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Department of Chemical Engineering

University of San Carlos Technological Center


Nasipit, Talamban, Cebu City

ChE 411N
Phase and Chemical Equilibria of Mixtures

Predictive Activity Coefficient Model:


Regular Solution Theory Activity Coefficient Model

Submitted to:
Engr. Luis K. Cabatingan

by:
Amantiad, Japhia Kim
Maguikay, Dia Fatima
Navalta, Carl John Louie
Raboy, Von Adrian

Regular Solution Theory Activity Coefficient Model


Wide variety of organic compounds are of interest in chemical processing. These
processes include a number of binary, ternary, and other mixtures. In some instances,
activity coefficient predictions are needed for systems where experimental data are not
available. One of the two predictive activity coefficient model is the Regular Solution
Theory activity coefficient model. The equations for this model is developed by Hildebrand
and others that are useful in obtaining a semi-quantitive estimates of phase equilibria of
nonpolar systems, and aims to predict the thermodynamic properties of a solution using
only the date for pure components.
A regular solution, by definition, is a solution where the components mix with no
excess entropy and that there is no volume change upon mixing. Mixing of the two
components in a regular solution is at constant temperature and volume. Regular solution
theory is based on van Laar assumption in which a binary mixture is composed of two
species with similar size, shape and energies of interaction. It is expected that for a
specific temperature and pressure, the molecules of each species is uniformly distributed
throughout the mixture so that "#$ = 0 or ($ = 0 and "#$ =

0
#12 #

ln # or ($ =

0. With this, the molar excess Gibbs free energy expression for this theory is:
($ = ($ ($

(1)

where, ($ = ($ + ($
($ = ($ + ($ ($
($ = ($

(2)

The excess molar Gibbs free energy expression for the regular solution theory is
based on the excess molar internal energy of the mixture. And although the excess molar
volume and entropy are approximately equal to zero for some solutions, only few obey
the van der Waals equation of state. Because of this, George Scatchard suggested that
instead of using an equation of state to predict the change in internal energy of
vaporization, the experimental data for internal energy change on vaporization at 25oC
be used.
Hildebrand and Scatchard improved the van Laar equations by disregarding the
limitations of the van der Waals equation of state. With this, a parameter c is defined:

where ;<= is the energy for a complete vaporization or the change in energy in which
a saturated liquid vaporizes isothermally to an ideal gas state at infinite volume. This
parameter is called the cohesive-energy density. The energy of a binary mixture relative
to the ideal gas at the same temperature and composition can be expressed as a
quadratic function of the volume fraction. Also, the volume of a binary mixture is the
average mole fraction of the pure component volumes. Equation 3 is generalized by
Hildebrand and Scatchard to a binary liquid mixture by writing:
?#@A#B CD

"#$

22 20 20 + 220 2 0 2 0 + 00 00 00
=
2 2 + 0 0

(4)

The 22 refers to the interaction between molecules of species 1, 00 refers to the


interaction between molecules of species 2 and 20 refers to the interaction between
unlike molecules (species 1 and 2). Both 22 and 00 are functions of temperature for
saturated liquid. To simplify equation 4, a volume fraction (# ) is introduced:
# =

2 2
2 2 + 0 0

(5)

Then equation 4 becomes:


?#@A#B CD

"#$

= 2 2 + 0 0 22 20 + 220 2 0 + 00 00

(6)

The molar internal energy change on mixing, which is also the excess molar
internal energy, is defined by:
"#$ = ($ = "#$ 2 2 0 0

(7)

Then substituting equations 3 and 6 to equation 7 and utilizing the relation for ideal gas
($
where the change in internal energy of the mixture "#$ is equal to #B(<?
gives the

expression for the excess molar internal energy change:


($ = (22 + 00 220 )2 0 I2 2 + 0 0 J

(8)

In the regular solution theory, the most important assumption is that molecules
having a force of attraction due to dispersion forces will have a simple relation between
22 , 00 and 20 that is:
20 = 22 00

2/0

(9)

2 =

0 =

2/0
22

2/0
00

;<=
=

;<=
=

2/0

(10)
2
2/0

(11)
0

These parameters are functions of temperature, but their difference is often nearly
independent of temperature. Then, equation 8 now becomes:
($ = I2 2 + 0 0 J2 0 (2 0 )0
Since ($ = ($ , the activity coefficient expression for regular solutions will be:
2 = 2 00 (2 0 )0

(12)

0 = 0 20 (2 0 )0

(13)

Equations 12 and 13 are called regular solution equations. These equations


always predict # to be greater than or equal to 1, and therefore regular solution can only
exhibit a positive deviation from Raoults law. Regular solution equations cannot be
applied to a gaseous state solute in liquid solution because in an isothermal dissolution
of gas in a liquid is not a constant volume process. These equations can only be applied
to nonpolar liquefied gases and other nonpolar and slightly polar substances listed in
table 9.6-1 of the book Chemical, Biochemical, and Engineering Thermodynamics 4th
edition by Stanley I. Sandler.