CHEMICAL ENGINEERING

THERMODYNAMICS - II
2150503

By Krunal J.S.

2. Solution thermodynamics: APPLICATION Lecture I

 Content
Local Composition
Models for the
Models: NRTL Thermodynamic
Excess Gibbs
Equation, Consistency,
Energy: Margules
UNIQUAC Equation Integral or Area
Equations and
and UNIFAC Test Method ,
Van-Laar Equations
Method

Excess Fugacity and

Gibbs Energy, Fugacity
Activity and Coefficient:
Activity coefficient Species in Solution

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Models for the Excess Gibbs Energy

Wohl’s three-suffix equation

Margules equation

Van Laar equation

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Models for the Excess Gibbs Energy

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Models for the Excess Gibbs Energy
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 equilibria of phases, 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.

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Models for the Excess Gibbs Energy
Van Laar equation

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Models for the Excess Gibbs Energy
Van Laar equation

For low pressure, VLE problem

When an azeotrope is formed, only azeotrope composition need to be

known, because it represents the composition off both the liquid and the
vapour phases. The activity coefficients can be evaluated by putting x = y

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 Solution: slide no. 10 to 22

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Solution
Azeotrope is formed when, the liquid phase acetone composition is 0.75

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 𝐺𝐸
= 𝑥1 𝑙𝑛𝛾1 + 𝑥2 𝑙𝑛𝛾2
𝑅𝑇

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Margules Van Laar

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Neglecting X1 as it is almost equal to 0 Neglecting X2 as it is almost equal to 0
γ2 = 1.132 γ1 = 1.067

We know γ2 We know γ2

0.124= (0.0331)2 [A21 + 2(A12 – A21) 0.9669] 0.066= (0.0348)2 [A12 + 2(A21 – A12) 0.9652]

Two equations, two unknowns

A12 = and A21 =
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Questions asked in GTU examination

May 2016, Dec 2015, June 2014, Nov 2011

γ1 = 1.4702 (1) Benzene
(2) Ethanol (alcohol)
γ2 = 1.5030 X1 = 0.552
X2 = 0.448

A = 1.3305
B = 1.9106

For, X2 (ethanol) = 0.1 γ1 = 1.0255

X1 (benzene) = 0.9
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 Thermodynamic Consistency
Using ln γi vs xi curve
Using data at the mid point
Redlich Kister Test (ZERO AREA TEST)
Using the coexistence equation

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Thermodynamic Consistency
Using ln γi vs xi curve

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 Thermodynamic Consistency
Maximum for ln γ1 curve
Using slope of ln γi vs xi curve

If the slope of ln γ1 curve at x1 = 0.75 is -0.62

Then the slope of ln γ2 curve at x1 = 0.75 is 0.62 Minimum for ln γ2 curve

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Both the cases here are consistent
 Thermodynamic Consistency

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Both the cases here are Inconsistent
 Thermodynamic Consistency
Using data at the mid point

For finding thermodynamic constancy of VLE data, the integral form of

Gibbs Duhem equation like Margules and Van Laar are very convenient.
Put X1 = X2 in the Excess Gibbs model and check;

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 Thermodynamic Consistency
Redlich Kister Test (ZERO AREA TEST)

It can be used when values of activity coefficients are known for the
entire range of composition.

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 Thermodynamic Consistency
Using the coexistence equation
Put the equation in Gibbs Duhem equation;

The equation is known as coexistence equation

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Thermodynamic Consistency
Using partial pressure data

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 LOCAL COMPOSITION MODELS
The local concentration around a molecule is different from the bulk
concentration.

This difference is due to a difference between the interaction energy of the

central molecule with the molecules of its own kind Uii and that with the
molecules of the other kind Uij

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Energy of interaction between a molecule of component i and a molecule j

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 WILSON EQUATION
Disadvantages:
• Not applicable to
systems where lnγ
exhibit maximum or
Advantages: minimum
It predicts • Not able to predict
temperature limited miscibility
dependence of the • Used only for
completely miscible or
activity coefficients
partially miscible system
in region where only 1
liquid phase exist

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Wilson parameter of the system nitromethane and CCl4 at 45C
are 0.1156 and 0.2879 respectively. Calculate activity
coefficient for the mixture with 30 mole% nitromethane

γ1 = 2.5126 and γ2 = 1.2958

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 NON-RANDOM TWO LIQUID (NRTL)
It is applicable to partially miscible as well as completely miscible system.

non-randomness
parameter
Usually the value
is 0.2, 0.3, 0.48
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 NON-RANDOM TWO LIQUID
The energy difference also introduces a non-randomness at the
local molecular level. The NRTL model belongs to the so-called
local-composition models

For a liquid, in which the local distribution is random around the

center molecule, the parameter α12 is set 0 and the equation
reduces to Margules equation. The parameter is less dependent
on temperature.

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 UNIQUAC (UNIversal QUAsiChemical Activity Coefficient)
The UNIQUAC model can be considered a second generation activity coefficient
because its expression for the Excess Gibbs energy consists of an entropy term in
addition to an enthalpy term. Earlier activity coefficient models such as the
Wilson equation and the Non-random two-liquid model (NRTL model) only
consist of enthalpy terms.

The UNIQUAC model also serves as the basis of the development of the group
contribution method UNIFAC

The UNIQUAC model the activity coefficients of the ith component of a two
component mixture are described by a combinatorial and a residual contribution.

• 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.
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Group Contribution Model: UNIFAC
The UNIFAC method (UNIversal Functional-group Activity
Coefficients) is a semi-empirical system for the
prediction of non-electrolyte activity in non-ideal
mixtures.
UNIFAC uses the functional groups present on the
molecules that make up the liquid mixture to calculate
activity coefficients

• Analytical Solution of Group (ASOG) method

• UNIquac Functional group Activity Coefficient method

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Questions asked in GTU examination

Dec 2012

May 2016, Dec 2015, June 2014, Nov 2011

Dec 2013

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• Write short note on Van Laar equation and Margulas eqation
• Discuss any two group contribution methods to determine
Activity coefficients.
• Show that the van Laar equation & Margules equation are
consistent with Gibbs - Duhem equations
• Define activity coefficient. Discuss Margules and Wilson
equations with their merits and demerits.
• Discuss various methods for checking the consistency of
experimental VLE data

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