Fluid Phase Equilibria, 39 (1988) Ill-128 111

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

THERMODYNAMIC PROPERTY PREDICTIONS WITH THE TREBBLE-BISHNOI EQUATION OF

STATE

M.A. TREBBLE anti P.R. BISHNOI

Department of Chemical and Petroleum Engineering, The University of Calgary,
2500 University Dr. N.W., Calgary, Alberta, Canada. T2N lN4

(Received July 20, 1987; accepted in final form October 19, 1987)

ABSTRACT

Trpbble, M.A. and Bishnoi, P.R., 1988. Thermodynamic property predictions with
the lrebble-Bishnoi equation of state. Fluid Phase Equilibria, 39: Vl'i-128.

Predictions of thermodynamic properties including second virial coefficients, enthalpies, isobaric

heat capacities, speed 01 sound, and Joule-Thomson coefficients are presented for the Trebble-Bishnoi
equation of state. These predictions are compared both to experimental data and 10 predictions from
the Peng-Robinson equation of state. Both equations of slate give reasonable and consistent values
for all of the above properties.

INTRODUCnON
A new four-parameter cubic equation of state (EOS) was recently developed by Trebble and

Bishnoi (1987) using extensive PVT data for 75 pure components representing a wide variety of chem-
ical fypes. Data from the entire PVT space were utiliied including saturated, single phase, and critical
regions. Extreme ranges of temperature and pressure were also considered. The Trebble-Bishnoi
(TB) equation was compared lo ten recently published cubicequationsof state and displayed improved
overall PVT predictions for pure components. Saturated liquid volumes were fii very well with roughly
a 3% error over the entire component library.
During the development of the Trebble-Bishnoi EOS if was discovered that the introduction of
temperature dependence into the “b” parameter could produce thermodynamic inconsistencies such as
the prediction of negative heat capacities (Trebble (1986), Trebble and Bishnoi (1986)). Consequently
in this paper a range of thermodynamic properties are evaluated to ensure that the improvements in
PVT predictions offered by the TB equation do not result in absurd or incorrect predictions of other
properties. Predictions of second virial coefficients, enthalpies, isobaric heat capacilies, speed of
sound, and Joule-Thomson coeflicients are compared to experimental data as well as predictions from
the Peng-Robinson (PR) equation of state (1976) in order lo demonstrate the thermodynamic

0378-3812/88/$03.50 0 1988 Elsevier Science Publishers B.V.

112

consistency 01 the TB equation.

We believe that any new or modified equation of state should be subjected to a similar analysis
of thermodynamic consistency in order to reduce the possibility of new equations being developed
which offer increased accuracy in one specitic property prediction but which are thermodynamically
incorrect.

SECOND VIRIAL COEFFICIENT PREDICTION

Second virial coefficients of hydrogen, water, carbon-dioxide and propane were calculated from
the Trebble-Bishnoi equation of state, the Peng-Robinson EOS, and the Soave-Redlich-Kwong (SRK)
EOS (1972) and reduced values (B divided by the experimental critical volume) are plotted in Figures 1
through 4. The equation of state predictions were compared to experimental data obtained from the
compilation of Dymond and Smith (1980). The most striking feature of these comparisons is that a
shit in the critical compressibility factor predicted by the equation of state (<,) causes a resulting shift
in the calculated second virial cuwe and that the largest shii occurs for water where:

EXP 2, = 0.2333

TB c, = 0.2440

PR 5, = 0.3074

SRK 4, = 0.3333

Clearly the shape of the second virtal plot is not exact for all three EOS and this is an obvious
indiiation that the cubic equation is not a cornpleteiy adequate model. This is consistent with Abbott’s
(1973) comment that “NO specialization of the generic cubic equation, when subjected to the classical
constraints (aP/&)r = ($PL#)r = 0 can provtie both accurate values for B and satisfactory
representation of the critical and high-pressure regions.”
Despite the enor in second virial coefficients, it has been shown by Trebble (1986) that accurate
predictions of both liquid and vspour volumes are still possible. The TB EOS, for example. matched
84 saturated liquid volumes of water with an average absolute error of 2.25% and 84 saturated vapour
volumes within 2.58% at reduced temperatures as low as 0.422 and as close to the critical as 0.998.
It is likely that if one were to predict PVT behaviour based on regression of second virial data alone,
the volume predictions would become much worse.
Virial coeffiients for the TB EOS are derived in the appendix along with all other properties
investigated. Reduction to the PR EOS is obtainabie for all properties by proper selection of pareme-
ters “c” and “d” (c-b, d-0) and by correct differentiation of “a” and “b” with respect to temperature.
Similarly for the SRK EOS the corresponding equations can be found by setting the parameters “c”
and “d” to zero.
 113

