MODIFIED WILSON EQUATION FOR VAPOR-LIQUID

AND LIQUID-LIQUID EQUILIBRIA

Takeshi TSUBOKAand Takashi KATAYAMA*
Department of Chemical Engineering, Faculty of Engineering
Science, Osaka University, Toyonaka, 560

A new equation is derived explicitly based on an excess energy equation with Wilson's local
volume fractions and the Gibbs-Helmholtz correlation.
The equation is expressed as the combination of the Wilson equation and a volumeratio term
which has been introduced as a result of the derivation. The new equation (modified Wilson equa-
tion) contains only two parameters for a binary system, and is applicable to both miscible and
partially miscible systems. The equation is readily generalized to multicomponent systems without
any additional parameters.
The wide applicability of the newequation is shownin representing vapor-liquid and liquid-
liquid equilibria for binary and ternary systems.
It is also shown that the original Wilson equation is obtained without obscurity by the same deri-
vation as for the new equation.

Introduction had some success in trying to surmount this defect by

proposing estimation rules for the third parameter
Phase equilibrium relations are one of the funda- (non-randomness factor) according to the constituents
mental properties necessary for the calculation of of the system. Guffey et al.12) and Marina et al.19\
separation processes in chemical industry, and many however, pointed out that in some cases these rules are
useful
relations.
equations have been proposed for expressing the ambiguous and appropriate values must be resorted to
a fitting against equilibrium data. Also, there are
Recently Wilson38) derived an expression based on some limitations in using the equation as suggested by
the concept of local composition which provides a Katayama et al.17).
very good representation of miscible systems including We have explicitly derived a new equation based on
strongly non-ideal mixtures. A particular advantage an excess energy equation with Wilson's local volume
of the Wilson equation is that it can be generalized fractions and the Gibbs-Helmholtz correlation. The
to multicomponentmixtures without any additional newequation (modified Wilson equation) contains
parameters. However, the Wilson equation having only two parameters for a binary system. Further-
two parameters, which is usually called "Wilson equa- more, the applicability of the new equation to experi-
tion", fails to describe the behavior of immiscible mental data in the literature has been compared with
liquid mixtures. To overcome this disadvantage, a that of the Wilson and the NRTLequations. The
third binary constant has been introduced, which comparison has been made for both vapor-liquid and
permits the Wilson equation to correlate partially liquid-liquid equilibria, including ternary systems.
miscible systems. Unless the third binary constants
are the same for all the constituent binary pairs, how- Modified Wilson Equation
ever, the three-parameter Wilson equation cannot be In deriving an excess function of a binary solution,
generalized for multicomponentsystems. In addition, we take into account non-randomness in the solution.
the derivation of both the Wilson and the three-param- Weassume that the probability of finding a molecule
eter Wilson equations has remained obscure. of one type about a central molecule is proportional to
On the other hand, based on the concept of local the local volume fraction, rather than the local mole
mole fraction and Scott's two-liquid theory, Renon fraction.
and Prausnitz28) proposed a new equation (NRTL By using a procedure similar to that of Scatchard31),
equation) which describes miscible and immiscible Hiranuma14), and Morisue et ai21), the excess enthalpy
systems with good accuracy. The NRTL equation of the binary solution is written as follows :
contains three parameters for a binary system even AhE-Xi£21(^21-^n)+-^2?12(^12-^22) (1)
for partially miscible systems. Renon and Prausnitz28)
Received June 5, 1974. ?21+fll=l, f»+f«=l (2)

