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 partial fugacity of component 1 in
the liquid phase to its partial fugacity in the vapor
phase.
 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 (left-hand side of the equation) is larger than it would
be for an ideal system; i.e., the component "doesn't like" to be
in the liquid phase.
• We see that this corresponds to smaller attractions between
molecules in the mixture than in the pure component.
3
Binary vapor-liquid equilibrium
Binary vapor-liquid equilibrium
 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.
+
 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
 Positive deviation from Raoult’s Law

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

8
Negative deviation from Raoult’s Law

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

9
 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
10
Method to predict  i

11
 Liquid Phase Properties from VLE Data

• Calculate activity coefficient at infinite dilution or

Margule’s constants or limiting activity coefficient
12
 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.

13
 Importance and use of infinite
dilution activity coefficient data
• Most difficult and costly stage of a separation
process is the removal of the last traces of
impurity.
• Greatest departure from ideality occurs in the
very dilute regions
• Synthesis, design and optimization of separation
processes
• Predicting the existence of an azeotropes
VLE data for methyl ethyl ketone(1)/toluene(2) at 500C

15
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18
19
VAPOR-LIQUID EQUILIBRIUM AT
LOW TO MODERATE PRESSURE

20
 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.

21
 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. 22
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24
25
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 Method to predict  i
• If we have experimental VLE data(P,x1,y1) for
chloroform(1)/1,4-dioxane(2) at T=500C .
• Note that the pressure is low, so we could
assume an ideal gas mixture, hence could use
the Modified Raoult’s Law.
• We will now develop a correlation of  i from
the data.
• We are going to see specifically how the
Margules equation was developed.
28
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
29
Method to predict  i

30
VLE data for chloroform(1)/1,4-dioxane(2) at 500C

31
Method to predict i

32
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38
Margules equations

39
Margules equations

40
Margules equations

41
42
Example

43
Example

44
 For liquid phase composition
• For a binary solution of two components 1 and 2, the
modified raoult’s law is given by,

45
 For vapor phase composition
• For a binary solution of two components 1 and 2, the
modified raoult’s law is given by,

46
 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.
47
 Answer
• Activity coefficient of methanol = 1.864
• Activity coefficient of methyl acetate = 1.072
• Total pressure (P) = 73.50 kPa
• The vapor phase composition is,
y1 = 0.282
y2 = 0.718

48
Concept of Azeotropes

49
 Topics
• Introduction – VLE at low pressure
• Azeotropes
• Types of Azetropes
• Activity models

50
VAPOR-LIQUID EQUILIBRIUM AT LOW PRESSURE

• Fugacity coefficient of a component in a

mixture  virial equation(or others eos) &
applying concept of residual properties.
• Activity coefficient of a component in a
solution From VLE data & applying concept
of excess properties.
 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.
• Because their composition is unchanged by
distillation, azeotropes are also called constant
boiling mixtures.
52
 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".

53
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55
 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.

56
 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

57
 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

58
 Azeotropes
• 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.
• For an ethanol-water mixture at P = 1 atm,
this point is xEtOH = yEtOH = 0.8943, which from
at T = 78.15oC.

59
 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

60
 Azeotropes
• 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 by
simple distillation.

61
• 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.

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 Separation of Azeotropes
• Azeotropic distillation
• Chemical action separation(MSA)
• Extractive distillation
• Pressure swing distillation
• etc..

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 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)

64
 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.

65
 Extractive Distillation
• An additive is used to increase the differences
in boiling points
• For example, add NMP O
N
(N-methylpyrrolidone) CH3
• This increases the boiling point of the
aromatics by “complexation” of the 
electrons in the aromatic ring with the NMP
and therefore facilitates separation

66
 Azeotropes

• Azeotropes are constant boiling mixtures.

• When the deviation from Raoults law is very
large p-x and p-y curve meets at this point
y1=x1 and y2=x2.
• A mixture of this composition is known as
Azeotrope.
• Azeotrope is a vapour liquid equilibrium
mixture having the same composition in both
the phases.

67
 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).

68
 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 2. Minimum Boiling Azeotropes

Negative azeotropes Positive Azeotropes
Maximum Boiling Mixtures Minimum boiling mixtures
Pressure Minimum Azeotropes Pressure Maximum Azeotropes
Negative deviation from ideality Positive deviation from ideality S

69
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 in the plot of
total pressure against the liquid and vapour
compositions at a constant temp passes
through a minimum at the azeotropic point.

70
Maximum Boiling Azeotropes or Negative
azeotropes

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

71
 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 vapor
pressures of the components are not much
different, the curve in plot of total vapor
pressure against the liquid & vapour
compositions at a constant temp passes
through a maximum at the azeotropic point.
72
Minimum Boiling Azeotropes or Positive
Azeotropes

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

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 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.
77
 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:

78
 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.
• 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.
79
 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).

