CHEMICAL ENGINEERING

THERMODYANAMICS-II
EVALUATION OF ACTIVITY COEFFICENT
Prepared By
Hitesh N. Panchal
Assistant Professor
D.D.University Nadiad.

1
 Vapor-Liquid Equilibrium
• Classical thermodynamics allows us to obtain a
relationship between the equilibrium mole fraction
in the liquid phase, x, and the vapor phase, y.
• Equilibrium between the liquid and vapor phases
requires that the temperatures, pressures, and
fugacities of each component be equal in the two
coexisting phases.
• By equating the fugacity of component 1 in the
liquid phase to its fugacity in the vapor phase.
 Activity coefficient from VLE data
• How activity coefficients can be calculated from
experimental VLE data obtained at low pressures?
• For our calculations we take advantage of the fact
that as P->0 the vapour phase molecular interactions
in a mixture at VLE become very weak, hence the
vapour behaves as an ideal gas.
• The modified form of Raoult’s law can then be used
for the estimation of the activity coefficients from
experimental low P VLE
y iP
i 
x i Pisat
3
 Positive deviation from Raoult’s Law
• Positive deviations correspond to values of iL > 1.
• Nonideality results in a variety of variations of (iL) with
composition If the activity coefficients are unity, then the
system is ideal and is said to obey Raoult's Law.
• Activity coefficients greater that unity give pressures that are
larger than the sum of the pure vapor pressures and are said
to have positive deviations from Raoult's Law.
• Positive deviations mean that the partial pressure in the vapor
phase is larger than it would be for an ideal system

4
 Binary vapor-liquid equilibrium

ChE 334: Separation Processes Dr Saad Al-Shahrani

 Binary vapor-liquid equilibrium

ChE 334: Separation Processes Dr Saad Al-Shahrani

 Positive deviation from Raoult’s Law

Repulsion Component(1)
Molecules that are dissimilar enough from each x1
other will exert repulsive forces 

+
e. g: polar H2O molecules – organic hydrocarbon
molecules.
i > 1
Component(2)
x2


When dissimilar molecules are mixed together due

to the repulsion effects, a greater partial pressure is
exerted, resulting in positive deviation from ideality.
+

ChE 334: Separation Processes Dr Saad Al-Shahrani

 Negative deviation from Raoult’s Law
Attraction
When dissimilar molecules are mixed together, due to the attraction effects,
a lower partial pressure is exerted, resulting in negative deviation from
ideality.
i < 1 are called negative deviation from ideality.

Component(1) Component(2)
x1 x2

- -

 1  2

ChE 334: Separation Processes Dr Saad Al-Shahrani

 Positive deviation from Raoult’s Law

Plot of experimental P-x-y, activity coefficient and molar excess Gibbs free energy data

9
Negative deviation from Raoult’s Law

Plot of experimental P-x-y, activity coefficient and molar excess Gibbs free energy data

10
 Liquid Phase Properties from VLE Data

• Calculate activity coefficient at infinite dilution or

Margule’s constants or limiting activity coefficient
11
 Infinite dilution
• It is the particular behavior of a two
substances mixture when the concentration of
one component approaches the limit of zero
and the other approaches 1(second
component being the solvent).
• Behavior when the mixture is sufficiently
dilute that solute-solute interactions are
negligeble.

12
 Importance and use of infinite
dilution activity coefficient data
• The most difficult and costly stage of a
separation process is the removal of the last
traces of impurity
• The greatest departure from ideality occurs in
the very dilute regions
 Importance and use of infinite
dilution activity coefficient data
• Synthesis, design and optimization of separation
processes
• Calculation of Henry`s law constants
• Predicting the existence of an azeotropes
• Development of predictive methods for
• Characterization of behaviour for liquid mixtures.
VLE data for methyl ethyl ketone(1)/toluene(2) at 500C

15
16
17
18
19
 Margules equation
Max Margules introduced in 1895 a simple
thermodynamic model for the excess Gibbs
free energy of a liquid mixture.

He had introduced the concept of the activity

coefficient, the model could be used to
derive an expression for the activity
coefficients of a compound i in a liquid.