1.0

0.0

-l.O

K
-2.0

-3.0 DATA IJ
....__.._..-. ...I
SRK _.-.-
q
-4.0

-5.0 r
: 24

FIGURE I: SECOND VIRIAL COEFFICIENT FOA HYDROGEN

-LO- -

-8.0
,B, , , ,
5lu lb
REDUCED TEMFfiWURf
FIGURE 2: SECOND VIRIAL COEFFICIENT FOR WATER
114

OD--

-0.6 - -

c -l.2--

-la-- DATA 0
. . .......“..__”

-2.4--

, I I, I
-3.0 4
!id lb
REDUCED TBiFQ?ATURE
FIGURE 3: SECOND VIRIAL COEFFICIENT FOR CARBON DIOXIDE

-Od--

-lS--

2 -l.8--

-2.4-- DATA q

.----“...l _.._ .
-.-.._
-3.0 - -
0

-3.8 y I 1 1I 1I I

5!40-' lb
TEMFERATURE
REDUCED
FIGURE 4: SECOND VIRIAL COEFFICIENT FOR PROPANE
 115

EN7HALPY PREDlC77ON

Predicted enthalpies for methane and water are presented for both the TB EOS and the PR
EOS in Figures 5 and 6. Enthalpy data as well as ideal heal capacities for methane are fmm Angus,
Armstrodg, and de Reuck (1976) and for water from Keenan and Keyes (1978). Numerical comparis-
ons of deviations of single phase enthalpies and enthalpies of vapurization are presented in Table I
for methane, carbon-dioxide, ammonia, and water. Data for catindioxide were obtained from Angus
et al (1973) while data for ammonia were taken from the work of Haar and Gallagher (1978). Enthalpy
predictions from the two equations gave very similar deviations from the data although the errors from
the Peng-Robinson equation for carbon-dioxide were notably smaller. The most obvious trend
apparent from inspectiin of Table I is that the accuracy of prediction worsens with increased molecular
polarity.

TABLE I: ENMALPY DEVlATlONS IN JOULES/MOLE

TB EOS
COMPONENT AAD MAX PTS A4D MAX PTS
ov ov ov VAP VAP VAP
METHANE 60 554 457 199 881 51
CARBON-DIOXIDE 233 1147 316 832 1615 46
AMMONIA 494 2264 359 1220 3676 57
WATER 874 5293 457 2302 7939 84

PR EOS
COMPONENT AAD MAX PTS AAD MAX PTS
ov ov ov VAP VAP VAP
METHANE 78 579 457 185 880 51
CARBON-DIOXIDE 119 1025 316 454 1345 46
AMMONIA 442 2267 359 1069 3523 57
WATER 809 6061 457 2418 7992 84

AAD . AVERAGE ABSOLUTE DEVIATION

MAX - MAXIMUM ABSOLUTE DEVIATION
OV - OVERALL AVERAGES
PTS - NUMBER OF EXPERIMENTAL DATA POINTS
VAP - ENTHALPIES OF VAPOURlZATlON

ISOBARIC HEAT CAPACITY PREDICTKIN

Figure 7 shows the isobaric heat capacity predictions for the TB EOS and the PR EOS overlaid
on the experimental data for the component methane given by Jones et al (1963). The TB EOS gave
an absolute average deviation of 3.72 % for 400 data points while the PR equation yielded an absolute
average of 3.66 %. It is imporiant to note that both equations predicted positive heat capacities over
the entire PVT space.
116

