Fluid PhaseEquilibria,89 (1993) 187-196

Elsevier Science Publishers B.V.,Amsterdam

CORRELATION
OF LLE IN l-ALKANOL + n-ALKANE BINARY MIXTURES
USING THE MODIFIED WILSON EQUATION

YASUHIKOARAI
Department of Chenicai Engineering, Hyushu University,
Fukuoka 812 (Japan)

HIDEKI HIGASHIUCHI and YUJIRO SAKURAGI

Department of Industrial Chenistry, Hurune College of Technology,
k’urune 830 (Japan)

ABSTRACT

Recommended liquid-liquid equilibrium (LLE) data for the six methanol

binary mixtures (methanol + n-hexane, n-heptane, n-octane, n-nonane,
n-decane. and n-hexadecane) and the ethanol + n-hexadecane binary mixture
were correlated by using a modified Wilson equation. By representing the
binary interaction parameters as a function of temperature, LLE of these
binary mixtures could be correlated with good agreement.

INTRODUCTION

LLE of l-alkanol + n-alkane binary mixtures were correlated using a

modified Wilson equation. The six methanol binary mixtures (methanol
+ n-hexane, n-heptane. n-octane, n-nonane. n-decane. and n-hexadecane)
and one ethanol binary mixture (ethanol + n-hexadecane) LLE were
correlated based on the recommended data by Skrzecz(l989).

0378-3812/93/!$06.00 01993 Elsevier Science Publishers B.V.All rights reserved

166

A IODIFIED WILSONEQUATION

The Wilson equation (Wilson. 1964) has been modified based on the
conservation of local mole fractions (Nagatani et a1.,1986; Higashiuchi
et al., 1987). This equation has a multicomponent parameter which does
not appear in binary systems.
The activity coefficient for component i in a multicomponent mixture
is expressed as

hYi=C(l-h Ai-~[(Xj/Aj)(Aj~-B,j+Cj)])
(1)
i

where
Aj= C Ajqxq (2)
4j = i .ri,AjqxqD (q=i; D-l) (3)
B,, = 0’
C, = C ?q Ajqxqajq (4)
q

(5)
Aii = 1

ri/= (gij- gti)/RT=Rrj/RT (6)

rii = 0

aij=Xj+DCXk (k#i, j) (7)

k

where x is the liquid-phase mole fraction, D is a characteristic multi-

component parameter and g,, is the energy parameter which characterizes
the interaction between molecules i and j. In this study, the value of
C in eqn. (1) is empirically determined as 1.5, and the vi / vi (ratio of
liquid molar volumes) in eqn.(5> is set to unity to give good correlations.

CORRELATION

In a binary mixture, LLE compositions can be computed using two para-

meters, RI= and RZI. in eqn. (6) because the parameter D is not needed.
These parameters were obtained based on the condition (~~y,)‘=(x,y,)~’
from the mutual solubilities. The values of RIZ and RZI were evaluated
at each temperature by solving the simultaneous equations (xiy,)’ = (xiy,)”
and (x2y2)‘=(x2y2)” , where x1 and x2 were given by experimental data
and y , and 7 2 were represented by the modified Wilson equation containing
unknown parameters RI z and RZ I. Using the Newton-Raphson method, their
values were determined and the parameters could be represented as a function
of temperature:
R,J=a,iT3 + bljT2 + c,,T+d,, (8)
where T is the temperature(K).
The values of coefficients a ii, bi,, c , j and d ij are presented in
Table 1. The calculated results using these interaction parameters are
shown in Pigs.l-7. As illustrated in these figures, a modified Wilson
equation is useful to correlate the LLE relation of l-alkanol + n-alkane
binary mixtures.

DISCUSSION

As shown previously (Higashiuchi et a1.,1987), the values of RI, could

be represented by a linear function of temperature in general. However,
in this study, many temperature coefficients were needed to correlated LLE
including the critical region. The interaction parameters R,, can only be
determined from a data fit. Prediction of LLE in other system is therfore
not possible.
Applicability of the interaction parameter set obtained for LLE to predict
VLE was examined. VLE of the methanol + n-heptane binary mixture at 298.15K
was studied and fairly good prediction could be obtained as illustrated in
Pig.& though discrepancy is shown in dilute region of methanol.

CONCLUSION

Recommended LLE data by Skrzecz for the six methanol binary mixtures
(methanol + n-hexane, n-heptane, n-octane, n-nonane. n-decane. and
n-hexadecane) and one ethanol binary mixture (ethanol + n-hexadecane) were
correlated using a modified Wilson equation. By representing the binary
interaction parameters as a function of temperature, LLE of these 1-alkanol
+ n-alkane binary mixtures could be correlated with good agreement up to
the critical region.
190