VOL 8 NO. 3 1975 181

where $id is the local volume fraction of molecule / The activity coefficient for any component i is found
in the immediate neighborhood of molecule j and by the exact relation
Xij is the interaction energy between i-j pair. Further-
more, in the manner of Wilson38}, we relate the local RT\n ri=^(nJgE)T,P,nm (12)
volume fractions to the over-all volume fractions by
02 exp(-^21/i?r)
01exp(-All/RT)
wherent is the numberof moles of component/ and
01exp(-Z12/RT)
02exp (-X22/RT)
(3)
nt is the total number of moles. By differentiating
Eq. (ll), namely Eq. (ll) being substituted into Eq.
(12), the following new equations for activity coeffici-
ents are obtained :
where
ln r,= -ln(*,+*,A0+4^t-1^r]
X1V1 +X2V2 X^ + XzVz
To obtain an expression for excess Gibbs free energy,
the Gibbs-Helmholtz equation is applied (13)

(5)

d(i/T)
which was used in explanation of the derivation of the
three-parameter Wilson equation by Renon et al.29).
Equation (5) is readily converted into an integration- (14)
type equation by selecting the lower limit of integra-
tion equal to zero (l/T=0). where in both equations we call the former two terms
+ the Wilson term and the latter two the volumeratio
Ag*
RT
(6)

l/71=0 term.

Now Eq. (1) is substituted into Eq. (6) and the integra- By the sameprocedure, the original Wilson equation
tion is carried out with respect to l/T. In the integra- can also be derived explicitly (see Appendix).
tion ofEq. (6), it is assumed that the quantities (X2i- Generalization to Multicomponent Systems
in) and (^12-^22) are independent of temperature.
Furthermore, when the boundary condition is con- The equations for binary solutions presented above
are readily generalized to solutions containing any
sidered as number of components, without any additional ternary
Ag*
RT or higher order parameters, as in the cases of other
1/T=O
(7)
local composition equations (Wilson and NRTL
the integration results in equations).
£-*-£ For a multicomponent solution, an excess Gibbs
-;dn-^-(^ln-^+Jcln-^-)
X%\ X\ (8) X2 /
energy is given as
The local volume fractions fn and £22 are derived ^ =-jtxjn[txjA^+txtIn[ZxiPit] (15)
Kl i 3 i 3

from Eq. (3) taking account of Eq. (2) where

£ __. X\

n~ x1+x2(v2/v1)Qxp [-(X21-/lll)/RT] ~~ xx+x2A21 At^ptj exp l-iXu-ljMRT]

Pii= (16)
(17)
VilVj
x2 x2
_
C22-
^i(^iM)exp[-(/^12-^22)/i^r]+x2 XiA12+x2. The activity coefficients can readily be found from
(9) Eq. (15) by using the relation ofEq. (12). The result,
where for any component /, is
A21=p21Qxp [-(221-Xn)/RT] In 77= -In [j] j XjA3i]- Z(xkAik/Z
k j
XjAjk)
A12=p12 exp [-(/(12-A22)/RT] +ln[£xiPit]+i(xkpik/ixjPjk) (18)
p2i=v2/v1 , p12=v1/v2 J k j

Substitution of Eqs. (4), (9) and (10) into Eq. (8)

Applicability of Modified Wilson Equation to Phase
yields Equilibrium Data
1. Binary vapor-liquid equilibria
-^jr= -x1 ln (x1+x2A21)-x2ln (x1Au+x2)
Selected vapor-liquid equilibrium data at low
+x1 \n (x1+x2p21)+x2ln (x1p12+x2) (1 1) pressures from the literature, shown in Table 1, were
182 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
 Table 1 Comparison of Modified Wilson, Wilson and NRTLequations for representation of binary vapor-liquid equilibria
Nosys tem T emp. ;v(D-(2 ) rq D-/t a W il s o n N T R L M o d i f i e d W i l s o n
R ef.
Ay¥ AP J l n ( r i/ r 2) J vi AP J ln ( r i/ r 2) A yi AP J l n ( r i/ r 2)

Ac eto ne -ac eto ni tri le 45 1 0 0.2 5 1. 7 6 1 .4 0 0 .2 5 1. 7 6 1. 4 1 0.2 5 1. 7 5 1. 3 9 蝣8 )

