Chemical Engineering

Thermodynamics II

CHE 415
(2 Units)

Dr. Ayoola A. Ayodeji

Covenant University, Nigeria
 Textbooks
1. Introduction To Chemical Engineering
Thermodynamics (J. M. Smith, H. C. Van Ness &
M. M. Abbot)
2. Thermodynamics: An Engineering Approach
(Yunus A. Cengel & Michael A. Boles)
3. Any other relevant text

Grading
Assignments/Tests = 30 marks
Examination = 70 marks
 MODULE TWO

CHEMICAL POTENTIAL
AND PARTIAL
PROPERTIES
 Fundamental Property Relations

OBJECTIVE:
The inter-relations of the thermodynamic
properties are expressed in mathematic forms (as
much as reasonably possible) in other to determine
the magnitudes of unknown properties, using the
known or given properties.
 Fundamental Property Relations
The first law for a closed system undergoing
reversible process with only PV work is given by
dU = δQrev + δ Wrev
From the second law, δQrev = TdS
Hence,
dU = TdS − pdV (1)
Therefore, change in Internal energy (dU) can be
expressed in terms of two independent variables, S
and V
U = U(S, V)
 Fundamental Property Relations
U = U(S, V)
𝜕U 𝜕U
partial differential, dU = dS + dV (2)
𝜕S V 𝜕V S
Comparing (1) and (2)
𝜕U
T= (3)
𝜕S V
𝜕U
P= - (4)
𝜕V S
Note: {U, S, V} form a Fundamental Group
 Fundamental Property Relations
Four thermodynamic properties (U, H, A, G) are
collectively called thermodynamic potentials.
where
dA = − S dT − P dV = Change in Helmholtz free energy
dG = − S dT + V dP = Change in Gibbs free energy
H = U + PV = Enthalpy

Therefore,
{A, T, V} form a Fundamental Group
{G, T, P} form a Fundamental Group
 Fundamental Property Relations
Change in Enthalpy (dH) is given as
dH = dU + d(PV)
= T dS − P dV + P dV + V dP
dH = T dS + V dP (5)
Hence, {H, S, P} form a Fundamental Group
That is, change in Enthalpy (dH) can be expressed in
terms of two independent variables, S and P
H = H(S, P)
𝜕H 𝜕H
dH = dS + dP (6)
𝜕S P 𝜕P S
 Fundamental Property Relations
Compare (5) and (6)
𝜕𝐻
T= (7)
𝜕S P
𝜕H
V = (8)
𝜕P S
Similarly, from the fundamental group
dA = − S dT − P dV
𝜕A 𝜕A
S=- and P=-
𝜕T V 𝜕V T
Similarly, from the fundamental group, dG = − S dT + V dP
𝜕G 𝜕G
S=- and V=
𝜕T P 𝜕P T
 Example
Given that h = h(T, P), S = S(T, P).
𝜕S
Show that Cp = T( )p
𝜕T
Solution h = h(T, P)
𝜕h 𝜕h
dh = dT + dP
𝜕T P 𝜕P T
𝜕h
= CP dT + dP ……1
𝜕P T

S = S(T,P)
𝜕S 𝜕S
dS = dT + dP ……2
𝜕T P 𝜕P T
 recall that dh = T dS + V dP …….3
substitute eqn. 1 in 3
𝜕h
i.e. dh = CP dT + dP = T dS + V dP
𝜕P T

𝜕S 𝜕S
dh = T dT + dP + V dP
𝜕T p 𝜕P T

collect like terms

𝜕S 𝜕S 𝜕h
CP − T dT = T +𝑉 − dP
𝜕T P 𝜕P T 𝜕P T

𝜕S
At constant P, CP − T dT = 0
𝜕T P
𝜕S
hence CP = T
𝜕T P
 CHEMICAL POTENTIAL AND PARTIAL
PROPERTIES

Introduction
To establish the theoretical foundation for the
applications of thermodynamics to gas mixtures
and liquid solutions.
In chemical, petroleum and pharmaceutical
industries, gas and/or liquid compositions varied
and experienced change of phases, when
subjected to different processes.
 CHEMICAL POTENTIAL AND PARTIAL
PROPERTIES
• Chemical Potential connotes tendency of a system
to give/release particles.

