Lecture 3 2021

KMM 543E
Advanced Chemical Engineering

Thermodynamics
Spring 2020
Vapor-Liquid Phase Equilibria
(SVA Ch. 10-11-12)
KMM 543E 2
VAPOUR / LIQUID EQULIBRIUM
The Nature of Equilibrium

Equilibrium is a static condition in which no changes occur in the
macroscopic properties of a system with time. This means there
is a balance between all potentials that may cause change.
An isolated system consisting of liquid and vapour phases in
intimate contact eventually reaches a final state wherein no
tendency exist for change to occur within the system. The
temperature, pressure, and phase compositions reach final
values which thereafter remain constant.
Composition of a system can be measured and characterised in

different ways. The three most important measures of
composition are
.
mi mi
 mass fraction, x i   . .
m m
 mole fraction, and n n
xi  i  . i .
 molar concentration. xin n ni
Ci 
KMM 543E Ci  3
V q
Phase Rules
A phase is homogeneous region of matter. Various phases can
coexist, but they must be in equilibrium for the phase rule to
apply.
The intensive state of a system at equilibrium is established

when its temperature, pressure, and the composition of all
phases are fixed. These are phase-rule variables.
Phase rule variables are intensive properties. Overall or total

compositions are not phase rule variables when more than one
phase is present.
The phase rule gives the number of variables from this set which
must be arbitrarily specified to fix all remaining phase rule
variables.
KMM 543E 4
Phase Rules
For any system at equilibrium, the number of independent
variables that must be arbitrarily fixed to establish its intensive
state is given by Gibbs phase rule :
F  2   N
F = the number of independent intensive variables in a system
(also called degrees of freedom or variance)
 = number of phases
N = number of chemical species in the entire heterogeneous

system
KMM 543E 5
Phase Rules
F  2   N
The number of degrees of freedom (F) of a system is the number of the
variable factors (temperature, pressure, and concentration of the
components) which must be arbitrarily fixed in order that the condition
of the system may be perfectly defined.
KMM 543E 6
Phase Rules
F  2   N
Gibbs phase rule is of
use in deciding whether
or not an equilibrium
problem is “well posed”
that is, whether enough
information is available
for the problem to be
solvable, but it is not of
use in actually solving
the equilibrium state.
KMM 543E 7
VLE : Qualitative Behaviour

Vapour/liquid equilibrium (VLE) is the state of coexistence of
liquid and vapour phases.
When N = 2, the phase rule becomes F = 4-.
Since there must be at least one phase ( =1), the maximum

number of phase-rule variables which must be specified to fix
the intensive state of the system is three: P, T and one mole
( or mass) fraction.
All equilibrium states of the system can therefore be represented

in three-dimensional P-T-composition space.
Within this space, the states of pairs of phases coexisting at

equilibrium (F=4-2=2) define surfaces.
KMM 543E 8

critical locus (vapour and liquid phases in
equilibrium become identical)
tie line (connect points

representing phases in equilibrium)
saturated liquid,
dewpoint
P-T-x1 surface
saturated vapour,
P-T-y1 surface
dewpoint surface,
P-T-y1 surface
KMM 543E 9
KMM 543E 10
KMM 543E 11
KMM 543E 12
KMM 543E 13
Raoult’s Law P_x1
KMM 543E 14
KMM 543E 15

Appreciable negative departures from P-x1 linearity
reflect stronger liquid phase intermolecular attractions
between unlike than between like pairs of molecules.
Conversely, appreciable positive departures result for

solutions for which liquid phase intermolecular forces
between like molecules are stronger than between
unlike.
Strong A B
interactions in liquid Strong A A or B B
phase interactions in liquid phase
KMM 543E 16
KMM 543E 17
L M V
Moles of L line MV

Moles of V line LM
KMM 543E 18
SIMPLE MODELS FOR VLE

When thermodynamics is applied to vapour/liquid equilibrium,
the goal is to find by calculation the temperature,
pressure, and compositions of phases in equilibrium.
Thermodynamics provides the mathematical framework for the
systematic correlation, extension, generalisation, evaluation,
and interpretation of data.
All these can not be accomplished without models for the
behaviour of systems in vapour/liquid equilibrium.
The two simplest models are
 Raoult’s law
 Henry’s law
KMM 543E 19
Raoult’s Law
The two major assumptions required to reduce VLE
calculations to Raoult’s law are :
· The vapour phase is an ideal gas,
· The liquid phase is an ideal solution.
The first assumption means that Raoult’s law can apply only
for low to moderate pressures.
The second implies that it can have approximate validity only
when the species that comprise the system are chemically
similar. Ideal solution behaviour is often approximated by
liquid phases wherein the molecular species are not too
different in size and are of the same chemical nature.
yi P  xi Pi KMM 543E
sat
(10.1)
20
Raoult’s Law
Examples of ideal mixtures
• Hexane – heptane
•benzene – methylbenzene
•propan-1-ol - propan-2-ol
KMM 543E 21
Raoult’s Law
yi P  xi Pi sat
xi = a liquid phase mole fraction,
yi = a vapour phase mole fraction, and

Pi sat= the vapour pressure of pure species i at the temperature
of the system.
An important and useful feature of Raoult’s law is valid for any species
present at a mole fraction approaching unity, provided only that the vapour
phase is an ideal gas.
Chemical similarity of the constituent species is not here a requirement.
KMM 543E 22
Dewpoint and Bubblepoint Calculations with Raoult’s Law
Engineering interest centres on dewpoint and bubblepoint

calculations; there are four classes:
BUBL P : Calculate (yi) and P, given (xi) and T

DEW P : Calculate (xi) and P, given (yi) and T
BUBL T : Calculate (yi) and T, given (xi) and P
DEW T : Calculate (xi) and T, given (yi) and P
KMM 543E 23
Bubblepoint Calculations with Raoult’s Law
Bubble Point Pressure:

Given a liquid composition at a specified temperature, find the
composition of the vapour in equilibrium and the pressure
Given T, x1, x2, ... xn find P, y1, y2,... yn
Bubble Point Temperature:

Given a vapour composition at a specified pressure, find the
composition of the liquid in equilibrium and the temperature
Given P, x1, x2, ... xn find T, y1, y2,... yn
Governing Equation - Bubble Line Equation:
P   x iPisat to find P or T
(10.2) i
then x iPisat
yi  KMM 543E 24
P
Dewpoint Calculations with Raoult’s Law
Dew Point Pressure:
Given a vapour composition at a specified temperature, find the
composition of the liquid in equilibrium and the pressure
Given T, y1, y2,... yn find P, x1, x2, ... xn,
Dew Point Temperature:

Given a vapour composition at a specified pressure, find the
composition of the liquid in equilibrium and the temperature
Given P, y1, y2,... yn find T, x1, x2, ... xn
Governing Equation - Dew Line Equation:

