Solution Thermodynamics

Outline:

➢ Introduction of Solution thermodynamics

➢ Multicomponent Mixture
o Partial Molar properties, Gibbs-Duhem Equation, Chemical Potential
o Fugacity and Fugacity Coefficient
o Estimation of pure gases through equation of state/compressibility factor corelation
➢ Thermodynamics Properties of Real Gas Mixture:
o Mixing rule
o P-V-T properties of real gas mixture, Departure function for real gas mixture
o Fugacity and fugacity coefficient of real gas mixture
o Fugacity of a component in a mixture, fugacity of liquid and solid
o Stability and phase transition in thermodynamics system, stability criteria, phase transition in
a pure substance, Gibbs phase rule
 Outline:
➢ Ideal Solution:
o Phase Equilibria, Phase equilibria for Ideal solution, Phase diagram for ideal solution
o Excess properties, Gibbs-Dehum relation
o Excess Gibbs Free Energy Model: Margules equation, Redlich- Kister equation, Wilson
equation, Non-random two liquid (NRTL) equation, UNIQUAC equation, Henry’s law
➢ Vapor Liquid Equilibrium (VLE):
o Basic equation for vapor-liquid equilibrium, Reduction of VLE data, VLE at low to moderate
pressure
o Excess Gibbs free models, Azeotrope data, VLE at high pressure, Multicomponent VLE
o Bubble point, dew point calculation, Thermodynamics consistency test of VLE data
➢ Chemical-Reaction Equilibria

1. Introduction to Chemical Engineering Thermodynamics- J. M. Smith, H. C. Van Ness,

Text Books M. M. Abbott, M.T. Swihart
2. Chemical Engineering Thermodynamics- Y. V. C. Rao
 Thermodynamics Properties

Intensive Property: Does not depend on mass of the system.

Eg: Temperature, pressure, density, specific volume, specific internal energy, specific enthalpy etc.

Extensive Property: Depend on mass of the system.

Eg: Mass, volume, internal energy, enthalpy, entropy etc.

➢ Reference Property ( P, V, T, S)
➢ Energy Property: (U, A, G, H)
➢ Derived Properties ( C, ƙ, λ, β)

Internal Energy (U): it is the energy of the substance in the absence of effect due to capillary, external electric,
magnetic or other field.
it indicate the total energy; potential or kinetic in a thermodynamics system.
 Energy Property: (U, A, G, H)

Helmholtz Free Energy (A): It measure the work of a closed system with constant temperature and volume.
It predict the spontaneity, equilibrium state direction of change and maximum work for a system at constant
temperature and volume.
A = U – TS [ -ΔA = - WR (reversible work done)

Enthalpy (H): It is the amount of total heat content in a system.

H = U + PV
Change in enthalpy determine whether a reaction is endothermic ( absorbed heat ΔH = +ve) or exothermic (
release heat ΔH = -ve)
It is used to calculate the heat of reaction of a chemical process.

Gibbs Free Energy (G): It measure the maximum amount of work done in a thermodynamic system at constant
temperature and pressure.
It determine whether a process will occur spontaneously or not.
G = H - TS
 Maxwell Relations:
Energy Property: A T
V
A
G Variables ( V, T, P, S)
G
U Born diagram
H
U
S P
H
Maxwell equations:
𝝏𝑽 𝝏𝑺
1. dG = -SdT + VdP 1. 𝝏𝑻 𝑷 = − 𝝏𝑷 𝑻
𝝏𝑽 𝝏𝑻
2. dH = TdS + VdP 2. 𝝏𝑺 𝑽 = 𝝏𝑷 𝑺
𝝏𝑻 𝝏𝑷
3. dU = TdS - PdV 3. 𝝏𝑽 𝑺 = −
𝝏𝑺 𝑽
𝝏𝑺 𝝏𝑷
4. dA = -PdV - SdT 4. 𝝏𝑽 𝑻 =
𝝏𝑻 𝑽
Solution Thermodynamics
 Multicomponent Mixture:
Content:

o Partial Molar Properties

o Chemical Potential
o Fugacity and Fugacity Coefficient of pure gas
o Thermodynamics properties of real gas mixture
o Fugacity of a component in a mixture
o Fugacity of a liquid and solid
 Multicomponent Mixture:
Solution Thermodynamics: Study of solution and change its properties is known as solution
thermodynamics

+ = Mixture
250 ml 250 ml Volume ??
Water Ethanol

Mixture Volume = 480 ml

 Multicomponent Mixture:
Partial Molar Properties:
Suppose we have n number of individual component in a solution. And at a particular temperature
and pressure all the n number of component have their unique properties. However, after mixing
they loose their identity (their properties changes in solution.
Now if in a mixture/solution, we changes the composition of any component by keeping T & P and
other components const., then the properties of this particular component is known as partial
molar properties.
𝝏(𝒏𝑴)
𝐌𝐢 = ( )T,P, nj≠i
𝝏𝒏𝒊

Some times it also called response function.

It is a measure of the response of total properties nM to the addition of an infinitesimal amount
of species ‘i’ to the finite amount of solution at const. Temp. and Pressure
 Multicomponent Mixture:
Measure of Composition:
mi mሶ i ni nሶ i
Mass or mole fraction (xi): xi = = or xi = = ሶ
m mሶ n n nሶ i

Molar concentration (Ci): x nሶ i

Ci = i or Ci =
q
V

Molar mass (M): It is define as mole fraction weighted sum of the molar mass of all species
present σ
M= 𝒙𝒊𝑴𝒊

Mi = Molar properties of species ‘i’

𝐌𝐢 = Molar properties of pure species ‘i’ in solution or partial molar properties of species ‘i’

M = Molar properties of solution (intensive properties)

Mt = Total properties of solution Mt = nM (extensive properties)
 Multicomponent Mixture:

Fundamental properties for partial molar properties:

Hi, Gi, Si, Ui, vi, …… 1. Given V = 3x12 + 2(1 – x2) + 4x1; then find
out V1 and V2.

Dependency of molar properties: 2. Given 𝐺1 = 60x12 + 40x2; then find out G1α .
3. 𝐻1 = 2 -60X22 +100x1x22; find 𝐻1α.
M = f(T, P, n1, n2, n3, ……..nn)

Concept of Pure properties & Infinite Dilution:

Pure Properties: Solution of infinite dilution:

M1 = lim 𝑀 or M1 = lim 𝑀 M1 = lim 𝑀 or M1 = lim 𝑀

𝑥1→1 𝑥2→0 𝑥1→0 𝑥2→1

M2 = lim 𝑀 or M1 = lim 𝑀 M2 = lim 𝑀 or M1 = lim 𝑀

𝑥2→1 𝑥1→0 𝑥2→0 𝑥1→1
Partial Molar Properties: 𝝏(𝒏𝑴)
𝐌𝐢 = ( )T,P, nj≠i
𝝏𝒏𝒊

Partial Molar volume: 𝒗𝒊 𝝏(𝒏𝒗)

= ( )T,P, nj≠i
𝝏𝒏𝒊

For binary system, phase rule

DOF = C – P + 2 Component, C =2
=2–1+2 Phase, P = 1 (gas/liquid)
=3

So, here we need to fixed three parameter (T,

P, n2) to define the system
 Derivation of Gibbs-Duhem Equation and Summability equation

So,
We know that ndM + Mdn = ∑𝑀𝑖 xi dn + ∑𝑀𝑖 ndxi
nM = f (T, P, n1, n2, n3, ……nj……nn) (M – ∑𝑀𝑖 xi ) dn + n (dM – ∑𝑀𝑖 dxi) = 0

d(nM) = (
𝜕(𝑛𝑀)
) dT + (
𝜕(𝑛𝑀)
) dP + σ𝑖(
𝜕(𝑛𝑀)
) dni So, (M – ∑𝑴𝒊 xi ) = 0; and (dM – ∑𝑴𝒊 dxi) = 0
𝜕𝑇 P, n 𝜕𝑃 T, n 𝜕ni P, T, ni≠j
𝜕(𝑛𝑀) 𝜕(𝑛𝑀)
From first part,
d(nM) = ( 𝜕𝑇 )P, n dT + ( 𝜕𝑃 )T, n dP + ∑ 𝑀𝑖 dni
(M – ∑𝑀𝑖 xi ) = 0
At constant temperature and pressure, dT = 0 and dP = 0 M = ∑𝑴𝒊 xi …………. Summability equation
d(nM) = ∑ 𝑀𝑖 dni (M = molar properties)
𝑛
We know that xi = 𝑛𝑖 ; ni = xi n ; nM = ∑𝑀𝑖 nxi as ni = xi n
dni = xi dn + ndxi nM = ∑𝑴𝒊 ni …………. Summability equation
For binary system
M = x1𝑴𝟏 + x2𝑴𝟐
From part 2 at constant temp and pressure Gibbs-Duhem equation for binary system:
(dM – ∑𝑴𝒊 dxi) = 0 ∑xi d 𝑀𝑖 = 0
dM = ∑𝑀𝑖 dxi) x1d𝑀1 + x2d𝑀2 = 0
from Summability equation: M = ∑𝑴𝒊 xi x1 d𝑀1 + x2 d𝑀2 = 0
𝑑𝑥1 𝑑𝑥1
dM = ∑𝑀𝑖 dxi + ∑xi d 𝑀𝑖
𝐝𝑴𝟏 𝒙
∑𝑀𝑖 dxi + ∑xi d 𝑀𝑖 = ∑𝑴𝒊 dxi = - 𝒙𝟐 𝐝𝑴𝟐
𝒅𝒙𝟏 𝟏 𝒅𝒙𝟏

∑xi d 𝑴𝒊 = 0 …………… Gibbs-Duhem relation (at Similarly

constant T & P) 𝐝𝑴𝟐 𝒙
= - 𝒙𝟏 𝐝𝑴𝟏
𝒅𝒙𝟐 𝟐 𝒅𝒙𝟐
Or
𝝏(𝒏𝑴) 𝝏(𝒏𝑴)
( )
𝝏𝑻 P, n
dT + ( ) dP -
𝝏𝑷 T, n
∑xi d 𝑴𝒊 = 0
Q1. If 𝑀2 = 5 x12; find 𝑀1 = ??