• That is, energy associated with the release of

particles

• Particles move from a system (or region) of higher

chemical potential to that of lower chemical
potential.
 Introduction
For a single-phase fluid in a closed system involving
no chemical reaction
d nG = nv dP − ns dT (1)
[ i.e G= f (P, T) n = constant]
Eqn. (1) becomes
𝜕(nG)
= nv (2)
𝜕P T,n

and
𝜕(nG)
= - ns (3)
𝜕T P,n
 Introduction
Generally, for open or closed system (n ≠ constant).
That is, nG becomes a function of the numbers of moles
of the chemical species present (n is also a variable).
Hence
nG = f (P, T, n1 , n2 , … … … … … … … ni ) (4)
where ni = number of moles of species i.
The total differential of nG is then
𝜕(nG) 𝜕(nG) 𝜕(nG)
d(nG) = dP + dT + σ𝑖
𝜕P T,n 𝜕T P,n 𝜕ni P,T,n
j

(5)
where
i. nj indicates that all mole numbers excepts
the ith are constant.
𝜕(nG)
ii. by definition is referred to as
𝜕ni P,T,n
j
Chemical Potential of species i in the
mixtures, 𝝁𝒊 .
That is,
𝝏(𝒏𝑮)
𝝁𝒊 = (6)
𝝏𝒏𝒊 𝑷,𝑻,𝒏
𝒋

Substituting equations(2) and (3) in (5) gives

 d nG = nV dP − ns dT + σ𝑖 𝜇𝑖 dn𝑖 (7)
Equation (7) is the fundamental property relation for
single-phase fluid systems of variable mass and
composition.
𝑥𝑖
For One mole of solution (nT = 1 and ni = = 𝑥𝑖 )
1
𝐝𝐆 = 𝐕𝐝𝐏 − 𝐒𝐝𝐓 + σ𝒊 𝝁𝒊 d𝒙𝒊 (8)
That is, molar Gibbs energy is expressed in terms of
its variables
G = G(T, P, 𝑥1, 𝑥2, …………………. 𝑥𝑖 ……)
One can infer that
𝜕G
V= (9)
𝜕P T, 𝑥
 𝜕G
S=- (10)
𝜕T P, 𝑥
Other solution properties come from the definitions.
For example,
Enthalpy, H = G + TS becomes
𝜕G
H=G–T (11)
𝜕T P, 𝑥
Remark
When the Gibbs energy is expressed as a function of
its canonical variables, it plays the role of a
generating function, providing the means for the
calculation of other thermodynamics properties by
simple mathematical operations (differential and
elementary algebra) and implicitly represents
complete property information.
 Other Definitions of Chemical Potential
Consider the statement and diagram given below,
G P H