80
• 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

81
 How to find whether an azetrope exist or not at the
given temperature? For example
Van Laar model
• We see that as x1->0(i.e. as x2->1),
– Infinite dilution ln =A or =exp(A) [For van Laar constants ]
– Also ln =0 or =1
• Similarly as x2-> 0(i.e. as x1->1),
– Infinite dilution ln =B or =exp(B) [For van Laar Constants ]
– Also ln =0 or =1.

82
How to find whether an azetrope exist or not at the
given temperature?

• If the mixture forms an azeotrope, one of

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

83
Other models for  i

84
VAPOR-LIQUID EQUILIBRIUM AT
LOW TO MODERATE PRESSURE

85
 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.
 Activity Models
• “Simple” empirical models
– Symmetric, Margule’s, vanLaar
– No fundamental basis but easy to use
– Parameters apply to a given temperature, and the models
usually cannot be extended beyond binary systems.
• Local composition models
– Wilsons, NRTL, Uniquac
– Some fundamental basis
– Parameters are temperature dependent, and multi-
component behaviour can be predicted from binary data.

87
 Activity Models
• Wohl’s equations & Redlich Kister Expansion
• Margules model
– Two suffix equation or one constant equation
• Porter equations
– Three suffix equation or two constant equation
• Vanlaar equation
• Wilson equation
• NRTL model
• UNIQUAC (Universal Quasi Chemical) model
– Abrams and Prausnitz
• UNIFAC (UNIQuac Functional Activity Coefficient
88
model) model
 Simple Empirical Models
• Van Laar, very good for alcohol containing
mixture, in general for alcohol & water and
alcohol & hydrocarbon mixtures
• Porter or Margules 1 parameter equations
• Margules 2 parameter equations
– Simple mixtures of hydrocarbons

89
 Local composition models
• Modern theoretical developments in the molecular
thermodynamics of liquid solution behaviour are based on
the concept of local composition.
• Within a liquid solution, local compositions, different from
the overall mixture composition, are presumed to account
non-random molecular orientations that result from
differences in molecular size and intermolecular forces.
– 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. 90
 Local composition models
• Models are principally useful for describing systems where the
constituent molecular species differ on account of both size/shape
as well molecular interaction energies.

91
 Local composition model
• Wilson’s model(molecular theory)(First LCM)
– It can not predict immiscibility
• NRTL(non random two liquid theory)
– Renon & prausnitz
– Immiscible mixtures
– Good for miscibility
• Guggenhein’s Quasi chemical theory
• Universal Quasi Chemical Theory(UNIQUAC)
– Model QUAC+LCM ideas
– Abrahms & Prausnits
– to multi-component prediction from binary data
• Regular solution theory derived by hilderbrand and
scott(two liquid theory) 92
 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.

93
 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. 94
Derivation of Margules
Equations

95
Margules one parameter Equation

96
 Margules one parameter Equations
• This model provide a good representation for many
simple liquid mixtures, i.e., for mixtures of molecules
which are similar in size, shape and chemical nature.
• When lny1 and lny2 are plotted against x2(or x1), the
two curves are mirror images.
• Symmetrical nature of activity coefficients for this
model

97
Margules Two parameter Equations

98
Margules Two parameter Equations

99
Margules Two parameter Equations

100
Margules Two parameter Equations

101
Margules Two parameter Equations

102
Wohl’s Expression

103
Wohl’s Expression
Activity Coefficient

104
Margules Two Parameter equation

105
Margules One Parameter equation

106
Van Laar equation

107
Van Laar Equation

108
Van Laar Equation

109
 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.
110
 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.
111
 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.

112
 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

113
Van Laar Equations

114
Van Laar Equations

115
116
Applicability of Activity Coefficient Models

117
 Wilson equation
• 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.

118
 Wilson equation for binary
solution
• 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,
119
Wilson equation for binary solution

120
 Wilson equation for binary solution

• Note that
• 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 & pressure. 121
Wilson equation for multi-component
system

• All indices in these equation refer to the

same species, and all summations are over all
species.
• For each ij pair there are two parameters
because
122
 Wilson equation for multi-component
system
• For example, in a ternary system three possible ij
pairs are associated with the parameters

123
 Wilson equation-advantage
• Provides a good representation of VLE of a
variety of miscible mixtures.
– Considered the temperature dependent of the
parameter
– Applicable to the completely miscible system
• Suitable for solutions of polar or associating
components like alcohols in non-polar
solvents for which the Margules and van Laar
equations are generally inadequate.
124
 Wilson equation-Disadvantage
• It is not suitable for systems showing maxima
or minima on the lnY versus x curves.
• It is not suitable for systems exhibiting limited
miscibility
– recommended only for liquid systems that are
completely miscible, or for partially miscible
systems in the region where only one phase exists.

125
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,

126
Non-Random Two-Liquid(NRTL) equation
Activity coefficients are

• here t12 and t21 are the dimensionless

interaction parameters, alpha,b12 and b21 are
independent of composition and temperature.
127
 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(For a
liquid, in which the local distribution is random
around the center molecule) & 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.