1
P
yi to find P or T
(10.3)
 P sat
i i
then y iP
x i  sat to find xi,…xn
Pi KMM 543E 25
Henry’s Law
Application of Raoult’s law to species i requires a value for satat the
Pi
temperature of application, and this is not appropriate for a species
whose critical temperature is less than the temperature of
application.
If a system of air in contact with liquid water is presumed at
equilibrium, then the air is saturated with water. The mole
fraction of water vapour in the air is usually found from Raoult’s
law applied to the water with the assumption that no air
dissolved in the liquid phase. Thus, at 25C and atmospheric
pressure :
P2sat 3.166
y2    0.0312
P 101.33
KMM 543E 26
Henry’s Law
If one wishes to calculate the mole fraction of air dissolved in
the water, then Raoult’s law cannot be applied, because the
critical temperature of air is such lower than 25C.
This problem can be solved by Henry’s law.
For a species present as a very dilute solute in the liquid phase,

Henry’s law then states the partial pressure of the species in the
vapour phase is directly proportional to its liquid phase mole
fraction.
yi P  xi ki (10.4)
ki is Henry’s constant.
KMM 543E 27
VLE BY MODIFIED RAOULT’S LAW

For low to moderate pressures a much more realistic equation
for VLE results when the second major Raoult’s law
assumption is abandoned, and account is taken of deviations
from solution ideality in the liquid phase by a factor inserted
into Raoult’s law :
yi P  xi  i Pi sat
(i  1,2,....., N ) (10.5)
i is called an activity coefficient. Activity coefficients are
functions of temperature and liquid phase composition, and
ultimately are based on experiment.
KMM 543E 28
VLE BY MODIFIED RAOULT’S LAW

yi P  xi  i Pi sat (i  1,2,....., N )
i y i  1 P   xi  i Pi sat
3.7 (10.6)
i
1
x P
i i 1
 yi /  i Pi 
sat
 3.8 (10.7)
i
KMM 543E 29
Relative Volatility and Azeotrope :

Relative volatility is a measure of the differences in volatility
between 2 components, and hence their boiling points. It indicates
how easy or difficult a particular separation will be.
y1 / x1
12  (10.8)
y 2 / x2
Thus if the relative volatility between 2 components is very close to

one, it is an indication that they have very similar vapour pressure
characteristics. This means that they have very similar boiling points
and therefore, it will be difficult to separate the two components via
distillation.
KMM 543E 30
Azeotrope:
y1 / x1
12 
y 2 / x2
At an azeotrope y1 = x1, y2 = x2 and then 12  1.
yi P  xi  i Pi yi  i Pi sat
 P
sat
 sat
xi P 12  1 1
 P 2 2
sat
KMM 543E 31
EXAMPLE 10.3
• For the system given in example 10.3, calculate the azeotropic pressure and the
azeotropic composition for T=318.15 K.
• Check whether azeotrope exists.
• For given conditions in the example

• x1=0, γ2=1 and γ1=exp(A)
• x1=1, γ1=1 and γ2=exp(A)
• Therefore
P1sat exp( A)
12 x 0   2.052
1
P2sat Azeotrope exists because this fnc is
P1sat continuous and passes through 1
12 x1 1  sat  0.224
P2 exp( A)
EXAMPLE 10.3
 1 P2sat
For 12  1  sat  1.4747
 2 P1
1
From given information ln  A(1  2 x1 )
2
Solving for x1 gives, x1az=0.325=y1az
Paz=γ1az P1sat = 73.76 kPa

Flash Calculations
•The name originates from the fact that a liquid at a pressure

equal to or greater than its bubble point pressure “flashes” or
partially evaporates when the pressure is reduced, producing a
two phase system of vapor and liquid in equilibrium.
•P,T-flash refers to any calculation of the quantities and
compositions of the vapor and liquid phases making up a two-
phase system in equilibrium at known T, P, and overall
composition.
Flash Calculations
Consider a system containing one mole of non-reacting chemical species
with an overall composition represented by the set of mole fractions (zi). Let
L be the moles of liquid, with mole fractions (xi) and let V be the moles of
vapour, with mole fractions (yi). The material balance equations are:
L V 1
zi  L xi  V yi .........( i  1,2,..., N )
yi (10.10)
Ki 
xi
zi K i zi K i
yi 
1  V ( K i  1)
(i  1,2,....,N) i 1  V ( K  1)  1
i
(10.16) (10.17)
EXAMPLE 10.5
• The system acetone(1)/acetonitrile(2)/nitromethane(3) at 80C and

110kPa has the overall composition z 1=0.45, z2=0.35, z3=0.20.
Assuming that Raoult’s law is appropriate to this system, determine
L, V, xi and yi. The vapor pressures of the pure species at 80C are:
• P1sat =195.75 P2sat = 97.84 P3sat = 50.32 kPa
• First do a BUBL P calculation with zi=xi to determine Pbubl.
• Pbubl=x1 P1sat + x2 P2sat + x3 P3sat = 132.4 kPa
• Second do a DEW P calculation with zi=yi to determine P dew.
• Pdew=1/(y1/P1sat + y2/P2sat + y3/P3sat )=101.52 kPa
• 101.52 < 110 < 132.40  2 phase exists

SOLUTION THERMODYNAMICS :THEORY
What is solution ?
The term solution includes homogeneous or heterogeneous mixtures of two or more
components whether in the gas, liquid, or solid phase.
Thermodynamic principles, which were developed for pure substances, are equally
applicable to solutions of fixed composition.
If the composition of the solution changes, the functional relations for all
thermodynamic properties require one additional term for each additional component
present.
KMM 543E 37
Many applications of chemical engineering thermodynamics are to systems wherein
multi component gases or liquids undergo composition changes as the result of
 mixing or separation processes

 the transfer of species from one phase to another
 or chemical reaction
The properties of such systems depend on composition as well as on temperature and

pressure.
KMM 543E 38
Solutions
• A mixture of two or more components that form a homogeneous

molecular dispersion
• one component - “solvent”; others - “solutes”
KMM 543E 39
TYPES OF SOLUTIONS
• Gas-in-gas: air
• Liquid-in-gas: water vapor in air
• Solid-in-gas: iodine vapor in air
• Gas-in-liquid: carbonated water
• Liquid-in- liquid: alcohol in water
• Solid-in-liquid: NaCl in water
• Gas-in-solid: hydrogen in Pd
• Liquid-in-solid: mineral oil in paraffin
• Solid-in-solid: mixture of alums
KMM 543E 40
Schematic of experimental determination of

the partial molar volume of water in a
specified mixture of ethanol (e) and water
(w).
Mixing of ethanol and water.
KMM 543E 41
Solutions could be homogeneous or heterogeneous.
S Homogeneous solution of variable composition