20
 Margules equation

• Activity coefficient of component i is derived

by differentiation to xi.
• Three suffix equation or two-constant or Two
parameter margules equation

• In here A12 and A21 are constants, which are

obtained by regression of experimental vapor-
liquid equilibrium data. 21
22
23
24
25
26
VLE data for chloroform(1)/1,4-dioxane(2) at 500C

• Calculate activity coefficient at infinite dilution or

Margule’s constants or limiting activity coefficient
27
VLE data for chloroform(1)/1,4-dioxane(2) at 500C

28
29
Example

30
Example

31
 For liquid phase composition
• For a binary solution of two components 1 and 2, the
modified raoult’s law is given by,

32
 For vapor phase composition
• For a binary solution of two components 1 and 2, the
modified raoult’s law is given by,

33
 Example
• For the system methanol(1)/methyl acetate(2), the
activity coefficients for components 1 and 2 are
represented by

Where pressure is in kPa and T in K.

Calculate P and yi at T=318.15 K and x1=0.25.
34
 Answer
• Activity coefficient of methanol(1)= 1.864
• Activity coefficient of methyl acetate(2) = 1.072
• Total pressure (P) = 73.50 kPa
• The vapor phase composition is,
y1 = 0.282
y2 = 0.718

35
THANK YOU
 Topics
• Introduction – VLE at low pressure
• Azeotropes
• Types of Azetropes
• Activity models

37
VAPOR-LIQUID EQUILIBRIUM AT LOW PRESSURE

• Fugacity coefficient of a component in a

mixture  virial equation & applying concept
of residual properties.
• Activity coefficient of a component in a
solution From VLE data & applying concept
of excess properties.
 Azeotropes
• In some real systems, the temperature / composition
curve is far from ideal.
• A maximum or minimum in the curve is possible; this
is an azeotrope.
• At the azeotrope, the liquid and vapor have the same
composition.
• Word azeotrope is derived from the Greek words,
overall meaning, "no change on boiling".

39
 Azeotropes
• Importance of boiling point diagram(T-x-y
diagram) & P-x-y diagram.
• An Azeotrope is a mixture of two or more
liquids in such a way that its components
cannot be altered by simple distillation.
• This happens because, when an azeotrope is
boiled, the vapor has the same proportions of
constituents as the unboiled mixture.

40
 Azeotropes
• Because their composition is unchanged by
distillation, azeotropes are also called
constant boiling mixtures.

41
 Azeotropes
• For a binary mixture consisting components A & B,
azeotropes are formed when there is a large
deviation from ideality and the vapor pressures of
the components A and B are not much different.
• Each azeotropes has a characteristic boiling point.
• Boiling point of an azeotropes is either less than the
boiling points of any constituents(positive
azeotropes) or greater than the boiling point of any
of its constituents (a negative azeotrope).

42
 Types of Azeotropes
• Azetrope consisting of two constituents, are
called binary azeotropes, consisting of three
constituents are called ternary azetropes.
• Types of Azeotropes:
1. Maximum Boiling Azeotropes or Negative
azeotropes or Maximum Boiling
Mixtures or Pressure Minimum Azeotropes
2. Minimum Boiling Azeotropes or Positive
Azeotropes or Minimum boiling azeotropes or
Pressure Maximum Azeotropes
43
 Ethanol-water system
• A example of a positive azeotrope is
89.44% ethanol and 11.56% water (by weight).
• Ethanol boils at 78.4 °C, water boils at 100 °C, but the
azeotrope boils at 78.2 °C, which is lower than either
of its constituents.
• 78.2 °C is the minimum temperature at which any
ethanol/water solution can boil at atmospheric
pressure.