128
 NRTL equations
• Applicable to partially miscible as well as
totally miscible systems.
• For moderately non-ideal systems, it offers no
advantage over the van laar and margules
equations. But for strongly non-ideal solutions
and especially partially miscible systems, the
NRTL equations provide a good representation
• Disadvantage:
– For moderately non-ideal systems, it offers no
advantage over the Van Laar & Margules equation
129
 Characteristics of Models
• NRTL is especially suited for acid gas adsorption, which
includes the removal of carbon dioxide and hydrogen
sulfide from a gas stream. Refineries routinely use this
process when making hydrogen.
• UNIFAC model is a group contribution method that allows
the model parameters to be estimated using the molecular
structure of each chemical. When experimental data is not
available, this is the only method that can be used.

130
 Characteristics of Models
• UNIQUAC model uses binary parameters, which
must be determined from experimental data. Once
found, however, the same parameters can be used in
multicomponent mixtures of three or more
chemicals.
• Both UNIFAC and UNIQUAC can be used when two
liquid phases or azeotropes are present.
• Wilson equation is an option if there is only one
liquid phase, and it does handle azeotroipes.

131
Applicability of Activity Coefficient Models

132
VLE model Selection

133
VLE model Selection

134
Models for the Excess Gibbs Energy and Activity
Coefficients for Binary Systems

135
Models for the Excess Gibbs Energy and Activity
Coefficients for Binary Systems

136
Relation between the model parameters and
infinite dilute activity coefficients

137
138
 Summary Local composition model
• Wilson’s model(molecular theory)(First LCM)
– It can not predict immiscibility
• NRTL(non random two liquid theory)
– Renon & prausnitz
– Immiscible mixtures
– Good for miscibility
• Guggenhein’s Quasi chemical theory
• Universal Quasi Chemical Theory(UNIQUAC)
– Model QUAC+LCM ideas
– Abrahms & Prausnits
– to multicomponent prediction from binary data
• Regular solution theory derived by hildebrand and
scott(two liquid theory) 139
 Example - 1
• An azeotrope consists of 42 mol per cent
acetone(1) and 58 mol per cent methanol(2) at
760 mm Hg and 313 K. At 313 K, vapor pressure of
acetone and methanol are 786 mm Hg and 551
mmHg respectively. Calculate the van Laar
constants.

140
Estimation of Vanlaar constants

141
 Answer
• A = -4.838
• B = 0.274

142
 Example - 2
• Liquids A and B form an azeotrope containing
46.1 mole per cent A at101.3 kPa and 345 k.At
345 K, the vapor pressure of A is 84.8 kPa and
that of B is 78.2 kPa. Calculate the constant of
2 suffix Margules equation and Van Laar
constants.

143
 Answer
• Margules one parameter constant
• A=0.893
• Van Lar Constants
• A=1.2955
• B=0.6530

144
 Example - 3
• 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.(use
van Laar equation)

145
 Answer
• Activity coefficient of benzene = 1.062
• Activity coefficient of cyclohexane = 1.002

146
 Example-4
• 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
147
Wilson equation

148
Non-Random Two-Liquid(NRTL) equation

• Activity coefficients are

149
 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

150
 Example-5
• Water(1)-hydrazine(2) systems forms an azeotrope
containing 58.5% (mol) hydrazine at 393 K and
101.3 kPa. Calculate the activity coefficients of
components 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.[use vanlaar equation]

151
 Answer
• R.V. of water to hydrazine =V.P. of water/V.P. of Hydrazine at 393K
• Sat. Vapor P1=199.62 Kpa and P2 = 124.76 KPa
• A=-1.3927
• B=-2.2822
• For solution containing 20%(mol) hydrazine,
• Activity coefficient of Water = 0.8891
• Activity coefficient of Hydrazine = 0.3171

152
 Example-6
• 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

153
 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

154
 Example-6
• 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.

155
 Answer
• Activity coefficient of acetone(1) = 1.5820
• Activity coefficient of water(2) = 1.4661
• The vapor composition,y1 = 0.7954

156
 Example-7
• 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.

157
 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.

158
 Example-8

• T=353.15K(800C)
• Does the above system form an azeotrope?
159
 Solution

0.1258
0.7292
= 2.3439
= 1.1900
160
 Solution cont…

= 10.422 20.37
= 3.287 0.595
• From these results, we conclude that an
azeotrope does indeed exist.
161
 Example-9
• The azeotrope of the benzene(1)/ethanol(2)
system has a composition of 44.8%(mol)
ethanol with a boiling point of 341.4 Kat 101.3
kPa. At this temperature the vapor pressure of
benzene is 68.9 kPa and the vapor pressure of
ethanol is 67.4 kPa. What are the activity
coefficients in a solution containing 10%
alcohol?

162
 Answer
• Let benzene be component 1 and alcohol
component 2.
• A=1.3305
• B=1.9106
• For a solution containing 10% alcohol x1=090
and x2=0.1
• Acitivity coefficient of component-1 = 1.0255
• Acitivity coefficient of component-2 = 4.1412
163
 Prove
• Using the van Laar constants and the vapor
pressures of the pure substances how would
you prove whether a given binary system
forms an azeotrope or not?

