tr(max) Pr(max) Tr Tr(max)
Methane
0.0 • I • 1 I > 1 . I ; 1
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0
Reduced Pressure, Pr
Figure 4.53 Inversion curve of propane calculated from the SRK, PR, and LM to
equations. CO
Figure 4.54 Inversion curve of n-butane calculated from the SRK, PR, and LM CO
equations. o
6.0
Carbon Monoxide
Figure 4.55 Inversion curve of carbon monoxide calculated from the SRK, PR,
LM, and GCP equations.
5.0
C a r b o n Dioxide
A Expt.
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0
Reduced Pressure, P r
Figure 4.56 Inversion curve of carbon dioxide calculated from the SRK, PR, and co
to
LM equations.
F i g u r e 4.57 Inversion curve of ethylene calculated from the S R K , PR, L M , and w
G C P equations. w
Figure 4.58 Inversion curve of p-hydrogen calculated from the S R K , PR, and L M co
equations.
Figure 4.59 Inversion curve of ammonia calculated from the S R K , PR, and L M co
equations. cn
Figure 4.60 Inversion curve of argon calculated from the SRK, PR, LM, and w
GCP equations. 0 5
CHAPTER 5. SECOND VIRIAL COEFFICIENT
5.1. INTRODUCTION
density is less than half the critical, the virial equation truncated after the
second term provides excellent estimate of the vapor phase fugacity coefficient.
For normal fluids, probably the most popular and accurate correlation for
factor as the third parameter for improving the accuracy of the prediction. The
Tsonopoulos correlation gives the reduced second virial coefficient as the sum of
two terms:
= f ( o ) + cjf ( 1 ) (5.1)
where f<°> and f ' ' are given by Eq.(5.1a) and (5.1b)
1
r r
(5.1a)
137
138
0.331 0.423 0.008
f' '
1
= 0.0637 + (5.1b)
The f < ) represents the reduced second virial coefficient of a simple fluid which
0
has zero acentricity and f < > is the correction term for a normal fluid. The
1
Argon, krypton, and xenon data were used b3' Pitzer and Tsonopoulos to obtain
the function f < >. However, both authors did not specify which compounds were
0
used for the f < > function. The data sources for the Tsonopoulos correlation were
1
taken from the 1969 compilation of second virial coefficient by Dymond and
Smith [26].
cubic equations of state for pure compound property predictions. These two
studies have shown that none of the currently popular cubic equations of state
are capable of giving accurate second virial coefficients except the equation
proposed by Kubic [57]. The Kubic equation uses the Tsonopoulos correlation to
determine one of its constants. Although the Kubic equation gives excellent second
virial coefficient prediction, it fails to give reasonable approximations for the more
proposed a modified Martin [72] equation specifically designed for second virial
constants, the slope of the vapor pressure curve at the critical point,
As it was pointed out in the previous section, most of the cubic equations
of state do not give accurate second virial coefficient predictions for the entire
temperature range. However, it is generally true that predictions from the cubic
equation of state are acceptable for reduced temperature above 0.8. Below this
understand why the cubic equation fails to give good representation of the second
B C
2 = 1 +
v
+
^ +
" • * ( 5
- 2 )
or
Z = 1 + B'P + C P 2
(5.3)
Eq.(5.2) is called the Leiden form whereas Eq.(5.3) is the Berlin form of the
virial equation. The coefficients B, B'... and C, C... are the second and third
coefficients, respectively. The two sets of virial coefficients, B and B' and C and
B = B'RT (5.4a)
C = C (RT) 2
+ B 2
(5.4b)
For pure gas, these coefficients are functions of temperature only. If the
RT a(T)
V-b V +ubV+wb 2 2 (1
' 2)
a(T)
B = b (5.5)
RT
where
a(T) = a ( T ) • a c ( 5 6 )
!Zc = _ a (
V p
c p
(5.7)
RT RT RT 2 2
C C C
where
F = a/T r
(5.8)
141
It was shown by Shaw and Lielmezs [105] that for most cubic E O S , the
C 2 C 3
F = Ci + +
7 (5
-9)
r r
Tsonopoulos correlation, it can readily been seen why the cubic E O S gives such
second virial coefficient increases rapidly with decreasing temperature (see Figures
5.1 and 5.2). With the dependence on reduced temperature of power of -1, it is
not possible to include the rapid changes in the low temperature region.
