ABSTRACT

Densitydependent local composition (DDLC) mixing rules (Whiting and
Prausnitz, 1981, 1982 and Mollerup, 1981) offer great promise to extend
equations of state to highly nonideal mixtures. In this work we investigate
various aspects of the DOLC concept and offer two useful forms. All
development is done with the PengRobinson (1976) equation of state, but the
results have general applicability.
INTRODUCTION
Practical models to describe phase equilibrium can be divided into two
broad categories: equations of state and activitycoefficient models.
Equations of state have been successfully applied to mixtures containing
,nonpolar and slightly polar components at all conditions of engineering
interest, including the critical and retrograde regions. On the other hand,
the mathematical flexibility of activity coefficient models has been
considered necessary to model systems which exhibit high liquidphase
nonideality. The activitycoefficient approach works well at low reduced
temperatures where the liquid phase is relatively incompressible and up to
moderate pressures. Serious problems arise when these bounds are violated.
,Further, the use of different models for the various phases precludes the
correct description of mixture critical points. Additional problems arise for
supercritical components (Abrams, et al., 1975). The equationofstate
approach does not inherently suffer from these limitations and thus it would
be very valuable to develop equations of state with the mathematical
flexibility to describe complex mixture behavior.
Recent research in equations of state has focussed on the mixing rules as a
promising way to achieve mathematical flexibility through a semitheoretical
development. Vidal (1978) has shown that the standard mixing rules used with
the Soave (1972) and PengRobinson (1976) equations of state are very similar
to regular solution theory and thus inadequate for "chemical" systems.
Further, Huron and Vidal (1979) have suggested improvements to the standard
mixing rules by applying the ideas of NRTL model (Renon and Prausnltz, 1968)
to the excess Gibbs energy of the Soave equation. The results are promising
but the Huron and Vidal model does not meet the important lowdensity 1 imit.
This has been pointed out by Mollerup (1981) and Whiting and Prausnitz (1981,
1982); these investigators have separately proposed a physically appealing
model to account for mixture nonideality: densitydependent local composition
(DDLC) theory.
In this work we have investigated densitydependent localcomposition
theory as applied to the popular PengRobinson (PR) equation of state. The
standard PengRobinson equation provides a very good description of
asymmetric, nonpolar systems but the DDLCPR model proposed by Mollerup (1981)
.can be inaccurate by up to 34 orders of magnitude for highly asymmetric
systems. Noting this, we have adopted a modlficatlon of an idea proposed by
Dimitrelis and Prausnitz (1982). The new model enables improved correlations
of a wide variety of complex mixtures. Our proposed DOLC model (along with
the other recently proposed forms) could prove to be too expensive in computer
time for systems with a large number of components. Thus we propose a
truncated version of the theory which, however, retains several attractive
qualities.
a
P=RT_ (1)
vb v(v+b) + b(vb)
b = 0.07780 R Tc/Pc
a = ace(T)
a = 0.45724 R=T,=/P,
C
below:
a = I E xixjaji (6)
ij
b = Z xibi (7)
i
a.. is given by the usual combining rules which include the pair dependent
biiary parameter kji
Lx a /q E
1 j j ji ji ji
P=RT_
zxq (9)
vb v(v+b) + b(vb) i i i 1 x. E..
J J'
j
RT
Aa =   Z xiqian BXjEji (13)
II. i j
[I
a
A =  Zxiqi Exjaji/qji
FV
i j
I I
r 1 Q
 2xiqi Exjafji/qZji  (Exjaj /qji)=  Fv2  .._._ (14)
i j j 2RT
\ r'
v+
In eqn. (14) we have used the simp ifying notation,
1
1 (1 + $ 2)b
Fv e  en (IS)
2$b Iv + (I 4)b
L J
It is interesting to note that the first term of eqn. (14) has exactly the
same functional dependence as the standard or VDW1 PengRobinson equation of
state. (A minor difference arises in the ij combining rule when qi # q., but
this could be absorbed by an appropriately chosen binary parameter, kji. ; To
fix ideas, we define the first term of eqn. (14) as the "equivalent" VDW1
contribution and lump all the remaining terms into the "asymmetric" or
"nonconformal" contribution.
It is illustrative to compare the fugacity coefficients of eqn. (13) with
those of its equivalent VDW1 form. Due to the complexity of the equations,
we only show the comparison for a binary with component 1 at infinite
dilution.
_!I
01
VDW1
1
= 9 2 1)  (16)
95
a12 a22 1
where, X =
The right