S Develop a fundamental property relation of this system
We will introduce the following thermodynamic properties and
concepts in this chapter.
Ü Chemical Potential
Ü Partial Properties
Ü Fugacity
Ü Excess Properties
Ü Ideal Solution
Ü Excess Gibbs Energy
Ü Activity Coefficient
KMM 543E 42
Fundamental Property Relation
d (nG )  (nV )dP  (nS )dT (6.6) in any closed system

This equation is applied to the case of a single phase fluid that
does not undergo chemical reaction. (constant composition)
  (nG )    (nG ) 
 P   nV  T    nS
T ,n   P ,n
6 What happens in case of an open system ?
KMM 543E 43
ğ In an open system
For a single phase application, the total Gibbs energy nG is not
only a function of T and P but also numbers of moles of chemical
species present in the system.
nG  g ( P, T , n1 , n2 ,......, ni )
The total differential of nG is
  (nG )    (nG )    (nG )    (nG ) 

d (nG )    dP   T  dT    dn1    dn2  .......
  P  T ,n   P ,n  n1  T , P ,n j  n2  T , P ,n j
  (nG )    (nG )    (nG ) 

d (nG )    dP    dT     dni
 P  T ,n  T  P ,n i  ni  T , P , n
j
KMM 543E 44
ü Chemical potential of species i in a mixture is
  (nG ) 
i    (11.1)
 ni  T , P ,n j
The general equation for d(nG) is
d (nG )  (nV )dP  (nS )dT   i dni (11.2)

i
Equation (4.3) is the fundamental property relation for single
phase fluid systems of constant or variable mass and constant or
variable composition.
This equation is the foundation equation upon which the structure
of solution thermodynamics is built.
KMM 543E 45
Chemical Potential as a Criterion for Phase Equilibria

d (nG )  (nV ) dP  (nS ) dT   i dni
   
i

d (nG )  (nV ) dP  (nS ) dT   i dni
   
where superscripts  and  identify the phases

at equilibrium, T and P are uniform throughout the entire system.
Total system property is expressed by an equation of the form :
nM  (nM )  (nM ) 
KMM 543E 46
Chemical Potential as a Criterion for Phase Equilibria
For a closed system consisting of more than one phase in equilibrium
i  i  .....  i (i  1,2,.... N ) (11.6)
Multiple phases at the same T and P are in equilibrium when the

chemical potential of each species is the same in all phases.
The application of equation (11.6) to specific phase equilibrium

problems requires use of models of solution behaviour, which
provide expressions for G or for i as a functions of temperature,
pressure and composition. The simplest of those, the ideal gas
mixture and ideal solution.
KMM 543E 47
Partial Properties
The mole number derivative of any thermodynamic properties has

a particular use in solution thermodynamics.
  (nM )  (11.7)
Mi   
 ni  T , P ,n j
This equation defines the partial molar property ( M i) of species i
in solution.
_
According to this definition : i  Gi
The definition of a partial molar property provides the means for
calculation of partial properties from solution property data. Or,
it is possible to calculate the solution properties from knowledge
of the partial properties. KMM 543E 48
Equations Relating Molar and Partial Molar Properties
nM  M (T , P, n1 , n2 ,......, ni ,.....)
6 What is the relationship between thermodynamic properties of the mixture and the
concentration of the species constituting the mixture?
M (T , P, x1 , x 2 ,..., xi )   xi M i (T , P ) For an ideal solution

i
V  x1V1  x2V2  x1V1  (1  x1 )V2 For an ideal binary

mixture
Total interactions:
1-1 ; 2-2 ; 1-2 ; 2-1
KMM 543E 49
In the derivation of the partial molar property an assumption has
been made :
the thermodynamic properties of homogeneous phase are
functions of temperature, pressure, and the numbers of moles of
the individual species which comprise the phase.
nM  M (T , P, n1 , n2 ,......, ni ,.....)
The total differential of nM is
  (nM )    (nM )    (nM ) 
d (nM )    dP    dT     dni
 P  T ,n  T  P ,n i  ni  T , P ,n j
  (nM )    (nM ) 
dM    dP    dT   M i dxi
 P  T , x  T  P , x i
KMM 543E 50
M   xi M i nM   ni M i
i i
These equations have a special importance.
They allow calculation of mixture properties from partial

properties.
_ _
dM   xi d M i   M i dxi
i i
  (nM )    (nM ) 
dM    dP    dT   M i dxi
 P  T , x  T  P , x i
KMM 543E 51
Gibbs-Duhem Equation :
 M   M  _
  dP    dT   xi d M i  0
 P T , x  T  P , x i
For the important special case of changes at constant T and P,

_
x d M
i
i i 0 cons tan t T, P
KMM 543E 52
The properties of solutions as represented by the symbol M may
be one unit mass basis as well as on a mole basis.
The three kinds of properties used in solution thermodynamics
are distinguished by the following symbolism:
Solution properties M , for example, U, H, S, G
Pure species properties Mi , for example, Ui, Hi, Si, Gi

_ _ _ _ _
Partial properties M i , for example, U i , H i , S i , G i
KMM 543E 53
Partial Properties in Binary Solutions
Equations for partial properties can always be derived from an
equation for the solution property as a function of composition by
direct application of Eq. (4.12).
  (nM ) 
Mi   
 ni  T , P ,n
j
For binary systems, the partial properties are readily calculated

from the following equations using an expression for the solution
property as a function of composition at constant T and P.
M  x1M 1  x2 M 2 From Eq.(4.15)
_
dM _
dM
M 1  M  x2 M 2  M  x1
dx1 dx1
KMM 543E 54
Relations among Partial Properties
_
d (nG )  (nV )dP  (nS )dT   G i dni
i
From this equation the following equations can be derived by the
application of the criterion of exactness.
 _
  _    (nV ) 
  Gi    (nS )  _   Gi  _
 T    n    Si  P    n  Vi
 i  P ,T , n j
T , n   P ,T ,n j
i
  P ,n 
For every equation providing a linear relation among
thermodynamic properties of a constant composition solution
there exists a corresponding equation connecting the
corresponding partial properties of each species in the solution.
_ _ _
H  U  PV or H i  U i  PV i
_ _ _
dG  V dP  S dT or d G i  V i dP  S i dT
KMM 543E 55
Ideal Gas Mixtures
For the Gibbs energy of an ideal gas mixture
_ _ _ _
G  H iig  T S
i
ig
i
ig
G  H iig  T Siig  RT ln yi
i
ig
  Gi  G  RT ln yi
ig
i
ig
i
ig
An alternative expression for the chemical potential