44
 Temperature-Composition Diagram
for Ethanol-Water, P = 1 atm
100

95
Superheated Vapor Phase
Two Phase
90
T( oC)

85

80

Subcooled Liquid Phase

75
z EtOH
0.0 0.2 0.4 0.6 0.8 1.0
xEtOH or yEtOH

45
 Equilibrium curve y vs x
• Ethanol-Water system
Ethanol-Water Equilibrium Data, P = 1 atm
yEtOH vs x EtOH

1.0

0.9

0.8

0.7

0.6
yEtOH

0.5

0.4

0.3

0.2

0.1

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
xEtOH

46
 Azeotropes-The problem
• Equilibrium curve is, in general, above the x =
y line when the more volatile component is
plotted, in this case ethanol.
• Point where the liquid and vapor mole
fractions touch the x = y line indicates that
they are equal – this is termed the azeotropic
point or azeotrope.
• Initially more volatile component is no longer
the more volatile component at the
azeotropes.
• For an ethanol-water mixture at P = 1 atm,
this point is xEtOH = yEtOH = 0.8943, which from
at T = 78.15oC.
47
 Ethanol-Water Equilibrium Data, P = 1 atm
yEtOH vs x EtOH

1.0

0.9
Azeotrope

0.8

0.7

0.6
yEtOH

0.5

0.4

0.3

0.2

0.1

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
xEtOH

48
 Azeotropes-The problem
• Azeotropes often present problems in equilibrium vapor-
liquid phase separations since their presence means that one
will not obtain enrichment between the vapor phase and the
liquid phase above the azeotrope – one cannot obtain
separation greater than the azeotropic point for a given set of
conditions.

• This limit is 0.8943 mole fraction of ethanol for an ethanol-

water mixture at P = 1 atm.

• To separate a mixture containing 0.9 ethanol liquid mole

fraction at 1 atm, one would not obtain a greater
concentration in the vapor phase than in the liquid phase.

49
• Azeotropes are dependent upon pressures and one
way to avoid this problem is to vary the pressure.

• For example, under a vacuum (P = 70 mmHg), no

azeotrope exists for the ethanol-water mixture. This
is one reason that vacuum distillation is often done
for many separations.

• Azetropes are often also component dependent.

• For example, the addition of a 3rd component to a

binary system, may change or “break” the azeotrope.

50
Maximum Boiling Azeotropes or Negative
azeotropes
• They are also called maximum boiling
mixtures, show negative deviation from
Raoult’s law lnYi < 0.
• If the deviation from ideal behaviour is
negative and large, the curve

51
Maximum Boiling Azeotropes or Negative
azeotropes

•Makes physical separation of the two components impossible.

52
 Minimum Boiling Azeotropes or Positive
Azeotropes
• They are also called minimum boiling
mixtures, show positive deviation from
Raoult’s law lnYi > 0.
• If the deviation from ideal behaviour is
positive & sufficiently large, and curve

53
Minimum Boiling Azeotropes or Positive
Azeotropes

•Makes physical separation of the two components impossible by simple distillation.

54
 Separation of Azeotropes
• Azeotropic distillation
• Chemical action separation
• Extractive distillation
• Pressure swing distillation
• etc..

55
 Use of MSA
• Can be used for close boiling mixtures,homogeneous
azeotropes and in order to reverse volatilities If a relatively
volatile MSA is used, it will be chosen so that it forms an
azeotrope (usually min boiling) with either or both of the
original components (Azeotropic Distillation)
• If a non-volatile solvent is used, it will be chosen to dissolve
one component preferentially, allowing other component to
leave in distillate (Extractive Distillation)

56
 Azeotropic Distillation to Isolate
Aromatics
• Best when high aromatic content
• The addition of strongly polar agents (amines,
alcohols, ketones, water) facilitates the removal of
alkanes and cycloalkanes as lower boiling azeotropes
• For example, add acetone to remove nonaromatics
from the benzene fraction and then extract the
acetone from the benzene with water.

