A critical discussion i s given of the use of local compositions for representation of excess
Gibbs energies of liquid mixtures. A new equation is derived, based on Scott's twoliquid
model and on an assumption of nonrandomness similar to that used by Wilson. For the same
activity coefficients a t infinite dilution, the Gibbs energy of mixing is calculated with the
new equation as well as the equations of van Laar, Wilson, and Heil; these four equations give
similar results for mixtures of moderate nonideality but they differ appreciably for strongly
nonideal systems, especially for those with limited miscibility. The new equation contains a
nonrandomness parameter a12 which makes it applicable to a large variety of mixtures. By
proper selection of a12, the new equation gives an excellent representation of many types of
liquid mixtures while other local composition equations appear to be limited to specific
types. Consideration i s given to prediction of ternary vaporliquid and ternary liquidliquid
equilibria based on binary data alone.
Interpolation and extrapolation of thermodynamic data Wilson obtained an expression for the excess Gibbs en
for liquid mixtures are common necessities in chemical en ergy by analogy with the FloryHuggins expression for
gineering. The model of ideal solutions is useful for pro athermal mixtures, where he replaces overall volume frac
viding a first approximation and a reference, but devia tions by local volume fractions:
tions from ideality are frequently large. These deviations
are expressed by excess functions which depend on the gE/RT = x 1 In (511/x1) + x2 In (522hZ) (2)
concentrations of the components and on the temperature.
As shown by Wohl ( 2 5 ) , excess functions have com where the local volume fractions 511 and 522 are derived
monly been expressed by algebraic expansions of mole from Equation (1):
fractions with arbitrary, temperaturedependent coefficients x1
= (3)
which are obtained by fitting experimental data. In these
expansions, as many terms and parameters as necessary and
ti1
+ x2 (u2/u1) exp ((g21 gd/W
are introduced in order to represent the experimental data. x2
A few years a o Wilson ( 2 4 ) showed that the excess = (4)
gl
Gibbs energy cou d be conveniently expressed by an alge
f22
x2 + XI (01/~2) exp ((glz g22)/fiT)
braic function of local composition and in his final equation In these equations the 0's are the molar volumes.
Wilson used local volume fractions. Subsequently Orye Heil (7) pursued the original analogy further and pro
( 1 1 ) showed that Wilson's equation is useful for repre posed an expression for the excess Gibbs energy similar
senting equilibrium data for a wide variety of liquid mix to the FloryHuggins equation for nonathermal mixtures.
tures. The Heil equation was derived for polymer solutions; it
While Wilson's equation represents one particular exam has the following form for solutions of small molecules:
ple of using local compositions, other examples can be
readily constructed; for example, Heil (7) recently showed
+
gE/RT = XI in ( t d x ~ ) x2 In ( 5 ' 2 2 / 4
how a modified form of Wilson's equation can be used  g22
successfully to represent equilibria in polymer solutions.
gz1
RT
611
Xd21 + g12
RT x25'12
We present here a critical discussion of the use of local
compositions, derive a new equation based on Scott's two where 5 ,21 = 1  511 and f12 = 1  f z .
r
liquid model theor , and compare experimental data with
results calculated rom several models. We consider both
vaporliquid and liquidliquid equilibria, including ternary
Both Equations ( 2 ) and (5) are useful, semiempirical
relations for thermodynamic excess functions; both equa
tions contain only two adjustable parameters per binary,
systems. ( g 2 1  gll) and ( g 1 2  g 2 2 ) , and both are readily gen
eralized to solutions containing any number of components.
THE WILSON AND H E I L E Q U A T I O N S However, the derivations of both equations contain two
To take into account nonrandomness in liquid mixtures, essentially arbitrary steps: the relation between the local
Wilson ( 2 4 ) suggested a relation between local mole frac mole fractions, Equation ( l ) , and the introduction of
tion x i 1 of molecules 1 and local mole fraction x21 of mole local compositions into the FloryHuggins equation. A
cules 2 which are in the immediate neighborhood of mole somewhat more satisfactory way to define and use local
cule 1: compositions is shown below. We shall return later to the
Wilson and Heil equations.
X2l x 2 exp (  g 2 1 / R T )
= (1)
X I ~ XI exp (  g d R T )
T H E NONRANDOM, TWOLIQUID E Q U A T I O N
where g 2 1 and g 1 1 are, respectively, energies of interaction
between a 12 and 11 pair of molecules ( g 1 2 = gzi). To define the local composition, we make an assumption
The overall mole fractions in the mixture are x 1 and xg. similar to that of the quasichemical theory of Guggenheim
Wilson 0 1 U,/V3 1
Heil 1 1 VJVj 1
NRTL 1 0 1
* 0111 = W C .
