Uniquac

ACTIVITY-COEFFICIENT MODEL FOR THE LIQUID PHASE
UNIQUAC MODEL
BY T.AJEETH PRABHU (096003) B.KRISHNA MOHAN (096011)
CONTENTS
INTRODUCTION

EQUATIONS COMBINATORIAL CONTRIBUTION RESIDUAL CONTRIBUTION CHOOSING THE PROPER ACTIVITY-COEFFICIENT MODEL
APPLICATIONS
PARAMETERS NEWER DEVELOPMENTS REFERENCES
INTRODUCTION
UNIQUAC (short for UNIversal QUAsiChemical) is an activity
coefficient model used in description of phase equilibria.
The model is a so-called lattice model The model is not fully thermodynamically consistent due to its two
liquid mixture approach.

In this approach the local concentration around one central molecule is
assumed to be independent from the local composition around another type of molecule
INTRODUCTION
Today the UNIQUAC model is frequently applied in the description of
phase equilibria (i.e. liquid-solid, liquid-liquid or liquid-vapor equilibrium).

The UNIQUAC model also serves as the basis of the development of
the group contribution method UNIFAC, where molecules are subdivided in atomic groups.
In fact, UNIQUAC is equal to UNIFAC for mixtures of molecules,
which are not subdivided; e.g. the binary systems water-methanol, methanol-acryonitrile and formaldehyde-DMF.
EQUATIONS
In the UNIQUAC model the activity coefficients of the ith
component of a two component mixture are described by the sum of two contributions.They are

Combinatorial contribution Residual contribution.
EQUATIONS
The first is an entropic term quantifying the deviation from ideal
solubility as a result of differences in molecule shape.

The latter is an enthalpic correction caused by the change in
interacting forces between different molecules upon mixing.
COMBINATORIAL CONTRIBUTION
The combinatorial contribution accounts for shape differences
between molecules and affects the entropy of the mixture.

The excess entropy
C
is calculated exclusively from the pure
chemical parameters, using the relative Van der Waals volumes ri and surface areas qi of the pure chemicals.
With the volume fraction per mixture mole fraction,
Vi, for the ith component given by:
And the surface area fraction per mixture molar
fraction, Fi, for the ith component given by:
In the limit of infinite dilution and a binary mixture the
equations for the combinatorial contribution reduces to:
This pair of equation shows that molecules of same shape, i.e.
same r and q parameters, have
RESIDUAL CONTRIBUTION
The residual term contains an empirical parameter,
which is derived from experimental or occasionally estimated activity coefficients. The expression for the residual activity coefficient for molecule i is:
ij,
with

uij [J/mol] is the binary interaction energy parameter. Theory defines uij = uij - uii, and uji = uji - ujj, where uij is the interaction energy between molecules i and j.
RESIDUAL CONTRIBUTION
Usually uij uji, because the energies of evaporation (i.e. uii), are in may cases
different, while the energy of interaction between molecule i and j is symmetric, and therefore uij=uji. If the interactions between the j molecules and i molecules is the same as between molecules i and j, than mixing has no excess energy effect upon mixing, uij= uji=0. And thus Alternatively, in some process simulation software
ij
can be expressed as follows:
ln( ij) = Aij + Bij / T + Cij * ln(T) + DijT2 + Eij / T2 . The "C", "D", and "E" coefficients are primarily used in fitting liquid-liquid equilibria (with "D" and "E" rarely used at that). The "C" coefficient is useful in vapor-liquid equilibria as well.
CHOOSING THE PROPER ACTIVITY COEFFICIENT MODEL
Activity Coefficient Model

NRTL Wilson SRK UNIQUAC UNIFAC
Conditions
Strongly non-ideal including electrolytes Slightly non-ideal Very near ideal Highly non-ideal systems Non-ideal systems below 10 bars
APPLICATIONS
y Activity coefficients can be used to predict simple phase equilibria
(vapour-liquid, liquid-liquid, solid-liquid), or to estimate other physical properties (e.g. viscosity of mixtures).
y Models such as UNIQUAC allow chemical engineers to predict the
phase behavior of multicomponent chemical mixtures.

y They are commonly used in process simulation programs to calculate
the mass balance
PARAMETERS
UNIQUAC requires two basic underlying parameters:
surface and volume fractions are chemical constants, which must be known for all chemicals. An empirical parameter between components that describes the intermolecular behavior. This parameter must be known for all binary pairs in the mixture.
Relative
Newer Developments
UNIQUAC has been extended by several research groups. Some selected
derivatives are:
UNIFAC: A method which permits the volume, surface and in particular, the
binary interaction parameters to be estimated. This eliminates the use of experimental data to calculate the UNIQUAC parameters.
Extensions for the estimation of activity coefficients for electrolytic mixtures. Extensions for better describing the temperature dependence of activity
coefficients
Solutions for specific molecular arrangements.
REFERENCES
1.Abrams D.S., Prausnitz J.M., Statistical Thermodynamics of Liquid Mixtures: A New Expression for the Excess Gibbs Energy of Partly or Completely Miscible Systems, AIChE J., 21(1), 116-128, 1975 2.McDermott (Fluid Phase Equilibrium 1(1977)33) and Flemr
(Coll.Czech.Chem.Comm., 41(1976)3347) 3. Separations process and principles by Henley and Seider 4. Introduction to chemical engineering thermodynamics by smith and van hess
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ACTIVITY-COEFFICIENT MODEL FOR THE LIQUID PHASE

BY T.AJEETH PRABHU (096003) B.KRISHNA MOHAN (096011)

PARAMETERS NEWER DEVELOPMENTS REFERENCES

liquid mixture approach.

phase equilibria (i.e. liquid-solid, liquid-liquid or liquid-vapor equilibrium).

Combinatorial contribution Residual contribution.

 The first is an entropic term quantifying the deviation from ideal

solubility as a result of differences in molecule shape.

interacting forces between different molecules upon mixing.

between molecules and affects the entropy of the mixture.

is calculated exclusively from the pure

Vi, for the ith component given by:

 And the surface area fraction per mixture molar

fraction, Fi, for the ith component given by:

 In the limit of infinite dilution and a binary mixture the

equations for the combinatorial contribution reduces to:

 This pair of equation shows that molecules of same shape, i.e.

same r and q parameters, have

can be expressed as follows:

CHOOSING THE PROPER ACTIVITY COEFFICIENT MODEL

Activity Coefficient Model

phase behavior of multicomponent chemical mixtures.

the mass balance

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The first is an entropic term quantifying the deviation from ideal

And the surface area fraction per mixture molar

In the limit of infinite dilution and a binary mixture the

This pair of equation shows that molecules of same shape, i.e.