Q2. The partial molar enthalpies of mixing (J/mol) for benzene (1) and cyclohexane (2) at 300 K and 1 bar
are given by Δ 𝐻1 = 3600 x22 ; and Δ 𝐻2 = 3600 x12 where x1 and x2 are the mole fraction. What should be
the enthalpy changes if one mole of benzene is added to 2 mol of cyclohexane?
 Partial Molar Properties of Binary mixture:

We know that M = x1𝑴𝟏 + x2𝑴𝟐

From Summability equation; M = x1𝑴𝟏 + x2𝑴𝟐
𝒅𝑴
M = (𝒅𝒙 + 𝑴𝟐 )x1 + x2𝑴𝟐
dM = x1d𝑀1 + 𝑴𝟏dx1 + x2d𝑀2 + 𝑴𝟐dx2 𝟏

………………(1) 𝒅𝑴
(x1 + x2) 𝑴𝟐 = M – x1𝒅𝒙
𝟏
From Gibbs -Duhem equation; x1d𝑀1 + x2d𝑀2 = 0
𝒅𝑴
……………………(2) 𝑴𝟐 = M – x1𝒅𝒙
𝟏

So equation (1) become Similarly,

dM = 𝑴𝟏dx1 + 𝑴𝟐dx2 𝒅𝑴
𝑴𝟏 = M – x2𝒅𝒙
𝟐
dM = ( 𝑴𝟏 - 𝑴𝟐)dx1
𝒅𝑴
= ( 𝑴𝟏 - 𝑴𝟐 )
𝒅𝒙𝟏 Q3. At constant T & P, the molar density of a binary mixture is given by
𝒅𝑴
𝑴𝟏 = (𝒅𝒙 + 𝑴𝟐 ) ρ = 1 + x2 , where x2 is the mole fraction of component 2. What should
𝟏
be the molar volume at infinite dilution for component 1, 𝒗𝟏?
Q4. At constant T & P, the molar enthalpy of a binary mixture is given by
h = 500x1 +1000x2 + (50x1 +40x2)x1x2, where h in J/mol.
a) Determine ℎഥ1 and ℎഥ2 as a function of x1 and numerical value of pure component enthalpies
h1 and h2.
b) Also determine the partial molar enthalpies at infinite dilution.
 Recap:

Gibbs-Duhem relation
Partial Molar Properties:
∑xi d 𝑴𝒊 = 0 …………… (at constant T & P)
𝝏(𝒏𝑴)
𝐌𝐢 = ( )T,P, nj≠i 𝝏(𝒏𝑴) 𝝏(𝒏𝑴)
𝝏𝒏𝒊 ( ) dT + ( ) dP - ∑xi d 𝑴𝒊 = 0
𝝏𝑻 P, n 𝝏𝑷 T, n

Summability equation For binary system

M = ∑𝑴𝒊 xi
𝐝𝑴𝟏 𝒙𝟐 𝐝𝑴 𝐝𝑴𝟐 𝒙𝟏 𝐝𝑴
nM = ∑𝑴𝒊 ni =- 𝟐 =− 𝟏
𝒅𝒙𝟏 𝒙𝟏 𝒅𝒙 𝒅𝒙𝟐 𝒙𝟐 𝒅𝒙
𝟏 𝟐
For binary system
M = x1𝑴𝟏 + x2𝑴𝟐

Partial Molar Properties of Binary mixture:

𝒅𝑴 𝒅𝑴
𝑴𝟏 = M – x2𝒅𝒙 𝑴𝟐 = M – x1𝒅𝒙
𝟐 𝟏
 Chemical Potential (µ):

Thermal Equilibrium: Energy tends to flow from high energy (temperature)

E1 E2
value to low energy (temperature) value until temperature of the both N1 N2
system are equal (T1 = T2). V V
Significant: System have tendency to give energy T1 = T2

Mechanical Equilibrium: Here volume is transfer from high pressure value V1 V2

to low pressure value until pressure of the both system are equal (P1 = P2). N1 N2
E1 E2
Significant: System have tendency to take volume
P1 = P 2

Chemical Equilibrium: Particles tends to flow from high potential value to low
potential value until the chemical potential of both system are equal (µ1 = µ2). N1 N2
Significant: It measure the energy change if you add or remove dni particle of V1 V2
E1 E2
any component i while keeping the other components constant.
µ1 = µ 2
It helps to know the behaviours of any individual component in the system.
 Chemical Potential (µ):

Chemical Potential (µ) is also known as Partial Gibbs Free Energy of any component i that can be add or
remove during the reaction.

𝝏𝑮
µi = 𝑮𝒊 =
𝝏𝒏𝒊 𝑻, 𝑷, 𝒏𝒋

It tells about the effect of free energy (any terms of free energy) if we change the any
component composition.
It measure the change of free energy
Chemical potential of a species is the energy that can be absorbed or released due to change
in composition/particle number of the given species in a chemical reaction.
If the chemical potential of both the system are equal then there will be no reaction. Then
the process is in chemical equilibrium.
 Chemical Potential (µ):

Chemical Potential with Gibbs Free Energy:

We know that
dG = -SdT + VdP
𝜕𝐺 𝑡
µi = 𝐺ഥ𝑖 = ( ) T, P, nj
𝜕𝑛𝑖 At const. temp At const. Pressure
G = f (T, P, n1, n2, n3, ….ni ……..)
dG = VdP dG = -SdT
𝜕𝐺 𝑡 𝜕𝐺 𝑡 𝜕𝐺 𝑡
d(Gt) =( ) dT+ ( ) T, nj dP + σ𝑖 dni 𝑑𝐺 𝑑𝐺
𝜕𝑇 P, nj 𝜕𝑃 𝜕𝑛𝑖 P, T, ni≠j V= -S=
𝑑𝑃 𝑑𝑇
𝜕𝐺 𝑡 𝜕𝐺 𝑡 In terms of total Gibbs free energy
d(Gt) =( ) dT + ( ) T, nj dP + ∑ µi dni
𝜕𝑇 P, nj 𝜕𝑃
𝑑𝐺 𝑡 𝑑𝐺 𝑡
At constant temp and pressure for a closed system Vt = - St =
𝑑𝑃 𝑑𝑇

d(Gt) = ∑ µi dni d(Gt) = - St dT + VtdP + ∑ µi dni

For a binary system

Gt = ∑ µi ni
G = µ1x1 + µ2x2
 Chemical Potential (µ):
Chemical potential in terms of Helmholtz Free energy
dA = -SdT – PdV +∑µidni
At const. temp and volume
Chemical potential in terms of
dA = ∑µidni Internal energy
𝒅𝑨
µi = ( )
𝒅𝒏𝒊 𝑻, 𝑽 dH = TdS + VdP +∑µidni

Chemical potential in terms of Internal energy At const. entropy and pressure

dU = TdS – PdV +∑µidni 𝒅𝑯

µi = ( )
At const. entropy and volume 𝒅𝒏𝒊 𝑺, 𝑷

𝒅𝑼 In any system it is very difficult to

µi = ( ) 𝑺, 𝑽
𝒅𝒏𝒊 keep constant to keep both entropy
and volume constant together
 Chemical Potential (µ):
Effect of Temperature on Chemical Potential Compare (3) & (4)
𝜕𝜇 𝜕𝑆 𝑇
𝜕𝐺 𝑡 ( 𝑖 )P, n =- ( )T, n
µi = Gi = ( ) T, P, nj ……………………. (1) 𝜕𝑇 𝜕𝑛𝑖
𝜕𝑛𝑖
𝜕𝜇𝑖
( )P, n = - 𝑆ഥ𝑖 …… Partial entropy
𝜕𝑇
𝑑𝐺 𝑡
- St = ( ) P, n …………………………… (2) 𝜕𝜇
𝑇 𝜕𝑇𝑖 − 𝜇𝑖
𝑑𝑇 𝜕𝜇𝑖/𝑇
( )P, n =
𝜕𝑇 𝑇2
Differentiate eqn (1) w.r.t T (P, n constant)
𝑇(−𝑆𝑖) − 𝐺𝑖
=
𝑇2
𝜕𝜇𝑖 𝜕2 𝐺 𝑡
( ) = ( ) ………….. (3) − 𝑇𝑆ഥ𝑖 − 𝐺𝑖 𝐺𝑖 − 𝐻𝑖 − 𝐺𝑖
𝜕𝑇 P, n 𝜕𝑇𝜕𝑛𝑖 P, n = =
𝑇2 𝑇2
Differentiate eqn (2) w.r.t ni (P, n constant)
𝝏𝝁𝒊/𝑻 𝑯𝒊
𝜕𝑆 𝑇 𝜕2 𝐺 𝑡 ( )P, n = −
- ( )T, n = ( ) ………….. (4) 𝝏𝑻 𝑻𝟐
𝜕𝑛𝑖 𝜕𝑇𝜕𝑛𝑖 P, n
 Chemical Potential (µ):
Effect of Pressure on Chemical Potential
Compare (3) & (4)
𝜕𝐺 𝑡
µi = Gi = ( ) T, P, nj ……………………. (1) 𝜕𝜇 𝜕𝑉 𝑇
𝜕𝑛𝑖 ( 𝑖 )T, n =- ( )T, P
𝜕𝑃 𝜕𝑛𝑖
𝝏𝝁𝒊
𝑑𝐺 𝑡 ( ) = 𝑽ഥ𝒊 …… Partial Volume
𝝏𝑷 T, P
Vt =( ) T, n …………………………… (2)
𝑑𝑃

Differentiate eqn (1) w.r.t P (T, n constant)

𝜕𝜇 𝜕2 𝐺 𝑡
( 𝑖 )T, n = ( ) ………….. (3)
𝜕𝑃 𝜕𝑃𝜕𝑛𝑖 T, n

Differentiate eqn (2) w.r.t ni (T, n constant)

𝜕𝑉 𝑇 𝜕2 𝐺 𝑡
( )T, P = ( ) ………….. (4)
𝜕𝑛𝑖 𝜕𝑃𝜕𝑛𝑖 T, n
 Recap:
For binary system
Partial Molar Properties: Gibbs-Duhem relation
𝐝𝑴𝟏 𝒙𝟐 𝐝𝑴
𝝏(𝒏𝑴) =- 𝟐
𝐌𝐢 = ( ) ∑xi d 𝑴𝒊 = 0 …………… (at constant T & P) 𝒅𝒙𝟏 𝒙𝟏 𝒅𝒙
𝟏
𝝏𝒏𝒊 T,P, nj≠i
𝐝𝑴𝟐 𝒙𝟏 𝐝𝑴𝟏
𝝏(𝒏𝑴) 𝝏(𝒏𝑴) =−
( 𝝏𝑻 )P, n dT + ( 𝝏𝑷 )T, n dP - ∑xi d 𝑴𝒊 = 0 𝒅𝒙𝟐 𝒙𝟐 𝒅𝒙𝟐
Summability equation
M = ∑𝑴𝒊 xi 𝝏𝑮𝒕
Chemical Potential, µi = 𝑮𝒊 = ( ) T, P, nj
nM = ∑𝑴𝒊 ni 𝝏𝒏𝒊
For binary system
G = ∑ µi xi
M = x1𝑴𝟏 + x2𝑴𝟐
𝒅𝑨 𝒅𝑼 𝒅𝑯
µi = ( ) µi = ( ) µi = ( )
Partial Molar Properties of Binary 𝒅𝒏𝒊 𝑻, 𝑽 𝒅𝒏𝒊 𝑺, 𝑽 𝒅𝒏𝒊 𝑺, 𝑷
mixture:
𝝏𝝁 𝝏𝝁𝒊/𝑻 𝑯𝒊
𝒅𝑴 𝒅𝑴 ( 𝒊)P, n = - 𝑺ഥ𝒊 ( )P, n = −
𝑴𝟏 = M – x2𝒅𝒙 𝑴𝟐 = M – x1𝒅𝒙 𝝏𝑻 𝝏𝑻 𝑻𝟐
𝟐 𝟏