A c e t o n e -m e th a n o l 760m m H g 12 0.45 - 2 .7 2 0 .4 7 2. 8 3 0. 42 - 2. 35 1)
Ac et on e- ni tr om et ha ne 45 1 3 0. 32 1 .4 5 l .S 0 .3 3 1. 4 1 2.0 7 0. 12 1. 5 8 1. 2 0 81
Ac eto ni tri le- be nze ne 45 1 2 0. 61 2. 21 3 .0 2 0 .6 8 2. 2 1 3. 3 7 0. 62 2. 2 1 3. 0 9 5)
Be nz en e- et ha no 1 2 5 0 .2 0 2 . 2 6 - - 0 . 1 7 - 3 5 ) *
B e n z e n e - w -h ep t a n e 60 1 4 0. 36 4.2 3 2.0 5 0. 38 4. 17 2.0 0 0. 35 4. 23 2. 05 3)
CC L -a c e t on i t ri l e 45 1 3 0.4 3 1. 4 7 1A 1 .2 2 1. 6 0 5. 7 3 0. 52 1. 3 9 2.36 4)
CCLt-cyclo hexane 70 1 2 0. 36 5. 0 2 1. 9 2 0 .3 5 5. 0 2 1. 9 2 0.35 5. 0 2 1 .9 2 2)
25 10 0.4 5 3.4 4 2. 50 0 .4 6 3. 4 4 2. 49 0. 45 3. 4 4 2 .5 0 37)
C h l o r o f o r m - a c e to n e 40 1 .9 3 1 . 3 1 - - 1 . 4 3 - 3 4 ) *
55 0 .9 6 1 . 2 8 - - 0. 9 2 -
Cy cl oh ex an e-w -h ep t an e 2 5 1 1 0. l l 0.74 0.93 0.l l 0.73 0.94 0. ll 0.74 0.93 1 6)
C y c lo h e x a n e - t o l ue n e 25 1 1 0.4 8 1. 5 2 2.2 8 0 .4 9 1. 5 1 2.30 0 .4 9 1. 5 2 2.2 8
Diethylamine-C Cl4 20 1 1 0.27 1. 1 4 2 .5 6 0 .3 2 1. 0 6 1. 6 3 0.39 1. l l 1. 8 5 1 8)
30 ll 0. 33 1. 5 5 1 .8 2 0 .3 3 1. 5 3 1. 7 2 0.3 5 1. 5 5 1. 8 3
^-Heptane-tol uene 25 1 1 0.35 2.40 2 . 16 0 .3 6 2.40 2 .2 4 0.3 5 2.40 2. 18 16)
w- H e x an e - e th a n o1 25 1 0 4.26 3 . 5 8 - - 3 . 8 1 3 5 ) *
Methanol- CCL 3 5 0 .4 0 0 .9 5 1 .6 4 1 .0 8 2. ll 4.30 0.74 1. 2 0 2. 15 32)
25 ll 0 .40 1. 2 9 1 .6 5 0 .7 4 1. 4 1 2.98 0.4 1 1. 4 0 1. 8 3 37)
760m m H g 20 1. 6 2 - 2 .5 5 2 .0 1 3. 0 6 1. 8 3 2.5 1 1 3)
Ni t ro m et h an e -b en z en e 45 1 2 0.4 6 2 .4 5 2 .6 5 0 .5 3 2.42 3. 19 0.4 7 2.44 2.8 1 6)
N i t r o m e th a n e - C C L 45 1 2 0 . 50 1 .9 6 2 .4 7 0 A 2.0 1 5 .4 3 0.4 2 1 .6 8 2. 17
w - P r op a n o l - b e n z en e 45 1 1 0. 63 2. 68 3. 34 0. 66 2. 70 3 .8 2 0 .6 5 2. 67 3 .34 7)
Tr ieth ylam ine- ｫｰbu tano1 6 4. 5 1 3 1. 1 0 0. 82 - 1. 5 1 - 9 )*
79. 8 13 1. 0 0 1 . 0 7 - - 1 . 2 0 -
T r ie t h y la m in e -ｫ ｰ p r o p a n o 1 70 .0 5 20 0. 59 0 . 7 9 - - 0 .5 9 -
80 . 1 0 19 0. 49 0 . 7 0 _ _ o . 3 8 -
90. 25 13 0. 30 0. 32 - 0 .2 4 -