‘2

I I I
--DATA ’ q i
- TB Iegend
.................... 0 = sat
t PR
0 = 100 K
A = 130 K
+ = 160 K
x =191 K
0 = 220 K
0 = 300 K
m = 450 K
* = 600 K
A_

I a , I I I
1o-2 I I I I I
-18.0 -12.0 ENlHALf’Y%
-6.0 J/Iii; 12.0 18.0
*lo”

FIGURE 5: ENTHALPY PREDICTION FOR METHANE

 117

legend
o=sat
0 =333 K
A=433 K
+ =533 K
x=647 K
0 =773 K
v =973 K
q =1273 K
* =I573 K

FIGURE 6: ENTHALPY PREDICTION FOR WATER

118

I I I I
DATA ’ 0
TB
PR ....................

.o PO.0 no.0 200.0 230.0 260.0 2

TEMPERATURE IN K

FIGURE 7: ISOBARIC HEAT CAPACITY PREDICTION FOR METHANE

 119

THERhfODYNAMlC SPEED OF SOUND

Figure 8 shows the predicted single phase speed 01 sound values for methane. Experimental
data for these comparisons were obtained from Angus et al (1976). Average absolute deviations for
277 data points were 4.0% for the TB EOS and 4.3% for the PR EOS. It is evident that the speed of
sound predictions from the TB EOS are worse at 100 K than the PR predictions although they are
better on all of the other isotherms.
In order to investigate the discrepancy at 100 K. a value of (aP@V), for the saturated liquid
phase was calculated from equation (66) by utilizing an experimental value for CD/C, of 1.636 obtained
from Goodwin (1974) and the experimental values of saturated liquid volume and speed 01 sound. At
100 K the PR EOS predicted a saturated liquid volume 11% lower than the experimental value, a ratio
ot C,lC, that was 5% low, a value of -(aP/W)r that was 16% high and a speed of sound 7% low.
The TB EOS, on the other hand, predicted a saturated liquid volume that was 2% low, a C,iC, ratio
that was 13% high, a value of -(aP/W)T 45% high, and a speed of sound prediction that was 25%

too large.
An immediate conclusion lrom this analysis is that regression of even a vary large amount of
PVT data does not guarantee accurate values of (aP/aV)T at low temperatures in the liquid region. It
may therefore be advantageous to include speed of sound data from this region in future EOS
development.

JOULE-THOMSON COEFFICIENT PREDlC77ON

Figure 9 shows the predicted values of the Joule-Thomson coefficient for methane from the TB
EOS and from the PR EOS as well as the experimental data of Budenholzer et al (1939). Average
absolute deviations for 42 data points were 17.5 % lor the TB equation and 16.9 % for the PR EOS
and neither equation reproduced the maxima exhibited by the data. It is interesting to note that the
IUPAC equation of state (International Union of Pure and Applied Chemistry) for methane given by
Angus et al (1976) was also unable to predtct these maxima even though it contains 33 optlmizable
parameters.

CONCLUSIONS

The cubic equations of stale do not seem to be able to simultaneously predict accurate values
of second virials, saturated volumes, and vapour pressures. Enthalpiss, on the other hand, were
predicted very well by both the Trebble-Bishnoi and the Peng-Robinson equations considering that no
enthalpy data were regressed in etther work. Predictions of isobaric heat capacity for methane were
also very good (less than 4 % average error) although no other substances were examined. The ther-
modynamic speed of sound in methane was predicted more accurately by the TB EOS at all tempera-
tures above 100 K. but along the 100 K isotherm it gave large deviations from the exerimental data.
Average deviations from experimental data were about 4 % for both equations. Joule-Thomson
coefficient data were not fit accurately by either equation although average deviations were less than
20 96. Both the TB and the PR equations yielded reasonable and thermodynamically consistent values
for all of the properties evaluated.
 ........ I.. . . . . . . . . . .