164
 Example-10
• For the binary system methanol(1) and
benzene(2), the recommended values of the
Wilson parameters at 341 K are ˄12=0.1751
and ˄21 =0.3456. The vapor pressures of the
pure species are p1=68.75 kPa and p2=115.89
kPa. Show that the given system can form an
azeotrope at 341 K. Assume that the vapor
behaves like an ideal gas.

165
 Answer
• Infinite dilution gamma1= 10.9879
• Infinite dilution gamma2= 6.6020
• Relative volatility when x1->0 = 6.5184
• Relative volatility when x2->0 = 0.0899
• Since the relative volatility at x1=0 is greater
than unity, and that at x2=0 is less than unity.
• It is clear that the system forms an azeotrope.

166
 Example-11
• From VLE measurements for benzene(1)-ethanol(2)
system at 318 K and 40.25 kPa it is found that the
vapor in equilibrium with a liquid containing 38.4
%(mol) benzene contained 56.6%(mol) benzene. The
system forms an azeotrope at 318 K. At this
temperature, the vapor pressures of ethanol and
benzene are 22.9 and 29.6 kPa respectively.
Determine the composition and total pressure of the
azeotrope. Assume that van Laar equation is
applicable for the system.

167
 Example-12
• A mixture of benzene(1) and toluene(2) is an
equilibrium with its vapor. The relative
volatility of benzene to toluene is 2.5. Find out
the mole fraction of benzene in the vapor if its
liquid mole fraction is 0.5.

168
 VLE CALCULATIONS
(NON-IDEAL BEHAVIOUR)
(LOW TO MODERATE PRESSURE)

169
VAPOR-LIQUID EQUILIBRIUM AT LOW
TO MODERATE PRESSURE

170
Non-ideal VLE (low to moderate pressure)

171
Formulation of VLE problems

172
Formulation of VLE problems

173
 ˆ v
k  k

 sat
k

174
Sources of data for VLE problems(Non-Ideal)

175
 Dew & Bubble point calculation
• Dew Point is the state at which condensation is about to occur.
- Dew point is when a vapor forms the first droplet of liquid and begins
to condense.
- Dew Point Temperature Calculation at a Given Pressure
- Dew Point Pressure Calculation at a Given Temperature
- Vapor Fraction is ‘1’ at Dew Point

• Bubble Point is the state at which vaporization is about to occur.

- Bubble point is when a liquid forms the first bubble of vapor and
begins to evaporate.
- Bubble Point Temperature Calculation at a Given Pressure
- Bubble Point Pressure Calculation at a Given Temperature
- Vapor Fraction is ‘0’ at Bubble Point
176
Dew and Bubble Point Calculations

177
Non-Ideal VLE Equations

178
 Non-Ideal VLE Equations
• Since

(3)

(4)

(5) (6)
179
 Non-Ideal VLE Equations
• When
• Modified Raoult’s law will reduce to,

From Eq. (4)

180
 ALGORITHM
FOR
BUBBLE P CALCULATION

181
182
Bubble P
 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.
184
 Answer
• Activity coefficient of methanol = 1.864
• Activity coefficient of methyl acetate = 1.072
• Total pressure (P) = 73.50 kPa
• The vapor phase composition is,
y1 = 0.282
y2 = 0.718

185
 Example
• 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

186
 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

187
 ALGORITHM
FOR
DEW P CALCULATION

188
189
Dew P
Non-ideal DEW P Calculation

191
Non-ideal VLE(Pbub& Pdew) calculations

192
 Example-1
• The following values refer to the Wilson parameters for the system
acetone(1) and water(2):
V1= 74.05*10-6 m3/mol , V2 = 18.07*10-6 m3/mol.
a12 = 1225.31 J/mol , a21 = 6051.01 J/mol
• The vapor pressures are given by
2795.817
ln P sat
 14.3915 
T  43.198
1

3799.88
ln P2sat  16.2620 
T  46.854
• Calculate the equilibrium pressure and composition of
– Vapor in equilibrium with a liquid composition x1=0.43 at 349 K. (Bubl P)
– The liquid in equilibrium with a vapor composition y1=0.8 at 349 K. (Dew P)

193
 Solution, Bubble Pressure
• = 190.37 kPa
• = 39.87 kPa
• = 0.1600
• = 0.5092
Solution, Bubble Pressure cont…
Solution Dew Pressure cont…
Solution Dew Pressure cont…
Solution Dew Pressure cont…
Solution Dew Pressure cont…
 Answer
• Bubble pressure (Pbubl)= 162.82 kPa & the
vapor phase composition(y1) is 0.7954.
• Dew pressure (Pdew) = 164.48 kPa & the liquid
phase composition(x1) is 0.4568.

