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.

COMBINATORIAL CONTRIBUTION
 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:

COMBINATORIAL CONTRIBUTION

 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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