Fluid Phase Equilibria, 34 (1987) 203-218 203

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

EFFECT OF CUBIC EQUATIONS OF STATE ON ENTHALPY

DEPARTURE CALCULATIONS

YOSHINORI ADACHI and HIDEZUMI SUGIE

Center of Information Processing Education, Nagoya Institute of Technology,
Nagoya 466 (Japan)
(Received July 1, 1986; accepted in final form December 29, 1986)

ABSTRACT

Ada&i, Y. and Sugie, H., 1987. Effect of cubic equations of state on enthalpy departure
calculations. Fluid Phase Equilibn‘a, 34: 203-218.

The dependence of the enthalpy departure calculation on a cubic equation of state is

analyzed for three sets of cohesion and covolume parameters, and the difference between the
calculated results for two cubic equations of state with the same cohesion parameter is shown
to be expressed by a linear function of the system pressure and the covolume parameters.
The dependence of the internal energy departure calculation on the attractive term is
analyzed and is evaluated in terms of the cohesion parameter.
Finally, the enthalpy departure calculation is found to be mainly controlled by the
covolume parameter, and an equation of state which gives good PVT predictions is found to
be a good choice for the enthalpy departure calculation.

INTRODUCTION

Enthalpy values for pure components and mixtures are important in

process design calculations. In a previous study (Ada&i and Sugie, 1987),
we showed that the heat of vaporization calculation was only controlled by
the cohesion parameter of a cubic equation of state (E-OS). However, there is
no systematic study of the effect of a cubic EOS on the enthalpy calculation.
This study concerns the effect of a cubic EOS upon the enthalpy depar-
ture calculation.

CUBIC EOS USED IN ANALYSES

The cubic EOS used in the analyses has the following generalized form

0378-3812/87,‘$03.50 0 1987 Elsevier Science Publishers B.V.

204

where a, bl, b2 and b, are constants, and a is the only quantity which is
temperature dependent. At the critical point, eqn. (1) satisfies the critical
constraints, (i3P/iW) = 0 and (a2P/W2) = 0. Then, fixing a and b, at the
critical point, b2 and b3 are obtained from these constraints.
In the subcritical region, a is obtained from the vapor pressure Ps, and its
temperature derivative da/dT is obtained from d PS/dT and the Clapeyron
equation which is expressed as follows

AH=AVT+g (2)
Therefore, if we calculate AV from eqn. (l), the da/dT value is obtained as
follows:
in the case of b, # b,

a- T(da/dT)In(Vv-b2)(V1-b,)
(3)
AH=PSAv+

b2- b3 (VI-b,)(V”-b,)

therefore, from eqn. (2)

da
-=;-AV (4

andinthecaseof b,=b,= -c
a - T(da/dT)
AH = psAv+ (V’ + c)( J7l + c) Av (5)
therefore
da
-=-- a dP”
-_fj(vv + c)( v’ + c)
dT T dT
In this study, Ps and dPS/dT are calculated from the Gomez-Nieto and
Thodos (1978) equation.
In the supercritical region, a and da/dT are calculated by extrapolation
using the Soave temperature dependence (Soave, 1972). The Soave tempera-
ture dependence is expressed as follows

u = a,[1 + m(l - p)]* (7)

and its temperature derivative is expressed as

T-g = -nq0*5/[1 + M(1 - TO.‘)]

The m value is obtained from an exact fit to Ps at T, = 0.9, and using eqns.
(7) and (8), a and da/dT are calculated at the temperature of interest.
 205

ENTHALPY DEPARTURE EQUATION OBTAINED FROM CUBIC EOS

Using the cubic EOS expressed by eqn. (l), we obtain the enthalpy
departure equation for pure components and mixtures as follows:
in the case of b2 f b3
a - T(da/dT) ln V- &
H-HO-RT(Z-l)+
b2 - b3 V- b3

and in the case of b, = b, = -c

a - T(da/dT)
H-HO =RT(Z-l)-
v+c
From the previous study (Ada&i and Lu, 1985), the terms, b2 - b3,
V - b,, V - b, and V + c, are functions of the cohesion parameter u only at
the specified state condition for pure components and mixtures (a linear
mixing rule is used for the covolume parameters bk). Therefore, the second
term of eqn. (9) or (10) is also a function of a only, and the EOS with the
same cohesion parameter gives the same second term value, However, the
first term is not a function of a only and differs from EOS to EOS used.