201
 Example-2

• Calculate the equilibrium pressure and composition of

– Vapor in equilibrium with a liquid composition x1=0.25 at 353.15K.(Bubl P)
– Liquid in equilibrium with a vapor composition y1=0.60 at 353.15K.(Dew P)
202
 Answer
• Bubble pressure (Pbubl)= 91.48 kPa & the vapor
phase composition(y1) is 0.538.
• Dew pressure (Pdew) = 96.72 kPa & the liquid
phase composition(x1) is 0.449.

203
 Example
• Methanol(1)-acetone(2) forms an azeotrope at
760 Torr with x1 = 0.2, T = 55.70C.
• Using Van Laar model predict the bubble
pressure for a system with x1=0.1 at 55.70C
1582.271
log P1sat  8.0897 
10 T  239.726
1210.595
log P2sat  7.1171 
10
T  229.664

Where T is in 0C & vapor pressures are in Torr

204
Van Laar Equation

205
 Answer
• Bubble pressure (Pbubl)= 757.62 Torr & the
vapor phase composition(y1) is 0.1067.

206
 ALGORITHM
FOR
BUBBLE T CALCULATION(NON-
IDEAL)

207
208
Equations for BUBL T
(7)

(8)

(9)
Non-Ideal BUBL T calculations(Method-2)

210
Non-Ideal BUBL T calculations(Method-2)

211
Non-Ideal BUBL T calculations(Method-2)

212
Non-Ideal BUBL T calculations(Method-2)

213
Bubble T(Method-2)
Bubble T(Method-3)
Non-ideal Bubble & Dew T Calculations
 ALGORITHM
FOR
DEW T CALCULATION

217
218
Equations for DEW T

(10)
Dew T (method-2)
Dew T (method-3)
 Example-3
• Consider the benzene(1)/ethanol(2) system
which exhibits an azeotrope at 760 mmHg and
68.240C containing 44.8 mole% ethanol. Using
the two-parameter Margules model, calculate the
composition of the vapor in equilibrium with an
equimolar liquid solution at 760 mmHg given the
following Antoine equations:
1196.76
log P sat
 6.87987 
T  219.161
1

1592.86
log P2sat  8.1122 
T  226.18 Where T is in degree Celsius
and the vapor pressures are in 222
mmHg
 Answer

• Bubble temp. (Tbubl)= 68.2620C & the vapor

phase composition(y1) is 0.542.
 Example-4

• Calculate T and {yk}, for P=101.33kPa and x1=0.85.(Bubl T)

• Calculate T and {xk}, for P=101.33kPa and y1=0.40.(Dew T)
224
 Answer
• Bubble temp. (Tbubl)= 353.92 K & the vapor
phase composition(y1) is 0.817.
• Dew temp. (Tdew) = 360.61 K & the liquid
phase composition(x1) is 0.0639.

225
 Example-5
• Methanol(1)-acetone(2) forms an azeotrope at
760 Torr with x1 = 0.2, T = 55.70C.
• Using Van Laar model predict the bubble
pressure for a system with x1=0.1 at 55.70C
1582.271
log P1sat  8.0897 
10 T  239.726
1210.595
log P2sat  7.1171 
10
T  229.664

Where T is in 0C & vapor pressures are in Torr

226
Van Laar Equation

227
 Answer
• Bubble pressure (Pbubl)= 757.62 Torr & the
vapor phase composition(y1) is 0.1067.

228
 Example-6
• Consider the benzene(1)/ethanol(2) system
which exhibits an azeotrope at 760 mmHg and
68.240C containing 44.6 mole% ethanol. Using
the two-parameter Margules model, calculate
the composition of the vapor in equilibrium
with an equimolar liquid solution at 760
mmHg given the following vapour pressure
data:

229
VLE Flash calculations
for
Non-Ideal Systems

230
VLE Flash Calculations for Non-Ideal Systems

231
232
Partition Coefficient, Ki

233
234
235
236
THANK YOU
 VLE CALCULATIONS
(NON-IDEAL BEHAVIOUR)
(HIGH PRESSURE)

238
 Vapor-Liquid Equilibrium at High Pressure
Introduction
• To estimate the VLE data at high pressure
– Necessary to consider the vaporization or vapor liquid
equilibrium constant K
– because the tendency of given components of the solution
to the partition between the vapor and liquid phases is
accounted by this K-factor or K-value.

• This quantity is called K-value or Partition coefficient

or Distribution coefficient.
 Partition coefficient or Distribution
coefficient(Ki)
• It shows the tendency of a component to vapourize.
• When Ki>1, component i exhibits a higher concentration in
the vapour phase and can be considered the lighter
component.
• When Ki<1, component i shows a higher concentration in the
liquid phase and is considered the heavier component.
• Distribution coefficient K is dependent upon temperature,
pressure, and composition.
• However, for a few systems K is independent of composition,
to a good approximation, which greatly simplifies the
problem.
 Partition coefficient or Distribution
coefficient(Ki)
• Mixtures of light hydrocarbons, in which the
molecular force fields are relatively weak and
uncompleted, we may assume as a reasonable
approximation that both the liquid and vapor
phases are ideal.