A r i th m e ti c av e r a ge 0 .4 6 1 .8 1 2 .1 6 0 .6 1 1. 9 1 2. 8 1 0 .4 9 1 .7 9 2. 1 3

A
yi =Jv 3=12 CF1exp-Jlcal)?/MX 100, JP=J i=iS{(^exp-Pcal)/Pexp}J/MX lOO, Jlnfrl/^^V 2 {infrl^exp-lnfrl/^cal^/MX
i=i 100
* total pressure data
fitted with the modified Wilson equation, the original from different equations with the same set of data
Wilson equation and the NRTLequation to compare gives an indication of relative adequacy of different
their relative advantages. equations. The systems examinedare shownin Table
In most cases, when the solution is remote from its 1. Most of the data are for strongly non-ideal systems
critical condition, the following approximate equilib- under isothermal conditions. Furthermore, Table 1
rium equation is acceptable : presents a comparison of experimental vapor-phase
mole fractions, total pressures and ratios of activity
y4iP= rtXtPlfi exp [vt(P-pi)/RT]
(19) coefficients with calculated results using two fitting
parameters determined for each system from the
The fugacity coefficient $t is given by the virial equa-
tion truncated after the second virial coefficient and binary data.
Wecan draw the following conclusion about re-
0|, the fugacity coefficient at p\9 also calculated from presentation of binary vapor-liquid equilibria. For
virial equation, all at the solution temperature.
Prausnitz et al.27) have discussed this calculation in both isothermal and isobaric conditions, it is found
detail. that the fit through the modified Wilson equation is
To obtain the optimum values of parameters from as good as those obtained using the Wilson and the
series of data, the Simplex optimization technique22) NRTL equations.
was adopted. The calculation method used in this 2. Binary liquid-liquid equilibria
work is similar to the one suggested by Prausnitz While the Wilson equation is not applicable to
et al.27\ but Ostrowski's method24) was applied^ to liquid-liquid systems, the modified Wilson equation
total pressure calculation for isothermal data and can express partial miscibility. The behavior of the
bubble point calculation for isobaric data. newequation was tested by use of experimental data
Since deviations come from both the scatter of the in the literature.
data and the inadequacy of the equation, they cannot The parameter calculation applied is based on the
provide directly a measure of the adequacy of equa- thermodynamic criterion of equilibrium that the activi-
tions. Only a comparison of the deviations obtained ty of each of two components is the same in both
VOL 8 NO. 3 1975 183
 Table 2 List of parameters of ModifiedE xWilson equation calculated from mutual solubility
p e rim e n ta l
data
S y ste m T em p . m u tu a l so lu b ilitie s P a ra m e ter s
R ef.
(l )-(2) [-C l
Xi Xi ^ 12- ^22 fa -^ n P 12

w -B u ta n o l-w a ter 25 0.4 888 0 . 0 18 9 62 8. 1 7 54 2. 6 0 4. 816 36)

Fu rf u ra l- wo o c ta ne 25 0.9 569 0. 0539 1 3 1 8. 9 6 22 24 . 25 0. 50 1 //
F u rfu r a l-w a ter 40 0.7 36 0. 016 1 1 3 9. 3 8 236. 16 4. 646 //
// 70 0. 647 0.0 22 1067.4 0 1 9 0. 4 1 4.70 8 //
ｫｰ He p ta ne -f ur fu ra l 4 8. 8 0.9000 0. 0887 2 14 0 . 5 1 1 2 9 2 . 10 1. 7 8 8 //
1 -H ex ane -D MSO 25 0. 9 8 0 2 0.0 136 2 8 10 . 1 4 2 124.95 1. 7 6 7 30)
M et h a n ol - c y cl o h ex a n e 25 0. 8 2 8 1 0. 1250 12 3. 0 3 1 9 7 5. 2 7 0. 374 37)
2 - Me th yl he p ta ne -fu rf ur al 2 5. 5 0. 948 3 0 .04 48 22 60 . 33 1 3 1 6. 4 8 1. 9 7 9 36)
T rie th y la m in e -w a te r 65 0 . 8 225 0 .00 36 22 27 . 4 8 - 1 3 5 5. 7 4 7.99 2 //

