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NEW SRK PARAMETER MIXING RULES

Research · September 2015

DOI: 10.13140/RG.2.1.3941.6806

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 Extension of the classical mixing rules of the Redlich-
Kwong equation of state

Giorgio S. Soave
Via Europa 7, I-20097 San Donato Milanese, Italy

E-mail: Giorgio_Soave@virgilio. it

Abstract
The classical quadratic mixing rules of the Redlich-Kwong equation of state are shown to be applicable with

success to the calculation of the VLE of systems containing polar components also, if pure-component vapor
pressures are enforced. A two-parameter extension of the classical mixing rules is proposed, which retains the
quadratic dependence on composition of the second virial coefficient and, unlike similar models, gives a correct

trend of liquid densities.

Keywords: Equation of state; Cubic; Mixing rules; Vapor-liquid equilibria

l.Introduction

The cubic equation of state proposed originally by Redlich and Kwong []:
P*
RTa (1)
v-bv(v+b)
is now currently used in the form proposed by this author [2], with an improved law of
dependence on the temperature of the attractive parameter, which for pure compounds is
expressed by:
f-t
a(T) = a(T.)[ + m(l - JT/T" )J (2)
with: m = .480 +1.574lo -.T76a2 (3)
rrl being the acentric factor of the compound, and the following mixing rules of parameters:

a= Ifijij x,*,au = IIx,x,(1-ku).p,a, (4)

b=fx'b' (5)
i
The only data required are the critical constants and the acentric factor of each component,
plus one binary parameter ki; for each component pair, which can be taken as zero in a first
approximation, for pairs of non-polar components like in the hydrocarbon mixtures.
Due to its simplicity and the reduced information required, such model has found a wide
application to the calculation of vapor-liquid equilibria and thermodynamic properties of
systems formed by non-polar components, like hydrocarbons.
The diftrsed assumption that such model is not applicable in presence of polar
components, like e.g. organic oxygenated ones, is generally attributed to a deficiency of its
mixing rules, eqs. (4) and (5). That is not exact, as in fact the main source of inaccuracy lies in
eqs. (2) and (3), which are acceptable only for non-polar compounds, and even for them they
are only fairly accurate below the normal boiling point. It is easy to understand that, if pure-
component vapor pressures are calculated inaccurately, no mixing rule can treat correctly their
mixtures.
It is surprising to see that, when the attractive parameters are adjusted so as to reproduce
the components' vapor pressures, mixing rules expressed by eqs. (4) and (5) enable in most
cases a fair reproduction of experimental vapor-liquid equilibrium (VLE) data of many
systems containing strongly polar components. Examples are given in Figs. 1 to 4 and in the
first column of Table 1. In all cases the pure-component attractive parameters were fitted to
their experimental vapor pressures by the direct procedure described in [3].
For other systems (mainly those containing associating components like water and
alkanols) the classical mixing rules yield poor results and must be replaced by more flexible
ones, containing two adjustable binary parameters. Among the numerous proposals a simple
one is a logical extension of the classical mixing rules where the covolume also is treated as
quadratic in the composition:

o= = + du,[+) (6)
TTx,x,b' TT*,*,(1
Eq. (6) reduces to eq. (5) when d,j:0. Such rules preserve the quadratic law for the second
virial coefficient, which a condition for a correct treatment of highly unsymmetrical systems,
but they have a serious drawback: k1 in eq. (4) and d1i in eq. (6) are strongly cross-conelated,
so they tend to assume anomalous values, which can yield very inaccurate values of the liquid
density, as it is shown in Figs. 5,6; that could be expected fom the fact that the liquid volume
is close to the covolume and any deviation of it from the linear rule results into a similar
deviation of the liquid volumes.