[ 912
 
qz d
side of eqn. (16)

RT
Fv
coefficient is reduced from its VDW1 value. (The opposite effect is obtained
for negative values of 0~. However, only positive values of (I are
physically meaningful.)
In general, it can be shown that the local composition effect reduces the
Helmholtz energy of a system at fixed T, V, g. This is a qualitatively
correct result since the DDLC configuration should be more favorable than its
equivalent VDW1 form.
q+y o.b
0.0 0.2
x(t&aM) OS6
10
/
k
$;
s 0.1:
U.H

 xiq=ro___
__

_,/H
,/
#H
_I All lx%
0.01
:__//
,
u. 40
I 1 I
t*;%l
I
0.0 0.2 0.4 0.8 0.8
%(Methano)
ei
i VOW~. q=l (DATAWITNIN 10%)
1 __
_ LC.qrlO _____c
u. q=s __ 
__
9
I l.c. q*o All u
,,i _
I
0.0 0:2 0:s 0.k
x(&a"*)
by Dimitrelis and Prausnitz (1982) who further point out that models analogous
to eqn. (9) make the rather stringent assumption that local compositions
Inevitably occur In the jl pair interaction whenever ai/qi # aj/qj. They
have proposed that local composition effects are not caused when ji
interactions are different from ii but rather when ji are different from some
a a0 aEX
U U + u..
ji = ji 31
a0 a FV
U (1  kji)  (19)
ji =_._._
al/T T I VP!.!
aEX a FV
= ~ (dji)  (20)
"ji
al/T T I V,N
a0 a0
U = E Z xjxj uji (21)
ij
aEX aEX
U = B Xrqi x ji j< (22)
i j
99
Eji
where = x.  (23)
'ji J
X 'k Eki
k
1 (24)
1 (25)
_a RT
A =  L E xixj (aiaj)'f2 (1  kji)Fv   X xiqi rn I: xj Eji
ij cri [j
aNC
a
A =  a Fv   Fvz (26)
2RT
NC
where a is given by the standard PengRobinson form (eqns. 6 and 8) and a ,
the NonConformal term, is given by
The parameters tii are the lumped contribution of all the nonconformal
effects. Note thatt is not symmetric (tji # tij) and thus the model has 3
parameters per binary pair; the third parameter is kji.
The truncated model defined by eqns. (6, 8, 26, and 27) may be derived by
expanding eqn. (25) analogously to eqn. (14) and retaining only the first
I
aNC
nonconformal term. Denoting this term as A we obtain,
1
aNC 1 2 P z
A = Zxiaci xj dji  (z xj dji) F, (28)
2RT i j
Notice that 01 and the qs and as have been absorbed in the ds, This does
not affect the composition dependence since only the first nonconformal term
Is used. Further, the temperature dependence of a (eqns. 3 and 5) has been
removed. This has facilitated good representation of data over a wide
temperature range with temperatureindependent parameters (e.g.,
waterhydrocarbon systems).
101
Equations (28) and (29) always give a negative contribution to the total
Helmholtz energy. This is physically correct but it could restrict the
Ref. Temp. Pressure Mix Rules Parameters %Kl max* XK2 max %Kl avg %K2 a"g
(OC) (Atml k d d
12 21 12
Methanol(l)
Benzene(2) Naga ta 60.876.7 1.0 vow1 0.10 57.0 62.1 17.1
1969 LC 0.61 0.17 7.0 14.3 3.0
Methanol(l)
Carbon Dioxide(P) Ohgak i 2540 5.780.0 VDW1 0.06 14.2 27.0 14.8
1976 LC 0.23 0.37 4.1 22.5 2":: 8.0
Acetone(l)
Water(2) Griswold 100 1.13.6 VDW1 0.23 49.6 22.6
1952 LC 0.35 0.02 :::: 29.7 10.6
Isobutylene(l)
Methanol(2) Churkin 50 3.16.1 VDW1 0.04 33.0 16.9 23.9
1976 LC 0.0 0.59 1.6 2.5 8.5