EFFECT OF CUBIC EOS ON ENTHALPY DEPARTURE CALCULATION

As indicated in the above section, using the &a.r mixing rule for b,,
mixtures can be treated in the same way as pure components. Therefore, in
the following analyses, we are only concerned by the pure component case.
Equations (9) and (10) can be modified in the following reduced forms,
respectively

H-H’ A - T,A’
=T,(Z-l)+T, B B In-ZmB2
,.=H,+H,
-
RT, 2- 3 3

and

H-H’ A - T,A’
=T,(Z-1)-T, z+c =H,+H, 02)
RT,
where A = aP/R2T2, A’ = (da/dT)P/R2T2, B, = b,P/RT, B3 = b3P/RT,
and C = cP,‘lkT.
To examine the effect of an EOS on the enthalpy departure calculation,
we chose methane as the representative substance and VDW (van der Waals,
1873) and PR (Peng and Robinson, 1976) EOS’s as the representative cubic
EOS.
206

Comparison between same cohesion parameter EOS’s

First of all, we compare the enthalpy departures derived from two EOS’s
with the same cohesion parameter. In this case, the second term (H,) values
of eqn. (11) or (12) remain the same. Therefore, the difference between the
enthalpy departures (SH) comes from the first term (Hi) only. Using the
fact that V- b, is a function of a only (Ada&i and Lu, 19851, we express
6H as follows

P
= -[{(~-%x1
RT,
- (v- ~I)EOS,} + {(b&S, - (b&oS2}]

where f& = b,P,/RT,. Equation (13) is a linear function of pressure, thus

the absolute value of 6H is small in the low-pressure region and becomes
larger with increasing pressure. Furthermore, it is independent of tempera-
ture and kind of substance.

Comparison between different cohesion and covolume parameters EOS’s

Secondly, we examine the enthalpy departures derived from VDW and

PR EOS’s which have different sets of cohesion and covolume parameters.
The Oa,( = a,P,/R!@)value of VDW EOS is 0.421875 and that of PR EOS
is 0.45724, and the S&;r~alue of VDW EOS is 0.125 and that of PR EC% is
0.0778. Since the ti,= values are not the same, SW depends on both HI and
Hz of eqn. (11) or (12).

Difference between the first terms

At low temperature, the volume prediction by a cubic EOS is strongly
related to the &,, value (Ada&i et al., 1985). Therefore, the difference
between the first terms (6H,) can be roughly estimated by eqn. (13), i.e.
P,(O.125 - O-0778), and is given in Table 1.

Difference between the second terms

The difference between the second terms (6H,) is also shown in Table 1.
Even though the Qac values of VDW and PR EOS’s are quite different, S&
is small except near the critical isotherm. Comparing SH, with 6H,, it can
be concluded that SH, is dominant in 8H.
From the above analyses, SH can be estimated by 6H, and can be much
more roughly estimated by eqn. (13).
TABLE 1
Differences between enthalpy departures derived from two different sets of cohesion and covolume parameters in VDW type EOS: EOS,
(QaC= 0.421875 and Cl,, = 0.125) Bnd EOS, ( fJac= 0.45724 and Qb, = 0.0778)

T, p,
0.10 0.20 0.40 0.60 0.80 1.00 1.50 2.00 5.00 10.0
-1
w
0.40 0.005 0.010 0.020 0.030 0.040 0.050 0.074
,‘l 0.099 0.245 0.486
0.60 0.005 0,010 0.021 0.031 0.041 0.052 0.077 0.102 0.252 0.495
0.80 0.008 0.015 0.022 0.033 0.044 0.055 0.081 0.107 0.259 0.505
1.00 0.008 0.016 0.032 0.047 0.061 0.071 0.089 0.115 0.269 0.515
1.20 0.008 0.017 0.033 0.048 0.063 0.077 0.108 0.131 0.279 0.526
1.40 0.008 0.017 0.033 0.048 0.063 0.078 0.111 0.141 0.290 0.536
2.00 0.008 0.016 0.031 0.047 0.061 0.076 0.111 0.144 0.314 0.563
4.00 0.007 0.013 0.026 0.039 0.052 0.065 0.096 0.127 0.302 0.570

