• The definition of fugacity is dG = R T ln f.

This is
valid for all systems. When the component is brought
from the pure state to the solution state, change in
free energy is given by:

G’I – Goi = R T ln (f’I / f0i) = R T ln ai

where ai is the activity of the component in the

solution.
• For any solution f’I = γi xi f0i and

therefore ΔGi = (G’I – G0i) = R T ln (xi γi)

• For ideal solution the activity coefficient is 1.

ΔGidi = R T ln xi

• Hence the excess free energy

GiE = ΔGi – ΔGiid = R T ln γi
• Thus excess free energy is related to the activity coefficient.

• So the correlations for activity coefficient are derived based on

the excess free energy.

• The activity coefficients will also vary with composition,

temperature and pressure.

• If such relations are available, then phase diagrams and phase

equations can be calculated.
• Such relations should satisfy the Gibbs – Duhem equation. Some of
the widely used ones are:

• 1) Wohl’s three suffix equation

• 2) Marugules equation
• 3) Van Laar equation
• 4) Wilson equation.
• 5) UNIQUAC equation (UNIversal QUAsi Chemical)
• 6) UNIFAC equation (UNIversal Functional Activity Coefficient)
• 7) NRTL equation.(Non Random Two Liquid).
• The following empirical relation was derived by Wohl.

• ln γ1 = Z22 [ A + 2( Bq1/q2 – A) Z1]

• ln γ2 = Z12 [ B + 2(Aq2/q1 – B) Z2],

where Z1 = x1 / [ x1 + x2 (q2/q1)] and

Z2 = x2 / [ x2 + x1 (q1/q2)]
 where ,

• Physically q is the effective molar volume and

Z is the effective volume fraction.

• A and B are dependent on the system.

• A, B, and the ratio q1/q2 form the three parameters.

• When q1/q2 = 1, we get Margules three suffix equation.

Here Zi = xi and the equations become:

ln γ1 = x22 [ A + 2(B-A)x1] and

ln γ2 = x12 [ B + 2(A-B)x2]

• Margules two suffix equation is obtained when A = B.

ln γ1 = A x22 and
ln γ2 = B x12
• When q1/q2 = A/B, we get Van Laar equation.

• Since q1/q2 = A/B

Z1 = x1/[x1 + (B/A)x2] and
Z2 = x2 /[x2 + (A/B)x1]

ln γ1 = A Z22 and
ln γ2 = B Z12

• Substituting for Z, we get

ln γ1 = A x22/[(A/B)x1 + x2]2
ln γ2 = B x12/[(B/A)x2 + x1]2
• Expressions for A and B can be obtained from these two
equations.
A = ln γ1 [ 1 + x2 ln γ2/(x1ln γ1)]2
B = ln γ2 [ 1 + x1 ln γ1/(x2ln γ2)]2

• Van Laar equations are widely used for VLE calculations

because of their flexibility and mathematical simplicity.

• Other activity coefficient - composition models are not

derivable from the Wohl’s model.
 ln γ1 = - ln(x1 + Λ12 x2) + x2 [Λ12/(x1 + Λ12 x2)
– Λ21 / (Λ21 x1 + x2)]
ln γ2 = - ln(x2 + Λ21 x1) + x1 [Λ21/(x2 + Λ21 x1)
– Λ12 / (Λ12 x2 + x1)]
• The Λ s are two adjustable parameters and are related to
pure component molar volumes and to the characteristic
energy differences.
Λ12 = (V2/V1) exp [ - (λ12 – λ11)/RT]
Λ21 = (V1/V2) exp [ - (λ21 – λ22)/RT]
• V’s are molar volumes of pure liquids and λ ‘s are the
energies of inter action between the molecules ( both inter
molecules and intra-molecule).
• Here the activity coefficients are estimated through group
contribution.

• The liquid is treated as a solution of different structural groups

from which the molecules are formed, rather than the solution
of molecules themselves.

• Here also we have two parts

a combinatorial part ( based on the molecular size contribution)
the residual part (the interaction contribution).
lnϒi = lnϒi C+ lnϒiR
• This is also based on the local composition theory. The form is
similar to Wilson equations. There are two adjustable
parameters G12 and G21.

G12 = exp ( - α12 τ12) and G21 = exp ( - α21 τ21);

where τ12 = b12/RT and τ21 = b21/RT

• bij are similar to the characteristic energy differences. α12 is

related to the non-randomness in the mixture. α12 = 0 for
completely random distribution but generally the typical value
is 0.3 ( experimental data varies from 0.2 to 0.47 )

• Note: NRTL equation is applicable to partially miscible as well

as totally miscible systems.
• Many practical cases like distillation are dependent on VLE
data and such data should be reasonably accurate if the results
are to be reliable.

• Thermodynamics provides tests for consistency of

experimental VLE data.

• Almost all these tests are based on the Gibbs- Duhem

equations written in terms of activity coefficients
 ln γ
• The Gibbs – Duhem equation in terms of activity coefficient
provides a very simple test for thermodynamic consistency.

x1 [∂ ln γ1 /∂x1]T,P = - (1- x1)[∂ln γ2 / ∂x1]

• Since x1 and (1 – x1) are positive, the slopes of lnγ1 vs x1 curve

and ln γ2 vs x1 curve must be opposite.
• If one is positive the other must be negative.
• If one curve shows a maximum the other must show a
minimum at the same composition.
• Only if ln γ curves show a maximum/minimum the values can
be of opposite signs. Otherwise both must be positive or
negative.
• Consider the van Laar equation. Put x1 = x2 = 0.5
• We observe that
ln γ1 / B = ln γ2 / A = A B /(A + B )2

• Case 1: A = B. Then lnγ1 = B/4 and lnγ2 = A/4.