TABLE 1

Coefficient of interaction paraaeter R,j for the modified Wilson equation

R,, [J mol -‘I * Dev. [%I**

a 12 b 12 Cl2 d I2

I-Alkanol( ) n-Alkane(2) art b 21 cri d 51

Methanol n-Hexane 0.0 -0.85053 433.77 -48795.0 3.96

0.0 0.24158 -123.20 21438.0

Methanol n-Heptane 0.0 -0.87155 461.92 -54725.0 2.42

0.0 0.22308 -111.54 20345.0

Methanol n-Octane 0.0 0.0 -57.620 22988.0 2.56

0.0 0.0 16.560 2442.4

Methanol n-Nonane 0.0 0.0 -42.733 18826.0 3.97

0.0 0.0 11.900 4143.0

Methanol n-Decane 0.0 0.0 -43.571 19421.0 1.02

0.0 0.0 5.9710 6253.6

Methanol n-Hexadecane 0.0 0.40033 -320.261 66972.7 3.41

0.0 -0.11823 70.941 -198.9

Ethanol n-Hexadecane -0.060711 57.9185 -18418.10 ~955710.0 1.26

0.0 0.37505 -226.636 41683.0

* Rij=aidT’+ biiT’+ c,JT + dij

** Dev. = 100 [rir $ i, ( I x$_’ - X:X@ I /x;;z)] /4N. where xi,‘,’ and
let
x(;,;p sre respectively the calculated and experimental mole fractions
of component i in phase p at tie-line t, and N denotes the number of
experimental tie-line data.
 191

3
;: 280

0. 0 0. 2 0. 4 0. 8 0. 8 1. 0
XI

Fig.1 LLE of the methanol(l) + n-hexane(2) binary system:

o , recommended data; -9 modified Wilson equation.

340

320

E
;: 300

280

280
0. 0 0. 2 0. 4 0. 6 0. 8 1. 0
%I

Fig.2 LLE of the methanol(l) + n-heptane(2) binary system:

o , recommended data: -9 modified Wilson equation.
192

34

32 0 -
3
h

30 0 -

28 0 -

I I I I

0. 0 0. 2 0. 4 0. 6 0. 8 1. 0
ZI

Fig.3 LLE of the methanol(l) + n-octane(Z) binary system:

o, recommended data; - , modified Wilson equation.

I I I I I
I
360 -

340 .
3
h

320 .

300 .

0. 0 0. 2 0. 4 0. 6 0. 8 1. 0
Xl

Fig.4 LLE of the methanol(l) + n-nonane(2) binary system:

o , recommended data; -9 modified Wilson equation.
 193

360

340

Li
h

320

300

0. 0 0. 2 0. 4 0. 6 0. 6 1. 0
Xl

Fig.5 LLE of the methanol(l) + wdecane(2) binary system:

o, recommended data; -9 modified Wilson equation.

450

400

z
h

360

300

0. 0 0. 2 0. 4 0. 6 0. 6 1. 0
Xl

Fig.6 LLE of the methanol(l) + n-hexadecane(2) binary system:

o. recommended data; -9 modified Wilson equation.
194

0. 0 0. 2 0. 4 0. 6 0. 8 1. 0

Fig. 7 LLE of the ethanol(l) + n-hexadecane(2) binary system:

o , recommended data: -t modified Wilson equation.

1. 0

0. 8
___---__----m-s
d
T---
0. 6

0. 4

0. 2

0. 0
0. 0 0. 2 0. 4 0. 6 0. 8 1. 0
Xl

Fig.8 VLE of the methanol(l) + n-heptane(2) binary system (298.15K):

o, exptl. data(Kusunoki et al., 1991); - , modified
Y; Ir,Tn nnllnt;nn
 195

LIST OF SYHBOLS

A, defined in eqn. (2)

a i.i coefficient in eqn.(8>(J mol-’ Ke3)

4 defined in eqn. (3)

bi., coefficient in eqn.(8>(J mol-’ K-‘-j
C constant in eqn. (1)

ci defined in eqn. (4)

c iJ coefficient in eqn.(8>(J mol-’ K-‘)
D characteristic multicomponent parameter; see eqns.(3) and (7)
dii coefficient in eqn.(8)(J mol-‘1
gij interaction energy between components i and j (J mol-‘)
gas constant(8.31441 J mol-’ KK’)
R
gz .J - g,,(modified Wilson equation)(J mol-‘1
Rij
T absolute temperature(K)
V liquid molar volume(m3 mol-‘)
x mole fraction(liquid phase)
Y mole fraction(vapor phase)

Greek letters

ali characteristic parameter; see eqn.(7)

Y activity coefficient
Ai, defined in eqn. (5)
7ij R,j/RT

Subscripts

i, J; k, 4 components
1.2 components(l=l-alkanol and 2=n-alkane)

REFERENCES

Higashiuchi,H., Sakuragi,Y., 1wai.Y.. Arai.Y. and Nagatani.H.. 1987.

Heasurement and correlation of liquid-liquid equilibria of binary and
ternary systems containing methanol and hydrocarbons. Fluid Phase
Equilibria, 36: 35-47.
1%

Kusunoki.M., Hongo.M., Mishima. K. and Arai, Y., 1991. Measurement and

correlation of vapor-liquid equilibria of the methanol-n-heptane system
at 25 “c. Preprint of 56th Annual Meeting of Chem.Engrs.Japan.
Paper No. E-110.
Nagatan i , M., 1wai.Y. and Arai.Y., 1986. Correlation of ternary vapor-liquid
equilibria by an improved Wilson equation. Tech.Rep.Kyushu Univ.,59:
231-242.
Skrzecz, A., 1989. Recommended data for LLE of l-alkanol + n-alkane mixtures
(IUPAC project, Commission 1.2).
Wilson. G. I., 1964. A new expression for the excess free energy of mixing.
J. Am.Chem.Sot., 86: 127-130.