part and two concave ones; this indicates that the

: Wilson term newequation is able to express the phase splitting.
: Volume ratio term The contributions of the Wilson and volume ratio
terms to excess Gibbs free energy are also shown in
b% the figure.
The fact that the Wilson equation cannot represent
immiscible behavior follows from its having a limit
value in the expression of a positive deviation on
excess Gibbs free energy. The three-parameter
Wilson equation has surmounted the limitation by
t multiplying the Wilson equation by a constant larger
two liquid phases -HA?^y than 1. On the other hand, the modified Wilson
equation has overcome the limitation by the addition
Fig. 1 Thermodynamic functions for the system of of the volume ratio term, which always gives positive
methanol (l)-cyclohexane (2) at 25°C (Contributions values.
of Wilson and volume ratio terms) Figure 2 shows good agreement between experimen-
tal activity coefficients from vapor-liquid equilibria and
:Exptl. calculated ones through themodified Wilsonequation
-: Modi. Wilson with parameters from the binary liquid-liquiddata.
3. Ternary vapor-liquid equilibria
With the modified Wilson equation, using binary
inZ* data only, six ternary vapor-liquid equilibria were
--à"^
estimated, and the calculated results have been com-
pared with experimental data as shown in Table 3.
two liquid
phases
Calculations were performed with the modified Wilson
and the Wilson equations. For all systems, differences
between experimental data and calculated values
0.0 ^ \r- through the new equation are almost the same as
mr2 005 those through the Wilson equation.
4. Ternary liquid-liquid equilibria
0-95

A1

The NRTL equation can predict ternary liquid-

(Calculated activity coefficient is determined by using
paramerters from binary liquid-liquid data.) liquid equilibria from binary data, if the best value of
Fig. 2 Experimental251 and calculated activity coefficients non-randomnessfactor for each constituent binary
for the system of acetonitrile (l)-/i-heptane(2) at 45°C system is chosen. The modified Wilson equation,
on the contrary, is generally applicable and needs no
phases of a system. The parameters of the modified empirical parameters to predict ternary liquid-liquid
Wilson equation for all systems studied are shown in equilibria.
Table 2. In the lower parts of Fig. 1, AgM\RTcurve To show the applicability of the modified Wilson
calculated by the new equation presents a convex equation to ternary liquid-liquid equilibria, four
In reference 30), Renon et al. estimated the ternary liquid- systems were chosen. The first one has a narrow
liquid equilibrium of the system through the NRTLequation two-liquid region, the second one has a similarly nar-
by using selected values of an to obtain a good representation row one and contains water as a constituent, and
of the ternary data. We, however, used recommended values
of a%j for the estimation. others have broad ones. Figures 3, 4, 5* and 6 give a
184 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
 Table 3 Comparison of Modified Wilson and Wilson equations for prediction of ternary vapor-liquid equilibria
Sv stem
sy T[OC
em ]p . N Do ata
. of W ilso n Modified Wilson
Ref.
Ay i A yz Ay% AP A y¥ A vz Ays JP
Acetonitrile(l )-benzene(2>
ｫｰhe ptan e (3 ) 45 3 3 0.8 0.7 8 0.92 4.74 0.6 5 0.4 6 0.4 3 3 .80 25)
Acetone (l)-methanol (2)-
zso -p ro p a n o l (3) 55 26 0.9 7 1. 0 2 0.9 1 0. 81 1. 4 2 1. 2 4 1 .3 4 1 .9 3 10 )