• Case 2: A = 2 B Then lnγ1 = 2B/9 and lnγ2 = 2A/9
• Case 3: A = 3 B. Then lnγ1 = 3B/16 and lnγ2 = 3A/16.

• In all cases ln γ is approximately one-fourth of the van Laar

constants.
• From the Margules three suffix equation it can be seen that as
x1 → 0 ( x2→ 1), ln γ1→ A
similarly as x2 → 0, ln γ2 → B

That is, the end values are A and B. So the mid point values are
one-fourth of the end values approximately. For consistency, the
curve which is maximum at the end must be minimum at the
midpoint.
• This is also known as zero area method.

• We know that the excess free energy of mixing

ΔGE = R T ∑ xi ln γi

• For a binary solution, it can be written as

ΔGE = R T ( x1 ln γ1 + x2 ln γ2 )

• Differentiating this with respect to x1, we get

d(ΔGE)/dx1 = R T [ln(γ1 / γ2) + x1 d(ln γ1)/dx1 + (1- x1) d(ln γ2)/dx1]

• Substitution of Gibbs – Duhem equation into the above gives

d(ΔGE)/dx1 = R T ln(γ1 / γ2)

• This can be integrated between the limits x1 = 0 and x1 = 1.

Since only pure components are involved at these two end
points and no mixing effects occur, ΔGE = 0 at these points.

1
• Hence 0 ln(γ1 / γ2) dx1 = 0
∫

• The net area of the diagram of ln(γ1 / γ2) against x1 must be

zero for consistent experimental data.
• The activity coefficients can be written as ( vapor is assumed
to behave ideally)

γ1 = P y1 / ( Pv1 x1) , γ2 = P y2 / ( Pv2 x2)

• The Gibbs – Duhem equation can be written as

x1 d ln γ1 = - (1- x1) d ln γ2

• Substituting the expressions for activity coefficients we get

x1d ln[P y1 / ( Pv1 x1)] = - (1 – x1) d ln [P y2 / ( Pv2 x2)]

• Since Pv1 is a constant at constant temperature, the above
equation can be simplified as

d P/dy1 = P (y1 – x1) / [y1 (1 – y1)]

• This is known as co-existence equation.

• The experimentally determined x, y, P values must satisfy this

equation.
• Gibbs – Duhem equation in terms of fugacity can be rewritten
in terms of partial pressures.

• The slopes of partial pressure data curve against x1, may be

used to check the accuracy of the data by comparing if the
values of
( x1 / p’1) d p’1/ d x1 + ( x2 / p’2) d p’2/ d x1 = 0

• VLE involving multi components and high pressures

• For any equilibrium, the fugacities of vapor and liquid must be

same.
• For any equilibrium, the fugacities of vapor and liquid must be
same.
• This can be expressed as

fi0v γiv yi = xi γiL fioL

Now we define vaporization equilibrium constants

Ki = (yi / xi) = [γiL fioL / ( γiv fiov)]

It can also be obtained as

Ki = φis γiL Pvi / (φ’I P)

• Here we have taken Poynting correction factor to be unity;

• But if it is not, it can also be included.

• For ideal solutions K factors depend only on temperature and

pressure and the component.
• The given compositions of the multi-component solution pertains to
the liquid compositions, xi.

• It is required to find the bubble point temperature (or pressure),

given pressure (or pressure, given temperature) and the vapor
composition.

• Ideal gas – ideal solution case: the Ki = Pvi / P

• Pvi can be calculated from the assumed temperature.

• Then yi can be calculated as yi = Ki xi

• If the assumed temperature were correct, ∑ yi should be equal
to 1. So iterate till this condition is met.

• An appropriate temperature may be found from the boiling

point of the major component.

• For Pvi either Antoine equation or tabulated values may be

given.
• Antoine equation is of the form

ln Pvi = Ai – [Bi/(T-Ci)]

• If the vapor pressure data is given in the form of a table,

curves can be drawn between vapor pressure and temperature
which can be used for interpolation.

• Similar procedure may be followed for finding bubble

pressure. Here temperature will be given but pressure will
have to be assumed to calculate Ki values.
• Here the given composition pertains to the vapor composition.

• So from Ki and yi calculate

xi = yi / Ki

• As in the case of bubble temperature, if the assumed

temperature were correct then ∑ xi should be equal to 1.
• Here the calculations are similar to the previous mentioned
procedure; except that the Ki values are obtained from the
DePriester nomographs.

• They can also be obtained using fugacity coefficient, activity

coefficient and Poynting correction factor
• The basic feature of flash vaporization is to heat the liquid
solution to the required level and introduce into a vessel
maintained at a lower pressure.
• Part of the liquid will vaporize.
• If F, V, and L are the flow rates of input, vapor and liquid
streams a mass balance gives
F=L+V
• If zi, yi, and xi are the composition of the ith component in the
input , vapor and liquid output streams then component
material balance gives
F zi = V yi + L xi
 Since yi = Ki xi, it can be eliminated to get the following:

xi = F zi /[Ki V + L] = (F/V) [zi/{Ki + (L/V)}]

• Since ∑ xi = 1, we have
∑ {zi / [Ki + (L/V)]} = V/F

• The above equation can be used for the calculation of T, P or

fractional vaporization in an iterative procedure.