𝝏𝝁𝒊
( )T, P = 𝑽ഥ𝒊
𝝏𝑷
 Ideal Gas-state Mixture Partial Properties Model

Ideal gas, PV = nRT (total volume, m3) Real gas, PV = ZnRT

PV = RT (molar volume, m3/mol) PV = ZRT
Z = compressibility factor
For ideal gas, Z =1 𝑃𝑣 𝑟𝑒𝑎𝑙 𝑣 𝑟𝑒𝑎𝑙
Z= =
𝑅𝑇 𝑣 𝑖𝑔
𝑅𝑇
Pvig = RT or, vig = 𝑃

Partial Properties:
𝒊𝒈 𝑹𝑻 𝝏(𝒏)
𝝏(𝒏𝑴) 𝒗𝒊 = ( ) 𝝏(𝒏)
( 𝝏𝒏𝒊 )T,P, ni≠j
𝐌𝐢 = ( ) 𝑷 𝝏𝒏𝒊 T,P, ni≠j
𝝏𝒏𝒊 T,P, nj≠i
𝒊𝒈 𝑹𝑻
𝝏(𝒏𝒗) 𝒗𝒊 = (
𝝏𝒏𝟏 + 𝝏𝒏𝟐
)T,P, ni≠j
𝒗𝒊 = ( ) 𝑷 𝝏𝒏𝒊
𝝏𝒏𝒊 T,P, ni≠j
𝒊𝒈 𝑹𝑻 𝒊𝒈 𝝏𝒏𝟏
𝑹𝑻 𝒗𝒊 = = 𝒗𝒊 = Vig ( )
𝝏𝒏𝒊 T,P, ni≠j
= 1
𝝏(𝒏 𝑷 ) 𝑷
𝒊𝒈
For Ideal gas 𝒗𝒊 = ( )T,P, ni≠j
𝝏𝒏𝒊 𝒚𝒊 𝑹𝑻
pi = yiP =
𝑽𝒊𝒈
 Ideal Gas-state Mixture Partial Properties Model
Case 3: Entropy (S)
Assumption: Molecules have zero volume that do not interact.
So according to the ideal gas mixture model Sig = f (T, P)
𝑖𝑔 𝑖𝑔 𝒊𝒈 𝒊𝒈
From Maxwell equation we know that
𝑀𝑖 𝑇, 𝑃 = 𝑀𝑖 (T, pi) 𝑴𝒊 ≠ 𝑽𝒊
dH = TdS +VdP
Case 1: Enthalpy (H) For ideal gas
TdSig = dHig – VigdP (At const. T, dHig = CpdT = 0)
Hig = f (T) = CpdT (independent of pressure)
𝑣 𝑖𝑔
dSig =- 𝑑𝑃
𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑇
𝐻𝑖 𝑇, 𝑃 = 𝐻𝑖 (T, pi) = 𝐻𝑖 (T, P)
𝑆ഥ𝑖 (𝑝𝑖 ,𝑇) 𝑝𝑖 𝑣 𝑖𝑔
‫𝑃( 𝑆׬‬,𝑇) 𝑑Sig = − ‫𝑇 𝑃׬‬ 𝑑𝑃
𝑖
𝒊𝒈 𝒊𝒈
So, 𝑯𝒊 = 𝑯𝒊 𝑖𝑔 𝑖𝑔 𝑝𝑖
𝑆𝑖 (𝑝𝑖, 𝑇) - 𝑆𝑖 (𝑃, 𝑇) = - R ln
𝑃
Case 2: Internal Energy (U) From ideal gas mixture model we know
Uig = f (T) (independent of pressure) 𝑖𝑔 𝑖𝑔
𝑆𝑖 𝑇, 𝑃 = 𝑆𝑖 (T, pi) or
𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑝𝑖
𝑈𝑖 𝑇, 𝑃 = 𝑈𝑖 (T, pi) = 𝑈𝑖 (T, P) 𝑆𝑖 𝑇, 𝑃 − 𝑆𝑖 (T, P) = - R ln pi = yiP
𝑃 𝒑𝒊
𝒊𝒈 𝒊𝒈 yi =
𝑼𝒊 = 𝑼𝒊 𝒊𝒈 𝒊𝒈 𝑷
𝑺𝒊 = 𝑺𝒊 - R ln yi
 Ideal Gas-state Mixture Partial Properties Model
Case 4: Gibbs free energy (g)
Gig = f (T, P)
From Maxwell equation we know that
dG = VdP - SdT
(for real gas and At const. dT = 0)
𝑅𝑇
dGig = 𝑣𝑖𝑔𝑑𝑃 = dP
𝑃

𝐺𝑖 (𝑝𝑖 ,𝑇) 𝑝 𝑅𝑇
‫𝑃( 𝐺׬‬,𝑇) 𝑑Gig = ‫𝑖 𝑃׬‬ 𝑑𝑃
𝑖 𝑃
𝑖𝑔 𝑖𝑔 𝑝𝑖
𝐺𝑖 (𝑝𝑖, 𝑇) - 𝐺𝑖 (𝑃, 𝑇) = RT ln
𝑃
From ideal gas mixture model we know
𝑖𝑔 𝑖𝑔
𝐺𝑖 𝑇, 𝑃 = 𝐺𝑖 (T, pi) or
𝑖𝑔 𝑖𝑔 𝑝𝑖
𝐺𝑖 𝑇, 𝑃 − 𝐺𝑖 (T, P) = RT ln
𝑃

𝒊𝒈 𝒊𝒈
𝑮𝒊 = 𝑮𝒊 + RT ln yi
 Change in Properties of Mixing
ΔMmix = M - ∑Mixi Case 2: Internal Energy (U)
ഥ𝑖 - Ui)
ΔUmix = ∑xi(𝑈
From Summability equation
For ideal gas
M = ∑𝑀𝑖 xi
𝑖𝑔 𝑖𝑔 𝑖𝑔
ΔMmix = ∑𝑀𝑖 xi - ∑Mixi Δ𝑈𝑚𝑖𝑥 = ∑yi(𝑈𝑖 - 𝑈𝑖 )

𝒊𝒈 𝑖𝑔 𝑖𝑔
ΔMmix = ∑xi(𝑴𝒊 - Mi) Δ𝑼𝒎𝒊𝒙 =0 (as 𝑈𝑖 = 𝑈𝑖 )

Case 1: Enthalpy (H) Case 3: Volume (V)

ഥ𝑖 - Hi)
ΔHmix = ∑xi(𝐻 ΔVmix = ∑xi(𝑉ഥ𝑖 - Vi)
For ideal gas
For ideal gas
𝑖𝑔 𝑖𝑔 𝑖𝑔
Δ𝐻𝑚𝑖𝑥 = ∑yi(𝐻𝑖 - 𝐻𝑖 ) 𝑖𝑔 𝑖𝑔
Δ𝑉𝑚𝑖𝑥 = ∑yi(𝑉𝑖 - 𝑉𝑖 )
𝑖𝑔

𝒊𝒈 𝑖𝑔 𝑖𝑔
Δ𝑯𝒎𝒊𝒙 = 0 (as 𝐻𝑖 = 𝐻𝑖 ) 𝒊𝒈
Δ𝑽𝒎𝒊𝒙 =0
𝑖𝑔 𝑖𝑔
(as 𝑉𝑖 = 𝑉𝑖 )
 Change in Properties of Mixing

Case 4: Entropy (S) Case 5: Gibbs Free Energy (g)

ΔSmix = ∑yi(𝑆ഥ𝑖 - Si) Δgmix = ∑yi(𝐺ഥ𝑖 - Gi)
For ideal gas For ideal gas

𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑖𝑔 𝑖𝑔
Δ𝑆𝑚𝑖𝑥 = ∑yi(𝑆𝑖 - 𝑆𝑖 ) Δ𝐺𝑚𝑖𝑥 = ∑yi(𝐺𝑖 - 𝐺𝑖 )

𝑖𝑔 𝑖𝑔
Δ𝑆𝑚𝑖𝑥 = ∑yi(−𝑅 𝑙𝑛𝑦𝑖) Δ𝐺𝑚𝑖𝑥 = ∑yi(𝑅𝑇𝑙𝑛𝑦𝑖)

𝒊𝒈 𝒊𝒈
Δ𝑺𝒎𝒊𝒙 = −𝑹∑(yi 𝒍𝒏𝒚𝒊) Δ𝑮𝒎𝒊𝒙 = 𝑹𝑻∑(yi 𝒍𝒏𝒚𝒊)

ΔGmix =ΔHmix - T ΔSmix

 Recap:
𝒊𝒈 𝑹𝑻 𝒊𝒈 ΔMmix = ∑xi(𝑴𝒊 - Mi)
𝒗𝒊 = = 𝒗𝒊 = Vig
𝑷

𝒊𝒈
𝒊𝒈 𝒊𝒈 Δ𝑯𝒎𝒊𝒙 = 0
𝑴𝒊 𝑻, 𝑷 = 𝑴𝒊 (T, pi)

𝒊𝒈
Δ𝑼𝒎𝒊𝒙 = 0
𝒊𝒈 𝒊𝒈
So, 𝑯𝒊 = 𝑯𝒊
𝒊𝒈
Δ𝑽𝒎𝒊𝒙 = 0
𝒊𝒈 𝒊𝒈
𝑼𝒊 = 𝑼𝒊
𝒊𝒈
Δ𝑺𝒎𝒊𝒙 = −𝑹∑(yi 𝒍𝒏𝒚𝒊)
𝒊𝒈 𝒊𝒈
𝑺𝒊 = 𝑺𝒊 - R ln yi
𝒊𝒈
Δ𝑮𝒎𝒊𝒙 = 𝑹𝑻∑(yi 𝒍𝒏𝒚𝒊)
𝒊𝒈 𝒊𝒈
𝑮𝒊 = 𝑮𝒊 + RT ln yi
ΔGmix =ΔHmix - T ΔSmix
 Problem:
For a given binary system at const. temp and pressure the molar volume (m3/mol) is given by
v= 30 xA + 20xB + xAxB(15xA – 7xB)
Then what should be the total volume of mixing Δvmix (m3/mol) at xA = 0.5 ?
 Excess Properties:
Any solution (liquid) is how much far from ideal solution is known as Excess properties (ME)
ME = M - Mid
Residual Properties (MR): Any solution (gas) is how much far from ideal solution
MR = M - Mid

Excess properties: Case 1: Enthalpy

𝑖𝑑
ME = M - Mid H = HE + Δ𝐻𝑚𝑖𝑥 + ∑Hixi
𝑖𝑑
Δ𝑀𝑚𝑖𝑥 = Mid - ∑Mixi 𝑖𝑑
H = HE + ∑Hixi Δ𝐻𝑚𝑖𝑥 =0
𝑖𝑑
Mid = Δ𝑀𝑚𝑖𝑥 + ∑Mixi
𝑖𝑑
ME = M - Δ𝑀𝑚𝑖𝑥 - ∑Mixi HE = H - ∑Hixi = Δ𝑯𝒓𝒆𝒂𝒍
𝒎𝒊𝒙