Since the data sets used by Tsonopoulos were materials found before
1968, and the 1980 compilation by Dymond and Smith [27] has included
possible with these new and more accurate experimental data and this prompted
Here, the a(T) function is modified such that it gives an accurate second virial
coefficient. The second virial coefficient from a cubic equation of state is given
earlier by Eq.(5.5)
a(T)
B = b (5.5)
RT
where
a(T) = a ( T J • a(T , o) r
RT 2 2
RT
2 2
a(T„) = Q Q — = 0.45724 —
c c
RT RT
b = b(T ) =0. — ^ = 0.07780 — *
P P
c c
Substituting a(T) and b into Eq.(5.5) and simphfying, the reduced second virial
coefficient is
BP C a
— = % ~ a —
fl
(5.11)
(5.12)
a J
where
BP
Br = (5.13)
RT
It is proposed here that the a-function for normal fluid be given by the
following expression:
where a '( 0
represents a of simple fluids and a ' (1
corrects for the deviation of
normal fluid from the simple fluid. The functional form of Eq.(5.14) is based on
the third parameter. In this work, all acentric factors of simple fluids are
assumed to be zero even though the actual values are slightly different than the
calculated a values of the simple fluids are curve-fitted with a power series. The
minimum variance is the criterion for determining the number of terms in the
a - a<°>
a (i> = ( 5
CO
r r r
r r r
2.5851948
T 4 (5.17)
r
a ( 0 )
and the variance resulted is 0.0003175. The compounds included in the
curve-fit are neon, argon, krypton, and xenon. The expression for a < ' is 1
obtained from 124 points with a variance of 0.01041. The compounds included
n-octane, benzene, ethylene, and propylene. All experimental data are taken from
145
the Dymond and Smith [27] 1980 compilation of second virial coefficients.
5.4. COMPARISON
The second virial coefficients of 24 normal and simple fluids have been
calculated from the proposed correlation, Eq.(5.14). In order to test its validitj',
the results are compared with the Tsonopoulos correlation and four other cubic
Lielmezs-Merriman, and Kubic. The results have been tabulated in Table 5.1 and
it has clearly shown that none of the cubic EOS is capable of representing the
second virial coefficient for a wide range of temperature except the Kubic
equation with reasons mentioned earlier. Figures 5.1 and 5.2 have the results of
n-butane, benzene, n-octane, and- argon. Since the L M equation gives almost
figures. Similarly, the Kubic equation is partly derived from the Tsonopoulos
All the cubic EOS considered here give satisfactory results for T r greater
than 0.8 but below this temperature, the predictions deviate greatly from the
experimental data. The proposed correlation gives excellent agreement for the
entire range of temperatures studied. For example, the average absolute deviation
estimated deviations of the experimental data shown in Table 5.1 are taken from
Dymond and Smith [27]. For the majority of the compounds studied, the
146
deviations from both the Tsonopoulos and the present proposed correlations are
correlation gives better predictions than the proposed correlation for a number of
compounds, the differences are small. The SRK equation seems to give slight^
better prediction than the PR equation for T f greater than 0.8. Figures 5.1 and
5.2 show that the SRK predictions lie right on the experimental data whereas
Figure 5.1 Second virial coefficients of n-butane and benzene versus reduced
temperature.
149
SRK PR
o EXPT THIS WORK __T?P!i—
oo
0.5
Figure 5.2 Second virial coefficients of n-octane and argon versus reduced
temperature.
CONCLUSIONS
this work have been successfully applied to calculate various physical and
surface. The predictions from the L M equation and the modification of it have
been compared with experimental data and with the predictions from two other
Along the saturated vapor-liquid equilibrium curve, it has been found that
the L M equation is the most accurate equation for predicting vapor pressure and
saturated liquid and vapor volumes. However, for the two derivative properties:
equation.
In the subcritical region, the predictions from the three equations are very
similar and very small differences have been observed. In the region where
T <0.95, the PR and L M equations are practically identical in accuracy for most
r
0.95<T <1.0.
r
For the supercritical region, the predictions of pressure and volume from
the PR and the proposed modification of the L M equation are again very similar
in accuracy. The overall average RMS % error from the SRK equation is about
150
151
prediction, all three equations are similar in accuracy. For derivative properties,
accurac.y for enthalpy, entropy, and internal energy departure function estimations.