  i (T )  RT ln yi P
ig
i
Application of the summability relation

G ig   yi i (T )  RT  yi ln yi P
i i
KMM 543E 56
Fugacity and Fugacity Coefficient for a Pure Species
Giig  i (T )  RT ln P
For a real fluid, Gi  i (T )  RT ln f i (11.30)
in which pressure P is replaced by a new property f i, which has
units of pressure. This equation serves as a partial definition of f i,
which is called the fugacity of pure species i.
fi
Gi  Gi  RT ln
ig
G R
 G  G ig
P i i i
The dimensionless ratio fi/P is a new property called the fugacity

coefficient and given by symbol i.
GiR  RT ln i (11.31)
fi
i  (11.32)
P KMM 543E 57
Fugacity and Fugacity Coefficient for a Pure Species
GiR  RT ln i f i ig  P (11.33)
P
dP
ln i   ( Z i  1) (cons tan t T ) (11.34)
0
P
P
1 RT
RT 0
ln i  (Vi  ) dP (const. T )
P
V
1 RT
ln i   (
RT V  Vi
 P) dV  ln Z  ( Z  1) (const. T )
Fugacity coefficients (and therefore fugacity) for pure species are

evaluated by this equation from PVT data or from an equation of
state.
Bii P Bii P
Zi  1  ln i  (11.35)
RT RT
KMM 543E 58
Fugacity of a Pure Gaseous Species
P V
1 RT 1 RT
 RT V  Vi
ln i  (Vi  ) dP (const. T ) ln i  (  P ) dV  ln Z  ( Z  1) (const. T )
RT 0 P
At very low pressure f i ig  P

BP Assuming one parameter
At low to moderate pressures ln i  ii virial equation of state
RT represent the system.
At higher pressures more complicated equation of state is needed
V a  PV   PV 
ln   ln    1  ln  van der Waals
V  b RTV  RT   RT 
 bP  a  Z  (1  2 ) bP / RT 
ln   ( Z  1)  ln Z    ln   Peng Robinson
 RT  2 2bRT  Z  (1  2 ) bP / RT 
KMM 543E 59
Vapour/Liquid Equilibrium for Pure Species
Giv  i (T )  RT ln f i v for sat. vapour
Gi  i (T )  RT ln f i Gil  i (T )  RT ln f i l for sat. liquid
v
fi
G  G  R T ln l
i
v
i
l
fi
An equation applicable to the change of state from saturated liquid to
saturated vapour, both at temperature T and at the vapour pressure
sat
. P i
According to Eq.(1.107) (6.66) Giv  Gil  0
fi  fi  fi
v l sat
KMM 543E
(11.39)
60
Fugacity of a Pure Liquid
The fugacity of pure species i as a compressed liquid is calculated

in two steps :
First, the fugacity coefficient of saturated vapour i  i is
v sat
determined from an integrated form of Eq.(11.34), evaluated for

P  Pi sat. Then by Eq.(11.39) f i sat  isat Pi sat , and this is the
fugacity of both saturated vapour and saturated liquid at the
system temperature. P
ln i   ( Z i  1)
dP
(cons tan t T)
0
P
Second is the calculation of the fugacity change resulting from the

pressure increase to P, that changes the state from saturated liquid
to compressed liquid.
KMM 543E 61
Fugacity of a Pure Liquid
For the isothermal change of state from saturated liquid to
compressed liquid at pressure P,
P P
fi 1
Gi  Gisat   V dP i
ln
fi sat

RT  V dP
sat
i
Pi sat Pi
fi fi Vi l ( P  Pi sat )
Gi  G i
sat
 R T ln ln 
f i sat f i sat RT
 V l
( P  P sat
)
f i  i Pi exp
sat sat i i

 RT 
The exponential is known as the Poynting factor.
KMM 543E 62
Fugacity and Fugacity Coefficient for Species in Solution
The definition of the fugacity of a species in solution is parallel to the definition of the
pure species fugacity.
i  i (T )  RT ln fî
Since all phases in equilibrium are at the same temperature, and
the chemical potentials of each phases in equilibrium are equal to
each other, the following general criterion from Eq.(11.42) can be
derived : ˆ ˆ ˆ
f i  f i  .......  f i (i  1,2,...., N )
The multiple phases at the same T and P are in equilibrium when
the fugacity of each constituent species is the same in all phases.
This criterion of equilibrium is the one usually applied by

chemical engineers in the solution of phase equilibrium problems.
KMM 543E 63
For the specific case of multicomponent vapour/liquid
equilibrium ˆf v  fˆ l (i  1,2,...., N )
i i
The residual property is given by

M  M M
R ig
nM  nM  nM
R ig
Differentiation with respect to ni at constant T, P, and nj gives:

  (nM R )    (nM )    (nM ig ) 
      
 ni  T , P ,n j  ni  T , P ,n j  ni  T , P ,n j
M  Mi  M
i
R
i
ig
KMM 543E 64
Since residual properties measure departure from ideal gas values,
their most logical use is as gas-phase properties, but in fact they
also find use as liquid phase properties.
Gi R  Gi  Gi ig
Gi R  R T ln ̂i
ˆ
f
î  i
yi P
The dimensionless ratio ̂i is called the fugacity coefficient of
species i in solution.
For an ideal gas ˆf ig  y P
i i
KMM 543E 65
The Fundamental Residual Property Relation
 nG  1 nG
d    d (nG )  2
dT
RT  RT RT
 nG  nV nH Gi
d    dP  2
dT   dni
RT  RT RT i RT
This equation is general relation expressing G/RT as a function of

all of its canonical variables T, P, and the mole numbers.
Knowledge of G/RT as a function of its canonical variables
allows evaluation of all other thermodynamic properties, and
therefore implicitly contains complete property information.
KMM 543E 66
 nG R  nV R nH R Gi R
d    dP  2
dT   dni
 RT  RT RT i RT
This equation is the fundamental residual property relation.

An alternative form of this equation
 nG R  nV R nH R
d    dP  2
dT   ln ̂i dni
 RT  RT RT i
Equations so general as the above equations are useful for

practical application only in their restricted forms.
V R
  (G R / R T )  HR   (G R / R T )  ˆ   (G / R T ) 
R
   T   ln i   
RT  P T ,x RT   T  P,x  ni  T , P ,n j
KMM 543E 67
ˆ   (G R
/ R T)
ln i   
  ni  T , P ,n j
ln ̂i values can be calculated from the compressibility factor data

by the following equation:
P
ln i   Z i  1
ˆ dP
0
P
KMM 543E 68
Fugacity Coefficients from the Virial Equation of State
Values of ̂i for species i in solution are readily found from

equations of state.
The simplest form of the virial equation provides a useful

example. Written for a gas mixture it is exactly the same as for a
pure species: Z=1+BP/RT.
B   yi y j Bij
Bij=Bji. i j
For a binary mixture i=1,2 and j=1,2