FIGURE 8: SPEED OF SOUND PREDICTION FOR METHANE

 121

12sI- I I I
DATA ’ q

Tl3
PR

1o.c
)-- I egend
= 294 K
0 = 311 K
A = 328 K
+=344K
I-- x = 361 K
0 = 378 K

l--

I--

2.0

0.0

FIGURE 9: JOULE-THOMSON COEFFICIENT PREDICTION FOR METHANE

122

NOMENCLATURE
equation Of state parameter
Ii dimensionless parameter defined by Equation (2)
b equation of slate parameter
B dimensionless parameter defined by Equalian (3), second virial coefficient
equation 01 state parameter
: dimensionless parameter defined by Equation (4), third virial coefficient
CP isobaric heat capacity
cv isochoii heat capacity
d equation of slate parameter
D dimensionless parameter defined by Equation (5), fourth virial coefficient
EOS equation of state
EXP experimental
f fugacity
H enthalpy
M molecular weight
MAX maximum
n number of moles
P absolute pressure
constant in Equation (7)
;: constant in Equation (11)
R universal gas constant
thermodynamic speed of sound
: entmpy
T temperature
u variable defined by Equation (37)
u internal energy
V m0lar volume
V total volume
X variable defined by Equation (35)
Y variable defined by Equation (36)
2 compressibitity factor

temperature dependence in the “a” parameter

temperature dependence in the “b” parameter
variable defined by Equatiin (41)
variable defined by Equations (36) and (39)
variable defined by Equation (44)
variable defined by Equation (47)
Joule-Thomson coefficient
density
variable defined by Equation (40)
compressibitity factor generated by equation of state

subscrpts
C

P
reduced
i temperature
V volume
vir virial

SuperscrIpts
l
property of an ideal gas
first derivative with respect to temperature
,I
second derivative withmsped to temperature
 123

ACKNOWLEDGEMENTS
Financial support received from the Natural Science and Engineering Research Council 01
Canada is greatly appreciated.

APPENDIX: SUMMARY OF EQUATIONS

A.1 Summaw of the TB EOS

The form of the TE EOS is summarized below:

p=RT a
v-b - v2 + (b+c) v - (bc+d2)
The following definitions also apply:

= experimental critical compressibility

s critical compressibility predicted by EOS

For temperature dependence in the “a” and “b” parameters the following functions have been
utilized:
a = a,*u (61
a= exp[qi(l-T,)] (7)

a” = -=
ba &
dp (3)
T$

b = b,+ (10)

p = 1.0 + qz(1 - 7, + hT,) T,<l .O (11)

B= 1.0 T,sl .O (12)

T&l .O (13)

T,>l .O (14)

TSl .O (15)

T,>l .O (16)
Expanding Equation (1) and rewriting In terms of dimensbnless variables the following cubic
equatton is easily derived:
124

23 + (C-l)? + (A-2BC-B-C-Bz-Da)2 + [B%+#C-AB+D2(/3+l)J = 0 (17)

At the crltttal point. Martin and Hou (1955) hava shown that the application of the van der
Waals’ (1873) conditions imply the following relationship:

(Z, - L)3 = 0 (18)

z,3 - 3r,z,2 + 3cz, - r: = 0 (19)

Comparison of Equations (17) and (19) leads to the following equations applicable at the critical
point:
C-1=-35, (20)

A, - 2 Bc C, - B, - C, - B,2 - C’,2= 3c (2’)

B,‘C, + B,C, - A& + D,2(Bc+1) = -(cJ3 (22)

Simultaneous solution of the above equations leads to a cubic equatttn in B, as given below:
B,3 + (2-35,)6: + 3{:B, - [D,‘+<;] = 0 (23)
Therefore once [, and d are selected, DC can be obtained from Equation (5) and 6, is calcu-
lated as the smallest positive root of Equation (23). C, can be determined directly from Equation (20)
and finally A, is calculated from Equation (21).