The SRK equation gives the lowest overall average RMS % error for the
In the compressed liquid region, it has been found that the overall
average deviation or R M S % error is the highest among the three single phase
and L M equations give similar results. These two equations are more accurate
are comparable.
For inversion curve calculation, the most reliable equation of state is the
SRK. Its estimation closely follows the experimental data right up to the
maximum inversion pressure. The predictions from all three equations are alike
up to T = 1.5.
r
calculating the second virial coefficient accurately for the region below T = 0.8.
r
The proposed a-function especially designed for second virial coefficient calculation
has been found to be equal, if not better, in accuracy than the Tsonopoulos
152
correlation. The proposed a-function is based on the latest and the most accurate
experimental data sources. The deviation from the proposed correlation has been
found to be well within the estimated uncertainty given in the data sources.
equally well in every region. Among the three equation of state studied, the
phase region. However, none of the three equations studied in this work can
1. There remain many compounds such as heavy hydrocarbons and alcohols for
constants is necessary.
4. The proposed a-function designed for second virial coefficient calculation can
5. Since the proposed a-function for calculating second virial coefficient is based
6. So far only pure compound properties have been studied, binary and
153
NOMENCLATURE
f fugacity
H molar enthalpy
AH V enthalpy of vaporization
m constant in Eq.(2.3)
m number of components
MW molecular weight
n constant in Eq.(2.8)
154
155
NC number of compounds
P pressure
S molar entropy
AS y entropy of vaporization
T absolute temperature
*
T dimensionless temperature coordinate defined by Eq.(2.9a) and (3.39)
V molar volume
x mole fraction
Z compressibility factor
Subscripts
A attraction
156
c crtiical property
r reduced property
R repulsion
Superscripts
1 liquid phase
v vapor phase
Greek Symbols
u chemical potential
u Joule-Thomson coefficient
co acentric factor
7r number of phases
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163
In this Appendix all the necessary constants and equations are derived
from the generalized cubic equation of state [103]. T h e exact equations of all the
properties considered in this work are given at the end of each section for the
three cubic E O S : the Soave-Redlich-Kwong [110], the Peng-Robinson [87], and the
RT a(T)
P = (A.l)
V-b V +ubV+wb
2 2
RT RT a
V 3
+ ub - b V 2
+ wb 2
- ub - ub — + -
2
P P P
RT ab
wb 3
+ wb — + — 2
= 0 (A.2)
P P
(V - v c ) 3
= 0 (A.3)
164
165
V 3
- 3V V 2
+ 3VV 2
- V 3
= 0 (A.4)
c c c
Compare the coefficients of Eq. (A.2) and (A.4), and we have the followings:
RT
ub - b = -3V (A..5)
P
RT a
wb 2
- ub 2
- ub — + - = 3V C
2
(A. 6)
P P
RT ab
wb 3
+ wb 2
— + — = V 3
(A. 7)
P P c
Let V c = Xb, then Eq. (A.5), (A.6) and (A.7) become (A.8), (A.9), and (A. 10),
respectively.
