Solution Thermodynamics

Chemical Engineering thermodynamics (Part II)

Why at low pressure (P → 0) real gas behaves like ideal gas?

https://chemistry.stackexchange.com/questions/107843/compressibility-factor-graph-which-gas-attains-a-deeper-minimum Silbey et al. Physical Chemistry

 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
 Residual Property or Departure Function

G 𝒗 𝑯
Prove That d( ) = dP - dT
𝑹𝑻 𝑹𝑻 𝑹𝑻𝟐

GR 𝑷 𝒅𝑷
Prove that at constant T,
𝑹𝑻
= ‫( 𝟎׬‬Z −1 )
𝑷

GR 𝑩𝑷
Prove that at constant T, =
𝑹𝑻 𝑹𝑻
 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.
 Fugacity (f)

➢ 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
For real gas dGR = RT dln
𝑓
At const. temp. 𝑃
dG = RT dlnf
dG = vdP (𝑮𝑹 = 𝒓𝒆𝒔𝒊𝒅𝒖𝒂𝒍 𝑮𝒊𝒃𝒃𝒔 𝒇𝒓𝒆𝒆 𝒆𝒏𝒆𝒓𝒈𝒚)
For ideal gas, Pv = RT 𝐺𝑅 𝑃 𝑓
dG - dGig = RT dln
𝑓 ‫=𝑅 𝐺׬‬0 𝑑GR = ‫→𝑃׬‬0 𝑅𝑇 dln
𝑃
𝑅𝑇 𝑃
v= d(G - Gig) = RT dln
𝑓
𝑃
𝑃 𝒇
𝒅𝑷 GR = RT ln
dGig = RT = RT dlnP 𝑷
𝑷
GR 𝒇
= ln
𝑹𝑻 𝑷
 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
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:

1. Given V = 3x12 + 2(1 – x2) + 4x1; then find out V1
Hi, Gi, Si, Ui, vi, …… and V2. (Ans. V1 = 9, and V2 = 0)
2. Given 𝐺1 = 60x12 + 40x2; then find out G1α .
Dependency of molar properties:
(Ans. 40)
M = f(T, P, n1, n2, n3, ……..nn) 1. 𝐻1 = 2 -60X22 +100x1x22; find 𝐻1α. (Ans. -58)

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)
( ) dT + ( ) dP - ∑xi d 𝑴𝒊 = 0
𝝏𝑻 P, n 𝝏𝑷 T, n Q1. If 𝑀2 = 5 x12; find 𝑀1 = ??
(Ans. 5 x12 - 10x)
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? (Ans. 2400 J)
Q1. Will it be possible to prepare 0.1 m3 of alcohol-water solution by mixing 0.03 m3 alcohol with 0.07
m3 pure water? (Ans. No)
If not possible, what volume should have been mixed in order to prepare a mixture of the same strength
and of the required volume? (Ans. 0.07189 m3)
Density of ethanol and water are 789 and 997 kg/m3 respectively. The partial molar volumes of ethanol
and water at the desired compositions are: Ethanol = 53.6x10–6 m3 /mol; water = 18x10–6 m3 /mol.

Q2. Laboratory alcohol containing 96% alcohol and 4% water is to be diluted to a solution containing
56% alcohol and 44% water. All percentages are on weight basis. The partial specific volumes are as
follows: In 96% alcohol solution, = 0.816x10–3 m3 /kg, = 1.273x10–3 m3 /kg. In 56% alcohol solution, =
0.953x10–3 m3 /kg, = 1.243x10–3 m3 /kg. The density of water may be taken as 0.997x103 kg/m3.
(a) How much water should be added to 2x10–3 m3 of the laboratory alcohol? (Ans. 0.001142 m3)
(b) What is the volume of the dilute alcohol obtained? (Ans. 0.0030468 m3)
 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? (Ans. 0.75)
Why is the term partial molar temperature and Partial molar pressure irrelevant?

Partial molar temperature” is irrelevant because temperature is an intensive property, it does not depend on the
amount of gas, but only in the energy content. Suppose we have mixed, two gases at two different temperatures,
the resultant mixture would again have a constant temperature.
While the partial molar temperature can be defined mathematically, it is often deemed irrelevant in practical terms
because temperature does not vary with composition in a way that provides useful insights for most
thermodynamic analyses of mixtures. Instead, focus is usually placed on properties that directly relate to the
energy and volume changes in the system.
 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
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. (Ans. ℎഥ1 = 500 J/mol, and ℎഥ2= 1000 J/mol)
b) Also determine the partial molar enthalpies at infinite dilution. (Ans. 540 J/mol and 1050
J/mol)
 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
Vt = - St =
𝑑𝑃 𝑑𝑇
At constant temp and pressure for a closed system
d(Gt) = ∑ µi dni d(Gt) = - St dT + VtdP + ∑ µi dni