B  y1 y1 B11  y1 y2 B12  y2 y1 B21  y2 y2 B22
B  y12 B11  2 y1 y2 B12  y22 B22
KMM 543E 69
P
ln i   Z i  1
ˆ dP
0
P
nBP   (nZ )  P   (nB ) 

nZ  n  Z1     1  
RT  n1  P ,T , n2 RT  n1  T , n2
ˆ 1
P
  (nB )  P   (nB ) 
ln 1     dP 
RT 0  n1  T ,n
 
RT  n1  T ,n
2 2
For a binary gas mixture

  (nB)  P
 ln ˆ1  ( B11  y2212 )
     2 12
2
  B11 (1 y1 ) y 2 12 B11 y RT
 n1  T ,n2
P
12  2 B12  B11  B22 ln ˆ 2  ( B22  y1212 )
KMM 543E
RT 70
The general equation for multicomponent mixtures :

P  1 
ˆ
ln k   Bkk   yi y j (2 ik   ij )
RT  2 i j 
 ik  2 Bik  Bii  Bkk

 ij  2 Bij  Bii  B jj
 ii  0,  kk  0 and  ki   ik
KMM 543E 71
Generalized Correlations for The Fugacity Coefficient
P  Pc Pr  dP  Pc dPr
Pr
dPr
ln i   ( Z i  1) at constant Tr (4.65) (11.62)
0
Pr
The Pitzer correlation is Z  Z 0   Z1

Pr Pr
dPr 1 dPr
ln    ( Z  1)
0
Z
0
Pr 0
Pr
ln   ln  0   ln 1
Pr Pr
dPr dPr
ln    ( Z  1)
0 0
and ln    Z
1 1
0
Pr 0
Pr
KMM 543E 72
Another method is based on an equation of state.

A procedure to calculate a fugacity coefficient of a gas based on
Lee and Kesler method 1 
   ( )
0
A useful generalised correlation for ln  results when the simplest

form of the virial equation is valid.
The simplest form of virial equation is
BP  BP  P
Z  1  1   c  r
RT  RTc  Tr
BPc
(BPc/RTc) can also be expressed as  B 0   B1
RTc
KMM 543E 73
Pr 0
Z 1  ( B   B1 )
Tr
Pr 0  Pr 0 1 
ln   ( B   B1 )   exp ( B   B ) 
Tr  Tr 
The simplest form of the virial equation has validity only at low to
moderate pressures where Z is linear in pressure.
The generalised correlation just described is for pure gases only.
How the virial equation may be generalised to allow calculation of

fugacity coefficients ̂i of species i in gas mixtures?
KMM 543E 74
P  1 
ˆ
ln k   Bkk   yi y j (2 ik   ij )
RT  2 i j 
Values of virial coefficients, Bkk, Bii, Bij, Bik, etc., can be found
from the generalised correlation represented in more general form
as follows:
RTc ij 0.422 0.172
Bij  ( B 0   ij B1 ) B 0  0.083  B1  0.139 
Pcij Tr1.6 Tr4.2
i   j Zcij R Tc ij
 ij  Pcij  Tc ij  (Tc iTc j )1/ 2 (1  kij )
2 Vcij
Zci  Zc j  Vc 1/ 3
 Vc 
1/ 3 3
Zcij  Vcij  
i j
 Trij  T / Tc ij
2  2 KMM 543E
 75
Ideal Gas Mixtures
Statement of Gibbs’s theorem
A partial molar property (other than the volume) of a constituent

species in an ideal gas mixture is equal to the corresponding molar
property of the species as a pure ideal gas at the mixture temperature
but at a pressure equal to its partial pressure in the mixture.
This expressed mathematically for generic partial property by the

equation
M iig (T , P )  M iig (T , pi ) (11.21)
KMM 543E 76
Ideal Gas Mixtures
na nb n a + nb
• P = const: Va+b = Va + Vb
• V = const: Pa+b = (na + nb)RT/V = Pa + Pb
• T = const: Umix = 0, Hmix = 0
KMM 543E 77
Ideal Gas Mixtures
The enthalpy of an ideal gas

H iig  H iig (11.22)
Application of the summability relation yields
H ig   yi H iig H ig   yi H iig  0
i i
For ideal gases, enthalpy change of mixing is zero
KMM 543E 78
Ideal Gas Mixtures
The entropy of an ideal gas
dSiig   R d ln P cons tan t T
_
S  Siig  R ln yi
i
ig
By the summability relation

S ig   yi Siig  R  yi ln yi
i i
1
S   yi S  R  yi ln
ig
i
ig
i i yi
KMM 543E 79
The Ideal Solution
The ideal solution is a useful model, which serves as a standard to

which real solution behaviour can be compared.
Gi ig  Giig  R T ln yi
Gi  Gi  R T ln xi
id
 Gi id   G 
Siid      i   R ln xi S id
 Si  R ln xi
 T  P,x  T P i
 Gi id   Gi 
      Vi  Vi
id
H id
 Hi
id
Vi
 P T , x  T T i
KMM 543E 80
The Ideal Solution
M id   xi M iid
i
G id   xi Gi  R T  xi ln xi
i i
S id   xi Si  R  xi ln xi
i i
V id   xiVi
i
H id   xi H i
i
The Lewis/Randall Rule ˆf id  x f ˆ

i  i
id
i i i
It shows that the fugacity of each species in an ideal solution is
proportional to its mole fraction.
KMM 543E 81
The Non-Ideal Solution
na nb n a + nb
Umix  0, Hmix  0
KMM 543E 82
Excess Properties
The mathematical formalism of excess properties is analogous to
that of the residual properties.
M  Mi  M
i
E
i
id
M  Mi  M
i
E
i
id
M  M R   xi M iR
E
i
 nG E  nV E nH E Gi E
d    dP  2
dT   dni
 RT  RT RT i RT
KMM 543E 83
The Excess Gibbs Energy and the Activity Coefficient
fî fî
Gi  Gi  RT ln Gi  RT ln  i
id E
i 
xi f i xi f i
 nG E  nV E nH E
d    dP  2
dT   ln  i dni
 RT  RT RT i
  (G E / RT 
ln  i   
 ni  P ,T ,n j
E
G
  xi ln  i  x d ln 
i i 0 (const T , P)
RT i
i
KMM 543E 84
Non-Ideal Solution Vapor Pressure
Henry’s Law: PA = PAo. A xA PB = PBo. A xB
“Repellent” components “Attracting” components
positive deviation negative deviation

P Ao P Ao
PB o PB o
0 0.5 1.0 0 0.5 1.0

Mole fraction of B (xB) Mole fraction of B (xB)
KMM 543E 85
Liquid Phase Properties from VLE Data
SVNA 12.1
•The mixture fugacity of a component in non-ideal liquid solution is
defined by:
li (T,P)  i (T )  RT ln f̂il