RT
b(u - 1 + 3X) = — (A.8)
P
RT a
b (w - u - 3X ) = ub —
2 2
(A.9)
P P
RT a
X b 3 2
-wb 2
- wb — = - (A. 10)
P P
(A. 11)
P
(w - u - 3X ) = (u - 1 + 3X)(u + w) + w - X
2
(A. 12)
X 3
- 3X 2
- 3(u + w)X + (w - uw - u ) = 0 2
(A. 13)
a P
c
0_
a = R 2 T £
2 (A. 14)
c
c
b P
(A. 15)
RT
p = RT^ _ a(T )
c
C
V-b V +ubV +wb
2 2 ( A
- 1 6 )
c c c
a
RT (V -b)
c c R T (V +ubV +wb )
2
c
2
c
2
c
2
(A. 17)
9P RT a(2V+ub)
— = - + (A IR)
3V „ (V-b) 2
(V +ubV+wb ) 2 2 2
3P
At the critical point = 0 and Eq. (A. 18) becomes
3V
(A. 19)
(V -b) c
2
(V +ubV +wb )
c
2
c
2 2
RT (V +ubV +wb )
2 2 2
a ( T
-
V
) = =
(A.20)
(V -b) (2V +ub)
c
2
c
Replace V c with Xb and substitute Eq. (A.20) into (A. 17) and simplify
(X +uX+w)
2 2
= (X -2X-u-w) 2
(A.21)
a. (X-l)*(2X+u) 2
Q h = (A.22)
(X-l) (2X+u)
2
J2 a
(A.23)
bRT
c
or
T_ = (A.24)
bRfi„
v "^ <A
- 25)
or
P = (A. 26)
b fl
2
By definition, Z _ is
c
PV
•7
Z
c - —C C -
(A.27)
169
Substitute Xb for v , T c with Eq. (A.24), and P c with (A.26), Eq. (A.27)
becomes
z
c = x f l
b (A. 2 8)
X(X -2X-u-w)
2
(A.29)
(X-l) (2X+u)2
u = 1
w =0
X = 3.8473221...
G 0 = 0.4274802...
= 0.0866403...
Z c = 0.3333333...
u = 2
w = -1
X = 3.9513730...
Q = 0.4572355.
a
= 0.0777960
= 0.3074013
u = 2
w = -1
X = 3.9513730.
0 = 0.4572355
3.
= 0.0777960
Z„
c = 0.3074013
2. CONSTANTS A AND B
aP
A =
R 2 T 2
bP
B = —
RT
where
a = a(T ) • a c
171
b
= ( >
b T
c (A.33)
Substituting a and b into Eq. (A.30) and (A.31), A and B can be rewritten as
A =
®a — a
(A.34)
B
= % — (A.35)
r
a = [ 1 + m(l - T r
0.5 ) ]. 2
The constant m is
a = [ 1 + K ( 1 - T r 0.5 ) ,2
]
The constant K is
a = 1 + p(T*) q
(T /T - 1)
T = -
(T /T - 1) b
a = 1 - p(T*) q
» _ (T/T, - 1)
(T /Tc b - 1)
PV
Z =—
RT
Z 3
+ (uB - B - 1)Z + (A + wB - uB - uB )Z
2 2 2
- (AB + wB + wB ) = 0
2 3
^ A 3 6 ^
Z 3
- Z 2
+ (A - B - B ) Z — AB = 0
Z
Z 3
- (1 - B ) Z + (A - 3 B
2 2
- 2B)Z - (AB - B 2
- B ) = 0
3
Z 3
- (1 - B)Z + (A - 3B - 2B)Z - (AB - B - B ) = 0
2 2 2 3
4. FUGACITY COEFFICIENT
equation :
174
f 1 P RT
in - = - ; V dP (A. 3 7)
P RT 0 P
f 1 P lnP
m - = — ; vdp - ; dinp
P RT P° lnP 0
( A 3 8 )
where P° is the reference state pressure of a pure substance in the ideal gas
given by
RT
The first term of the right hand side of Eq. (A.38) can be integrated by parts,
that is
The second term of the right hand side of Eq. (A.40) can be evaluated by
dV adV
J PdV = RT J / ( A - 4 1 )
V-b V +ubV+wb
2 2
175
The upper limit of the integral is V and the lower limit is V°. Integrating Eq.