SH,
0.40 - o.aoo - 0.001 - 0.002 - 0.002 - 0.003 -0.004 - 0.005 -0.007 - 0.014 - 0.021
0.60 - 0.006 - 0.007 - 0.009 - 0.010 - 0.012 - 0.013 - 0.016 -0.019 - 0.032 - 0.043
0.80 - 0.001 - 0.002 - 0.035 - 0.039 - 0.043 - 0.046 - 0.052 - 0.057 - 0.077 - 0.091
1.00 - 0.001 - 0.003 - 0.006 - 0.009 - 0.013 - 0.017 - 0.075 - 0.087 - 0.120 - 0.142
1.20 - o.oM - 0.000 - 0.001 - 0.001 - 0.001 - O*ool - 0.004 - 0.017 - 0.066 - 0.086
1.40 0.000 0.001 0.002 0.003 0.004 0.006 0.008 0.009 - 0.020 -0.040
2.00 0.002 0.003 0.006 0.009 0.012 0.015 0.022 0.028 0.052 0.059
4.00 0.002 0.005 0.009 0.013 0.018 0.022 0.032 0.042 0.094 0.160

SH
0.40 0.005 0.009 0.018 0.028 0.037 0.046 0.069 0.092 0.232 0.466
0.60 -0.001 0.003 0.012 0.021 0.030 0.038 0.061 0.083 0.220 0.453
0.80 0.007 0.014 - 0.013 - 0.006 0.001 0.009 0.029 0.050 0.183 0.414
1.00 0.007 0.014 0.026 0.038 0.047 0.054 0.014 0.028 0.148 0.374
1.20 0.008 0.016 0.032 0.047 0.062 0.076 0.104 0.114 0.212 0.440
1.40 0.009 0.017 0.035 0.051 0.068 0.084 0.120 0.150 0.270 0.496
2.00 0.009 0.019 0.037 0.056 0.073 0.091 0.133 0.172 0.365 0.621
4.00 0.009 0.018 0.035 0.053 0.070 0.087 0.129 0.169 0.397 0.730
5

._ ._ ._ _. .- - . - - -.. ._ - - .-
TABLE 2
Differences between enthdpy departures derived from EOS’s with the same covolume parameter (EOS,: tin.= 0.421875 and 51,, = 0.0778,
EOS,: OoC= 0.45724 and Q& = i&0778)

r, P,
0.10 0.20 0.40 0.60 0.80 1.00 1.50 2.00 5.00 10.0

6%
0.40 0.090 0.001 0.001 0.002 0.002 0.002 0.004 0.005 0.010 0.015
0.60 O.WB 0.001 0.002 0.003 0.004 0.004 0.006 0.008 0.016 0.024
0.80 0.003 0.006 0.003 0.005 0.006 0.008 0.010 0.013 0.024 0.034
1.00 0.003 0.007 0.013 0.019 0.023 0.022 0.018 0.021 0.033 0.044
1.20 O.OM 0.007 0.014 0.020 0.025 0.030 0.037 0.037 0.043 0.055
1.40 O.GQ4 0.007 0.014 0.020 0.026 0.031 0.041 0.047 0.054 0.065
2.00 0.003 0.006 0.013 0.018 0.024 0.029 0.040 0.049 0.078 0.091
4.00 0.002 0.004 UIo7 0.011 0.014 0.018 0.026 0.033 0.067 0.099

SH
0.40 -0.000 -o.ooo - 0.001 -‘E).WJl - 0.001 - 0.001 - 0.002 - 0.002 - 0.004 - 0.006
0.60 -0.006 - 0.006 - 0.007 - 0.007 - 0.008 - 0.009 - 0.010 - 0.011 - 0.015 -0.018
0.80 0.002 0.004 0.032 0.034 - 0.036 - 0_038 - 0.042 - 0.044 -0.053 - 0.057
1.00 0.002 0.004 0.007 0.010 0.010 -0.002 - 0.057 - 0.067 - 0.087 - 0.097
1.20 0.003 0.007 0.013 0.019 0.024 Q-029 0.033 0.020 - 0.023 -0.031
1.40 0.004 0.008 0.016 0.023 0.030 0_036 0.049 0.056 0.034 0.025
2.00 0.005 0.009 0.019 0.027 0.044 0.062 0.078 0.130 0.150
4.00 0.004 0.008 0.016 0.024 0.032 0.040 0.058 0.075 0.161 0.259
 209

Comparison between same covolume parameter EOS’s

Thirdly, we examine the effect of the covolume parameter b, on the

enthalpy calculation. For this purpose, VDW EOS is revised to have the
same !&, value as that of PR EOS, i.e. !&,, = 0.0778.
Because H, is a function of a only, SH, (between the revised VDW EOS
and PR EOS) is the same as SH, in Table 1.
Because 6H, is roughly estimated by eqn. (13), SH, is quite small, as
shown in Table 2. Furthermore, i3H, in Table 2 is about one-third of 6H, in
Table 1.
6H is also given in Table 2. Comparing 6H in Tables 1 and 2, 6H in
Table 2 is smaller by about half in the high-temperature region and much
smaller in the low-temperature region than SH in Table 1.