241
 DePriester chart for K values-High
pressure VLE
• DePriester charts present an efficient method in finding
equilibrium ratios for different substances at different
conditions of pressure and temperature.
• One convenient source of K values for hydrocarbons, as
a function of temperature and pressure, are the
DePriester charts.

Ki 
yi

Pi   i
sat sat
i

exp 
Vi
L
P  Pi
sat
 
xi P  V
 RT 
i

Ki  Ki  P , T , y , x 
242
• For an ideal solution the fugacity coefficient of
a species in solution is equal to the fugacity
coefficient of the pure species at mixture T
and P and in the same physical state(liquid or
gas).

243
 High Pressures - K-Values for Light Hydrocarbon
Systems
• Assuming ideal solutions in both phases, the K-values
become functions of temperature and pressure only (no
composition dependence).
i  i 
yi Pi  i
sat sat V L
P  P sat

Ki   exp  
xi P iV
 RT 
 
Ki  Ki  P , T 
• This equation allows K-values for light hydrocarbons to
be calculated and correlated as functions of T and P.
• This is the basis for the DePriester Charts.

244
• Limitations:
– Assumptions will be good ones for similar species
which form ideal solutions in both phases.
– Results are good for light hydrocarbon mixtures.

245
 DePriester Charts
For
Light Hydrocarbons

246
 DePriester Charts

• Nomograms have a coordinate each of

pressure and temperature and have “K”
values plotted in between.

247
K-value from
DePriester
chart
-Low T range
K-value from
DePriester chart
-High T range
 DePriester Charts For Light Hydrocarbons
• Figures 10.13 & 10.14 give K-value charts for some
Iight hydrocarbons.
• DePriester plots are presented over two different
temperature ranges.
• Figure 10.13 is used for low temperatures and Figure
10.14 high temperatures.
• To find the appropriate K-values, a straight line is
drawn on the diagram connecting the temperature and
pressure of the system, intersection of this line with K-
value curve for each hydrocarbons, its K-value at this
temperature and pressure.
 Using DePriester Charts – Boiling Temperatures of
Pure Components

• It is possible to determine boiling point for a given

component directly from the DePriester Charts – one
can then determine which component in a mixture is
the more volatile – the lower the boiling point.
• For a pure component, K = 1.0.
• Assume one wishes to determine the boiling point
temperature of ethylene at a pressure of P = 3000 kPa.

251
Tbp = - 9.5 oC

252
 Question – DePriester Charts
• What are the equilibrium distribution coefficients, K, for
a mixture containing:

Ethylene
n-Pentane
n-Heptane
at T = 120 oC and P =1500 kPa?

253
254
 Answer – DePriester Charts
• The equilibrium distribution coefficients, K,
are:
K
Ethylene 8.5
n-Pentane 0.64
n-Heptane 0.17

at T = 120 oC and P =1500 kPa.

255
 Question – Volatility
• What about the volatility of each component
from the K values?
K
Ethylene 8.5
n-Pentane 0.64
n-Heptane 0.17

256
 Answer – Volatility
K T boiling
Ethylene 8.5 -35.5 oC
n-Pentane 0.64 153 oC
n-Heptane 0.17 >200 oC

• Boiling point temperatures of the pure components at

P = 1500 kPa have also been determined from the DePriester
charts for K = 1.0 for each component.

• From the K values and the boiling point temperature of each

pure component, one can say that the volatility follows the
trend that ethylene>n-pentane>n-heptane.

257
 BUBL P and Dew P
Calculations
Using DePriester Charts
 To solve the bubble point and dew point problems
we must find the unspecified temperature or
pressure which satisfies the following expressions.
For binary systems to solve for bubble point calculation

 y 1 i i

Hence,  K x 1
i i i

For binary systems to solve for dew point calculation

x i i 1
yi
Hence, i K  1
i
 Methodology for Bubble Point Pressure(Given Xi,T)

• Step 1: For a given T, assume a value for the pressure.

• Step 2: Get Ki values from the DePriester chart with respect to
known T and assumed P.
• Step 3: Using the relation yi = Ki*Xi, get yi.
• Step 4: Sum up the values of y1 and y2(binary system) and verify
that it equals to 1 or not. i K i xi  1
• Step 5: If i yi  1 , then assume another P and repeat the
procedure until the summation becomes 1.
The satisfying P is the actual bubble point pressure value
 Methodology for Dew Pressure calculation(Given Yi,T)

• Step 1: For a given T assume a value for the pressure.

• Step 2: Get Ki values from the DePriester chart with respect to
known T and assumed P.
• Step 3: Using the relation xi = yi/Ki ,get xi.
• Step 4: Sum up the values of x1 and x2(binary system) and verify
y
that it equals to 1 or not. i i  1
• Step 5: If i xi  1 , then assume another P and repeat the
Ki

procedure until the summation becomes 1.