(A.41) gives
v-b V+(9 b 2
S P d V = RTln In
V°-b 2b6 1 V+0 b3
v + e 2 b
In (A.42)
2b6 1 v»+e b 3
where
6* X = - w (A.43)
u
e 2 = - - 0i (A.44)
2
u
6, =
(A. 45)
2
Combining Eq. (A.38), (A.40), and (A.42), the fugacity coefficient becomes
V-b V+f?,b
In - = (Z - 1) - In In
P V°-b V+0 b
2bRT<9i 3
a V°+0 b 2 P
+ In - In —
(A. 46)
2bRT0 x V +e9 b
0
3 po
176
zero. The fugacity coefficient for a pure compound is then given by Eq. (A.47):
f A Z+t? B
2
0 a = 0.5
e 2 = o.o
e 3 = 1.0
f A z
In - = (Z-l) - ln(Z-B) + - In
P B Z+B
6 1 = Jl
6 2 = 1 - y/2
e 3 = i + »/2~
f A Z-0.414B
In - = (Z-l) - ln(Z-B) + In
P 2v^B Z+2.414B
177
e, = 1/2
e 2 = 1 - vT
t9 3 = 1 + /2
f A Z-0.414B
In - = (Z-l) - ln(Z-B) + — — I n =
P 2\/2B Z+2.414B
H = U + PV (A. 48)
But
au rp
" 3S "
— X
(A.51)
3v T 3v
r
3H 1
3P 3(PV)
—
= T — - P + (A.53)
3V T 3T 3V
V T
3P
H 2 " H x = / T( — > dV + A(PV) (A. 5 4)
3T V
3P da
(A.55)
3T JV V-b V +ubV+wb
2 2
dT
da dV
H 2 - H x - a - T + A(PV)
dT V +ubV+wb
2 2
(A. 5 6)
a - T(da/dT) V+0 b 2
H 2 - H, = In + P V2 2 - P V
1 1
26yb v+e b 3
(A. 5 7)
a - T(da/dT) Z+t? B
2
H - H° = RT(Z-l) + In (A.58)
2c9ib Z+t9 B
3
a = a(T ) • [ 1 + m(l - T - ) ] r
0 5 :
da a
= - ma(T ) c
dT TTC J
180
da ,
T — = - ma(T )(aT )
dT c r
da
a - T — = (1 + m)
dT
A T Z
H -- H° == RT(Z-l) + R(l+m) In
B a • 0 5
Z+B
a = a(T ) • [ 1
c + K ( 1 - T/- 5 ) ] 2
da a
— = - K3(T )
dT c
TT
c J
da ,
T — = - Ka(T_)(oT_)
dT c r
da
a - T — = (1 + K)
dT
R(l+»c) A T Z-0.414B
H - H° = RT(Z-l) + In
2v^2 B a" Z+2.414B
5.3. This Work
a = a ( T ) • [ 1 + p(T )
c
q
]
(T /T - 1)
c
T =
(T /T c b - 1)
da qa(T )(o-l) c
dT T (T -T)
r c
da qT a(T )(g-l)
c c
T — =
dT (T -T)
c
da qT r
a - T — = a 1 +
dT (T -T)
c
where
qT qT,
4> = 1 +
(T -T) c a(T -T)
c
182
a = a ( T ) • [ 1 - p(T )
c
q
]
(T/T c - 1)
T =
(T /T
c b - 1)
da qa(T )(a-l)
c
dT (T-T )
da qa(T_)T(o-l)
T — =
dT (T-Tc )
da cjT qT
T — = a 1 - = a • 4>
dT (T-T ) c a(T-T ) c
where
qT qT
1 -
(T-T )c a(T-T ) c
RT$ A Z-0.414B
H H° = RT(Z-l) + In
2y/2 B Z+2.414B
183
The constant pressure heat capacity departure function is given by the following
thermodynamic relation:
9(H-H°)
(C p - C ") =
p
(A.59)
9T
JP
The enthalpy departure function is given by Eq. (A.58) and differentiating Eq.
(A. 5 8) gives
9 a - T(da/dT) V+0 b 2
— ( ) In
9T 26^ .P V+0 b 3
a - T(da/dT) 9 v+e b
2
( — In
2e b x 9T V+0 b
3
(A. 60)
or
9V V+c? b 2
(C p - C «) = P
p
- R + x ln
x
9T V+(9,b
a - T(da/dT)
(A.61)
2c? bx
184
where
a - T(da/dT)
(A.62)
dT 26 b x
d a
2
Xx = - (A.63)
dT 2
and
v+e b 9V
2
X 2 = ( — In (A.64)
9v V+f9 b 3 9T
26 b
x 9V
X 2 = (A.65)
V +ubV+wb
2 2
9T
JP
9V d a
2
V+6 b
2
(C p - C ") = P
p - R - In
9T 26 b dT 2
V+0 b
JP x 3
a - T(da/dT) 9v
(A.66)
V +ubV+wb
2 2
9T
P
185
RT T(da/dT) 3V
(C - C ") =
3T
p p
V-b V +ubV+wb
2 2
T d a 2
V+t? b
2
In - R (A.67)
26 h x dT 2
V+t? b
3
V = f(P,T) (A.68)
av 3V
dV = — dP + — dT (A.69)
3P T JP
At constant volume
9V 9V
0 = — dP + — dT (A. 70)
3P T
3v 3V 3P
(A. 71)
3T P
3P T
3T
Or
3V (3P/3T)
v
(A.72)
3T (3P/3v) r
(3P/3V) T is given by Eq. (A.18) and (3P/3T) V is given by Eq. (A.55). Let
T(da/dT) RT
X 3 = (A. 73)
V +ubV+wb
2 2
V-b
3P RT 2
2RT(da/dT)
+
3T (V-b) 2
(V-b)(V +ubV+wb )
2 2
da
(A. 74)
dT (V +ubV+wb )
2 2 2
The numerator of the first term of the right hand side of Eq. (A. 6 7) is Eq.