Benzene
w -p r o p a n(l)-w-heptane
o l (3) (2)- 15 38 2.1 2.8 1 2.52 2.79 2.8 3 2.7 6 2.4 7 2. 16 l l)
C yc l oh e xa ne (l ) -w -h e pt a ne (2 )-
to lu en e (3 ) 25 1 6 0. 34 0. 19 0. 30 1. 5 3 0. 32 0. 19 0.2 9 1 .5 3 1 6)
ｫｰ H ex an e (l ) -e th a no l (2 ) -
b e n ze n e ( 3 ) 5 5 43 3. 0 6 2.7 4 2.4 7 2. 91 2.9 1 2. 62 2. 37 2.4 6 1 5)
M e th a n o l (l )-eth a n o l (2 )-
ac eton e ( 3) 76 0mm Hg 3 7 1. 0 2 0.4 9 0. 87 0. 29* 1. 1 2 0. 53 0. 98 0 .2 9 * 1)
Me t h an o l ( l ) - CC l 4 (2 >
b en z en e (3 ) 55 0. 77 0. 76 1. 6 5 1. 2 9 0. 87 0. 73 0. 76 1 .5 5 3 3)

Ayi=J S(^exp-^cai)J/Mxl00, AP=^ SK^exp-PcaO/PexplJ/MxlOO, * Jr=^/ S[(rexp-T^lT^IMx100

Benzene 5-Nonanone

/\ A - \ Exptl.NRTL Exptl.
NRTL
Modi. Wilson
A \ Modi. Wilson

Acetonitrile ( mole fraction) n-Heptane 1- Hexene( mole fraction) DMSO

Fig. 3 Experimental251 and calculated liquid-liquid equilib- Fig. 5 Experimental301 and calculated liquid-liquid equilib-
ria for the system of acetonitrile (l)-zi-heptane (2)-benzene ria for the system of 1-hexene (l)-dimethyl sulfoxide (2)-5-
(3) at 45°C nonanone (3) at 60°C
Ethanol CCl4
/\ ~'~ExptL
- Exptl.
f\- NRTL
NRTL
/ \ Modi. Wilson Modi. Wilson

rX
S^\

Ethyl acetate ( mole fraction ) Water Methanol

( molefraction )
Cyclohexane

Fig. 4 Experimental20) and calculated liquid-liquid equilib- Fig. 6 Experimental37' and calculated liquid-liquid equilib-
ria for the system of ethyl acetate (l)-water (2)-ethanol (3) ria for the system of methanol (l)-cyclohexane (2)-carbon
at40°C tetrachloride (3) at 25°C
comparison of experimental data with the results Estimation of liquid-liquid equilibrium relations is
calculated from three sets of binary parameters by much more sensitive to the parameter values than in
use of the new equation and the NRTLequation. As the case of vapor-liquid equilibrium relations, especial-
shown in these figures, the modified Wilson equation is ly when the two-liquid phase region is small in the
generally superior to the NRTLequation in represent- triangular diagram.
ing ternary liquid-liquid equilibrium data.
VOL. 8 NO. 3 1975 185
Conclusion Nomenclature
= parameter in Eqs. (A-3) and (A-4) [-]
Based on an excess energy equation with Wilson's = excess Gibbs free energy per mole [cal/mole]
local volume fractions and the Gibbs-Helmholtz cor- = excess enthalpy of mixing per mole [cal/mole]
relation, a new equation (modified Wilson equation) = numberof observations [-]
has been derived explicitly. The equation which has = molar number of component / [-]
only two parameters for a binary system can explain = total number of moles [-]
= total pressure [atm]
the behavior of both miscible and immiscible systems. = saturation pressure of pure component / [atm]
The wide applicability of the modified Wilson equation = gasconstant [cal/mole à"°K]
has been tested for binary and ternary systems. = absolute temperature [°K]
For binary mixtures, in representation of binary = molar liquid volume of component / [cc/mole]
vapor-liquid equilibria, the modified Wilson equation = liquid-phase mole fraction of component / [-]
= vapor-phase mole fraction of component i [-]
gives as good fit for all types of mixtures as the Wilson
equation. It also, like the NRTL equation, can = activity coefficient of component i at
represent the shape of excess Gibbs energy which temperature T adjusted to zero pressure [-]
gives the existence of a two-liquid phase region, while = energy of interaction between i-j pair [cal/mole]
the Wilson equation cannot. = coefficient defined as Eq. (16) [-]
For multicomponent systems, the modified Wilson = local volume fraction of component i in
immediate neighborhood of component j
equation can be generalized without introducing any volume ratio defined as v%/vj
additional assumptions and parameters. It predicts over-all volume fraction of componenti
ternary vapor-liquid equilibria well and ternary liquid- fugacity coefficient of component i
liquid equilibria fairly well. fugacity coefficient of component i at pi
:-]
-]
-]