COMPARISON WITH THE LEE-KESLER METHOD

We analyze the accuracy of an EOS to predict the enthalpy departure. For

this purpose, the Lee-Kesler method (Lee and Kesler, 1975) is used to
generate data at 15 T, conditions from 0.40 to 4.0 and 10 P, conditions from
0.1 to 10.0 for a total of 150 points, because this method has been
recommended as the accurate estimation method of thermodynamic proper-
ties for normal hydrocarbons (Reid et al., 1977). Ten normal hydrocarbons,
i.e. methane to n-decane, are selected for comparison.

Effect of attractive term on internal energy departure

For VDW type EOS’s, the internal energy depends only on the attractive
term. Then, the comparison of the calculated internal energy with
Lee-Kesler’s data should be effective for examining the accuracy and
limitation of the attractive term.
The internal energy departure is obtained from H,, which is a function of
a only, at, the specified state condition. Therefore, the accuracy of the
internal energy prediction is evaluated by the SJ,= value. The results are
depicted in Fig. 1. Because the Soave expression incorrectly predicts a
minimum at a reduced temperature of (1 + l/m)2, an exponential-form
function, a = a,lOm(l-T,), proposed in the earlier article (Ada&i and Lu,
1984) is also investigated. The difference between the average absolute
deviations obtained from the two temperature expressions is about 0.01 at
most, and the effect of the existence of the minimum onthe internal energy
calculation is not so significant in the investigated temperature range.
The Q;2,cvalue of PR EOS gives better predictions than that of VDW
EOS. However, the difference between the average absolute deviations
obtained from VDW and PR EOS’s is not larger than 0.03.
 METHANE
/

not
Fig. 1. Effect of the cohesion parameter on internal energy departure calculations: ( -)
Soave temperature dependence; (- - - - - -) exponential-form temperature dependence.

Effect of covolume parameter on enthalpy departure

Because Hz is not much different from EOS to EOS, the accuracy to

predict enthalpy departure mainly depends on H,, indicating that the
enthalpy prediction is strongly related to the Pm prediction. Therefore,
using an EOS to predict PVT well, one can obtain a good enthalpy
departure prediction.
By the volume translation (Pkreloux et al., 1982), the ability of an EOS to
predict PVT can be improved. Because the volume translation is identical to
changing the !&I value, we analyze the effect of the !&,I value on the
enthalpy calculation.
Changing Q,, values from 0.055 to 0.125 for VDW EOS and from 0.055
to 0.10 for PR EOS, the average absolute deviations of the calculated
enthalpy departures are obtained and depicted in Figs. 2 and 3. The optimal
&,, value differs from substance to substance investigated. However, in
general, the tib, value around 0.08 gives fairly good predictions in both Figs.
2 and 3. Then, the &,I value of PR EOS, i.e. St,, = 0.0778, is found to be a
fairly good for calculation of the enthalpy departure.
Three cubic EOS’s, i.e. Q2,== 0.45724 and Gt,, = 0.0778 (PR EOS), G2,c=
0.421875 and S&, = 0.125 (VDW EOS) and SIac= 0.421875 and at,, = 0.0778
 211

0.05 0.10

.flbl

Fig. 2. Effect of the covolume parameter on enthalpy departure calculations. The cohesion
parameter is fixed to that of VDW EOS.

0.10

n.c=o.45724
- \

-1
METHANE

0.05

PROPANE

Fig. 3. Effect of the covolume parameter on enthalpy departure calculations. The cohesion
parameter is fixed to that of PR EOS.
TABLE3
Comparison between enthalpydeparturescalculated
by PR EOS and the Lee-Kesler method
Deviationin(H- H’)/RT,
2
r, p, N