(A. 7 4) and the denominator is (3P/3V) . Now T multiply this fraction by the
fraction:
(V-b)(V +ubV+wb ) 2 2
-R Tb 2
187
and get
3P V +ubV+wb
2 2
2 da
Numerator = x :
3T b(V-b) Rb dT
JV
(V-b) da
(A.75)
R b V +ubV+wb
2 2 2
dT
and
3P V +ubV+wb
2 2
a(2V+ub)(V-b)
Denominator =
9V Rb(V-b) R Tb(V +ubV+wb )
2 2 2
(A. 76)
3P Z +uBZ+wB
2 2
2 da B da (Z-B)
3T B(Z-B) Rb dT Rb dT B(Z +uBZ+wB )
2 2
JV
(A. 7 7)
and
3P Z +uBZ+wB
2 2
A(2Z+uB) (Z-B)
(A. 78)
3V RB(Z-B) RB Z +uBZ+wB
2 2
188
Let
Z +uBZ+wB
2 2
M =
(Z-B)
and
B da
N =
Rb dT
Substituting M and N into Eq. (A.77) and (A.78). The first term of right hand
X»OP/3V) T R(M-N) 2
(A. 79)
(9P/3V) t M -A(2Z+uB)
2
R(M-N) 2
T d a
2
Z+6» B
2
In - R
M -A(2Z+uB)
2
20ib dT 2
Z+t? B
3
(A.80)
C - C 0
' Cp - Cy " " Cp" " Cy"
<~p l_p
R R R R
(A. 81)
189
where
C - C 0
d a
2
Z+0 B
2
In (A.82)
dT 2
Z+t9 B
3
c p c v
(M-N) 2
(A.83)
M -A(2Z+uB)
2
= 1 (A.84)
d a 2
a(T )m
c m
dT 2
2TT °•
C
5
Z(Z+B)
M =
(Z-B)
B da
N =
Rb dT
d a 2
(Z+B) R(M-N) 2
C - C 0
= — In + - R
dT 2
M -A(2Z+B)
2
6.2. The Peng-Robinson Equation
d a a" •
2 5
a(TjK K
+
dT 2
2TT •0 5
^•0 .5 0. 5
C C
Z +2BZ-B
2 2
M =
Z-B
B da
N =
Rb dT
d a
2
Z+2.414B R(M-N) 2
C - C 0
= In
2/2 b dT 2
z-o. 414B M -2A(Z+B)
2
d a
2
(2T -q-l) da
r
dT 2
T (T -T) dT
r
d a
2
(q-D da
dT 2
(T-T ) dT
191
Z +2BZ-B
2 2
M =
Z-B
B da
N =
Rb dT
d a
2
Z+2 .414B R(M-N) 2
CP
U -*-
Cp =0
In + -R
2|/2~ b dT 2
Z-0 .414B M -2A(Z+B)
2
7. JOULE-THOMSON COEFFICIENT
-1 T(3P/3T),
M = +V (A.85)
OP/3V).