57
 Extractive Distillation
• An additive is used to increase the differences
in boiling points
• For example, add NMP O
N
(N-methylpyrrolidone) CH 3
• This increases the boiling point of the
aromatics by “complexation” of the 
electrons in the aromatic ring with the NMP
and therefore facilitates separation

58
 VAPOR-LIQUID EQUILIBRIUM AT LOW TO
MODERATE PRESSURE
• Experimental data on activity coefficients of various types
of liquid solutions are often not available at conditions (of
temperature and/or composition) of interest.
• In such cases activity coefficient models - which relate GE
to solution composition (at a given T&P) - are useful.
• These models are all characterized by a set of parameters
that are temperature dependent.
• Vapour-liquid equilibrium (VLE) data at low pressures are
readily used for computing the value of such parameters.
 VAPOR-LIQUID EQUILIBRIUM AT LOW PRESSURE

• Various activity coefficient models commonly used for

VLE calculations.
• Divided into two major groups depending upon their
applicability to various types of solutions:
1. Margules/Van Laar models
• Homogeneous Mixture models
2. Wilson/NRTL (Non-Random Two Liquid)/UNIQUAC
(Universal Quasi Chemical) Models
• Local Composition models
• Non-ideal behavior of liquid solutions derives from
two sources:
– difference in molecular size/shape of constituent
– difference between the inter-species molecular
interaction energies.
• Type 1 models generally apply to systems in which
the inter-species and intra-species molecular
interaction energies differ from each other.
• Type 2 models are principally useful for describing
systems where the constituent molecular species
differ on account of both size/shape as well
molecular interaction energies.

61
Applicability of Activity Coefficient Models

62
 Activity Models
• Margules model
– Two suffix equation or one constant equation
– Three suffix equation or two constant equation
• Vanlaar equation
• Wilson equation
• NRTL model
• UNIQUAC (Universal Quasi Chemical) model

63
 Margules equation
Max Margules introduced in 1895 a simple
thermodynamic model for the excess Gibbs
free energy of a liquid mixture.

He had introduced the concept of the activity

coefficient, the model could be used to
derive an expression for the activity
coefficients of a compound i in a liquid.

64
 Margules equation

• Activity coefficient of component i is derived

by differentiation to xi.
• Two suffix equation or one-constant or one
parameter margules equation

65
 Margules equation

• Activity coefficient of component i is derived

by differentiation to xi.
• Three suffix equation or two-constant or Two
parameter margules equation

• In here A12 and A21 are constants, which are

obtained by regression of experimental vapor-
liquid equilibrium data. 66
 Positive deviation from Raoult’s Law

Plot of experimental P-x-y, activity coefficient and molar excess Gibbs free energy data

67
Negative deviation from Raoult’s Law

Plot of experimental P-x-y, activity coefficient and molar excess Gibbs free energy data

68
 Vanlaar Equation
• Van Laar equation is an activity model, which
was developed by Johannes van Laar in 1910-
1913, to describe phase equilibria of liquid
mixtures.

– Where A12 and A21 are known as vanlaar

constants, if the constants are known the activity
coefficients can be estimated.
69
 Vanlaar Equation
• Van Laar equation is an activity model, which
was developed by Johannes van Laar in 1910-
1913, to describe phase equilibria of liquid
mixtures.

– Where A and B are known as vanlaar constants, if

the constants are known the activity coefficients
can be estimated.
70
 Estimation of Vanlaar constants
• First method:
– If the activity coefficients are known at any one
composition, then vanlaar constants A and B can
be estimated by rearranging the equation.

71
 Estimation of Vanlaar constants
• Second method:
– For a systems forming azeotrope, if the
temperature and pressure are known at
azeotropic composition then activity coefficients
can be calculated as,
– At azeotrpic composition x1=y1

72
 Example - 1
• The azetrope of the benzene(1) & cyclohexane(2)
system has a composition of 53.2 mol % benzene
with a boiling point of 350.6 K at 101.3 kPa. At this
temperature the vapor pressure of benzene(1) &
cyclohexane(2) is 100.59 kPa and 99.27 kPa
respectively. Determine the activity coefficient for
the solution containing 10 mol % benzene.