(11.46)
•We also define the activity coefficient:

l
f̂i
i 
x i fil
(11.91)
which is a measure of the departure of the component behaviour from an

ideal solution.
l l
i (T,Pequation
•Using the activity coefficient, )  i (T11.46
)  RT ln  i x i fi
becomes:
KMM 543E 86
Liquid Phase Properties from VLE Data
•Suppose we conduct VLE experiments on our system of interest.
• At a given temperature, we vary the system pressure by changing the cell
volume.
• Wait until equilibrium is established (usually hours)
• Measure the compositions of the liquid and vapour
KMM 543E 87
7. Liquid Phase Properties from VLE Data SVNA
12.1
The mixture fugacity of a component in non-ideal liquid solution is
defined by:
li (T,P)  i (T )  RT ln f̂il
(11.46)
f̂il
 i coefficient:
We also define the activity
x i fil
(11.91)
which is a measure of
li (Tthe
,Pdeparture
)  i (T ) ofRT
the component
ln  i x i fil behaviour
from an ideal solution.
Using the activity coefficient, equation 11.46 becomes:
KMM 543E 88
Liquid Solution Fugacity from VLE Data
Our understanding of molecular dynamics does not permit us to

predict non-ideal solution fugacities, fil . We must measure them by
experiment, often by studies of vapour-liquid equilibria.
Suppose we need liquid solution fugacity data for a binary mixture

of A+B at P,T. At equilibrium,
f̂il  f̂iv
The vapour mixture fugacity for component i is given by,
f̂iv  ˆ iv y iP
(11.52)
f̂iv  y iPat low pressure, but at the required

If we conduct VLE experiments
temperature, we can use
by assuming that iv = 1.

KMM 543E 89
Liquid Solution Fugacity from Low P VLE Data
Since our experimental measurements are taken at equilibrium,
f̂il  f̂iv
 y iP
What we need is VLE data at various pressures (all relatively low)

Table 12.1
KMM 543E 90
Activity Coefficients from Low P VLE Data
With a knowledge of the liquid solution fugacity, we can derive
activity coefficients. Actual
f̂il
fugacity i  l
x i fi
Idealysolution
iP fugacity
 
Our low pressure vapouri fugacity l simplifies f l to give:
x i fi i
l sat sat
 V l
i (P  P i
sat
)
fi  i Pi exp 
and if P is close to Pi :
sat
 RT 
 Pisat
y iP
i 
leaving us with x i Pisat
KMM 543E 91
Activity Coefficients from Low P VLE Data
Our low pressure VLE data can now be processed to yield
experimental activity coefficient data:
y iP
i 
x i Pisat
Table 12.2
KMM 543E 92
7. Correlation of Liquid Phase Data SVNA 12.1
The complexity of molecular interactions in non-ideal systems

makes prediction of liquid phase properties difficult.
 Experimentation on the system of interest at the conditions
(P,T,composition) of interest is needed.
 Previously, we discussed the use of low-pressure VLE data
for the calculation of liquid phase activity coefficients.
As practicing engineers, you will rarely have the time to conduct

your own experiments.
 You must rely on correlations of data developed by other
researchers.
 These correlations are empirical models (with limited
fundamental basis) that reduce experimental data to
mathematical equations.
KMM 543E 93
Correlation of Liquid Phase Data
Recall our development of activity coefficients on the basis of the
partial excess Gibbs energy :
E id
Gi  Gi  Gi
where the partial molar Gibbs energy of the non-ideal model is
provided by equation 10.42:
Gi  li  i (T )  RT ln f̂ il
and the ideal solutionidchemical potential is:

Gi  id
i  i ( T )  RT ln x f
i i
l
Leaving us with the partial excess Gibbs energy:

E
Gi  RT ln f̂il  RT ln x i fil
f̂il
 RT ln l
x i fi
 RT ln  i
(11.91)
KMM 543E 94
The partial excess Gibbs energy is defined by:
E (nGE )
Gi 
ni T,P,nj
In terms of the activity coefficient,
 (nG E / RT )
ln  i  
ni T , P , nj
(11.96)
ln(i) is a partial molar property
GE
GE/RT and activity coefficients are related using the summability
  x i ln  i
relationship for partial properties.
RT i
KMM 543E 95
(11.99)
We can now process our MEK/toluene data one step further to give
the excess Gibbs energy,
GE/RT =
x1ln1 + x2ln2
KMM 543E 96
Note that GE/(RTx1x2) is reasonably represented by a linear
function of x1 for this system. This is the foundation for the simplest
correlations for experimental activity coefficient data
 yP 
ln  1  ln 1 sat 
 x 1P1 
 y P 
ln  2  ln 2 sat 
 x 2P2 
GE / RT  x 1 ln  1  x 2 ln  2
KMM 543E 97
The chloroform/1,4-dioxane system
exhibits a negative deviation from
Raoult’s Law.
This low pressure VLE data can be

processed in the same manner as the
MEK/toluene system to yield both
activity coefficients and the excess
Gibbs energy of the overall system.
KMM 543E 98
Models for the Excess Gibbs Energy
Models that represent the excess Gibbs energy have several
purposes:
 they reduce experimental data down to a few parameters
(Data Reduction)
 they facilitate computerized calculation of liquid phase
properties by providing equations from tabulated data
 In some cases, we can use binary data (A-B, A-C, B-C) to
calculate the properties of multi-component mixtures (A,B,C)
A series of GE equations for activity coefficients are derived from

the Redlich/Kister expansion:
GE
 B  C( x1  x 2 )  D( x1  x 2 )2 (cons tan t T )
RTx 1x 2
Equations of this form “fit” excess Gibbs energy data quite well.
However, they are empirical and cannot be generalized for multi-
component (3+) mixtures or multiple temperatures.
KMM 543E 100

Symmetric Equation for Binary Mixtures
The simplest Redlich/Kister expansion results from C=D=…=0
GE
B
RTx 1x 2
To calculate activity coefficients, we express GE in terms of moles:

n1 and n2.
nG Bnn
E
 1 2
RT (n  n ) 1 2
And through differentiation,

(nGE / RT )
ln 1 
n1 T,P,n 2
we find: ln 1  Bx 22 and ln  2  Bx12
KMM 543E 101

Excess Gibbs Energy Models
Practicing engineers usually get information about activity
coefficients from correlations obtained by making assumptions
about excess Gibbs Energy. These correlations:
 reduce vast quantities of experimental data into a few
empirical parameters,
 provide information an equation format that can be used in
thermodynamic simulation packages (Provision, Unisym,
Aspen)
Simple empirical correlations
 Symmetric, Margules, van Laar
 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
 Wilson, NRTL, Uniquac
 Some fundamental basis
 Parameters are temperature dependent, and multi-
KMM 543E
component behaviour can be predicted from binary data. 102
Excess Gibbs Energy Models
Our objectives are to learn how to fit Excess Gibbs Energy models
to experimental data, and to learn how to use these models to
calculate activity coefficients.
 yP 
ln  1  ln 1 sat 
 x 1P1 
 y P 
ln  2  ln 2 sat 
 x 2P2 
GE / RT  x 1 ln  1  x 2 ln  2
KMM 543E 103