M = ME + Δ𝑴𝒊𝒅
𝒎𝒊𝒙 + ∑Mixi
 Excess Properties:
Case 2: Internal Energy Case 4: Gibbs Free Energy
𝑖𝑑
U= UE + 𝑖𝑑
Δ𝑈𝑚𝑖𝑥 + ∑Uixi G = GE + Δ𝐺𝑚𝑖𝑥 + ∑Gixi
𝑖𝑔
G = GE + ∑Gixi + 𝑅𝑇∑(xi 𝑙𝑛𝑥𝑖 ) Δ𝐺𝑚𝑖𝑥 = 𝑅𝑇∑(xi 𝑙𝑛𝑥𝑖 )
𝑖𝑑
U = UE + ∑Hixi Δ𝑈𝑚𝑖𝑥 =0
G - ∑Gixi = GE + 𝑅𝑇∑(xi 𝑙𝑛𝑥𝑖 )
UE = U - ∑Uixi = Δ𝑼𝒓𝒆𝒂𝒍
𝒎𝒊𝒙
Δ𝑮𝒓𝒆𝒂𝒍 E
𝒎𝒊𝒙 = G + 𝑹𝑻∑(xi 𝒍𝒏𝒙𝒊)

Case 3: Volume Case 5: Entropy

𝑖𝑑 𝑖𝑑
V = VE + Δ𝑉𝑚𝑖𝑥 + ∑Vixi S = SE + Δ𝑆𝑚𝑖𝑥 + ∑Sixi
𝑖𝑔
𝑖𝑑
Δ𝑉𝑚𝑖𝑥 =0
S = SE + ∑Sixi − 𝑅∑(xi 𝑙𝑛𝑥𝑖 ) Δ𝑆𝑚𝑖𝑥 = 𝑅∑(xi 𝑙𝑛𝑥𝑖 )
V = VE + ∑Vixi
S - ∑Sixi = SE − 𝑅∑(xi 𝑙𝑛𝑥𝑖 )
VE = V - ∑Vixi = Δ𝑽𝒓𝒆𝒂𝒍
𝒎𝒊𝒙
Δ𝑺𝒓𝒆𝒂𝒍 E
𝒎𝒊𝒙 = S − 𝑹∑(xi 𝒍𝒏𝒙𝒊)
Problem:

A binary system at a constant pressure with species 1 & 2 is described by two-suffix Margules equation
𝑔𝐸
= 3𝑥1 𝑥2 (where 𝑔𝐸 𝑖𝑠 𝑚𝑜𝑙𝑎𝑟 𝑒𝑥𝑐𝑒𝑠𝑠 𝑓𝑟𝑒𝑒 𝑒𝑛𝑒𝑟𝑔𝑦, 𝑅 𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑎𝑙 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡)
𝑅𝑇
𝑔1 𝑔2
At temperature T, = 1 and = 2, where g1 and g2 are molar Gibbs free energy. What is the value
𝑅𝑇 𝑅𝑇
𝑔
of for a binary mixture with 40 % of species 1?
𝑅𝑇
 Fugacity (f)
𝑖𝑔 𝑖𝑔 𝑖𝑔 𝒊𝒈 𝒊𝒈
∑yi(𝐺𝑖 - 𝐺𝑖 ) = Δ𝐺𝑚𝑖𝑥 = 𝑅𝑇∑(yi 𝑙𝑛𝑦𝑖 ) 𝑮𝒊 = µi = 𝑮𝒊 + 𝑹𝑻 𝒍𝒏𝒚𝒊

➢ Fugacity define the escaping tendency of real gas in the heterogenous system
Ex: LPG operation
➢ Fugacity also define as a particular pressure at which it changes it phases (liquid to gas or vice
versa).
➢ When the escaping tendency of the both phases are same, then the system are in equilibrium

dG = vdP – SdT 𝑓
For real gas dGR = RT dln
𝑃
At const. temp. (𝑮𝑹 = 𝒓𝒆𝒔𝒊𝒅𝒖𝒂𝒍 𝑮𝒊𝒃𝒃𝒔 𝒇𝒓𝒆𝒆 𝒆𝒏𝒆𝒓𝒈𝒚)
dG = RT lnf
dG = vdP 𝐺𝑅 𝑃 𝑓
For ideal gas, Pv = RT 𝑓
‫=𝑅 𝐺׬‬0 𝑑GR = ‫→𝑃׬‬0 𝑅𝑇 dln
𝑃
dG - dGig = RT dln
𝑅𝑇 𝑃
v= 𝑓 𝒇
𝑃 d(G - Gig) = RT dln GR = RT ln
𝑃 𝑷
𝒅𝑷
dGig = RT = RT lnP GR 𝒇
𝑷 = ln
𝑹𝑻 𝑷
 Fugacity Coefficient (Ф)
𝒇 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑟𝑒𝑎𝑙 𝑔𝑎𝑠
Ф= =
𝑷 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠

GR 𝒇
= ln = 𝒍𝒏Ф
𝑹𝑻 𝑷

Problem:

The vapor pressure of a pure substant at a temp. T is 30 bar. The actual and
𝑔
ideal gas value of for the saturated vapor at this temp. and pressure are
𝑅𝑇
7.0 and 7.7 respectively. Here, g is the molar Gibbs free energy and R is gas
constant. What is the fugacity of the saturated liquid at this condition?
Fugacity in terms of Compressibility Factor:

𝑷𝒗 𝒗𝒓𝒆𝒂𝒍 𝐺𝑅 𝑃
Z= = ‫= 𝑅 𝐺׬‬0 𝑑GR = ‫→𝑃׬‬0(Z vig –𝒗𝒊𝒈 )dP
𝑹𝑻 𝒗𝒊𝒅𝒆𝒂𝒍

vreal = Z videal 𝐺𝑅 𝑃
‫= 𝑅 𝐺׬‬0 𝑑GR = ‫→𝑃׬‬0(Z − 1 )𝒗𝒊𝒈 dP
𝑃 𝑹𝑻
dG = vdP – SdT GR = ‫׬‬0 (Z − 1 ) dP
𝑷
At const. temp.
𝑮𝑹 𝑷 𝒅𝑷
dG = vdP 𝑹𝑻
= ‫( 𝟎׬‬Z −1 )
𝑷

For ideal gas, Pv = RT

dG - dGig = (v – vig)dP GR 𝒇 𝑷 𝒅𝑷
= ln = 𝒍𝒏Ф = ‫( 𝟎׬‬Z − 1 )
𝑹𝑻 𝑷 𝑷
𝐺𝑅 𝑃
‫=𝑅 𝐺׬‬0 𝑑GR = ‫→𝑃׬‬0(v – 𝒗𝒊𝒈 )dP
Fugacity in terms of Residual Volume (VR):

VR = V - Vig
GR 𝒇 𝑷 𝒅𝑷 𝑷 𝒗𝑹
dG = vdP – SdT = ln = 𝒍𝒏Ф = ‫( 𝟎׬‬Z −1 ) = ‫𝟎׬‬ dP
𝑹𝑻 𝑷 𝑷 𝑹𝑻
At const. temp.
𝐵𝑃
dG = vdP Z=1+
𝑅𝑇

For ideal gas, Pv = RT 𝑍 −1

=
𝐵
𝑃 𝑅𝑇
dG - dGig = (v – vig)dP
𝑷 𝒅𝑷 𝑷 𝑩 𝑩𝑷
‫( 𝟎׬‬Z − 1 ) = ‫𝟎׬‬ dP =
𝐺𝑅 𝑃 𝑷 𝑹𝑻 𝑹𝑻
‫= 𝑅 𝐺׬‬0 𝑑GR = ‫→𝑃׬‬0 vR dP

𝑮𝑹 𝑷 𝒗𝑹 GR = BP
= ‫𝑻𝑹 𝟎׬‬ dP
𝑹𝑻
Problem:
𝑃𝑣 𝐵𝑃
A pure gas obeys the equation =1+ where P is pressure and T is absolute
𝑅𝑇 𝑅𝑇
temperature, v is molar volume, R is gas constant and B is parameter depended of T & P. The
GR 𝑷 𝒅𝑷
residual Gibbs free energy is given by 𝑹𝑻
= ‫( 𝟎׬‬Z − 1 )
𝑷
Z is compressibility factor, B = 10-4 m3/mol. Integral is evaluated at constant temperature.
What is the residual molar enthalpy in (J/mol) of the gas at 1000 kPa at 300 K?
GR 𝑣R 𝐻R
Given: d( ) = 𝑅𝑇 dP - 𝑅𝑇2 dT (at constant pressure)
𝑅𝑇

GE 𝒗E 𝑯E
= dP - 𝑹𝑻𝟐
dT
𝑹𝑻 𝑹𝑻
 Activity and Activity Coefficient
dG = vdP – SdT ෢𝑖
𝑓
At constant temp. 𝐺𝐸 = 𝑅𝑇𝑙𝑛 ෢id
𝑓𝑖
dG = vdP 𝑮𝑬 𝒇෡𝒊
= 𝒍𝒏 ෡ id= ln𝜸𝒊 (activity coefficient)
𝑹𝑻 𝒇𝒊
For ideal liquid
d𝐺ҧ 𝑖𝑑 = 𝑅𝑇𝑑𝑙𝑛𝑓෡𝑖 id ……. (1) 𝒇𝒖𝒈𝒂𝒄𝒊𝒕𝒚 𝒊𝒏 𝒓𝒆𝒂𝒍 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
𝜸𝒊 =
For real liquid 𝒇𝒖𝒈𝒂𝒄𝒊𝒕𝒚 𝒊𝒏 𝒊𝒅𝒆𝒂𝒍 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏

d𝐺ҧ = 𝑅𝑇𝑑𝑙𝑛𝑓෡𝑖 ………. (2) 𝑓𝑢𝑔𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖 𝑖𝑛 𝑟𝑒𝑎𝑙 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Activity (𝑎𝑖 ) =
𝑓𝑢𝑔𝑎𝑐𝑖𝑡𝑦 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑠𝑝𝑒𝑐𝑖𝑒𝑠
(2) – (1)
෢𝑖 𝒇෡𝒊
d(𝐺ҧ - 𝐺ҧ 𝑖𝑑) =
𝑓
𝑅𝑇𝑑𝑙𝑛 ෢id (𝒂𝒊 ) =
𝒇𝒊
𝑓𝑖

෢𝑖
𝑓 𝒇෡𝒊 𝒇෡𝒊 𝑎𝑖
𝑓෡𝑖 𝜸𝒊 = = =
𝒇෡𝒊 id 𝒇𝒊 .𝒙𝒊 𝑥𝑖
𝐺𝐸 = න 𝑅𝑇𝑑𝑙𝑛 id
𝑓෡𝑖
0 𝒂𝒊 = 𝜸𝒊 𝒙𝒊
 Activity and Activity Coefficient
𝑮𝑬
𝝏(𝒏𝑴) 𝒅𝑴 𝑮𝑬 𝑮𝑬 𝒅
𝐌𝐢 = ( )
𝝏𝒏𝒊 T,P, ni≠j 𝑴𝟏 = M – x2
𝒅𝒙𝟐 𝑹𝑻
=
𝑹𝑻
– x2 𝑹𝑻
𝒅𝒙𝟐