0.10 0.20 0.40 0.60 0.80 1.00 1.50 2.00 5.00 10.0
Methane
0.40 -0.226 -0.227 -0.228 -0.231 -0.232 -0.234 -0.238 -0.243 -0.270 -0.314
0.50 -0.101 -0.102 -0.102 -0.103 -0.103 -0.104 -0.106 -0.107 -0.116 -0.133
0.60 -0.026 -0.026 -0.025 -0.024 -0.023 -0.022 -0.021 -0.019 -0.011 -0.003
0.70 -0.038 -0.028 -0.025 -0.022 -0_019 -0.017 -0.010 -0.004 0.023 0.053
0.80 -0.017 -0.039 -0.078 -0.070 -0.063 -0.056 -0.042 -0.030 0.021 0.073
0.90 -0.005 -0.011 -0.028 -0.139 -0.115 -0.095 -0.059 -0.034 0.053 0.133
1.00 0.002 0.004 0.006 0.006 -o*cKKl -0.183 -0.116 -0.056 0.091 0.205
1.10 0.005 0.010 0.020 0.028 0.033 0.032 -0.047 -0.085 0.051 0.187
1.20 0.007 0.014 0.027 0.039 0.048 0.053 0.039 -0.012 0.019 0.164
1.30 0.008 0.015 0.031 0.043 0.054 0.064 0.068 0.047 0.010 0.141
1.40 0.008 0.017 0.032 0.046 0.057 0.067 0.081 0.077 0.020 0.122
1.50 0.008 0.016 0.031 0.045 0.058 0.069 0.087 0.091 0.041 0.111
2.00 0.007 0.013 0.026 0.037 0.047 0.058 0.077 0.093 0.114 0.120
3.00 0.004 0.006 0.012 0.018 0.024 0.029 0.040 0.051 0.095 0.139
4.00 0.001 0.002 0.005 0.006 0.009 0.011 0.016 0.022 0.053 0.105
n-Pentane
0.40 -0.053 -0_054 -0.056 -0.058 -0.060 -0.061 -0.066 -0.071 -0.098 -0.146
0.50 -0.087 -0.089 -0.090 -0.092 -0.093 -0.095 -0.100 -0.103 -0.128 -0.174
0.60 -0.019 -0.019 -0.020 -0.021 -0.021 -0.022 -0.026 -0.028 -0.046 -0.081
0.70 -0.092 0.008 0.009 0.010 0.010 0.010 0.011 0.013 0.009 -0.011
0.80 -0.042 -0_097 -0.030 -0.026 -0.021 -0.017 -0.008 -0.001 0.022 0.023
0.90 -0.017 -0.037 -0.090 -0.100 -0.079 -0.061 -0.027 -0.001 0.072 0.107
1.00 -0.004 -0.008 -0.017 -0_031 -0.055 -0.345 -0.158 -0.070 0.110 0.197
1.10 0.002 0.005 0.009 0.012 0.012 0.005 -0.079 -0.126 0.026 0.151
1.20 0.005 0.011 0.021 0.030 0.036 0.039 0.020 -0.034 -0.039 0.094
1.30 0.007 0.013 0.026 0.036 0.045 0.052 0.052 0.027 -0.061 0.039
1.40 0.007 0.015 0.027 0.039 0.048 0.056 0.063 0.053 -0.053 -0.007
1.50 0.007 0.014 0.027 0.038 0.047 0.055 0.065 0.062 -0.036 -0.040
2.00 0.004 0.008 0.015 0.020 0.025 0.030 0.036 0.038 -0.007 -0.094
3.00 -0.001 -0.002 -0.005 -0.007 -0.010 -0.013 -0.021 -0.028 -0.077 -0.154
4.00 -0.004 -00.006 -0.012 -0.019 -0.024 -0.030 -0.044 -0.056 -0.121 -00.198
TABLE 4
Comparison between enthalpy departures calculated by VDW EOS and the Lee-Kesler method