Margules’ Equations
While the simplest Redlich/Kister-type correlation is the Symmetric
Equation, but a more accurate equation is the Margules correlation:
GE
 A 21x1  A12 x 2
RTx 1x 2
(12.9a)
GE
Note that as x1 goes to zero,  A 12
RTx 1x 2 x
1 0
E
G 
lim  ln  1
Also, x10 RTx 1x 2
A12  ln 1 A 21  ln  2
so that
KMM 543E 104

Margules’ Equations
If you have Margules parameters, the activity coefficients can be
derived from the excess Gibbs energy expression:
GE
 A 21x1  A12 x 2
RTx 1x 2
(12.9a)
ln 1  x 22 [ A12  2( A 21  A12 )x1]
to yield:
ln  2  x12 [ A 21  2( A12  A 21 )x 2 ]
(12.10ab)
These empirical equations are widely used to describe binary

solutions. A knowledge of A12 and A21 at the given T is all we
require to calculate activity coefficients for a given solution
KMM 543E 105
van Laar Correlation
Another two-parameter excess Gibbs energy model was
developed from an expansion of (RTx1x2)/GE instead of
GE/RTx1x2. The end results are:
2
 A /
x1 
(12.16)
 A12 and:
/
ln 1energy
for the excess Gibbs 1 / 12 
 A 21x 2 
2
 A /
x2 
ln  2  A 211  /
/ 21 
 A12 x1 
(12.17a)
(12.17b)
KMM 543E 106

Local Composition Models
Unfortunately, the previous approach cannot be extended to
systems of 3 or more components. For these cases, local
composition models are used to represent multi-component
systems.
 Wilson’s Theory
 Non-Random-Two-Liquid Theory (NRTL)
 Universal Quasichemical Theory (Uniquac)
While more complex, these models have two advantages:

 the model parameters are temperature dependent
 the activity coefficients of species in multi-component liquids
can be calculated using information from binary data.
A,B,C A,B
A,C B,C
KMM 543E tertiary mixture binary binary 107

Wilson’s Equations for Binary Solution Activity
A versatile and reasonably accurate model of excess Gibbs Energy

was developed by Wilson in 1964. For a binary system, G E is
provided by:
GE
 x1 ln( x1  x 2 12 )  x 2 ln( x 2  x1 21 )
RT
(12.18)
V2  a  V1  a 
12  exp 12   21  exp 21 
V1  RT  V2  RT 
where
(12.24)
Vi is the molar volume at T of the pure

component i.
aij is determined from experimental data.
KMM 543E 108
Wilson’s Equations for Binary Solution Activity
Activity coefficients are derived from the excess Gibbs energy

using the definition of a partial molar property:
E nGE
RT ln  i  Gi 
ni T,P,n
j
When applied to equation 11.16, we obtain:

 12  21 
ln 1   ln( x1  x 2 12 )  x 2   
x
 1  x 
2 12 x 2  x 
1 21 
 (12.19a)
12  21 
ln  2   ln( x 2  x1 21 )  x1  
 x1  x 2 12 x 2  x1 21 
(12.19b)
KMM 543E 109
Wilson’s Equations for Multi-Component Mixtures
The strength of Wilson’s approach resides in its ability to describe

multi-component (3+) mixtures using binary data.
 Experimental data of the mixture of interest (ie. acetone,
ethanol, benzene) is not required
 We only need data (or parameters) for acetone-ethanol,
acetone-benzene and ethanol-benzene mixtures
The excess GibbsEenergy for multicomponent mixtures is written:

G
   xi ln(  x j  ij )
RT i j
(12.22)
x 
ln  i  1  ln  x j  ij   k ki
i k  x j  kj
and the activity coefficients become: j
(12.23)
KMM 543E 110
Wilson’s Equations for 3-Component Mixtures
For three component systems, activity coefficients can be

calculated from the following relationship:
x 1 1i
ln  i  1  ln( x 1  i1  x 2  i2  x 3  i3 ) 
x 1  x 2  12  x 3  13
x 2  2i

x 1 21  x 2  x 3  23
x 3  3i

x 1 31  x 2  32  x 3
Model coefficients are defined as (ij = 1 for i=j):
Vj   aij 
 ij  exp 
Vi  RT 
KMM 543E 111

Comparison of Liquid Solution Models
Activity coefficients of 2-methyl-
2-butene + n-methylpyrollidone.
Comparison of experimental
values with those obtained from
several equations whose
parameters are found from the
infinite-dilution activity
coefficients.
(1) Experimental data.
(2) Margules equation.
(3) van Laar equation.
(4) Scatchard-Hamer equation.
(5) Wilson equation.
KMM 543E 112

SOLUTION THERMODYNAMICS :APPLICATION
Models for The Excess Gibbs Energy
NRTL equation
GE G21 21 G1212
 
x1 x2 RT x1  x2G21 x2  x1G12
  G 
2
G1212 
ln  1  x2  21 
2 21
  
  x1  x2G21  ( x2  x1G12 ) 
2
  G 
2
G21 21 
ln  2  x1 12 
2 12
  
  x2  x1G12  ( x1  x2G21 ) 
2
G12  exp(12 ) ; G21  exp( 21 ) ; 12  b12 / RT ;  21  b21 / RT
ln  1   21  12 exp(12 ) ln  2  12   21 exp( 21 )
KMM 543E 113

UNIQUAC (UNIversal QUAsi Chemical) Model
G E G E (combinatorial ) G E (residual )
 
RT RT RT
G E (combinatorial )  z  G E (residual )  
  xi ln i   xi qi ln i   xi qi ln   j ji 

RT i xi 2 i i RT i  j 
ln  i  ln  i (combinatorial )  ln  i (residual )
 Ji J 
ln  i (combinatorial )  1  J i  ln J i  5qi 1   ln i 
 Li Li 
 
   
ln  i (residual )   qi 1  ln   j ji    
j ij
j   k  kj
 
  j  
k
KMM 543E 114
UNIFAC (UNIquac Functional-group Activity Coefficient) ) Model
The UNIFAC Method estimation of activity coefficients depends on the

concept that a liquid mixture may be considered a solution of structural
units from which the molecules are formed rather than a solution of the
molecules themselves.
ln  i  ln  i (combinatorial )  ln  i (residual )
 Ji Ji 
ln  i (combinatorial )  1  J i  ln J i  5qi 1   ln 
 Li Li 
   ik  ik 
ln  i (residual )  qi 1     k  eik ln 
 k  sk sk 
KMM 543E 115
Property Changes of Mixing
G E  G   xi Gi  R T  xi ln xi
i i
S  S   xi Si  R  xi ln xi
E
i i
V  V   xiVi
E
H E  H   xi H i
i
M  M   xi M i
i
KMM 543E 116