+
+'' +=O1ll
X1 XZ
(31)
GENERAL FUNDAMENTAL EQUATION
For comparison, it is convenient to generalize the Wil Equation (31) immediately shows why Wilson's equa
son, Heil, and NRTL equations. To simplify the notation, tion is not compatible with phase instability. Substituting
let the parameters given in the first horizontal row of Table
GIZ= P I Z exp ( a 1 2 d 1, all terms on the lefthand side of Equation (31) are
(25)
greater than zero and therefore Equation (31) can never
GZI= P Z exp
~ ( (26)
~ I Z ~ Z I ) be satisfied. As mentioned by Wilson ( 2 4 ) , his equation
cannot account for partial miscibility.
The generalized expression for the excess Gibbs energy
We now want to compare the Wilson, Heil, and NRTL
of a binary mixture is equations with each other and with the van Laar equation.
To facilitate this comparison we consider symmetric sys
gE
=
RT
q [XI In (XI + xzGzd + xz In + x 1 G d I
(XZ tems.
+
xi + xzG21 xz +
] (27)
712G12
xiGiz
SYMMETRIC SYSTEMS
The Wilson, Heil, and NRTL equations follow from We call those binary systems symmetric for which the
Equation (27) by substituting for p, q, ~ 1 and 2 a12 the
excess Gibbs energy is not changed if we change x to
values indicated in Table 1, taking i = 1 and i = 2. (1  x ) . We also assume that v p = ul. The condition
The adjustable parameters are (g12  g22) and (gzl  for symmetr in the local composition equations is the
g11). We may consider a12as a third adjustable parameter
hy
equality of t e parameters '12 and 721, and we note
or, as discussed later, set it at a predetermined value. For 712 = 721 = T (32)
the Wilson equation, independent specification of liquid
molar volumes is not strictly necessary since GI2 and G21 We write the van Laar equation in the form
can be taken as adjustable temperaturedependent param
eters. (33)
We now indicate some properties of Equation (27).
The activity coefficients are found by appropriate differ where A and B are temperaturedependent parameters.
entiation; they are For a symmetric system A = B, Equation (33) is then
identical with the twosuffix Margules and RedlichKister
equations.
For the NRTL equation, we need to specify the con
stant a12.In our comparison, we consider two values of
a12, namely, 0.50 and 0.25; the two corresponding equa
tions are designated, respectively, by NRTL (0.50) and
NRTL (0.25).
We define the parameter a as follows:
a = A for the van Laar equation
a = 27 for Heil's equation
a = 7 for Wilson's equation and the NRTL
equation
2 , Glz, and G2l are given, respectively, in
where ~ ~ 721,
Equations (23), (24), (25), and (26). All these equations become asymptotically equivalent
A condition for phase instability is that for Ag', the for small values of the parameter a. In each case, the first
molar Gibbs energy of mixing term in the power series expansion of g E / R T in terms of
a is 2 ~ ~ 1 x 2 .
(Eg>, = o Figure 2 presents a comparison of the four symmetric
equations. In all four equations, the parameters a are
selected such that, for each one, at infinite dilution
for at least one vaIue of x1 in the interval zero to one.
Substituting Equation (25) into Equation (30), we obtain y1a = y2'Q = 11.0
1.0
0.8
G 0.6
N
x
b
2 0.4
4 0.2
NORMALIZED PARAMETER a
Fig. 3. Activity coefficient for symmetric equimolar mixture as a Fig. 4. Activity coefficient for symmetric mixture as a function of
function of activity coefficient a t infinite dilution. normalized parameter a.
TABLE
2. COMPARISONBETWEENLOCAL COMPOSITION
AND VAN LAAREQUATION
FOR REPRESENTATIONOF BINARYVAPORLIQUID
DATA
la 4 4 4 4 3 3 3 3 0.30 8
Ib 7 7 7 7 6 6 6 6 0.30 10
Ic 7 7 7 7 9 9 9 9 0.30 11
I1 7 8 13 6 8 10 21 8 0.20 9
111 15 7 11 7 15 4 8 4 0.40 3
IV 26 22 10 14 34 28 11 24 0.47 13
V 13 10 5 5 16 11 4 5 0.47 2
VI 10 10 13 10 16 16 21 16 0.30 2
VII     12 13 15 13 0.47 2
r
types alread considered, are scarce. However, we tenta
tively identi y three more types:
Type V is represented by two systems of polar sub
hydrocarbon (they are given in reference 1 6 ) ; in all cases,
the temperature dependence of the parameters is linear
and the parameters are consistent with parameters de
stances ( acetonitrile and nitromethane) with carbon tetra rived from vaporliquid data. Therefore, for this type of
chloride which present a high degree of nonrandomness mixture, it is possible to predict vaporliquid equilibria by
and are best fitted by the NRTL (0.47) equation and the linear extrapolation with temperature of the parameters
Wilson equation. We recommend 0112 = 0.47. obtained from liquidliquid data at lower temperature.