A.2 V/r&l Coetbclents

Virial coefficients can be calculated for the TB EOS by examination of the virial equation written
as:
Z = 1 + Bti,p + C,,p’ + C&p3 + ... .. .. . (24)
Hence:

a22
2Cd, = lim (p)r (26)
p-6 ap

(27)

Equation (1) may be rewritten in a 2 explicit form as:

Z=L-_ p(atRT)
I-bp (28)
1 + (b+c)p - (bc+&)p’
Application of the above Ilmtts yields:

(30)

&=b3-+(b2+c+‘+&+3bc) (31)

A.3 Pure Component Fugaclty Coeffkient

The fugactty coefficient for a pure fluid is derived from the following relationship:

(32)
 125

Inserting Equation (1) we obtain:

an2
)“I$ +/nz=
$I,:(& - RT( p + (b+c)nV - [bc+dTn2) - +dV 1 (33)

Completing the squares in the denominator of the second term 01 the above integral gives:
1
V2 + (b+c)nV - (bc+d2)n2 (34)

where:

x=v+.!!!?!
2 (35)

y=L!I!?
2 W)

u=i+c (37)
b

0 = (r)‘fZ (case 1 ; 720) (38)

0 = (-x)lt2 (case 2 ; ~4) (39)

z=, +6c+c1+462
b b2 b2 (40)

6= v2+ (b+c)v - (bc+d’) (41)

Integration is therefore subject to two cases depending on the sign of “r”. For case 1 we find:
fa
'~l-j;I+'Q=$nhlV_bn
-4 (42)

/nIfl=Z-I-/nIZ-L)I+AX, (43)
P Be
where:

i
1= ,” , 22 + w-e)
22 + Eqlf+q I (44)

For case 2 we have :

+ $&pan-‘(~) - 7~)] (45)

/nl$l =Z-1 -InIZ-t3I (46)

where:

La = [2tan-1(v) - x] (47)

A.4 Internal Energy Deptum

Internal energy departure is deriied from the following relationship:

u- U’= i [T($y),- PI& w

Inserting Equation (41), we can write the TB EOS in a slightly abbreviated form as:
126

p=RT_a (49)
v-b 6
then:

(50)

Inserting into (4.5) we find:

C _ U. = ![(a-;‘T) : RTib’ I aT(v-c)b’ldv

(51)
e (v-b)2 #

For case 1 theinternal energy departure becomes:

u - U” = $(a-a’T) + b’T (2 a
+ b5[ v(3c+b) - bc + c2 - 28 (3c+b&
s
+bBl I (52)

Similarly for case 2 we find:

U-C’= g(a-a’T) + b’T (s + _!t[ t3c+b)

‘ - T + c2- 28 + (3cit)b I ) (53)

A.5 fnthalpy Departure

Enthalpy departure is then given by the folfowing relationship for both cases:
H-H’=Pv-RT+(U-U’) (54)

H - H’ = RT(Z-1) + (U - LP) (55)

A.6 Entropy Departure

For both cases the entropy departure is given by the following relationship:

s-s*+LRln,$, (55)

A.7 laochark Heat Ca/.wclty

Constant volume heat capacity is defined to be:

c,-c”+=+J-iJ’), (57)

For case 1 this yields the following equatbn:

Cv - C,’ = &‘(a-a’T) - h,a”T - &(a-a’+ + $)]

$] v(3c+b) - ; + c2 - 2dz (3c+b)k, *

+ T1)

r y _ s+ v(3c+b)-p2-2ff + (3c;;)& l
+ b’T(s - - + -$a’-
($ b%

b’(v-c)(&2cv-c*+&~ W
&a
W
where the following defined constants apply:
3 zT’=
 127

5’ = -
aT
aT
= +e (6C + zg+s!$
(61)

The isochoric heat capacity departure for case 2 is exactly the same as given by Equation (58) except
that h, is replaced by kz and the following relationships apply:
8 = (-r)‘R

A.8 lsoberfc Ifea CafJEclty

Isobaric heat capacity departure is given by the following equation:

(64)

where:

(PiaT), is given by Equation (50)

-RT a(2v+b+cl
wwr = (v-b)’ + g (65)
The value of C, - C,’ which is used in Equation (64) depends upon whether case 1 or case 2
applies. Also by utilizing the relationship:
Cp’-C;=R (66)

we can develop an expression for C, given as :

(67)

A.9 Thetmodynamlc speed of sound

Thermodynamic speed of sound is calculated from the following relationship:

where:
M I molecular weight

A.10 Joule-Thomson Coefficient

The Joule-Thomson coetfttiem ts given as:

T(&=IaT), + qamav),
p= -
cp(aptav),
128

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Fluid State, Carbon Dioxide. Pergamon Press, New York.
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