Scope of this work was to find a simple expansion of the classical mixing rules which
obeys three conditions:
a) it can be reduced to the classical, one-parameter mixing rules
b) it preserves the quadratic dependence on composition of the second virial coeffrcient
c) it gives a correct (i.e., not far from linear) trend of the liquid volumes
2. The new mixing rules

Let us write the Redlich-Kwong equation in the form:

RT
P_ (7)
v-b v(v+c)
When compared to the previous form, the new one is based on the following assumptions:
1. For pure compounds the parameter c is still equal to the covolume b. As a consequence, all
parameter values and the law for the temperature dependence of the attractive parameter
remain unchanged.
2. The attractive parameter "a" holds a quadratic mixing rule:
u= II*iXjoù = lf x,xl(1 - ku)!6Jt (4)
rJ rJ
3. The covolume b in the repulsive term of eq. (7) holds a linear mixing rule:
b: lx,b, (5)
i

so as to ensure a correct composition dependence of the volumes of liquid mixtures.

4. A quadratic mixing rule is assumed instead for the new parameter c:
(8)
": Ilx,x,cu
ij
 with:
lu, +u,l
c.,=(l+d,)l î | (e)
\2.)
As a particular case, when all d;; values aÍe zeto, c becomes equal to mixture's b as well
and the new mixing rules are reduced to the classical ones. In the more general case d;; is a
second adjustable parameter, by which VLE data can be reproduced with greater accuracy.
The new mixing rule for c does not affect that of the second virial coefficient: B:b-a./RT,
which remains quadratic in the composition.
The presence of a parameter c which is in general different from the covolume requires to
rewrite the cubic equation in a more general form. Introducing the usual adimensional
parameters: Z:PviRT, A:aPlR2T2, B:bP/RT and similarly: C:cP/RT, the cubic equation
takes the more general form:
z3 -22(l+B-c)+ z(A-C-BC)-AB=0 (10)
The procedure for its resolution is that used for all cubic equations and needs not be
described here.
Finallv" the coefficients in a mixture are given

rnq, =
\,r-r) - tn(z-", -['+- r+.'p,{, . l)
(1 1)

I *,t, 1

Note that when dil:0 then c:b and 2J I: so the last term of eq. (1 1) vanishes
c - ?,
and eq. (11) reduces to the expression of the R-K EOS:
I F *,u,,
" I
-rr \g-1\-tn(z-B)-lri
rnq, =
b'- a -+bJB
l+r"[r.]l
\ z)
l.
3. Application to VLE data correlations

The proposed mixing rules, eqs. (4), (5), (8), (9), were applied to the correlation of several
sets of experimental isothermal VLE data of systems containing polar components, comparing
the results to those obtained with the classical rules (i.e. assuming d,j:O) and with both a and b
quadratic in the composition, eqs. (4), (6). In all cases the pure-component attractive
parameters were adjusted so as to reproduce experimental their experimental vapor pressures.
The results are given in Table I for 25 systems and graphically in figs.l to 4 for 4 systems.
It can be seen that in many cases the classical mixing rules can reproduce fairly well the
experimental bubble pressures, while for strongly non-ideal systems, mainly those containing
associating components like water and alkanols, it was necessaly to extend the classical rules
to have acceptable results. That is particularly evident for a 'difficult' system like the 1-
propanoliwater one (figure 3).
 The two-parameter mixing rules expressed by eqs. (4),(6) gave slightly worse results than
those by the new mixing rules, tending to fail in case of strong non-ideality (see figure 3 in
particular). That was often associated to anomalous densities of the liquid phase, as it is
shown in the next section.

4. Liquid densities - discussion

Liquid densities were calculated for several liquid mixtures at bubble-point conditions,
using the same binary interaction parameters which best reproduced the experimental VLE
data. In order to enforce pure-component densities, a volume translation was introduced, as
proposed by Peneloux [4]. According to a common practice, and in order not to affect the
calculated VLE values, a linear mixing rule was adopted for the volume shift.
Figs. 5 to 8 show that quadratic mixing rules of a and b can give anomalous deviations of
the volumes from the linearity. That did not happened with the classical one-parÍìmeter mixing
rules and with the proposed new ones.
Experimental liquid density data were not available, so no final conclusion can be drawn.