The satisfying P is the actual dew point pressure value
 Methodology for Bubble Point T Calculations(Given Xi,P)

• Step 1: For a given P, assume a value for the temperature.

• Step 2: Get Ki values from the DePriester chart with respect to
known P and assumed T
• Step 3: Using the relation yi = Ki*Xi, get yi.
• Step 4: Sum up the values of y1 and y2(binary system) and verify
that it equals to 1 or not. i K i xi  1
• Step 5: If  yi  1 , then assume another T and repeat the
i
procedure until the summation becomes 1. The satisfying
T is the actual bubble point temperature value
 Methodology for Dew Point T Calculations(Given Yi,P)

• Step 1: For a given P, assume a value for the temperature.

• Step 2: Get Ki values from the DePriester chart with respect to
known P and assumed T
• Step 3: Using the relation xi = yi/Ki ,get xi.
• Step 4: Sum up the values of x1 and x2(binary system) and verify
yi
that it equals to 1 or not. i K  1
• Step 5: If  xi  1 , then assume another T and repeat the
i

i
procedure until the summation becomes 1. The satisfying
T is the actual dew point temperature value
 Example-1
• A hydrocarbon mixture contains 10%(mol)
methane, 20%(mol) ethane and 70%(mol)
propane at 500F (Use DePriester chart).
Calculate :
– Bubble point pressure & composition of vapor
– Dew point pressure & composition of liquid

264
265
266
 Answer
• Bubble Point Pressure = 385 psia
 Answer
• Dew Point Pressure = 126 psia
 Example-2
• A hydrocarbon mixture contains 20%(mol)
methane, 30%(mol) ethane and 50%(mol)
propane at 860F (Use DePriester chart).
Calculate :
– Dew point pressure & composition of liquid

269
 Answer
• The dew pressure is 2150 KPa or 311.831 psia and
composition of the liquid drop, x1=0.0247, x2=0.1648
and x3=0.8065

270
 BUBL T and DEW T
Calculations
Using DePriester Charts
 Bubble point Temp.calculation
Trial-and-error method
Given the composition of a subcooled liquid and PTOTAL,
Find Tbp and (yi)bp

Steps:
VLE: y i = Ki xi
1. Pick a temperature T and find the
corresponding Ki(T) values for
mole balance: each component
2. Calculate the yi value for each
åy i
= 1.0 Ki(T)
i 3. Check to see if Syi = 1
4. If not, pick a new temperature,
y i 1 K x i i repeat
How to pick a temperature?
How to pick the next temperature?

273
 To achieve rapid convergence:
Initial guess: T = å ziTi (K i = 1)
i
(weighted average of boiling points of pure components)
Next guess:
pick a reference component (A)

K A (Tprev )
K A (Tnext ) =
å(y ) i prev
i

find Tnext using DePriester Chart

 Dew point Temp.calculation
Trial-and-error method
Given the composition of a superheated vapor and PTOTAL,
find Tdp and (xi)dp

yi
VLE: xi = Steps:
Ki
1. Pick a temperature T and find the
corresponding Ki(T) values for
mole balance:
each component
2. Calculate the xi value for each
åx i
= 1.0 Ki(T)
3. Check to see if Sxi = 1
i

x  1   y i / Ki
4. If not, pick a new temperature
i and repeat
 To achieve rapid convergence:
Initial guess: T = å ziTi (K i = 1)
i
(weighted average of boiling points of pure components)
Next guess:
pick a reference component (A)

K A (Tprev )
K A (Tnext ) =
å(x ) i prev
i

find Tnext using DePriester Chart

 Example-2
• A hydrocarbon mixture contains 25%(mol)
propane, 40%(mol) n- butane and 35%(mol) n-
pentane at 1447.14 kPa or 210 psia. Assume
ideal solution behaviour and calculate
– Bubble point temperature & composition of vapor
– Dew point temperature & composition of liquid

277
 Answers
• Bubble point temperature = 361 K or 190.13oF

Component xi Ki yi = Ki * xi

Propane 0.25 2.12 0.530

n – butane 0.40 0.85 0.340

n – pentane 0.35 0.37 0.130

 K i xi  1 1.000

278
 Answers(cont…)
• Dew point temperature = 387 K

Component yi Ki xi = yi / Ki

Propane 0.25 2.85 0.0877

n – butane 0.40 1.25 0.3200

n – pentane 0.35 0.35 0.5932

 yi / K i  1 1.000

279
 Example-3
• Find the dew-point and bubble-point
temperatures for a mixture that is 20 mole%
n-butane, 50 mole %n-pentane, and 30 mole
% n-hexane. Pressure is 1 atm.(Use DePriester
chart)
 Answer
• Bubble point temperature = 27.80C

Component Xi Ki yi = Ki * Xi

n – butane

n – pentane

n – hexane

K x i i 1

281
 Answers(cont…)
• Dew point temperature = 48.40C

Component Yi Ki Xi = Yi / Ki

n – butane

n – pentane

n – hexane

y i / Ki  1

282
 Example-4
• Use the DePriester chart to generate the
temperature-composition diagram for isobutane and
propane at 1000 kPa.

