DIFFERENT MODELS THAT PREDICT LIQUID ACTIVITY COEFFICIENTS

2.1 INTRODUCTION:
The liquid-phase activity coefficient is the most important requirement for vapourliquid equilibrium calculations, which describe the activity coefficient as a function
of liquid composition. In the following we will consider the Wilson, NRTL, and
UNIQUAC equations. Each of these allows the prediction of multi component activity
coefficients from binary data alone.
2.2 The Wilson equation:
In this activity coefficient equation applicable to homogeneous systems, the activity
coefficient of component i in an N component system is given by

where

In equations above, (ij - ii ) and (ij - JJ) are

two Wilson parameters characteristic of the components I and j, obtainable from
binary data. The parameters
( ij - ii ) are assumed to be independent of
temperature over a narrow temperature range. V j is the liquid molar volume of pure
component. We will be using this equation to find the liquid activity coefficients in
the chapter.
2.3 The NRTL (Non Random, Two-liquid) equation:
This activity coefficient equation is applicable to both heterogeneous and
homogeneous systems. The activity coefficients of two components are given by

Where

In the above equations (g 12 g11) and (g12 g22) are two NRTL parameters
(equivalent to Wilson parameters) Characteristic of both the components. ij is a
third parameter, a constant varying roughly between 0.2 and .47 according to the
type of system concerned.
2.4 The UNIQUAC (Universal Quasi Chemical) equation:
In this activity coefficient equation, applicable to both heterogeneous systems, the
activity coefficient of component I in an N component system is given by

Where

jj = ii = 1 and coordination number z = 10.

In the above equations the parameter Aij characterstic of the components i and j
that can be obtained from binary data. i is the area fraction and i the segment
fraction : ri and qi are the measures of , respectively, molecular vander Waals
volumes and molecular surface and are constants for a pure component.
2.5 The margules equation for binary systems:
Margules assumed that (r) could be expressed by a geometric series expansion in
terms of concentration, where thenumber of required would depend upon the
degree of non ideality of the binary system considered.Concentration terms
higher than cubic area, however ,usually dropped, since introduction of any higher
terms greatly complicates use of the final relations.
Employing a three-term expansion and the DUhem equation
temperature,neglecting the effect of pressure, it may be shown that

at

constant

Here A12 and A21 are constants which are equal to the logarithm of the limiting
activity coefficients.

2.6 The van Laar Equations for binary system:

The Van Laar equations are

In the Van Laar derivation, the constants A 12 and A21 may be related to physical
properties, although it is usually the case that the values A 12 and A21 fitted from
experimental data do not agree well with calculated values.