73
 Answer
• Activity coefficient of benzene = 1.062
• Activity coefficient of cyclohexane = 1.002

74
 Local composition models
• Concept of LCMs is based on the hypothesis of that 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 and that with the molecules of
the other kind .
• Energy difference also introduces a non-randomness at
the local molecular level.
• The models of this type are the NRTL
model, Wilson model, the UNIQUAC model, and the
group contribution model UNIFAC.
75
 Wilson equation
• The concept of local composition was
introduced by G.M.Wilson in 1964 with the
development of model in which he was
proposed that the local composition is
different from the overall mixture composition
or bulk composition.
• Local composition model is postulated to
account for the non-random molecular
orientations that result from differences in
molecular size and intermolecular forces.
76
 Wilson equation
• Wilson proposed the following expression for
the excess Gibbs energy of a binary solution

• Wilson equation have two adjustable

parameters and known as Wilson
parameter. These are related to pure
component molar volume and characteristic
energy difference and are given by,
77
 Wilson equation

• V1 and V2 – molar volumes of pure liquids at

temperature.
• - Energies of interaction between molecule
• a - constant for a given pair of components
independent of temp & prssure. 78
 Wilson equation
• Activity coefficient derived from the excess
Gibbs free energy are given by

79
Wilson equation- Advantages & Disadvantages

• Advantages:
– Considered the temperature dependent of the
parameter
– Applicable to the completely miscible system
• Disadvantages:
– It can not be applied for the systems in which ln Y
shows maxima or minima.
– Not applicable to partial miscible system

80
Non-Random Two-Liquid(NRTL) equation
• NRTL equation was developed by Renon &
Prausnitz in 1968 & this equation is applicable
to miscible or partially miscible systems.
• NRTL equation for the excess Gibbs free
energy is given by,

81
Non-Random Two-Liquid(NRTL) equation

• Activity coefficients are

82
 Non-Random Two-Liquid(NRTL) equation

• Here are independent of composition &

temperature & it is related to the non-
randomness of the solution.
• If = 0, the solution is completely random &
NRTL equation reduces to the one parameter
Margules model.
• The value of varies from 0.20 to 0.57, in
absence of the experimental data = 0.3.

83
NRTL - Advantages & Disadvantages
• Advantages:
– Applicable to strongly non-ideal solutions and
partially miscible solutions, equation provides a
good representation.
• Disadvantage:
– For moderately non-ideal systems, it offers no
advantage over the Van Laar & Margules equation

84
Models for the Excess Gibbs Energy and Activity
Coefficients for Binary Systems

85
Models for the Excess Gibbs Energy and Activity
Coefficients for Binary Systems

86
Relation between the model parameters and
infinite dilute activity coefficients

87
 Example-1
• Using the Wilson equations, estimate the activity coefficients
of the components of a binary system consisting of acetone(1)
and water(2) at 349 K and x1 =0.43.At this temperature , the
molar volumes of the components are V1= 75.05*10-6 m3/mol
& V2 = 18.07*10-6 m3/mol.
• Wilson parameters for the system are,
a12 = 1225.31 J/mol
a21 = 6051.01 J/mol
• Find the vapor composition in equilibrium with liquid at
given temperature.

88
 Answer
• Activity coefficient of acetone(1) = 1.5820
• Activity coefficient of water(2) = 1.4661
• The vapor composition,y1 = 0.7954

89
 Example-2
• Using the Wilson & NRTL equations, estimate the activity
coefficients of the components of a binary system consisting
of iso-butanol(1) and iso-propanol(2) at 500C and x1 =0.3.At
this temperature , the molar volumes of the comonents are
V1= 65.2 cm3/mol & V2 = 15.34 cm3/mol.
– For wilson equation,
• a12 = 300.55 cal/mol
• a21 = 1520.32 cal/mol
– For NRTL equation,
• b12 = 685.21 cal/mol
• b21 = 1210.21 cal/mol
• = 0.552
90
Wilson equation

91
Non-Random Two-Liquid(NRTL) equation

• Activity coefficients are

92
 Answer
• Activity coefficient using Wilson equation:
– For component 1 = 2.27
– For component 2 = 1.25
• Activity coefficient using NRTL equation:
– For component 1 = 2.164
– For component 2 = 1.263

93
 Relative volatility
• In order to separate a binary mixture using distillation process, there
must be a differences in volatilities of the components.
• The greater the difference, the easier it is to do so.
• A measure for this is termed the relative volatility.
• We define volatility of component-i as
• partial pressure of component-i divide by mole fraction component-i in
liquid
• For a binary mixture of A and B, therefore:
– Volatility of A = pA / xA
– Volatility of B = pB / xB
– where p is the partial pressure of the component and x is the liquid
mole fraction.
94
 Relative volatility
• Relative volatility is the ratio of volatility of A (MVC) over volatility of B (LVC)

• Relative volatility is therefore a measure of separability of A and B.