15
1,
A
X
x (Methanol)
Fig 5. Comparison of new LC model (eqn. 25) with experimental data (Nagata,
1969).
Fig 6. Comparison of new LC model (eqn. 25) and VI@1 form with experimental
data (Nagata, 1969).
TABLE 2
1 2 3
System REP Temp Mix Rules Parameter %l avg w avg
0
c k k d d d
12a 12b 21a 12a 12b
1Butanol(l)
Water(e) Hill 580 VDW1 0.18 49.1 26.7
1926 LC 0.1 0.05 0.05 0.14 1.0 0.7
Benzene (l)
Water(e) Tsonopoulos 10200 ZW' 0.08 132.1 2691.1
Hexane(1)
Water(Z) @clpoulos 10200 VDW1 0.24 "X >10000
LC 0.15 0.24 2.39 0.15 12.0
LCItr) 0.48 0.0 1.35 16:7 12.9
IHethylnaph
thalene(l)
Water(P) 1982
Brady 37277 ZW' :z 0.16 1.16 0.21 23.2
1036.0 '"Z
i_C(tr) 0:31 0.01 1.36 3.5 618
1
d =d + d
12 12a T 12b
2
Average absolute deviation in calculated mole fraction of component 1 in liquid phase 2.
3
Average absolute deviation in calculated mole fraction of component 2 in liquid phase 1.
4
For LC(tr), read "de as et".
106
0.1
0.01
0.001
0.0001
o.oooo1
van der Waals onefluid and local composition (including the truncated) mixing
rules. Table 2 presents average absolute deviations in calculated mole
fractions for these methods. One parameter was fit to the van der Waals
mixing rule, four parameters (to include temperature dependence) were fit to
the local composition and three to the truncated local composition mixing
rules. Although the overall improvement is substantial with four local
composition parameters, it should be noted that temperature dependence in the
and d12 parameters must be correlated for an accurate fit. In this
k12
regard, the local composition equation of state is analogous to the current
local composition activity coefficient models. It should be noted that even
with four binary parameters (also typically used with the UNIQUAC activity
coefficient model) the local composition method provides a significant
improvement beyond methods like Peng and Robinson (1980) for correlation of
liquidliquid equilibria. These methods use separate interactlon parameters
(temperature dependent) for each phase. No ambiguity or discontinuity arises
with the local composition method at a critical end point where (any) two
phases merge.
The results with the truncated local composition model are particularly
encouraging since the (three) interaction parameters are not temperature
dependent. Figures 7 and 8 present a comparison of model calculations against
experimental data. Note that tZII for water in the hydrocarbons are nearly
zero. A twoparameter fit would yield about the same accuracy.
CONCLUSION
In this work we have investigated the densitydependent local composition
theory as applied to the PengRobinson equation of state. We propose two
useful models to account for nonconformal or asymmetric effects. The approach
is also applicable to any other equation of state derived from the generalized
van der Waals partition function.
ACKNOWLEDGEMENT
The authors wish to thank Professors J. M. Prausnitz and F. P. Stein and
D. Dimitrelis for helpful discussions.
The work reported in this paper was sponsored in part by the International
Coal Refining Company and the United States Department of Energy under
Contract DEAC05780R03054.
107
List of Symbols
Helmholtz Energy
PengRobinson parameter, eqn. 1
Second Virial Coefficient
PengRobinson parameter, eqn. I
Binary Interaction Parameter
Binary Interaction Parameter
Surface Area Size Parameter
Number of Moles
Pressure
Gas Constant
Temperature
Binary Interaction Parameter
Volume
Molar Volume
Mole Fraction
Non Randomness Parameter
Temperature Dependent Pure Component Parameter, eqn. 5
Fugacity Coefficient
Superscipts
a Attractive Contribution
Infinite Dilution
Subscripts
i Component i
i Comoonent 5
i ComPonent k
C Critical
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