Alquizola, Emmanuel D.

Bungabong, Nika A.
Mendaros, Czarina M.
Pestano. Jason Moen V.
Suico, Ariel Danielle Anjelu D.

Van Laar Equations

The original van Laar equations consisted two energy parameters and two size parameters
based on the van der Waals equation of state, which characterize the components of a binary
system. However, it was observed that the calculated activity coefficients do not coincide with
the experimental data. Also, the equation is only applicable to mixtures with positive excess
Gibbs free energy since it is based on the assumption that the mixture exhibits positive deviation
from the Raoults Law. With that, van Laar reformulated the equation so that it would apply to
mixtures of both positive and negative deviation.
The van Laar equation is based on the assumption that upon mixing, there is no volume
change and that the entropy of mixing is identical to that of an ideal solution. From that, the
excess Gibbs free energy of the reformulated van Laar equation is equal to the heat of mixing
which can be expressed as
2a x q x q
G ex
=( x 1 q 1+ x 2 q2 ) 2 a12 z 1 z 2= 12 1 1 2 2
RT
x 1 q 1+ x 2 q2
where z i is the molar volume fraction and

qi

is the liquid molar volume. The expression is

based from the Wohl expansion truncated up to the first term as it is further assumed that
a112 =a122 =0.

a12

The

parameter however is dependent on temperature and so does not

necessarily represent the best parameter values in the reformulated van Laar equation. This
adjustable interaction parameter can be determined experimentally from a single set of
measurements at either a fixed temperature or a fixed pressure covering the whole binary
composition range. Ultimately, van Laar lumped up the two parameters into
which, =2 q1 a12 and
Gex=RT

x 1 x 2
x1 + x2

=2 q2 a12 . Finally, the expression now becomes

and

in

The van Laar equation is a good estimate for unsymmetrical solutions wherein the applicability

equations is limited by the ratio of the two parameters

( )

of which it must not exceed 2. 1

(Narayanan 2004)

1 The ratio of the two parameters is the ratio of the liquid molar volumes of the two
components.