Deviation in (H - H’)/RT,

r, 4
0.10 0.20 0.40 0.60 0.80 1.00 1.50 2.00 5.00 10.0
Methane
0.40 - 0.23o - 0.236 - 0.247 - 0.258 - 0.269 - 0.280 ~ 0.307 - 0.335 - 0.502 - 0.780
0.50 - 0.105 - 0.110 -0.119 -0.129 -0.138 - 0.148 - 0.173 -0.197 - 0.344 - 0.595
0.60 - 0.025 - 0.029 - 0.037 - 0.045 - 0.053 -0.061 - 0.082 - 0.102 - 0.231 - 0.456
0.70 - 0.045 - 0.022 - 0.026 - 0.032 - 0.037 - 0.043 - 0.058 - 0.074 - 0.182 - 0.3R4
0.80 - 0.024 - 0.052 - 0.064 - 0.064 - 0.064 - 0.065 - 0.071 - 0.080 - 0.162 -0.340
0.90 - 0.012 - 0.024 - 0.053 - 0.118 - 0.097 - 0.083 - 0.063 - 0.056 - 0.098 - 0.246
LOO - 0.005 - 0.010 - 0.020 - 0.031 - 0.047 - 0.237 - 0.130 - 0.084 - 0.057 - 0.169
1.10 - 0.003 - 0.005 - 0.010 - 0.015 - 0.024 - 0.037 - 0.120 - 0.151 - 0.131 - 0.221
1.20 - 0.001 - 0.002 - 0.005 - 0.008 - 0.014 - 0.023 - 0.065 - 0.125 - 0.194 - 0.276
1.30 -0.001 - O.ool - 0.003 - 0.007 -0.011 -0.017 - 0.045 - 0.091 - 0.232 - 0.328
1.40 -O.ool - O.ool - Oslo3 - 0.006 - 0.010 - 0.016 - 0.039 - 0.074 - 0.249 - 0.374
1.50 -0.001 - OS@2 -0.004 - 0.007 - 0.012 - 0.017 - 0.037 - 0.067 -0.254 - 0.411
2.00 - 0.003 - 0.006 -0.011 - 0.019 - 0.026 - 0.033 - 0.055 - 0.080 - 0.252 - 0.501
3.00 -0.006 - 0.013 - 0.025 - 0.037 - 0.049 - 0.062 - 0.093 - 0.124 -0.302 - 0.570
4.00 - 0.008 - 0.015 ~ 0.030 - 0.046 - 0.060 - 0.076 -0.112 - 0.147 - 0.344 - 0.624