A new interpretation of the original Wilson equation <Subscripts>

is shown in Appendix. cal = calculated
exp = experimental
Appendix: NewInterpretation of Wilson Equation /,j, k = components
An ambiguity is found in the derivation of the original Wilson t = total
equation, as Wilson intuitively replaced the over-all volume <Superscripts>
fractions of the Flory-Huggins equation with his local volume M = mixing
fractions.
N = numberof componens
In the derivation of the modified Wilson equation, Eq. (ll),
the boundary condition in Eq. (6) is considered as Eq. (7). On the Literature Cited
other hand, there is another way of assumption that at 1/T=O
(infinite temperature) the behavior of the solution is expressed by 1) Amer, H. H. and R. R. Paxton: Ind. Eng. Chem., 48, 142
(1956).
the Flory-Huggins equation for athermal solutions26] as follows :
Ag* 2) Brown, I. and A. H. Ewald: Aust. J. Sci. Res. A., 3, 306
(1950).
RT
=^ ln
i/r=o -+JC2
xi Ill- x2 (A-l)

3) ibid., 4, 198 (1951).

By use of the boundary condition of Eq. (A-l), the integration 4) Brown, I. and F. Smith: Aust. J. Chem., 7, 269 (1954).
of Eq. (6) results in 5) ibid., 8, 62 (1955).
^ 6) ibid., 8, 501 (1955).
-^In^+^ln
RT ^xi '^x2 ^ 7) ibid., 12, 407 (1959).
= -x In Oi+X2A21)-x2 In (xi^i2+x2) (A-2) 8) ibid., 13, 30 (1960).

That is, the original Wilson equation has been clearly derived 9) Copp, J. L. and T. J. V. Findlay: Trans. Fraraday Soc,
from another boundary condition by the same procedure 56, 13 (1960).

through which the modified Wilson equation is derived. 10) Freshwater, D. P. and K. A. Pike: /. Chem. Eng. Data, 12,
179 (1967).
If some other equation, e. g. the Flory-Huggins type equation
ll) Fu, S. J. andB. C. -Y. Lu: ibid., 13, 6 (1968).
with a parameter, is used for the boundary condition in Eq. (6),
the following new equation is derived : 12) Guffey, C. G. and A. H. Wehe: AIChEJ., 18, 913 (1972).
13) Hipkin, H. and H.S. Myers: Ind. Eng. Chem., 46, 2524
-^r= -X!In(xi+X2A2O-X2In(xiAu+x2).+A0i02 (A-3) (1954).