Type VI is represented by two systems of water plus Figure 5 shows the variation of the parameters with
a polar, nonassociated substance (acetone and dioxane) ;
they are best represented by the van Laar and the NRTL
(0.30) equations. We recommend a 1 2 = 0.30.
Type VII is represented by two systems of water plus
a polar selfassociated substance (butylglycol and pyri I I I I I I
dine); they present a high degree of nonrandomness and X VAPORLIQUID DATA N R T L EQ.
I 500 LIQUIDLIQUID DATA 9,=0.20 
we recommend a12 = 0.47.
We can draw the following conclusions about repre I EXPERIMENTAL ERROR
sentation of binary vaporliquid equilibria.
The Wilson equation is especially suitable for alcohol
hydrocarbon systems, but it can never predict phase split
ting. The Heil equation can predict phase splitting but
provides only a small improvement over the van Laar
equation.
The NRTL equation gives the best fit for all types of
mixtures by proper selection of the constant a12,taking
into account only the nature of the binary system. It is the
simplest of the local composition equations (it contains
no logarithmic term in the expression of g E ) and has per
haps the best semitheoretical basis. When justified by the
data, it can be used as a threeparameter equation for
highly nonideal systems, but it can also be used as a
twoparameter equation by using for a 1 2 the values recom
mended and listed in Table 2.
95%
Mean arithmetic Confidence
deviation in vapor 95% Mean relative limit in
Temp., mole fraction y for Confidence deviation in relative
"C. or No. of individual component limit in y pressure pressure
pressure, data x 1,006 x 1,000 x Lo00 x 1,000
System mm. Hg points Heil Wilson NRTL* NRTL Heil Wilson NRTL* NRTL Ref.
nHexane 2 2 2 4
Cyclohexane 70 21 3 3 3 4 8 8 7 2 22
Benzene 1 1 1 5
nOctane 5 1 4 4
Isooctane 35 25 0 7 0 10 16 1.4 6 13 4
Nitroethane 5 8 4 8
nHeptane 3 3 3 2
Toluene 760 39 2 2 2 1 15 14 11 33 20
Methylethyl
ketone 5 5 5 2
nHeptane 5 4 4 3
Benzene 760 47 6 2 2 4 4 14 13 5 23
Ethanol 11 6 6 6
nHeptane 7 4 5 7
Benzene 400 50 9 4 3 4 15 4 4 9 9
Ethanol 16 8 7 9
nHeptane 1 2 5 4
Toluene 760 8 2 2 3 5 3 1 7 9 2
Methanol 1 4 +8 8
Benzene 1 0 1 5
Carbon tetra
chloride 35 6 3 3 3 4 9 4 3 9 17
Methanol 4 3 4 7
Benzene 3 1 3 3
Carbon tetra
chloride 55 8 6 2 2 4 11 0 2 6 17
Methanol 9 3 5 7
nHexane 1 0 1 4
Hexene1 760 16 4 3 4 4 11 10 12 9 21
1,4Dioxane 3 3 3 6
Acetone 5 5 5 4
Chloroform 50 30 3 3 3 4 23 21 23 16 19
Methanol 8 8 8 3
Acetone 4 4 4 3
Methanol 50 35 1 1 1 7 12 13 12 12 19
Methyl acetate 3 3 3 5
Ethanol 0 10 4 7
Ethyl acetate 760 96 1 7 5 22 6 9 9 8 5
Water 1 3 1 17
am is selected for each binary mixture according to the values given in Table 3.
temperature for a typical binary system. The temperature GENERALIZATION OF THE EQUATIONS
range extends from below to above the critical solution TO MULTlCOMPONENT SYSTEMS
temperature. The probable in the parameters are The equations for binary solutions, presented earlier,
indicated by the vertical lines in Figure 5. For liquid are readily to so~utionscontaining any number
liquid data this error iS smaller than for vaporliquid data. of components~ The requires no additional
It is of the order of 10 cal./mole for Heirs parameters assumption; all the local compos~tionequations considered
and 20 cd./mole for parameters in the Wilson and NRTL here take into account only Wobody interactions and
equations*The temperature dependence of the Parameters therefore the assumptions needed for 3, 4, ...component
cannot be neglected in this case. Within experimental solutions are the same as those for binary solutions.