283
CONSISTENCY TESTS
FOR
VLE DATA

284
CHECKING CONSISTENCY OF THERMODYNAMIC DATA

• Experimental data of vapor–liquid equilibrium

(VLE) are essential to the design of chemical
and separation processes.
• Normally VLE measurements are prone to
inaccuracies, it is essential that we have same
means for checking consistency of measured
results.
• Main principle behind checking consistency of
any thermodynamic data is Gibb’s-Duhem
equation.
i
 xi d ln  i  0 285
• Five methods are available depending upon
measured data available:
1. Using Slop of ln curves
2. using data at the mid-point
3. Redlich-Kister Method
4. Coexistence equation
5. Using slop of Partial pressure

286
 1.Using Slop of ln curves
• According to GD equation

 d ln  1   d ln  2 
x1    x2  
 dx1 T ,P  dx2 T ,P
 d ln  1   d ln  2 
x1    1  x1  
 dx1 T ,P  dx1 T ,P

287
 1.Using Slop of ln curves
• According to Gibbs Duhem equation both slopes
must have oppsite sign then only the data is
consistent, otherwise it is inconsistent.
• For the data to be consistent it has satisfy the
following condition.
– If one of ln curves has maximum at certain
concentration and the other curve should be
minimum at same composition.
– If there is no maximum or minimum point both must
have +ve or –ve on entire range.

288
Test for thermodynamic consistency of VLE data

289
 2. Using data at the mid-point

• Use integrated form of GD equation using any of the

activity coefficient model.
• Lets take Van-Laar equation
Ax 22 Bx12
ln  1  2
and ln  2  2
A   B 
 x1  x 2   x1  x 2 
B   A 

• Now calculate activity coefficient values at

mid point that is x1 = x2 = 0.5.
• Above equation reduces to,
290
 ln  1 ln  2 AB
 
B A A  B2

• Lets check above equation for various

combination of A and B
• Case I A = B ln1 = B/4 and ln2 = A/4
• Case II A = 2B ln1 = (2/9)B and ln2 = (2/9)A
• Case II A = 3B ln1 = (3/16)B and ln2 = (3/16)A

291
• In all the cases,
– ln1 at mid point (x1 = x2 = 0.5) ¼ of B
– ln2 at mid point (x1 = x2 = 0.5) ¼ of A
• And as x1  0 , ln1 = A,
• And as x2  0, ln2 = B.
• Observations
– ln1 value at mid point will be approximately one
fourth the terminal value of the other ln curve.
– The curve which is highest at the end point will be
minimum at mid point.

292
293
 3. Redlich-Kister Method
• The excess free energy of mixing for a solution is
given as
G  RT  x ln   RT  x ln   x ln  
E
i i 1 1 2 2
i

dG E   d ln  1 d ln  2 
 RT ln 1  x1  x2 
dx1  2 dx1 dx1 
dG E 
 RT ln 1
dx1 2

• Now integrating above equation from x1  0 to

x1 1
• In both conditions one will get pure component
and for that GE = 0.
294
 1
1
RT  ln dx1  0
0
2
• To have consistent thermodynamic data, one has to
satisfy above condition.
• But in engineering certain errors are always tolerable
so instead of going for exact zero if equation given
below is satisfied one can say measured data is
thermodynamically consistent.
A B
 0.02
A B

• It is also called as ZERO AREA METHOD.

295
296
 4. Coexistence equation

• If vapor in equilibrium with binary liquid

mixture is Ideal, modified Raoult’s Law can be
reduced to, yP
i  i

xi Pi sat
• Using this equation in GD equation,
x1d ln  1  1  x1 d ln  2

 1  x1 d ln
y1 P y2 P
x1d ln sat
x1 P1 x2 P2sat

297
• Since P1sat and P2sat are fixed at constant T,
y1  x1
d ln P  dy1
y1 1  y1 
dP  y1  x1 
P
dy1 y1 1  y1 
• Above equations are called as Coexistence equations.
• This equation can be used to calculate any of the 3
variables, P, y1 and x1.
• If experimental values of any 2 variables are
measured, then 3rd variable can be calculated using
above equation.
• If values of all 3 variables are known, this can be
used to check consistency of measured data.
298
Coexistence equation cont…
Coexistence equation cont…
Coexistence equation cont…
Coexistence equation cont…
Coexistence equation cont…
Coexistence equation cont…
Coexistence equation cont…
Coexistence equation cont…
 5. Using slop of Partial pressure

• At lower pressures, fugacity in mixture equals

partial pressure. So GD equation becomes,
 d ln p1   d ln p 2 
x1    1  x1  
 dx1  T , P  dx1 T ,P
x1  dp1 
   
1  x1   dp 2



p1  dx1  p 2  dx1 
• Now plot both partial pressures vs x1. Calculate slop
at any selected composition and check for LHS and
RHS. To have consistent set of data above equation
should be satisfied.
307
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THANK YOU