𝑮𝑬
= ln𝜸𝒊
𝑹𝑻 𝑮𝑬 𝑮𝑬
𝑮𝑬 𝒅
𝑹𝑻 𝑮𝑬 𝒅
𝑹𝑻
𝑮𝑬
ln𝜸𝟏 = – x2 ln𝜸𝟐 = – x1
𝝏(𝒏𝑹𝑻) 𝑹𝑻 𝒅𝒙𝟐 𝑹𝑻 𝒅𝒙𝟏
𝑮𝑬
= ( )T,P, nj≠i
𝑹𝑻 𝝏𝒏𝒊

𝑮𝑬
𝝏(𝒏𝑹𝑻) Problem:
ln𝜸𝟏 = ( )T,P, n2 Fugacity of component 1 in a binary liquid mixture of component I
𝝏𝒏𝒊
and 2 at 303 K and 10 bar is given by
𝑮𝑬
𝝏(𝒏
𝑹𝑻
) 𝑓෡1 = 50 x1 + 100x1x2 +20 𝑥22
ln𝜸𝟐 = ( )T,P, n1
𝝏𝒏𝒊 Find out the activity coefficient of component 1 for equimolar
composition.
 ෢
𝑓𝑖 ෢𝑖
𝑓
Phase Equilibrium for Ideal Solution
𝛾𝑖 = ෢𝑖 id =
𝑓 𝑓𝑖 .𝑥𝑖
For liquid system 𝒇෡𝒊 = 𝒇𝒊 . 𝒙𝒊 Lewis and Randall Rule
id

𝑓෡𝑖𝑙 = 𝑥𝑖 𝛾𝑖𝑙 𝑓𝑖𝑙

For gas system
𝑓෢𝑖
𝑣
= 𝑦 𝑣
𝑖 𝑖 𝑃
Ф
Now vapour phase is assume to be ideal gas state and liquid phase is
an ideal solution
𝛾𝑖 = Ф𝑖 = 1
Limitation:
And if the system is in equilibrium and the pressure of the liquid
o Ideal solution
system will be saturated pressure (𝑷𝒔𝒂𝒕 𝒊 )
o Low to moderate pressure
𝑓෡𝑖𝑙 =𝑓෢𝑖
𝑣

𝑥𝑖 𝛾𝑖 𝑓𝑖 = 𝑦𝑖 Ф𝑣𝑖 𝑃
𝑙 𝑙
𝒚𝒊 𝑷 = 𝒙𝒊 𝜸𝒊 𝑷𝒔𝒂𝒕
𝒊
𝑥𝑖 𝛾𝑖𝑙 Ф𝑖𝑠𝑎𝑡 𝑃𝑖𝑠𝑎𝑡 = 𝑦𝑖 Ф𝑣𝑖 𝑃
Ф𝑣𝑖
Modified Raoult’s Law
𝑥𝑖 𝛾𝑖𝑙 𝑃𝑖𝑠𝑎𝑡 = 𝑦𝑖 P
Ф𝑠𝑎𝑡
𝑖
𝑥𝑖 𝛾𝑖𝑙 𝑃𝑖𝑠𝑎𝑡 = 𝑦𝑖 Ф𝑖 P 𝒚𝒊 𝑷 = 𝒙𝒊 𝑷𝒔𝒂𝒕
𝒊
….. Raoult’s law
 Vapour Liquid Equilibrium (VLE)

➢ Vapour pressure depends on the temperature and quantity of liquid and vapour

Vapour pressure can be calculated from Clausius-Clapeyron equation or Antoine equation

Clausius-Clapeyron equation: Antoine equation:

𝑩
𝒑 𝒗
𝝀 𝟏 𝟏 ln 𝒑𝒗 =A-
ln( 𝒗) = ( − ) 𝑻+𝑪
𝒑𝟏 𝑹 𝑻𝟏 𝑻

𝜆 = molar latent heat

𝑝𝑣, 𝑝1v = vapour pressure in pascal
T-x-y diagram at Constant Pressure:

Superheated vapour

Dew Point Curve (DPC)

(y vs. T)

Bubble Point Curve (BPC)

(x vs. T)
Subcooled Liquid

Fig. Constant pressure vapor liquid equilibria

Constant pressure Binary T-x-y
and x-y diagram
➢ Vapor-liquid equilibria at increased pressures

Fig. Vapor liquid equilibria at increased pressures

Relative volatility (α)
▪ This is the ratio of the concentration ratio of A and B in one phase to that in the other and is a measure of the
separability. *
y
(1 − y* ) y* (1 − x )
= = (1)
x x (1 − y* )
(1 − x )
x
y* =
1 + ( − 1) x

x − mole fraction of the more volatile substance in the liquid

y − mole fraction of the more volatile substance in the vapor
*

• The value of  will ordinarily change as x varies from 0 to 1.

• If y* = x (except at x = 0 or 1),  =1 and no separation is posssible.
• The larger the value of  above unity, the greater the degree of separability.
➢ P-x-y diagram for methanol-water

Subcooled Liquid

Bubble Point Curve (BPC)

(x vs. P)

Superheated vapour

Dew Point Curve (DPC)

(y vs. P)

Fig. Constant temperature vapor liquid equilibria

 Raoult's Law: (Ideal gas-liquid system)
PA

*
distance FG P P x
y* = = A = A (5)
PB distance EG Pt Pt
PB* PB (1 − x )
1− y =
*
= (6)
Pt Pt
The relative volatility  is, by substitution in equation (1)
PA
= (7)
PB

Fig. Ideal solutions

➢ Positive deviations from ideality

▪ A mixture whose total pressure is greater than that

computed for ideality (eq. 4) is said to show positive
deviations from Raoult’s law.
 ➢ Negative deviations from Ideality

▪ When the total pressure of a system at equilibrium is less than the ideal value, the system is said to deviate negatively from
Raoult’s law.
➢ Maximum boiling mixtures - azeotropes

(b) (c)

(a)

Fig. Maximum-boiling azeotropism in the system acetone-chloroform: (a) at constant temperature; (b) and (c) at constant
pressure.
 Enthalpy
Dew –line (y – Hv)
Concentration
Diagram
o 40 wt% ethanol water
mixture at 84 oC

✓ xethanol = 0.28
✓ yethanol = 0.28
✓ HF = 165 Kcal/kg
✓ Hv = 380 Kcal/kg Boiling –line (x– HL)
✓ HL = 70 Kcal/kg 0.28 0.69
Enthalpy Concentration Diagram to Equilibrium Diagram
Problem 01:
A binary liquid mixture of n-pentane (1) and n-heptane (2) make a ideal solution. The vapor
pressure of the pure component are given by Antoine equation. Prepare
a) P-x-y diagram at 70 oC.
b) T-x-y diagram at 10.325 kPa pressure.
c) If the equimolar vapor mixture of this two at 90 oC is isothermally compressed till
condensation starts. Determine the pressure at which condensation begins and
composition of the liquid that form.

Components A B C
n-pentane (1) 6.87633 1075.780 233.205
n-heptane (2) 6.89386 1264.370 216.640
 Excess Gibbs Free Energy Model (Binary Mixture)
Behaviour of several liquid solution can not be express by equation of state to estimate the
Gibbs free energy
Use empirical or semi empirical relation Models
For pure component activity coefficient, γ will be unity
1. Margules Equation
𝑮𝑬
Then ( ) → 𝟎 (𝒂𝒔, 𝒙𝟏 → 𝟏 𝒂𝒏𝒅 𝒙𝟐 → 𝟎) a. Two suffix Margules Equation
𝑹𝑻
𝑮𝑬 𝑮𝑬
= (x1, x2) b. Three suffix Margules Equation
𝑹𝑻 𝑹𝑻
𝑮𝑬 2. Redlich –Kister equation
Then ( ) → 𝟎 (𝒂𝒔, 𝒙𝟏 → 𝟏 𝒂𝒏𝒅 𝒙𝟐 → 𝟎)
𝑹𝑻
3. Wohl’s equation
𝑮𝑬
So (𝑹𝑻) = 𝟎 (𝒂𝒔, 𝒙𝟏 = 𝟏 𝒂𝒏𝒅 𝒙𝟐 = 𝟏) 4. Van Laar equation
5. Wilson and NRTL equation
6. UNIQUAC equation
 Excess Gibbs Free Energy Model (Binary Mixture)
1. Margules Equation
b. Three suffix Margules Equation
a. Two suffix Margules Equation
𝑮𝑬
𝑮𝑬 = 𝒙𝟏𝒙𝟐(𝑨𝟐𝒙𝟏 + 𝑨𝟏𝒙𝟐)
= 𝑨𝒙𝟏𝒙𝟐 𝑹𝑻
𝑹𝑻 A = adjustable parameter
ln𝜸𝟏 = 𝒙𝟐2 [A1 – 2(A2 –A1)]X1
ln𝜸𝟏 = 𝑨𝒙𝟐2
ln𝜸𝟐 = 𝑨𝒙𝟏2 ln𝜸𝟐 = 𝒙𝟏2 [A2 – 2(A1 –A2)]X2

➢ Limitation:
A=1 ➢ Applicable for the components of similar size,

A=1 shape and chemical nature

➢ Symmetric about x1 = 0.5 (activity coefficient
is mirror image to each other
 Excess Gibbs Free Energy Model (Binary Mixture)
o Redlich –Kister equation

𝑮𝑬
A=B=C=1
= 𝒙𝟏𝒙𝟐[𝑨 + 𝑩(𝒙𝟏 – x2)+ C(x1 – x𝟐)2 + ……]
𝑹𝑻

A, B, C = temperature dependent adjustable parameter 𝑮𝑬

𝑹𝑻

ln𝜸𝟏 = 𝑥1𝑥2[𝐴 + 𝐵(𝑥1 – x2)+ C(x1 – x2)2 + ……] + 𝑥2[𝐴(𝑥2 −

x1) + 𝐵 6𝑥1𝑥2 − 1 + 𝐶 𝑥1 − x2 8𝑥1𝑥2 − 1 + … . ]
ln𝜸𝟐 = 𝑥1𝑥2[𝐴 + 𝐵(𝑥1 – x2)+ C(x1 – x2)2 + ……] − 𝑥1[𝐴(𝑥2 −
x1) + 𝐵 6𝑥1𝑥2 − 1 + 𝐶 𝑥1 − x2 8𝑥1𝑥2 − 1 + … . ]

𝜸𝟏
ln = 𝐴 𝑥1 − x2 + 𝐵 6𝑥1𝑥2 − 1 + 𝐶 𝑥2 − x1 8𝑥1𝑥2 − 1 + … . ]
𝜸𝟐
Problem 02:
A binary liquid mixture is an equilibrium with its vapour at 300 K temperature. The liquid
mole fraction x1 is 0.4 and molar excess Gibbs free energy is 200 J/mol, R = 8.314 J/mol/K and
𝛾1 is liquid phase activity coefficient, where ln𝛾1 = 0.09. then find out the value of 𝛾2 ?