error, however, the parameters derived from vaporliquid For a multicomponent solution, let xji stand for the local
data are consistent with those derived from liquidliquid mole fraction of molecule j and let x k i stand for the local
data. mole fraction of molecule k in the immediate neighborhood
r
The activit coefficient is obtained by appropriate dif
ferentiation o Equation (35):
TABLE 4. COMPARISON
OF NRTL AND WOHLEQUATIONS
FOR PREDICTION
OF TERNARYVAPORLIQUID
EQUILIBRIA
Mean arithmetic
deviation in
N individual
components 95% Confidence
vapor mole limits in vapor
fraction mole fraction
x 1000 x 1000
NRTL Wohl NRTL Wohl
I k='l k=l (with no (with best (with no (with best
ternary ternary ternary ternary
System constant) constant) constant) constant)
PREDICTION OF TERNARY
VAPORLIQU ID EQU ILI BRlA
nHeptane 3 3 2 8
Toluene 2 4 1 5
With the local composition equations, prediction of Methylethyl ketone 5 1 2 8
the properties of multicomponent systems is possible with nHeptane 4 0 3 4
out any additional ternary or higher order parameters. Benzene 2 8 4 7
For the NRTL equation, the excess Gibbs energy is de Ethanol 6 8 6 8
rived from the twoliquid theory by taking into account 760 mm. Hg
only twobody interactions; there is no need to introduce nHeptane 5 0 7 4
higherorder interactions in the treatment of multicom Benzene 3 5 4 7
ponent systems when they were neglected for binary Ethanol 7 5 9 a
mixtures. 400 mm. Hg
Table 3 presents a comparison of experimental vapor
phase mole fractions and total pressures with calculated nHeptane 5 8 4 14
results using only two fitting parameters determined from Toluene 3 2 5 8
Methanol 8 6 8 19
each of the binary data. For the NRTL equation, the val
ues of a12are selected according to the rules given earlier. Benzene 1 13 5 22
We compare the mean arithmetic deviations in the Carbon tetrachloride 3 3 4 20
vapor mole fractions (absolute) and total pressures (rela Methanol 35°C. 4 10 7 39
tive) for the three local composition equations. These Benzene 3 15 3 21
quantities are a measure of the accuracy of the prediction Carbon tetrachloride 2 7 4 13
of the ternary equilibria. We indicate also 95% confidence Methanol 55°C. 5 8 7 29
limits for the NRTL equation, as suggested recently by
Adler et al. (1). Acetone 5 11 4 18
The results indicated in Table 3 lead to conclusions Chloroform 3 11 4 8
Methanol 8 0 3 12
which parallel those reached from fitting binary systems.
For systems of type I, where the deviations from ideal Acetone 4 9 3 12
ity are not too large, all equations give similar results. In Methanol 1 8 7 15
Table 3 systems belonging to this type are nhexanecyclo Methyl acetate 3 1 5 8
hexanebenzene, nhexanehexene1dioxane, nheptane Ethanol 4 6 7 22
toluenemethylethylketone, acetonechloroformmethanol, Ethyl acetate 5 1 22 57
and acetonemethanolmethylacetate. Water 1 5 17 49
d \ rC. NRTL

EXPTL.
c HElL
C NRTL
"
(MOLE PER CENT)
Fig. 6. Calculated and observed liquidliquid equilibria for the sys Fig. 8. Calculated and observed liquidliquid equilibria for the rys
tem isooctane (I)nhexane (2)furfural (3) a t 30°C. tern noctane (l)octene1 (2lnitroethane (3) a t 0°C.
CONCLUSION
Two major conclusions result from our comparison of
the local composition equations for the representation of
the excess Gibbs energy of liquid mixtures.
Considerin , at first, binary mixtures, it appears that
binary data for many different types of mixtures cannot
be represented with the same twoparameter equation.
Even if the activity coefficients at infinite dilution are the
V V V V same for two different mixtures, it does not follow that the
(WEIGHT PERCENT) activity coefficients at other concentrations are even ap
Fig. 7. Calculated and observed liquidliquid equilibria for the proximately the same if the mixtures belong to different
system chloroform (1 )acetone (%water (3) at 25°C. types. A very sensitive test of mixture type is provided by