CORRELATIONS FOR LIQUID-PHASE ACTIVITY

COEFFICIENTS

The term “Vapor-Liquid Equilibrium (VLE)” refers to systems in which a single

liquid phase is in equilibrium with its vapor, schematic diagram of the vapor-liquid
equilibrium. In studies of phase equilibrium, however, the phase containing gradients is
not considered. Wherever gradients exist there is a tendency for change with time; hence
there is no equilibrium. On the other hand, there can be two or more phases, each of
which is homogenous throughout, with no tendency for any change in properties with
time, even though the phases are in intimate physical contact with one another. The latter
is the condition that we denote by the term “phase equilibrium”. In a condition of phase
equilibrium there are some properties that are drastically different between the phases
and others that must be identical for all phases to prevent a change in properties within
individual phases from occurring . The thermodynamic equilibrium determines how
components in a mixture are distributed between phases.

Liquid-phase activity coefficients γi play a vital role in the gamma/phi formulation

of VLE. They are directly related to the excess Gibbs energy. In general, GE∕RT is a
function of T, P, and composition, but for liquids at low to moderate pressures it is a
very weak function of P. Therefore its pressure dependence is usually neglected, and for
applications at constant T, excess Gibbs energy is treated as a function of composition
alone:
GE
 g x1 , x2 ,  xn  const T 
RT

Margules Equation

Max Margules introduced in 1895, a simple thermodynamic model for the excess
Gibbs free energy of a liquid mixture. After Lewis had introduced the concept of the
activity coefficient, the model could be used to derive an expression for the activity
coefficients γi of a compound i in a liquid and the activity coefficient is a measure for the
deviation from ideal solubility. In Chemical Engineering the Margules' Gibbs free energy
model for liquid mixtures is better known as the Margules activity or activity coefficient
model. Although the model is old it has the characteristic feature to describe extrema in
the activity coefficient, while modern models like UNIQUAC, NRTL and Wilson
cannot.

Margules expressed the excess Gibbs free energy of binary liquid mixtures is as follow,

GE
 x1 x2  A21 x1  A12 x2 
RT
The activity coefficient of component i is found by differentiation of the excess Gibbs energy
towards xi. This yields, when applied only to the first term and using the Gibbs-Duhem equation,

ln  1  x22  A12  2 A21  A12 x1 

ln  2  x12  A21  2 A12  A21 x2 

Van Laar Equation

The Van Laar equation is an activity model, which was developed by Johannes Van
Laar in 1910- 1913, to describe phase equilibria of liquid mixtures. The equation was
derived from the Van der Waals equation. The original Van der Waals parameters didn't
give good description of vapor-liquid phase equilibria, which forced the user to fit the
parameters to experimental results. Because of this, the model lost the connection to
molecular properties, and therefore it has to be regarded as an empirical model to
correlate experimental results.

Van Laar expressed the excess Gibbs free energy of binary liquid mixtures is as follow,
GE A21 x1 x2

RT x1  A12 / A21   x2
In here A12 and A21 are constants, which are obtained by regression of experimental
vapor-liquid equilibria data.
The activity coefficient of component i is derived by differentiation to xi. This yields:
2
 A21 x2 
ln  1  A12  
 A12 x1  A21 x2 
2
 A12 x1 
ln  2  A21  
A x
 12 1  A x
21 2 

Wilson Equation
Based on molecular considerations, Wilson (1964) presented the following expression for
the excess Gibbs energy of a binary solution:
GE
  x1 ln x1  A12 x2   x2 ln x2  A21 x1 
RT
Activity coefficients derived from this equation are
 A12 A21 
ln  1   ln  x1  A12 x2   x2   
 x1  A12 x2 x2  A21 x1 
 A12 A21 
ln  1   ln  x2  A21 x1   x1   
 x1  A12 x2 x2  A21 x1 
Wilson’s equation has two adjustable parameters, A12 and A21. In wilson derivation,
these are related to the pure-component molar volumes and to characteristic energy
differences by
v2    
A12  exp  12 11 
v1  RT 
v    
A21  1 exp  21 22 
v2  RT 

NRTL Equation

The basic idea in Wilson’s derivation follows from the concept of local composition.
This concept was also used by Renon (1968) in his derivation of the NRTL (nonrandom,
two-liquid) equation; however, Renon’s equation, unlike Wilson’s is applicable to partially
miscible as well as completely miscible systems. The NRTL equation for the excess
Gibbs energy is

GE   G  G 
 x1 x2  21 21  12 12 
RT  x1  x2G21 x 2  x1G12 

  G 
2
G12 12 
2
ln  1  x  21  21
  
  x1  x2G21  x2  x1G12  
2 2

  G 
2
G21 21 
2
ln  2  x  12  12
  
  x2  x1G12  x1  x2G21  
1 2

G12  exp  12  G21  exp  21 

b12 b21
 12   21 
RT RT

where α, b12, and b21, parameters specific to a particular pair of species, are independent
of composition and temperature.
FITTING ACTIVITY COEFFICIENT MODELS TO VLE DATA
 EXERCISES

For the propanol(1)/water(2) system, make the following calculations:

(a) BUBL T:P = 101.33 kPa, x1 = 0.3
(b) DEW T:P = 101.33 kPa, y1 = 0.3

1. Margules Equation
2. Van Laar Equation
3. Wilson Equation

Use Excel for iteration calculation.

Physical Constants and Model Parameters

COMPONENTS
CONSTANTS (1) 1-Propanol (2) Water
1. Antoine Constants
A 17.5439 18.3036
B 3166.3800 3816.4400
C -80.1500 -46.1300
2. Molar Volume (ml/mol) 60.096 18.07
3. Binary Interacting Parameters
Ā12 2.2939
Margules
Ā21 0.97366
A12 2.57597
van Laar
A21 1.20101
Λ12 – λ11 775.48
Wilson (calmol–1)
Λ21 – λ22 1351.90