Problem 03:
The constant A and B of three suffix Margules equation for the system Ethanol (1)- toluene
(2) at 85 oC are 1.6409 and 1.7540 respectively. Estimate ln𝛾1 and ln𝛾2 at x1 = 0.1, 0.3, 05,
0.7, 0.9 ant plot ln𝛾1 and ln𝛾2 versus x1. Compare the constant A and B with the values of
ln𝛾1 and ln𝛾2 as x1 → 0 𝑎𝑛𝑑 𝑥2 → 0.
Problem 04:
The constant A, B and C of Redlich –Kister equation for the system methanol (1)- benzene (2)
at 85 oC are 1.601, 1.704 and 1.025 respectively. Estimate bubble pressure and composition of
vapour at x1= 0.4 by using Redlich –Kister equation
The Antoine constant of the components are
Components A B C
Methanol (1) 8.08097 1582.271 239.726
Benzene (2) 6.89787 1196.760 219.161
 Excess Gibbs Free Energy Model (Binary Mixture)
Wohl’s equation:
Gibbs free energy of binary liquid solution talking into account of two-body and three-body interaction
between like and unlike constituent molecules.

two-body interaction between unlike components

is called two suffix term.

𝑮𝑬
= 2a12z1z2 + 3a112𝒛𝟐𝟏 z2 + 3a122z1𝒛𝟐𝟐 …….. Three suffix equation
𝑹𝑻(𝒒𝟏 𝒙𝟏 +𝒒𝟏 𝒙𝟏 )

three-body interaction between unlike components

is called three suffix terms.

Where qi = a measure of volume of component i molecule

𝑥𝑖 𝑞𝑖
zi = = effective volume fraction of component i
𝑥1 𝑞1 +𝑥2 𝑞2

a12, a112, a122 = empirical constant

 Excess Gibbs Free Energy Model (Binary Mixture)
Wohl’s equation:
z1 + z2 = 1
𝑮𝑬 𝒒𝟐
= (x1 + x ) z z {z q (2a12 + 3a112)+ z2q1 (2a12 + 3a122)}
𝑹𝑻 𝒒𝟏 2 1 2 1 1

Now for q1 =q2 this Wohl’s equation reduce to

𝑮𝑬 𝒒𝟐
= (x1 + x ) z z (z q B+ z2q1A) three-suffix Margules equation
𝑹𝑻 𝒒𝟏 2 1 2 1 1

𝑮𝑬
Where, A = q1 (2a12 + 3a122) = (Bx1+ Ax2)x1x2 = (A21x1+ A12x2)x1x2
𝑹𝑻

B = q2(2a12 + 3a112)
ln𝜸𝟏 = 𝒙𝟐𝟐 [ A + 2(B − 𝑨)x1] = (2B − A)𝒙𝟐𝟐 + 2(A – B) 𝒙𝟑𝟐
𝒒𝟏
ln𝜸𝟏 = 𝒛𝟐𝟐 [ A + 2(B − 𝑨) z1] = 𝒙𝟐𝟐 [A12 + 2(A21 – A12)x1]
𝒒𝟐

𝒒 ln𝜸𝟐 = 𝒙𝟐𝟏 [ B + 2(A − 𝑩) x2] = (2A − B)𝒙𝟐𝟏 + 2(B – A) 𝒙𝟑𝟏

ln𝜸𝟐 = 𝒛𝟐𝟏 [ B+ 2(A 𝟏 − 𝑩) z2]
𝒒𝟐
= 𝒙𝟐𝟏 [A21 + 2(A12 – A21)x2]
 Excess Gibbs Free Energy Model (Binary Mixture)
Wohl’s equation:

If x1 = 0 If x2 = 0
ln𝜸𝟏 = A and ln𝜸𝟐 = 0 ln𝜸𝟏 = 0 and ln𝜸𝟐 = B

ln𝜸𝟏 = 𝒙𝟐𝟐 [ A + 2(B − 𝑨)x1] = A𝒙𝟐𝟐

If A = B then Margules two-suffix equation
ln𝜸𝟐 = 𝒙𝟐𝟏 [ B + 2(A − 𝑩) x2] = B)𝒙𝟐𝟏
 Excess Gibbs Free Energy Model (Binary Mixture)
Van Laar equation:

If q1/q2 = A/B then Wohl’s equation become Van Larr equation

𝑮𝑬 𝑨𝒙𝟏 𝒙𝟐 If x1 = 0 If x2 = 0
= 𝑨
𝑹𝑻 𝒙𝟏 + 𝒙𝟐
𝑩 ln𝜸𝟏 = A and ln𝜸𝟐 = 0 ln𝜸𝟏 = 0 and ln𝜸𝟐 = B

𝑨
ln𝜸𝟏 = 𝑨𝒛𝟐𝟐 = 𝑨𝒙 Problem:
𝟏+ 𝑩𝒙𝟏 𝟐
𝟐 Ethanol (1) and benzene (2) system forms an azeotropes with 44.8
𝑩
ln𝜸𝟐 = 𝒃𝒛𝟐𝟏 = 𝑩𝒙 mol% ethanol with a boiling point of 68.24 oC at 760 torr. The
𝟏+ 𝑨𝒙𝟐 𝟐
𝟏
saturation pressure of ethanol and benzene at 68.24 oC are 506
and 517 torr respectively. Estimate the Van Laar constants for the
𝑿2 ln𝜸𝟐 𝟐
A = ln𝜸𝟏 𝟏 + system and evaluate the activity coefficient for a solution
𝑿𝟏 ln𝜸𝟏

𝑿1 ln𝜸𝟏 𝟐
containing 10 mol% ethanol.
B = ln𝜸𝟐 𝟏 + 𝑿𝟐 ln𝜸𝟐
 Excess Gibbs Free Energy Model (Binary Mixture)
Wilson equation:

The mixture in which component differ from each other in molecular size and interaction between
unlike and like component are different

𝑮𝑬
= -x1ln(x1 + Ʌ12x2) – x2ln(x2 - Ʌ21x1)
𝑹𝑻

Where Ʌ12 and Ʌ21 are two adjustable parameter which related to pure component molar volume and
characteristic energy differences. λ

𝒗𝟐 λ12 −λ11
Ʌ12 = exp[- }
𝒗𝟏 𝑅𝑇 vi = molar volume of pure component ‘i’
λ𝒊𝒋 = energy of interaction between a molecule of component i
𝒗𝟏 λ12 −λ22 and a component j.
Ʌ21 = exp[- }
𝒗𝟐 𝑅𝑇
 Excess Gibbs Free Energy Model (Binary Mixture)
Wilson equation:
Ʌ12 Ʌ21
ln𝜸𝟏 = − ln(x1 + Ʌ12x2) + x2[ − ]
𝒙𝟏 + Ʌ12x2 𝒙𝟐 + Ʌ21x1

Ʌ12 Ʌ21
ln𝜸𝟐 = ln(x2 + Ʌ21x1) − x1[
𝒙𝟏 + Ʌ12x2
− 𝒙𝟐 + Ʌ21x1
]

Advantage:
➢ It is applicable to several miscible binary system
➢ It predict the temperature dependence activity coefficient
It is useful for completely miscible or
Disadvantage:
partially miscible system in the region
o It is not applicable in which ln𝜸𝒊 exhibits a maxima or minima
where only one liquid phase exit
o Inability to predict limited miscibility.
Problem 02:
Wilson’s parameter Ʌ12 and Ʌ21 for the nitromethane (1) and carbon tetrachloride (2) at 45
oC are 0.1156 and 0.2879 respectively. Calculate the activity coefficient for the solution at
x1 = 0.3.
 Excess Gibbs Free Energy Model (Binary Mixture)
Non-random Two Liquid (NRTL) Equation:
Applicable for partially miscible and completely system.
𝐺21 𝜏12 𝐺12
ln𝜸𝟏 = 𝒙𝟐𝟐 [ 𝜏21 ( ) 2+ ]
𝑮𝑬 𝜏 𝐺 𝜏12 𝐺12 𝒙𝟏 + 𝒙𝟐 𝐺21 (𝒙𝟐 + 𝒙𝟏 𝐺12 )2
= x1x2 [ 21 21 + ]
𝑹𝑻 𝑥1 + 𝑥2 𝐺21 𝑥2 + 𝑥1 𝐺12
𝐺12 𝜏21 𝐺21
ln𝜸𝟐 = 𝒙𝟐𝟏 [ 𝜏12 ( )2+ ]
𝒙𝟐 + 𝒙𝟏 𝐺12 (𝒙𝟏 + 𝒙𝟐 𝐺21 )2
𝐺12 − 𝐺22
𝜏12 =
𝑅𝑇
𝐺21 − 𝐺11 ➢ 0.20 < α12 < 0.47
𝜏21 = ➢ General case α12 = 0.3 (no other information is there)
𝑅𝑇
➢ If α12 = 0 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 𝑖𝑠 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑒𝑙𝑦 𝑟𝑎𝑛𝑑𝑜𝑚
𝐺12 = exp(−α12 𝜏12 )
➢ NRTL equation reduce to two-suffix Margules equation
𝐺21 = exp(−α12 𝜏21 )

o α12 𝑖𝑠 𝑎 𝑝𝑎𝑟𝑎𝑚𝑒𝑡𝑒𝑟 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑡𝑜 𝑎 𝑝𝑎𝑟𝑡𝑖𝑐𝑢𝑙𝑎𝑟 𝑝𝑎𝑖𝑟 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠.

➢ No additional information over
o α12 𝑖𝑠 𝑛𝑜𝑛 − 𝑟𝑎𝑛𝑑𝑜𝑚𝑛𝑒𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑚𝑖𝑥𝑡𝑢𝑟𝑒 Margules and Van Laar equation
o It is independent of composition and temperature for moderately non-ideal solution
 Excess Gibbs Free Energy Model (Binary Mixture)
Universal Quasi Chemical (UNIQUAC) Equation:
𝑮𝑬 𝑮𝑬 𝑮𝑬
= (combinatorial) + (residual)
𝑹𝑻 𝑹𝑻 𝑹𝑻

Where,
𝑮𝑬 ∅ ∅ 𝑧 𝜃 𝜃
Composition, size and shape
(combinatorial) = 𝑥1 𝑙𝑛 1 + 𝑥2 𝑙𝑛 2 + 𝑞1 𝑥1 𝑙𝑛 1 + 𝑞2 𝑥2 𝑙𝑛 2 → (pure component property only)
𝑹𝑻 𝑥1 𝑥2 2 ∅1 ∅2
𝑮𝑬
(residual) = - 𝑞1 𝑥1 ln 𝜃1 + 𝜃2 𝜏21 − 𝑞2 𝑥2 ln 𝜃2 + 𝜃1 𝜏12 → Intermolecular forces
𝑹𝑻
(contains two adjustable parameter)
Where,
𝑥𝑖 𝑟𝑖
∅𝑖 = 𝑠𝑒𝑔𝑚𝑒𝑛𝑡 𝑜𝑟 𝑣𝑜𝑙𝑢𝑚𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖 = σ𝑗 𝑥𝑗 𝑟𝑗
(𝑟𝑖 = relative molecular volume)
𝑥𝑖 𝑞𝑖
𝜃𝑖 = 𝑎𝑟𝑒𝑎 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖 = σ𝑗 𝑥𝑗 𝑞𝑗
𝑞𝑖 = surface area parameter of component i
( 𝑢𝑗𝑖 − 𝑢𝑖𝑖 ) 𝑎𝑗𝑖
𝜏21 = exp{ - } = exp ( - ) = Adjustable parameter Z = Coordination number
𝑅𝑇 𝑇
𝑢𝑗𝑖 = average interaction energy of i and j. (usually taken as 0)
 Excess Gibbs Free Energy Model (Binary Mixture)
Universal Quasi Chemical (UNIQUAC) Equation:

ln𝜸𝒊 = 𝒍𝒏𝜸𝒄𝒊 (combinatorial) + 𝒍𝒏𝜸𝑹

𝒊 (residual)