• Since xB = 1 - xA , we have;

• Replace with pA = yA PT ; pB = ( 1 - yA ) PT so as to express everything in MVC,

• Dropping subscript 'A' for more volatile component, and simplifying: we obtain
the equation for relative volatility:

95
 Relative volatility

• When = 1, no separation is possible:

• both component-A and component-B are equally
volatile. They will vapourise together when heated.
• Solving the above equation for a = 1.0, we obtain: y = x.
• The larger the value of a above 1.0, the greater the
degree of separability, i.e. the easier the separation.
• When a system has reached equilibrium, no further
separation can take place - the net transfer rate from
vapour to liquid is exactly balanced by the transfer rate
from liquid to vapour.
96
 Importance of Relative volatility
• This quantity is widely used in designing large industrial distillation
processes.
• It indicates the ease or difficulty of using distillation to separate the
more volatile components from the less volatile components in a
mixture.
• Relative volatilities are used in the design of all types of distillation
processes as well as other separation or absorption processes that
involve the contacting of vapor and liquid phases in a series
of equilibrium stages.
• Relative volatilities are not used in separation or absorption
processes that involve components reacting with each other (for
example, the absorption of gaseous carbon dioxide in aqueous
solutions of sodium hydroxide).

97
 Example-3
• Water(1)-hydrazine(2) systems forms an aeotrope
containing 58.5% (mol) hydrazine at 393 K and
101.3 kPa. Calculate the equilibrium vapour
composition for a solution containing 20%(mol)
hydrazine. The relative volatility of water with
reference to hydrazine is 1.6 and may be
assumed to remain constant in the temperature
range involved. The vapor pressure of hydrazine
at 393 K is 124.76 kPa.

98
 Answer
• y1 = 0.9472
• y2 = 0.0528
• The composition of the vapor in equilibrium
with the liquid containing 20% hydrazine is
5.28% hydrazine and 94.72% water.

99
 Example-4
• Construct the P-x-y diagram for the cyclohexane(1)-
benzene(2) system at 313 K given that at 313 K the
vapour pressures are and

• The liquid phase activity coefficients are given by

100
 Answer
X1 0 0.2 0.4 0.6 0.8 1.0

1.5809 1.3406 1.1793 1.0760 1.0185 1.0

1.0 1.0185 1.0760 1.1793 1.3406 1.5809

P 24.41 26.49 27.37 27.41 26.61 24.62

Y1 0 0.2492 0.4243 0.5799 0.7540 1.0

101
• How to find whether an azetrope exist or not
at the given temperature?

• This quantity becomes unity at an azeotrope.

• BY modified raoult’s law,

• Therfore

102
How to find whether an azetrope exist or not at the
given temperature?

• We see that as x1->0(i.e. as x2->1),

– ln =A or =exp(A) [For van Laar constants ]
– Also ln =0 or =1
• Similarly as x2-> 0(i.e. as x1->1),
– ln =B or =exp(B) [For van Laar constants ]
– Also ln =0 or =1.

103
How to find whether an azetrope exist or not at the
given temperature?

• If the mixture forms an azeotrope, one of the

above values will be greater than 1 and the
less than 1, because is a continuous
function of x1 and must then pass through the
values of 1 at some intermediate composition.

104
Example-5

105
Relation between the model parameters and
infinite dilute activity coefficients

106
 Solution

0.1258
0.7292
= 2.3439
= 1.1900
107
 Solution cont…

= 10.422 20.37
= 3.287 0.595
• From these results, we conclude that an
azeotrope does indeed exist.
108
THANK YOU