5. Conclusions

Unlike the usual belief, the classical, one-parameter mixing rules result adequate to
describe the VLE of systems containing strongly polar components, if care is taken to enforce
pure-component vapor pressures. Such rules should be tried first for the correlation of
experimental VLE data.
When the correlations with one-parameter rules are not satisfactory, the extended form
expressed by the proposed new rules can improve notably the correlation of the VLE data,
without affecting the quadratic dependence on composition of the second virial coeffrcients
and keeping a realistic dependence of the liquid densities from composition.
The formerly proposed two-parameter mixing rules with a quadratic covolume, which also
give acceptable VLE results but tend to fail with systems containing associating components,
often yield anomalous trends of the liquid density.
The new mixing rules are thus proposed as a simple and effective extension of the classical
quadratic mixing rules, to which they can be reduced.

References
lll O. Redlich, J.N.S. Kwong, Chem. Rev.44 (1949)233
l2l G. Soave, Chem. Eng. Sci. 27 (1972) ll97
t3l G. Soave, Fluid Phase Equil. 31 (1986) 203
t4l A. Peneloux, E.Rauzy; Fluid Phase Equil.8 (1982) 7
t5l L.S. Kudryatseva, M.P. Susarev; Zh.Prikl.Khim.(Leningrad) 36 (1963) 1231
16l Z.Maczynska, K.Zieborak; Bull. Acad. Pol. Sci., Ser. Sci. Chim., 1963,I1,225.
Í71 E.Schreiber, E.Schuettau, D.Rant, H. Schuberth; Z.Phys.Chem.(Leipzig),1971,247(l-
2),23.
t8l H. Sugi, T. Katayama; J. Chem. Eng.Jpn., l1 (1978), 3,167
Table I - Results of correlations of experimental VLE data with various mixing rules
SYSTEM t,C
l,2dichloroethane / heptane 70
nitromethane / benzene 45
acetonitrile I ethylacetate 60
vinyl acetate / n-hexane 50
propionic acid /chlorobenzene 40
diethylketone / n-heptane 80
n-heptane/pyridine 80
chloroform I 1,4-dioxane 50
chloroform/diethylether 25
chloroform / acetone 35
chloroform / acetonitrile 40
acetone / cyclohexane 55
butyl acetate / n-heptane 75
pyridine / n-octane 80
Systems with assoc. components:
methanol / dioxane 60
methanol / water 65
methanol/ methylformate 30
methanol / acetone 55
acetonitrile / ethanol 40
ethanol / water 90
ethanol/ diethylamine 40
2-propanol / water 80
1-propanol I water 60
1-propanol / n-heptane 60
1-propanol/ n-butylamine 65
b=lx;b;
b=fx;bi b=Ifxix;bii "=IIxixlc;;
(eqs. 4,5) (eqs. 4,6) (eqs. 4,5,8,9)
Kij LPo/o K;.1 Dij LPo/o kij dij LPo/o
.037 1.44 .710 -.758 0.73 .347 -1.195 O.B2
.059 1.41 .145 -.102 0,77 .160 -.415 0.79
.028 0.25 .030 -.003 0.25 .030 -.010 0.25
.079 1.70 .277 -.239 0.88 .383 -1.226 0.48
.034 2.99 .174 -.158 0.81 .164 -.506 1.20
.058 1.01 .277 -.262 0.52 .296 -.965 0.27
.042 1.86 .276 -.280 A.74 .260 -.885 0.50
-.068 2.62 -.251 .202 0.69 -.257 .744 0.59
-.110 1.56 -.198 .096 1.12 -.211 .391 1.08
-.063 0.94 .183 -.274 0.32 .117 -.688 0.47
.014 0.78 -.124 .162 0.35 -.150 .684 0.29
.114 3.34 -.100 .275 .54 -.041 .701 1.94
1
.045 I .68 .096 -.061 I .14 .092 -.195 1.21
.024 2.23 .575 -.609 0.92 .423 -1.474 0.73
.039 2.O2 -.112 .176 0.99 -.083 .505 1.04
-.080 2.26 -.035 -.049 0.55 -.035 -.169 0.60
.058 4.35 .161 -.123 2.57 .168 -.453 2.45
.004 1.07 .142 -.160 A.24 .142 -.549 0.15
.063 1.46 .252 -.219 0.84 .301 -.937 0.49
-.080 8.85 .075 -.171 0.69 .077 -.593 0.26
-.106 3.33 .050 -.169 1.36 .059 -.612 1.21
-,132 23.10 .109 -.246 2.25 .116 -.855 0.92
-.090 10.82 .371 -.454 3.88 .357 -1.457 0.90
.085 16.06 .654 '.664 6.58 .605 -1.977 3.43
-.084 1.39 .025 -.120 0.54 .A25 -.415 0.48
 0,50