Property Changes of Mixing
G  G  RT  xi ln xi
E
G  RT  xi ln xi
id
i i
S  S  R  xi ln xi
E
S   R  xi ln xi
id
i
i
V  V
E
H E  H V id
0
H id
0
KMM 543E 117

Property Ideal Mixture Real Mixture
Volume
Vi id  Vi Vi E  Vi  Vi
V id  0 V E  V
Internal Energy
U iid  U i U iE  U i  U i
U id  0 U E  U
Enthalpy
H iid  H i H iE  H i  H i
H id  0 H E  H
Entropy
S iid  S i  R ln xi S iE  S i  S i  R ln xi
n
S id
  Rxi ln xi S  S  R  xi ln xi
E
i 1
Gibbs Free Energy
Gi id  Gi  RT ln xi Gi E  Gi  Gi  RT ln xi
G id  RTxi ln xi G E  G  RTxi ln xi
Helmoltz Free Energy
Aiid  Ai  RT ln xi Ai E  Ai  Ai  RT ln xi
A id  RTxi ln xi A E  A  RTxi ln xi
KMM 543E 118

Non-Ideal VLE to Moderate Pressures: Overview SVNA 14.1
We now have the tools required to describe and calculate vapour-

liquid equilibrium conditions for even the most non-ideal
systems.
1. Equilibrium Criteria:
 In terms of chemical potential
 iv   li
 In terms of mixture fugacity
f̂iv  f̂il
2. Fugacity of a component in a non-ideal gas mixture:
f̂iv (T,P, y 1, y 2 ,..., y n )  y i ˆ iv (T,P, y 1, y 2 ,..., y n ) P
3. Fugacity of a component in a non-ideal liquid mixture:
f̂il (T,P, x 1, x 2 ,..., x n )  x i  i (T,P, x 1, x 2 ,..., x n ) fil
 Vi (P  Pisat ) 
 x i  i (T,P, x 1, x 2 ,..., x n )  Psat sat
i i exp 
 RT 
KMM 543E 119
g, f Formulation of VLE Problems
To this point, Raoult’s Law was only description we had for VLE
behaviour: y P  x P sat
i i i
We know that calculations based on Raoult’s Law do not predict

actual phase behaviour due to over-simplifying assumptions.
Accurate treatment of non-ideal phase equilibrium requires the use

of mixture fugacities. At equilibrium, the fugacity of each
component is the same in all phases. Therefore,
f̂iv  f̂il
or,
ˆ  V (P  P sat
)
y i i P  x i  i i Pi exp
v sat sat i i

 RT 
determines the VLE behaviour of non-ideal systems where Raoult’s
Law fails.
KMM 543E 120
Non-Ideal VLE to Moderate Pressures
A simpler expression for non-ideal VLE is created upon defining a

lumped parameter, F.
ˆ iv   Vil (P  Pisat ) 
 i  sat exp 
i  RT 
ˆ iv
 sat
i
sat
y ibecomes,
The final expression iP  x i  iPi
(i = 1,2,3,…,N)
14.1
To perform VLE calculations we therefore require vapour pressure

KMM 543E 121
Non-Ideal VLE to Moderate Pressures
Sources of Data:
1. Vapour pressure: Antoine’s Equation (or similar correlations)
Bi
ln Pisat  A i 
T  Ci
14.3
Bii (P  Pisat )  0.5 P  y j y k (2 ji  jk ) 

 i  exp Coefficients: Viral EOS (or others) 
2. Vapour Fugacity j k
 RT 
 
14.6
3. Liquid Activity Coefficients

KMM 543E  Binary Systems - Margules,van Laar, Wilson, NRTL, 122
Recomended Activity Coefficient Models
KMM 543E 123

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KMM 543E

Advanced Chemical Engineering

The Nature of Equilibrium

Composition of a system can be measured and characterised in

The intensive state of a system at equilibrium is established

Phase rule variables are intensive properties. Overall or total

N = number of chemical species in the entire heterogeneous

VLE : Qualitative Behaviour

When N = 2, the phase rule becomes F = 4-.

Since there must be at least one phase ( =1), the maximum

All equilibrium states of the system can therefore be represented

Within this space, the states of pairs of phases coexisting at

VLE : Qualitative Behaviour

tie line (connect points

VLE : Qualitative Behaviour

VLE : Qualitative Behaviour

VLE : Qualitative Behaviour

VLE : Qualitative Behaviour

VLE : Qualitative Behaviour

Raoult’s Law P_x1

VLE : Qualitative Behaviour

VLE : Qualitative Behaviour

Conversely, appreciable positive departures result for

VLE : Qualitative Behaviour

VLE : Qualitative Behaviour

SIMPLE MODELS FOR VLE

The two simplest models are

xi = a liquid phase mole fraction,

yi = a vapour phase mole fraction, and

Dewpoint and Bubblepoint Calculations with Raoult’s Law

Engineering interest centres on dewpoint and bubblepoint

BUBL P : Calculate (yi) and P, given (xi) and T

Bubble Point Pressure:

Bubble Point Temperature:

Governing Equation - Bubble Line Equation:

Dew Point Temperature:

Governing Equation - Dew Line Equation:

This problem can be solved by Henry’s law.

For a species present as a very dilute solute in the liquid phase,

VLE BY MODIFIED RAOULT’S LAW

VLE BY MODIFIED RAOULT’S LAW

Relative Volatility and Azeotrope :

Thus if the relative volatility between 2 components is very close to

At an azeotrope y1 = x1, y2 = x2 and then 12  1.

• Check whether azeotrope exists.

• For given conditions in the example

Solving for x1 gives, x1az=0.325=y1az

Paz=γ1az P1sat = 73.76 kPa

•The name originates from the fact that a liquid at a pressure

• The system acetone(1)/acetonitrile(2)/nitromethane(3) at 80C and

• P1sat =195.75 P2sat = 97.84 P3sat = 50.32 kPa

• First do a BUBL P calculation with zi=xi to determine Pbubl.

• Pbubl=x1 P1sat + x2 P2sat + x3 P3sat = 132.4 kPa

• Second do a DEW P calculation with zi=yi to determine P dew.

• Pdew=1/(y1/P1sat + y2/P2sat + y3/P3sat )=101.52 kPa

• 101.52 < 110 < 132.40  2 phase exists

 mixing or separation processes

The properties of such systems depend on composition as well as on temperature and

• A mixture of two or more components that form a homogeneous

Schematic of experimental determination of

Mixing of ethanol and water.

S Homogeneous solution of variable composition

d (nG )  (nV )dP  (nS )dT (6.6) in any closed system