n-Pentane
0.40 - 0.058 - 0.063 - 0.074 - 0.086 - 0.097 - 0.107 -0.135 - 0.163 -0.329 - 0.609
0.50 - 0.092 - 0.097 - 0.108 -0.118 - 0.129 - 0.139 -0.167 - 0.193 - 0.356 - 0.633
0.60 - 0.020 - 0.025 - 0.035 - 0.044 - 0.053 -0.063 - 0.088 - 0.113 - 0.266 - 0.532
0.70 - 0.099 0.011 0.004 - 0.003 - 0.011 - 0.019 - 0.039 - 0.059 -0.196 - 0.446
0.80 - 0.049 -0.111 - 0.016 - 0.019 - 0.021 - 0.024 -0.035 - 0.048 -0.155 - 0.381
0.90 - 0.024 - 0.049 - 0.113 - 0.068 - 0.050 - 0.037 - 0.017 - 0.010 - 0.050 - 0.249
LOO -0.011 - 0.021 - 0.043 - 0.068 -0.101 - 0.399 -0.160 - 0.084 -0.018 -0.153
1.10 -0.006 - 0.010 -0.022 - 0.033 - 0.047 - 0.065 - 0.160 - 0.195 - 0.149 - 0.248
1.20 - 0.003 - 0.006 - 0.012 - 0.020 - 0.029 - 0.041 - 0.090 - 0.160 - 0.258 - 0.350
1.30 - 0.002 -0.004 - 0.009 - 0.016 -0.024 - 0.033 - 0.070 - 0.122 - 0.321 - 0.447
1.40 - 0.002 - 0.004 - o.oo9 - 0.015 ~ 0.024 - 0.033 - 0.065 - 0.108 - 0.350 -0.531
1.50 -0.oo2 - 0.005 - 0.011 - 0.019 - 0.027 - 0.037 - 0.068 - 0.107 - 0.362 -0.598 E
w
2.00 - 0.006 -0.013 - 0.025 - 0.039 - 0.053 - 0.067 - 0.106 - 0.146 - 0.404 - 0.775
3.00 -0.011 - 0.022 - 0.043 - 0.065 - 0.086 - 0.108 - 0.160 - 0.211 - 0.499 - 0.918
4.00 -0.013 - 0.024 - 0.047 - 0.072 - 0.094 -0.118 - 0.175 - 0.229 -0.533 - 0.970
TABLE5
Comparison between enthalpydeparturescalculated
by the revisedVDW EOS (a,== 0.421875 and P,,= 0.0778)and the Lee-Kesler
method
Deviationin(H-H')/RT, z
P
T, Pr
0.10 0.20 0.40 0.60 0.80 1.00 1.50 2.00 5.00 10.0
Methane
0.40 -0.225 -0.226 -0.228 -0.230 -00.231 -0.233 -0.237 -0.241 -0.266 - 0.309
0.50 -0.100 -0.101 -0.101 -0.101 -0.101 -0.101 -0.102 -0.103 -0.109 -0.123
0.60 - 0.021 -0.020 -0.018 -0.017 -0.015 -0.014 -0.011 -0.008 0.005 0.015
0.70 -0.041 -0.012 -0.008 -0.003 0.000 0.004 0.012 0.020 0.053 0.087
0.80 -0.020 -0.043 -0.046 -0.036 -0.026 -0.018 -0.000 0.014 0.074 0.131
0.90 -0.007 -0.015 -0.034 -0.090 -0.060 -0.036 0.008 0.038 0.138 0.225
1.00 -O.OCKI -0.001 -0.001 -0.003 -0.010 -0.181 -0.059 0.011 0.179 0.302
1.10 0.002 0.005 0.009 0.013 0.014 0.010 -0.050 -0.057 0.104 0.250
1.20 0.003 0.007 0.014 0.020 0.024 0.024 0.006 -0_031 0.042 0.195
1.30 0.004 0.008 0.016 0.022 0.027 0.030 0.025 0.003 0.003 0.143
1.40 0.004 0.009 0.016 0.023 0.027 0.031 0.032 0.021 -0.014 0.097
1.50 0.004 0.008 0.015 0.021 0.026 0.030 0.033 0.028 -0.019 0.060
2.00 0.002 0.004 0.007 0.009 0.012 0.014 0.015 0.015 -0.016 -0.030
3.00 -0.001 -0.003 -0.006 -0.009 -0.012 -0.015 -0.022 -0_029 -0.067 -0.099
4.00 -0.004 -0_006 -0.011 -0.018 -0.023 -0.029 -0.042 -0_053 -0.108 -0.153
n-Pentane
0.40 -0.053 -0.054 -0.055 -0.058 -0.059 -0.060 -0.064 -00.068 -0.093 -0.138
0.50 -0.087 -0.088 -0.089 -0.090 -0.091 -0.092 -0.096 -0_099 -0.120 -0.162
0.60 -0.015 -0.015 -0.016 -00.016 -0.016 -0.016 -0.018 -0.019 -0.031 -0.061
0.70 -0.095 0.021 0.023 0.025 0.026 0.028 0.031 0.035 0.040 0.025
0.80 -0.044 -oo.lol 0.003 0.010 0.017 0.023 0.036 0.047 0.081 0.090
0.90 - 0.019 -0.040 -0.094 -0.040 -0.013 0.010 0.053 0.085 0.176 0.222
1.00 -o.oM -0.012 -0.024 -0.040 -0.064 -0.342 -0_090 0.010 0.218 0.318
1.10 - 0.001 -0.001 -0.003 -0_005 -0.009 -0.018 -0.090 -0.101 0.086 0.223
1.20 0.002 0.003 0.007 0.009 0.009 0.006 -0_019 -0.066 -0.023 0.121
1.30 0.003 0.005 0.010 0.012 0.014 0.014 0.001 -00.028 -0_086 0.024
1.40 0.003 0.005 0.009 0.013 0.014 0.014 0.006 -0.014 -0.114 -0.060
1.50 0.003 0.004 0.007 0.010 0.011 0.010 0.003 -0.013 -0.126 -0.127
2.00 -0.002 -0.003 -0.006 -0.011 -0.016 - 0.020 -0.035 -0.052 -0.169 -0.304
3.00 -0.006 -0.013 -0.024 -0.037 -0.049 -0.061 -0.090 -0_117 -0.264 -0.447
4.00 -0.008 -0.015 -0.029 -0.044 -0.057 -0.071 -0.104 -0.135 -0.297 -0.498
 215

(revised VDW EOS), are also investigated to see the effect of the covolume
parameter on the enthalpy calculation. The calculated enthalpy departures
for 10 normal hydrocarbons are compared with Lee-Kesler’s data and the
results of methane and n-pentane are shown in Tables 3-5. In Tables 3 and
4, the deviations obtained from PR EOS and from VDW EOS are quite
different from each other, especially in the high-pressure region. Comparing
the deviations obtained from the revised VDW EOS in Table 5 with those in
Table 3, the deviations are fairly close to each other, especially in the

TABLE 6
Comparison of calculated internal energy and enthalpy with Lee-Kesler method

Substance Average absolute deviation

(U - iYO)/RT, (H - @>/RT,
EOSl EOSl EOS, EOSl EOS, EOS,
Soave temperature dependence