where A is a parameter which is independent of temperature. 14) Hiranuma, M: Kagaku Kogaku, 33, 695 (1969).
15) Ho, J. C. K. and B. C. -Y. Lu: /. Chem. Eng. Data, 8, 549
If the Scatchard-Hildebrand type equation for regular solutions (1963).
is adopted for the boundary condition, a corresponding new
16) Katayama, T., E. K. Sung and E. N. Light foot: AIChE J.,
equation is introduced as follows : ll, 924 (1965).
-= -xi In (xi +X2A21) -x2 In (X1A12+x2) 17) Katayama, T., M. Kato and M. Yasuda: /. Chem. Eng.
RT Japan, 6, 357 (1973).
+xiIn(xi+x2p2i)+x2In(^1^12+x2)+A0i@2 (A-4)
18) Kilian, H. and H. -J. Bittrich: Z. physik. Chem., 230, 383
(1956).
Addition of a physical term to the original Wilson equation has
been suggested recently by Nitta and Katayama23 '. 19) Marina, J. M. and D. P. Tassios: Ind. Eng. Chem., Process
186 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
 Design and Develop., 12, 271 (1973). 28) Renon, H. and J. M. Prausnitz: AIChEJ., 14, 135 (1968)
20) Mertl, I.: Coll. Czech. Chem. Comm., 37, 366 (1972). 29) ibid., 15, 785 (1969).
21) Morisue, T., K. Noda and K. Ishida: /. Chem. Eng. Japan, 30) Renon, H. and J. M. Prausnitz: Ind. Eng. Chem., Process
5, 219 (1972).
Design and Develop., 7, 220 (1968).
22) Nelder, J. and R. Mead: Computer J., 7, 308 (1965). 31) Scatchard, G.: Chem. Revs., 8, 321 (1931).
23) Nitta, T. and T. Katayama: /. Chem. Eng. Japan, 8, 89 32) Scatchard, G. and C. L. Raymond: J. Am. Chem. Soc, 60,
(1975). 1278 (1938).
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VAPOR-LIQUID EQUILIBRIUM RELATIONS FOR THE

SYSTEM ACCOMPANIED BY HYPOTHETICAL
CHEMICAL REACTION CONTAINING SALT
Yasuhide NISHI
Faculty of Engineering, Ehime University, Matsuyama, 790

In a system accompanied by hypothetical chemical reaction vapor-liquid equilibrium ratio, Ki,

of component i has been expressed by
logKi = -AilT+Bi

where T is the absolute temperature, A%is a constant determined by reaction system and component
/, and Bi is a constant determined from vapor-liquid equilibrium data for the liquid composition at
conversion 0 and/or 1. The object of this paper is to show that the equation mentioned above can
also be applied to the system including salt. Following two systems are herein discussed:
z-propanol-w-propanol-calcium chloride
methanol-ethanol-water-calcium chloride
In these systems A%implies the salt effect, but its behavior was not definitely observed.

Introduction chemical reaction. That is, in a system accompanied

Salts may be used as a separating agent for dis-
tillation or a catalyst in the operation of distillation
accompanied by chemical reaction. It may be there-
fore useful to investigate the salt effects for vapor-
liquid equilibria of systems accompanied by chemical
reaction.
The authorM) has previously reported that vapor-
liquid equilibrium relations for systems accompanied
by hypothetical chemical reaction could be expressed
in the same way as for a system accompanied by
Received August 12, 1974.
Presented at the 7th Autumn Meeting (at Nagoya, October
1973) and at the Hokuriku Meeting (at Toyama, July 1974)
of the Soc. of Chem. Engrs., Japan.
VOL. 8 NO. 3 1975
by chemical or hypothetical chemical reaction vapor-
liquid equilibrium ratio, Ki9 for component i is cor-
related by
logK^0)
-AJT+Bi
where T is the absolute temperature, At is a constant
determined by reaction system and component /, and
Bt is a constant determined from vapor-liquid equilib-
rium data for the liquid composition at conversion 0
and/or 1. If vapor-liquid equilibrium relations for
their liquid compositions are known, vapor-liquid
equilibrium relations for the system accompanied by
chemical reaction can be predicted. The object of the
present paper is to show that the equation can be
applied to systems including salt.
187