0,45

(5
-o
o
J 0,40
a
a
q)
o-

0,35

0,30
0,2 0,4 0,6 0,8

mole fr. chloroform

Figure I

Fig.l - VLE of the chloroform/acetone system at 35 C.

Circles: experimental data [5]; broken lines: classical mixing rules (k12: -.0628); solid
lines:new mixing rules (k12: .ll'7, dtz: -.688)
 0,45

0,40

0,35

(5
-o 0,30
o-

0,25

0,20

0,15
0,4 0,6 0,8
mole fr. pyridine

Figure 2
F'ig.2 - VLE of the pyridineln-octane system at 80 C.
Circles: experimental data [6]; broken lines: classical mixing rules (k12:.0238); solid lines:
new mixing rules (k12:.4234, dt2: -I.4737)
 0,45

0,40
/
/
/
0,35
-_..-.._
1
Q
-o 0,30
o-

0,25

0,20

0,15
0,4 0,6
mole fr. propanol

Figure.3

Fig.3 - VLE of the l-propanollwater system at 60 C

Circles: experimental data [7]; broken lines: classical mixing rules (k12: -.0901); dotted lines:
quadratic a,b (k12:.3714, d12:-.4541); solid lines: new mixing rules (k12: .3575, drz:-l .4571)
 0,30

0,25
$
-o
o
5
a
a
o
o_
0,20

0,1 5
0,2 0,4 0,6 0,9
mole fr. acetonitrile

Figure 4

Fig.4 - VLE of the acetonitrile/ethanol system at 40 C.

Circles: experimental data [8]; broken lines: classical mixing rules (k12:.063a); solid lines:
new mixing rules (krz:.3012, dr2: -.9367)
 85

:
o
E80
(J
(J
o
E75
=
o
o
a7n
(ú '\'
o-
p
=AAv\.|
6.
:

0,2 4,4 0,6 0,9

nrcle fr. chloroform

Figure 5

Fig. 5 - liquid-phase molar volumes of the chloroform/acetone system at 35 C

Broken lines: classical mixing rules; dotted lines: quadratic a,b; solid lines: new mixing rules.
 180

q) 160
o
E
o
o 140
o
E
o 120
o
a
o
-c
o- 100
p
=
.g

0,2 0,4 0,6 0,8

mole fr. pyridine

Figure 6

Fig. 6 - liquid phase molar volumes of the pyridine/n-octane system at 80 C

Broken lines: elassical mixing rules; thick lines: quadratic qb; solid lines: new mixing rules.
 80

-70
o
E
È60
o

E=50
E40
(u
-c
o-
p30
J
g
2A

10
0,2 0,4 0,6 0,8
mole fr. propanol

Figure 7

Figs. 7 -liquid phase molar volumes of the 1-propanollwater system at 60 C

Broken lines: classical mixing rules; thick lines: quadratic a,b; solid lines: new mixing rules
 o
E60
o
o
o
E
J

E5s
o
a
$
-c
o-
p
5Rn
:ovv

0,4 0,6 0,8

mole fr. acetonitrile

Figure 8

Figs. 8 -liquid phase molar volumes of the acetonitrile/ethanol system at 40 C

Broken lines: classical mixing rules; thick lines: quadratic a,b; solid lines: new mixing rules

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