Methane 0.0507 0.0507 0.0537 0.1176 0.0544 0.0634

Ethane 0.0450 0.0450 0.0369 0.1054 0.0493 0.0453
Propane 0.0477 0.0477 0.0364 0.1085 0.0509 0.0416
n-Butane 0.0537 0.0537 0.0409 0.1165 0.0561 0.0435
n-Pentane 0.0599 0.0599 0.0493 0.1322 0.0611 0.0474
n-Hexane 0.0693 0.0693 0.0511 0.1255 0.0687 0.0494
n-Heptane 0.0757 0.0757 0.0582 0.1392 0.0741 0.0541
n-Octane 0.0963 0.0963 0.0767 0.1509 0.0930 0.0710
n-Nonane 0.1309 0.1309 0.1041 0.1713 0.1244 0.0958
n-Decane 0.1759 0.1759 0.1465 0.2071 0.1672 0.1349

overall 0.0805 0.0805 0.0654 0.1374 0.0799 0.0646

Exponential-form temperature dependence

Methane 0.0572 0.0572 0.0593 0.1161 0.0601 0.0655

Ethane 0.0495 0.0495 0.0422 0.1047 0.0527 0.0493
Propane 0.0502 0.0502 0.0409 0.1080 0.0526 0.0456
n-Butane 0.0549 0.0549 0.0436 0.1159 0.0563 0.0463
n-Pentane 0.0592 0.0592 0.0508 0.1314 0.0592 0.0458
n-Hexane 0.0666 0.0666 0.0517 0.1240 0.0656 0.0490
n-Heptane 0.0714 0.0714 0.0578 0.1369 0.0697 0.0520
n-Octane 0.0918 0.0918 0.0758 0.1480 0.0890 0.0681
n-Nonane 0.1234 0.1234 0.1015 0.1662 0.1176 0.0913
n-Decane 0.1665 0.1465 0.1417 0.1999 0.1581 0.1285

Overall 0.0791 0.0791 0.0665 0.1351 0.0781 0.0644

EOS,: iJaC- 0.421875 and ii&, = 0.125 (VDW EOS).

EOS,: iI,== 0.421875 and Q,, = 0.0778 (revised VDW EOS).
EOS,: GaC= 0.45724 and Qg, = 0.0778 (PR EOS).
216

low-temperature and pressure region. The average absolute deviations ob-

tained from these three EOS’s are compared in Table 6. Using the same
covolume parameter as that of PR EOS, the results obtained from the
revised VDW EOS are fairly close to those from PR EOS. This indicates
that the covolume parameter is a controlling quantity for the enthalpy
departure calculation. The comparison betken the two temperature depen-
dences is also shown in Table 6, and the results do not strongly depend on
the type of the expressions.

CONCLUSION

The difference in the enthalpy departures derived from the cubic EOS’s is
evaluated for the three cases and the following conclusions are obtained.
The difference between the enthalpy departures obtained from two EOS’s
with the same cohesion parameter is expressed by a linear function of the
system pressure and the covolume parameters. The difference resulting from
different cohesion and covolume parameters EOS’s is not expressed analyti-
cally, but is roughly estimated by the system temperature and the calculated
compressibility factors, and is more roughly estimated by the system pres-
sure and the covolume par&meters. The difference obtained from two EOS’s
with the same covolume parameter is fairly small, indicating that a control-
ling quantity of the cubic EOS in the enthalpy departure calculation is the
covolume parameter.
From the analyses of the effect of cohesion and covolume parameters on
the enthalpy and the internal energy calculations, the internal energy calcu-
lation is found to be only controlled by the cohesion parameter, and the
enthalpy calculation is found to be mainly controlled by the covolume
parameter and to be related to the PI/T prediction. Finally, a cubic EOS
which gives good PVT predictions is found to be able to predict enthalpy
departures well, and PR EOS is a good choice for this purpose.

LIST OF SYMBOLS

aP/R2T2
(da,‘dT)P/R2T2
cohesion parameter
b,P/RT, k = 1, 2, 3
covolume parameter
cP/RT
covolume parameter
enthalpy
the first term in eqn. (11) or (12)
 217

Hz the second term in eqn. (11) or (12)

m constant in the Soave expression
P pressure
R universal gas constant
T temperature
U internal energy
V molar volume
Z compressibility factor = PV/RT

Greek letters

52 a,PJR2TC2
s2;; bkPJRT,
A difference between vapor and liquid phases
8 difference between EOS, and EOS2

Superscripts

0 ideal gas state

1 liquid phase
S saturated value
V vapor phase

Subscripts

C critical value
r reduced value

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