For a binary system

Gt = ∑ µi ni
G = µ1x1 + µ2x2
 Chemical Potential (µ):
Effect of Temperature on Chemical Potential Compare (3) & (4)
𝜕𝜇 𝜕𝑆 𝑇
𝜕𝐺 𝑡 ( 𝑖 )P, n =- ( )P, n
µi = 𝐺ഥ𝑖 = ( ) 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 = −
- ( )P, n = ( ) ………….. (4) 𝝏𝑻 𝑻𝟐
𝜕𝑛𝑖 𝜕𝑇𝜕𝑛𝑖 P, n
 Chemical Potential (µ):
Effect of Pressure on Chemical Potential
Compare (3) & (4)
𝜕𝐺 𝑡
µi = 𝐺ഥ𝑖 = ( ) T, P, nj ……………………. (1) 𝜕𝜇 𝜕𝑉 𝑇
𝜕𝑛𝑖 ( 𝑖 )T, n =- ( )T, P,N
𝜕𝑃 𝜕𝑛𝑖
𝝏𝝁𝒊
𝑑𝐺 𝑡 ( ) = 𝑽ഥ𝒊 …… Partial Volume
𝝏𝑷 T, n
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, n = ( ) ………….. (4)
𝜕𝑛𝑖 𝜕𝑃𝜕𝑛𝑖 T, P, n
 Ideal Gas-state Mixture Partial Properties Model
Ideal gas, PV = nRT (total volume, m3)
PV = RT (molar volume, m3/mol) Real gas, PV = ZnRT
PV = ZRT
𝑃𝑣 𝑟𝑒𝑎𝑙 𝑣 𝑟𝑒𝑎𝑙 Z = compressibility factor
For ideal gas, Z =1 Z= =
𝑅𝑇 𝑣 𝑖𝑔
𝑅𝑇
Pvig = RT or, vig =
𝑃 Gibbs’ Theorem:
Partial Properties:
𝒊𝒈 𝑹𝑻 𝝏(𝒏) A partial molar properties (other than volume) of a
𝝏(𝒏𝑴) 𝒗𝒊 = ( )
𝐌𝐢 = ( ) 𝑷 𝝏𝒏𝒊 T,P, ni≠j constituent species in an ideal gas-mixture is equal to
𝝏𝒏𝒊 T,P, nj≠i the corresponding molar property of the species as a
𝝏(𝒏𝒗) 𝒊𝒈 𝑹𝑻
𝒗𝒊 = ( ) 𝒗𝒊 = pure ideal gas at mixture temperature but at a
𝝏𝒏𝒊 T,P, ni≠j 𝑷
pressure equal to its partial pressure in the mixture.
For Ideal gas 𝒊𝒈 𝑹𝑻 𝒊𝒈
𝒗𝒊 = = 𝒗𝒊 = Vig So according to the ideal gas mixture model
𝑷
𝑹𝑻
𝒊𝒈 𝝏(𝒏 𝑷 )
𝒊𝒈 𝒊𝒈 𝒊𝒈 𝒊𝒈
𝒗𝒊 = ( )T,P, ni≠j 𝒚𝒊 𝑹𝑻 𝑴𝒊 𝑻, 𝑷 = 𝑴𝒊 (T, pi) 𝑴𝒊 ≠ 𝑽𝒊
𝝏𝒏𝒊 p i = yi P =
𝑽𝒊𝒈
𝝏(𝒏) 𝝏𝒏𝟏 + 𝝏𝒏𝟐 𝝏𝒏
( 𝝏𝒏𝒊 )T,P, nj≠i ( )T,P, nj≠i ( 𝝏𝒏𝒊𝟏)T,P, nj≠i = 1
𝝏𝒏𝒊
 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)
𝑆𝑖 (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

𝐺 ((𝑝 ,𝑇) 𝑝 𝑅𝑇
‫𝑃(𝑖 𝐺׬‬,𝑇)𝑖 𝑑Gig = ‫𝑖 𝑃׬‬
𝑃
𝑑𝑃
𝑖
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

 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 ? (Ans = 1 m3/mol)
 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? (Ans. 1.64)
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 dlnf
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 dlnP 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?
(Ans. f = 14.89 bar)
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 1:
𝑃𝑣 𝐵𝑃
A pure gas obeys the equation =1+ where P is pressure and T is absolute temperature, v is
𝑅𝑇 𝑅𝑇
molar volume, R is gas constant and B is parameter depended of T & P. The residual Gibbs free energy
GR 𝑷 𝒅𝑷
is given by 𝑹𝑻
= ‫( 𝟎׬‬Z − 1 )
𝑷
Z is compressibility factor, B = 10-4 m3/mol.
What is the residual molar enthalpy in (J/mol) of the gas at 1000 kPa at 300 K? (Ans. HR = 100 J/mol)
GR 𝑣R 𝐻R
Given: d( ) = 𝑅𝑇 dP - 𝑅𝑇2 dT
𝑅𝑇