3P R 1 da
3T V-b V(V+b) dT
3P -RT a(2V+b)
+
3V (V-b) 2
V (V+b)
2 2
7.2. The Peng-Robinson Equation
ap da
3T V-b V +2bV-b
2 2
dT
3P -RT 2a(V+b)
+
av JT (V-b) 2
(V +2bV-b )
2 2 2
ap da
3T V-b V +2bV-b
2 2
dT
JV
ap -RT 2a(V+b)
+
av (V-b) 2
(V +2bV-b )
2 2 2
8. INVERSION CURVE
ap ap
T — + V — = 0
3T
V av T
where
3P RT 1 da
3T V-b V +ubV+wb
2 2
dT
JV
193
Since
a = a(T ) c • a (A.32)
da da
T — = a(T ) • T — (A.88)
dT dT
Let
da
<j> = T — (A. 89)
dT
Therefore
3P RT
a(T W (A. 90)
9T V-b V +ubV+wb
2 2
or
9P T
r c P 1
°a c* p
(A. 91)
9T \ <S-l) fl
b
2
(5 +u5+w) 2
where
I = V/b (A.92)
9P -RTV aV(2V+ub)
(A.93)
9V (V-b) 2
(V +u±»V+wb )
2 2 2
JT
194
or
9P -T P
r c fi P a S(2$+u)
a c (A. 94)
9V Ojj ($-l) 2
0^ ($ +u5+w)
2 2
JT
$(2$+u)a - (£ +u$+w)c6
2
(A. 95)
(o-D :
($ +u$+w)
2 2
°b
C^^+uS+w) 2
+ C $(2$+u)(S-l)
2
2
+ C,<S-l> (S +u$+w) = 0
a a
(A. 96)
where
(A. 9 7)
C 2 = -R a a
(A. 98)
C 3 = K<t> (A.99)
RT r 1 R a
a 1
p
r = (A. 100)
($-1) f^ 2
(S +u$+w)
2
195
0 = - m(aT ) - r
0 5
C x = 0.08664T r
C 2 = - 0.42748 [ 1 + m(l - T - ) ] r
0 5 :
C 3 = - 0.42748 m ( a T ) - r
0 5
+ C (2$+l)($-l>* + C,<5+1)<5-1> = 0
2
CiSCS+l) 2
2
T 1 0a 1
P
r " ~
0 = - rc(aT ) - r
0 5
C x = 0.07780T r
C 2 = - 0.45724 [ 1 + /c(l - T «- ) ] r
S :
C 3 = - 0.45724 *c(aT ) - r
0 5
196
C1(S +2S-1)
2 2
+ 2C 2 S($+1)(S-1) + C ( $ + 2 $ - l ) ( $ - l )
2
3
2 2
= 0
r
% (S-D V S +2$-l
2
a-1
<S> = - q
1-T
r
C x = 0.07780T r
C 2 = - 0.45724 [ 1 + p ( T * ) q
]
a-1
C 3 = - 0.45724 q
1-T
r
and for T r > 1.0
T (1-a)
* = - q —
T -1 r
C x = 0.07780T r
197
C 2 = - 0.45724 [ 1 ~ p ( T * ) q
]
T (l-a)
r
C 3 = - 0.45724 q
T -1r
C1(S +2S-1)
2 2
+ 2C2S(S+D(S-1) + 2
C ($ +2$-im-l) = 0
3
2 2
T 1 0 a 1
P = _E 2
Ou (s-i) n h
2
s +2$-i
2
9. VIRIAL COEFFICIENTS
RT
(A.l)
V-b V +ubV+wb
2 2
RT RT 1
(A. 101)
V-b V 1-b/V
or
198
RT RT b b 2
b 3
1 + - + — + — + (A. 102)
V-b V V V 2
V 3
(A.103)
V +ubV+wb
2 2
V V+ub+(wb /V) 2
or
a 1 ub (u -w)b 2 2
— - — + +
(A. 104)
V +ubV+wb
2 2
V V V 2
V 3
uab 1
Z = 1+ b - b 2
+
RT RT V 2
(w-u )ab 2 2
b 3
+ (A. 105)
RT V 3
B C D
Z = 1 + - + — + — + (A. 106)
V V 2
V 3
r
199
a
B = b (A.107)
RT
uab
C = b 2
+ (A.108)
RT
(w-u )ab 2 2
D
= b 3 +
(A. 109)
RT
a
B = b
RT
ab
C = b 2
+ —
RT
ab 2
D = b 3
-
RT
a
B - b
RT
2ab
C = b 2
+
RT
200
5ab 2
D = b 3
RT
a
B = b
RT
2ab
C = b 2
+
RT
5ab 2
D = b 3
RT