∅𝒊 𝒛 𝜽𝒊 𝑞𝑖
𝒍𝒏𝜸𝒄𝒊 = 𝒍𝒏 + 𝒒𝒊 𝒍𝒏 + 𝑙𝑖 − σ 𝑥𝑗 𝑙𝑗
𝒙𝒊 𝟐 ∅𝒊 𝑥𝑖 Advantage:

𝜽𝒋 𝝉𝒊𝒋 ➢ It contains two adjustable parameter a12 and a21

𝑹
𝒍𝒏𝜸𝒊 = 𝒒𝒊 [ 𝟏 − 𝒍𝒏(෍ 𝜽𝒋 𝝉𝒋𝒊 ) − ෍ ]
σ𝒌 𝜽𝒌 𝝉𝒌𝒋 ➢ parameter a12 and a21 are less dependent on
𝒋 𝒋
𝑧
temperature
Where, 𝑙𝑖 = 𝑟𝑖 − 𝑞𝑖 − (𝑟𝑖 − 1)
2 ➢ It is applicable to the solution containing small
𝑟𝑖 = σ𝑘 𝑣𝑘𝑖 𝑅𝑘 as well as large molecules

𝑞𝑖 = σ𝑘 𝑣𝑘𝑖 𝑄𝑘

𝑣𝑘𝑖 = number of group of type k in a molecule of component i

Problem:
Estimate the activity coefficient for the ethanol (1) and benzene (2) system at 345 K and at x1 = 0.8
using the QNIQUAC equation.
The group identification and Rk and Qk of the groups are given bellow

Molecule i Name Main No Sec No. 𝒗𝒊𝒌 𝑹𝒌 𝑸𝒌

Ethanol (1) CH3 1 1 1 0.9011 0.848
CH2 1 2 1 0.6744 0.540
OH 5 14 1 1.0 1.20
Benzene (2) ACH 3 9 6 0.5313 0.40

𝑢12 − 𝑢22 = - 241.2287 J/mol K

𝑢21 − 𝑢11 = 2799.5827 J/mol K
 Thermodynamics Consistency Test of VLE Data

➢ It obeys Gibbs Duhem equation

𝜕(𝑛𝑀) 𝜕(𝑛𝑀) Integral Method

( )
𝜕𝑇 P, n
dT + ( ) dP -
𝜕𝑃 T, n
∑xi d 𝑀𝑖 = 0

∑xi d 𝑴𝒊 = 0 …………… (at constant T & P) 𝒙𝟏 =𝟏

𝜸𝟏
න 𝒍𝒏 =𝟎
𝒉𝑬 𝒗𝑬 𝜸𝟐
𝐝T + dP - ∑xi dln𝜸𝒊 = 0 𝒙𝟏 =𝟎
𝑹𝑻𝟐 𝑹𝑻

∑xi dln𝜸𝒊 = 0 (at constant T & P)

For binary mixture

𝒅𝒍𝒏𝜸𝟏 𝒅𝒍𝒏𝜸𝟐
𝒙𝟏 = 𝒙𝟐
𝒅x𝟏 𝒅x𝟐
 Thermodynamics Consistency Test of VLE Data
Problem:
From the isobaric VLE data for acetone – carbon tetrachloride at 450 Torr calculate T and y1 at
x1 = 0.447, 0.6525 and 0.8955 using van Laar and three suffix Margules equation. Compare with
experimental data

T (oC) x1 y1 T (oC) x1 y1
Antoine constants
55.29 0.049 0.189 42.42 0.6525 0.728
49.50 0.1625 0.393 41.92 0.741 0.784 A B C
46.26 0.297 0.515 41.54 0.8955 0.9015 Acetone 7.11714 1210.595 229.664
44.06 0.447 0.61 41.53 0.926 0.927 Carbon 6.84083 1117.91 220.576
43.05 0.565 0.667 41.16 0.945 0.945 tetrachloride

𝑩
ln 𝒑𝒗 =A-
Test for thermodynamics consistency of VLE data mentioned above. 𝑻+𝑪
 Thermodynamics Consistency Test of VLE Data
Three suffix Margules Equation

𝑮𝑬
= 𝒙𝟏𝒙𝟐(𝑨𝟐𝒙𝟏 + 𝑨𝟏𝒙𝟐)
𝑹𝑻

ln𝜸𝟏 = 𝒙𝟐2 [A1 – 2(A2 –A1)]X1

ln𝜸𝟐 = 𝒙𝟏2 [A2 – 2(A1 –A2)]X2

𝜸 𝜸
x1 ln(𝜸𝟏 ) x1 ln(𝜸𝟏 )
𝟐 𝟐

0.049 0.8235 0.6525 - 0.3496

0.1625 0.8115 0.741 - 0.4668
0.297 0.2234 0.8955 - 0.6396
0.447 - 0.415 0.926 - 0. 6908
0.565 - 0.2245 0.945 - 0. 7056
 Thermodynamics Consistency Test of VLE Data

(a) (b) (c)

Activity coefficient ratio of (a) simple mixture [ hexane (1) – toluene (2) at 1.013 bar, (b) mixture of intermediate complexity [
benzene (1) – isooctane (2)] at total pressure ranging from 0.981 to 1.013 bar, © highly complex mixture [ ethanol (1) –
methylcyclohexane (2) in the region 30 – 35 oC.

J. M. Prausnitz, R. N. Liehtejthaler and E. G. De Azevedo, Molecular

Thermodynamics of fluid phase equilibria, 3rd edition, prentice hall
 Thermodynamics Consistency Test of VLE Data
o Redlich –Kister equation

𝑮𝑬
A=B=C=1
= 𝒙𝟏𝒙𝟐[𝑨 + 𝑩(𝒙𝟏 – x2)+ C(x1 – x𝟐)2 + ……]
𝑹𝑻

A, B, C = temperature dependent adjustable parameter 𝑮𝑬

𝑹𝑻

ln𝜸𝟏 = 𝑥1𝑥2[𝐴 + 𝐵(𝑥1 – x2)+ C(x1 – x2)2 + ……] + 𝑥2[𝐴(𝑥2 −

x1) + 𝐵 6𝑥1𝑥2 − 1 + 𝐶 𝑥1 − x2 8𝑥1𝑥2 − 1 + … . ]
ln𝜸𝟐 = 𝑥1𝑥2[𝐴 + 𝐵(𝑥1 – x2)+ C(x1 – x2)2 + ……] − 𝑥1[𝐴(𝑥2 −
x1) + 𝐵 6𝑥1𝑥2 − 1 + 𝐶 𝑥1 − x2 8𝑥1𝑥2 − 1 + … . ]

𝜸𝟏
ln = 𝐴 𝑥1 − x2 + 𝐵 6𝑥1𝑥2 − 1 + 𝐶 𝑥2 − x1 8𝑥1𝑥2 − 1 + … . ]
𝜸𝟐
 Phase Diagram of Pure Substance

Phase diagram of Water ( P-T diagram) Phase diagram of CO2 ( P-T diagram)

www.chemistrylearner.com/phase-diagram.html
Retrograde Condensation

o The critical point can be defined as the

point at which the liquid and vapour
phase are indistinguishable.
o The maximum pressure on the P-T curve is
called the maxcondenbar point or
criconderbar point (MP)
o The maximum temperature on the P-T
curve is called the maxcondentherm
point or cricondertherm point (MT)

https://topdogengineer.com/phase-diagram/
 Retrograde Condensation

(a) (b) (c)

Typical pressure –temperature diagram for a binary component mixture in which (a) both the
maxcondenbar and maxcondentherm points lies on the dew point curve (b) the maxcondenbar point lies
on the bubble point curve and maxcondentherm points lies on the dew point curve (c) both the
maxcondenbar and maxcondentherm points lies on the bubble point curve.

Y.V.C Rao – Chemical Engineering thermodynamics- universities press

 Retrograde Condensation
Retrograde condensation of 1st kind:
➢ Constant temperature line twice cross the dew point curve
o Retrograde dew formation at constant temperature: phenomena of liquid formation when
pressure is reduced at constant temperature
o Retrograde dew formation at constant pressure: phenomena of liquid formation when
temperature is raised at constant pressure

Retrograde condensation of 2nd kind:

➢ Constant pressure line twice cross the bubble point curve
o Retrograde bubble formation at constant temperature: phenomena of vapour phase formation
when pressure is increased at constant temperature
Retrograde Condensation

Y.V.C Rao – Chemical Engineering thermodynamics- universities press

Retrograde Condensation

Retrograde condensation at constant

temperature and pressure with
different composition

Y.V.C Rao – Chemical Engineering thermodynamics- universities press

 Partial and complete immiscibility

➢ If the system is miscible then Δgmix of the system will decrease

➢ Δgmix is increase then the system will preferred to stay separated

𝝏𝑮𝒎𝒊𝒙
( ) = 𝒗𝒎𝒊𝒙
𝝏𝑷 𝑻,𝒙

∆𝑮𝒎𝒊𝒙 < 𝟎

𝝏𝟐 𝑮𝒎𝒊𝒙
𝟐
> 𝟎 𝒇𝒐𝒓 𝒂𝒍𝒍 𝒙
𝝏𝒙
Δ 𝒗𝒎𝒊𝒙 = f (T, P)
∆𝑮𝒎𝒊𝒙 = 𝒇(𝒙)
 Partially Miscible System

F=C–P+2
F=2–3+2
F=1

Molar Gibbs energy of mixing at constant temperature and

pressure of a binary mixture, 1) partially miscible and 2)
totally miscible
 Partially Miscible System

Effect of pressure on miscibility: a) low Effect of pressure on miscibility: a) low

pressure, no immiscibility; b) high pressure, pressure, immiscible for x1’<x1<x1”; b) high
immiscible for x1’<x1<x1” pressure, no immiscibility.

Y.V.C Rao – Chemical Engineering thermodynamics- universities press

 Partially Miscible System

a) T-x-y diagram and b) P-x-y diagram for a partially miscible system

Y.V.C Rao – Chemical Engineering thermodynamics- universities press

 Partially Miscible System

Temperature compositing diagram at different pressure

Y.V.C Rao – Chemical Engineering thermodynamics- universities press
 Completely Immiscible System

a) b)

a) T-x-y diagram and b) P-x-y diagram for a completely immiscible system

Problem:
Assuming that benzene and water form a completely immiscible system, prepare a temperature-
composition (T-x-y) diagram for benzene (1) water (2) system at a pressure 760 Torr.

Antione constant are as follows:

A B C
Benzene (1) 6.87987 1196.760 219.161
Water (2) 16.3872 3885.700 230.170
 Chemical Reaction Equilibrium:
aA + bB → cC + dD 𝜺 = reaction coordinate/extend of reaction
𝝂𝟏 𝑨𝟏 + 𝝂𝟐 𝑨𝟐 → 𝝂𝟑 𝑨𝟑 + 𝝂𝟒 𝑨𝟒 ❖ It characterizes the extend or degree to which
a reaction has taken place
𝜈𝑖 = stoichiometric coefficient/number
d𝑛𝑖 = 𝜈𝑖 𝒅𝜺
= positive (+) for product
𝜺
= Fractional mole conversion
= negative (-) for reactant 𝑛𝑖

𝒏𝒊 𝜺
𝑁2 + 3𝐻2 = 2N𝐻3
න 𝒅 𝒏𝒊 = න 𝝂𝒊 𝒅𝜺 𝒏𝒊 = 𝒏𝒊𝟎 + 𝝂𝒊 𝜺
𝜈𝑁2 = −1; 𝜈𝐻2 = −3; 𝜈𝑁𝐻3 = 2
𝒏𝒊𝟎 𝟎
The changes in the number of moles of species Summation over all species yields
present are directly proportional to stoichiometric n = σ𝑖 𝑛𝑖0 + 𝜀 σ𝑖 𝝂𝑖 n = 𝒏𝟎 + 𝝂𝜺
number
𝑑𝑛1 𝑑𝑛2 𝑑𝑛3 𝑑𝑛4 𝒏𝒊 𝒏𝒊𝟎 + 𝝂𝒊 𝜺
= = ……. = = = … … . . = 𝒅𝜺 𝒚𝒊 = =
𝜈1 𝜈2 𝜈3 𝜈4 𝒏 𝒏𝟎 + 𝝂𝜺
 Chemical Reaction Equilibrium:
Problem 1:
The following reaction occurs in a system initially consist of 3 moles nitrogen and one mole
hydrogen.
𝑁2 + 3𝐻2 → 2N𝐻3
Find out the expression for he mole fraction as a function of reaction coordinate.

Problem 2:
Consider a vessel that initially contain only n0 mol of water vapor. If decomposition occurs
according to the reaction
𝐻2 𝑂 → 𝐻2 + 0.5𝑂2
Find out the expression that relate the number of moles and mole fraction of each chemical
species to the reaction coordinate.
 Chemical Reaction Equilibrium:
For Multi-reaction stoichiometry:

𝒏𝒊𝟎 + σ𝒋 𝝂𝒊,𝒋 𝜺𝒊
𝒚𝒊 =
𝒏𝟎 + σ𝒋 𝝂𝒋 𝜺𝒋

Problem 3:
Consider a system in which following reactions occurs
𝐶𝐻4 + 𝐻2 𝑂 → 𝐶𝑂 + 3𝐻2
𝐶𝐻4 + 2𝐻2 𝑂 → 𝐶𝑂2 + 4𝐻2
Where the number 1 and 2 indicate the value of j, the reaction index. If 2 mol of CH4 and 3
mol of H2O are initially present, determine expression of yi as a function of 𝜺1 and 𝜺2.
 Chemical Reaction Equilibrium:
➢ For a closed system at constant T and P, total Gibbs free energy must decrease of a reversible
process.
➢ For minimum total Gibbs free energy (dGt)T,P = 0
 The Standard Gibbs Energy Changes and Equilibrium Constant
𝜇𝑖 = 𝜞𝐼 𝑇 + 𝑅𝑇𝑙𝑛𝑓෡𝑖
𝐺𝑖0 = 𝜞𝐼 𝑇 + 𝑅𝑇𝑙𝑛𝑓𝑖0
d(nG) = (nV)dP – (nS)dT + σ𝑖 𝜇𝑖 𝑑𝑛𝑖
෢
𝑓
𝜇𝑖 − 𝐺𝑖0 = RTln 00
𝑓𝑖
𝒏𝒊 = 𝒏𝒊𝟎 + 𝝂𝒊 𝜺
෢
𝑓
𝝂𝒊 (𝜇𝑖 − 𝐺𝑖0 ) = 𝝂𝒊 RTln 0𝑖
𝑓𝑖
𝒅𝒏𝒊 = 𝝂𝒊 𝒅𝜺
𝑓෡𝑖 𝝂
෍[ 𝝂𝒊 𝐺𝑖0 + RTln( 0 ) 𝒊 ] = 0
d(nG) = (nV)dP – (nS)dT + σ𝑖 𝜇𝑖 𝝂𝒊 𝒅𝜺 𝑓𝑖
𝒊

෢𝑖
𝑓 − σ𝑖 𝝂𝒊 𝐺𝑖0
lnς𝑖( 0 ) 𝝂𝒊 =
𝑓𝑖 𝑅𝑇
𝜕 𝑛𝐺 𝜕𝐺 𝑡
෍ 𝜇𝑖 𝝂𝒊 = T, P = =0
𝑖
𝝏𝜺 𝜕𝜀 𝑇, 𝑃
𝑓෡𝑖 𝝂
ෑ( 0 ) 𝒊 = 𝐾𝑒𝑞
𝑓𝑖
𝑖
σ𝑖 𝜇𝑖 𝝂𝒊 = 0 ln𝑲𝒆𝒒 =
− σ𝒊 𝝂𝒊 𝑮𝟎𝒊
=
−∆𝑮𝟎
𝑹𝑻 𝑹𝑻

∆𝑮𝟎 = −𝑹𝑻𝒍𝒏 𝑲𝒆𝒒

 Equilibrium Constant with Composition
෢
𝑓
ς𝑖( 0𝑖 ) 𝝂𝒊 = 𝑲𝒆𝒒
𝑓𝑖
Calculation of Ky:
(at standard state for a gas is a ideal gas, P0 = f0
෢
𝑓
ς𝑖( 0𝑖 ) 𝝂𝒊 = 𝑲𝒆𝒒 aA + bB → cC + dD
𝑃
෢𝑖 𝑦𝑖 𝑃
𝑓෡𝑖 = ∅
(𝒚𝒄 )𝒄 . (𝒚𝒅 )𝒅
෢𝑖 𝑦𝑖 𝑃
∅
ς𝑖( 0 )𝝂𝒊 = 𝑲𝒆𝒒
𝑲𝒚 =
𝑃 (𝒚𝒂 )𝒂 . (𝒚𝒃 )𝒃
෢𝑖 𝑦𝑖 )𝝂𝒊 ( 𝑃 ) 𝝂𝒊 ] = 𝑲𝒆𝒒 σ𝒊 𝝂𝒊 = 𝝂
ς𝑖[(∅
𝑃0

𝑷
ς𝒊[ ∅෡𝒊 𝒚𝒊 )𝝂𝒊 ( 𝟎 )𝝂 = 𝑲𝒆𝒒
𝑷 𝑷 𝝂
𝑲𝒆𝒒 = 𝑲𝒚 ( 𝟎 )
𝑷 𝝂 𝑷
𝑲𝒆𝒒 = 𝑲𝒚 𝑲∅ ( 𝟎 )
𝑷

෢𝑖 )𝝂𝒊
𝑲𝒚 = ෑ(𝑦𝑖 )𝝂𝒊 ; 𝑲∅ = ෑ(∅ ∆𝑮𝟎 = −𝑹𝑻𝒍𝒏 𝑲𝒆𝒒
𝑖 𝑖
𝒏𝒊 𝒏𝒊𝟎 + 𝝂𝒊 𝜺
𝑲∅ = 1 for ideal gas 𝑷 𝒚𝒊 = =
𝑲𝒆𝒒 = 𝑲𝒚 ( 𝟎 )𝝂 𝒏 𝒏𝟎 + 𝝂𝜺
𝑷
 Effect of Temperature on Equilibrium Constant

∆𝑮𝟎 = ෍ 𝝂𝒊 𝑮𝟎𝒊 ∆𝑴𝟎 = ෍ 𝝂𝒊 𝑴𝟎𝒊 For standard Gibbs energy and enthalpy
𝒊 𝒊
𝐺𝑖0 𝐻𝑖0
𝑑 = − 𝑑𝑇
𝐺 1 1 𝐺 𝑅𝑇 𝑅𝑇 2
𝑑 = 𝑑 𝐺. = 𝑑𝐺 − dT
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇 2
𝑑𝐺 = 𝑣𝑑𝑃 − 𝑠𝑑𝑇; 𝐺 = 𝐻 − 𝑇𝑆 σ𝑖 𝜈𝑖 𝐺𝑖0 σ𝑖 𝜈𝑖 𝐻𝑖0
𝑑 = − 𝑑𝑇
𝑅𝑇 𝑅𝑇 2
𝐺 1 𝐻 −𝑇𝑆
𝑑 = (𝑣𝑑𝑃 − 𝑆𝑑𝑇) − dT
𝑅𝑇 𝑅𝑇 𝑅𝑇 2
∆𝐺 0
𝑑( 𝑅𝑇 ) ∆𝐻0
𝐺 𝑣 𝑆 𝐻 𝑆 =−
𝑑 = 𝑑𝑃 − 𝑑𝑇 − 𝑑𝑇 + 𝑑𝑇 𝑑𝑇 𝑅𝑇 2
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑅𝑇 2 𝑅𝑇

𝐺 𝑣 𝐻 𝒅(𝒍𝒏𝑲𝒆𝒒 ) ∆𝑯𝟎 van’t Hoff Equation

𝑑 = 𝑑𝑃 − 𝑑𝑇 =
𝑅𝑇 𝑅𝑇 𝑅𝑇 2 𝒅𝑻 𝑹𝑻𝟐
If Gibbs energy is only function of T, then
𝑮 𝑯
𝒅 = − 𝒅𝑻
𝑹𝑻 𝑹𝑻𝟐 𝑲𝒆𝒒 ∆𝑯𝟎 𝟏 𝟏
𝒍𝒏 ′ = − ( − ′)
𝑲𝒆𝒒 𝑹 𝑻 𝑻
Problem:
Acetic acid is esterified in the liquid phase with ethanol at 90 oC and atmospheric pressure to
produce ethyl acetate and water according to the reaction:
CH3COOH (l) + C2H5OH (l) → CH3COOC2H5 (l) + H2O (l)
If initially there is one mole of acetic acid and two mol of ethanol present, estimate the mole
fraction of acetic acid, ethyl acetate, ethanol, and water in the reacting mixture at equilibrium.

CH3COOH (l) C2H5OH (l) CH3COOC2H5 (l) H2O (l)

𝑜 - 484500 - 227690 - 480000 - 285830
Δ𝐻𝑓298 (J)
𝑜 - 389900 - 174780 - 332200 - 237129
Δ𝐺𝑓298 (J)
 Degree of freedom with reaction:
➢ To define the number of independent variable
➢ To control the system degree of freedom should be zero
DOF = 𝑪 − 𝑷 + 𝟐 − 𝒓 − 𝒔
2 = Temperature and pressure
C = No. of component
r = no of independent chemical reaction
P = no. of phase
s = special constraint

Problem 3:
Determine degree of freedom, F for each of the following system
a) A system of two miscible nonreacting species that exits as an azeotropes in vapour/liquid equilibrium
b) A system prepared by decomposing CaCO3 into an evacuate space
c) A system prepare by partially decomposition NH4Cl into an evacuate space
NH4Cl (s) → NH3 (g) + HCl (g)
d) A system consisting of the gases CO, CO2, H2, H2O, and CH4 in chemical equilibrium
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