T S

A V U

Great People Have Studied

Under Very Able Teachers
 Other Definitions of Chemical Potential
Consider the fundamental grouping {U, S, V},
that is, U = U(S, V)
For a multi-component system (with N = 3), the
internal energy can be expressed as
U = U(S, V, n1 , n2 , n3 )
The differential change in U is given by
𝜕U 𝜕U
dU = ( )V, n1, n2 , n3 dS + ( )S, n1, n2, n3 dV
𝜕S 𝜕V
𝜕U 𝜕U
+ ( )S, V, n2, n3 dn1 + ( )S, V, n1 , n3 dn2
𝜕n1 𝜕n2
𝜕U
+ ( )S, V, n1, n2 dn3
𝜕n3
 Other Definitions of Chemical Potential
In general,
If U = U(S, V, n1 , n2 , ........., nT )
𝜕U 𝜕U nT 𝜕U
dU = ( )V, ni dS + ( )S, ni dV + σi=1( )S,V,nj dni
𝜕S 𝜕V 𝜕ni
Note:
• subscript j denotes a component different from i.
• the first two terms refer to conditions of constant
composition.
𝜕U 𝜕U
that is dU = ( )V dS + ( )S dV
𝜕S 𝜕V
 Other Definitions of Chemical Potential
𝜕U
From dU = ( )V, ni dS
𝜕S
𝜕U
+ ( )S, ni dV
𝜕V
nT 𝜕U
+ σi=1( )S,V,𝑛j d𝑛𝑖
𝜕ni
By definition, chemical potential (𝜇𝑖 )
𝛛𝐔
𝝁𝒊 = ( )𝐒,𝐕,𝒏𝒋 (12)
𝛛𝐧𝐢
Hence,
𝜕U 𝜕U nT
dU = ( )V, ni dS + ( )S, ni σ
dV + i=1 𝜇𝑖 d𝑛𝑖 (13)
𝜕S 𝜕V
 Other Definitions of Chemical Potential
Let us consider the diagram given again,
G P H G P H

T S T S

A V U A V U
Therefore
𝜕U 𝜕U
( )V,ni = T ( )S, ni =-P
𝜕S 𝜕V
 Other Definitions of Chemical Potential
When substituted, Equation 13 can now be written as
nT
dU = T dS - P dV + σi=1 𝜇𝑖 d𝑛𝑖 (14)
Add d(PV) to each side of the equation (14),
nT
dU + d(PV) = T dS - P dV + P dV + V dP + σi=1 𝜇𝑖 d𝑛𝑖
nT
dH = T dS + V dP + σi=1 𝜇𝑖 d𝑛𝑖 (15)
Subtract d(TS) from each side of Equation (14),
nT
dU - d(TS) = T dS - P dV – T dS – S dT + σi=1 𝜇𝑖 d𝑛𝑖
nT
dA = - S dT – P dV + σi=1 𝜇𝑖 d𝑛𝑖 (16)
 Other Definitions of Chemical Potential

Subtract d(TS) from each side of Equation 15 to yield

nT
dH – d(TS) = T dS + V dP – T dS - S dT + σi=1 𝜇𝑖 d𝑛𝑖
nT
dG = V dP – S dT + σi=1 𝜇𝑖 d𝑛𝑖 (17)

Remarks
• Equations 14 - 17 are applicable to open systems
where the change is from a transfer of matter.
• They are also applicable to closed systems where
change in the number of moles of one or more
components is caused by a chemical reaction.
 Other Definitions of Chemical Potential
𝜕U
G P H Recall that 𝜇𝑖 = ( )𝑆,𝑉,𝑛𝑗
𝜕𝑛𝑖
T S Similarly, by using Equations 15 -17,
A V U 𝜇𝑖 can also be defined in terms of H,
A, G.
That is,
𝜕H 𝜕A 𝜕G
𝜇𝑖 = ( )𝑃,S,𝑛𝑗 = ( ) 𝑇,𝑉,𝑛𝑗 = ( ) 𝑇,P,𝑛𝑗
𝜕𝑛𝑖 𝜕𝑛𝑖 𝜕𝑛𝑖
Assignment/Classwork
*Confirm these 3 equations using the diagram illustration
 Chemical Potential and Phase Equilibria
For a closed system having two phases in equilibrium and
there is mass transfer between the two phases, Equation
7 may be expressed as
d nG α = nV α dP - nS α dT + σ𝑖 𝜇𝑖 𝛼 dn𝑖 α (18)
d nG β = nV β dP - nS β dT + σ𝑖 𝜇𝑖 β dn𝑖 β (19)
where α and β represent the two phases.
At equilibrium, T and P are constant and change in total
Gibbs energy of the two phase system is given as
α β
d(nG) = d nG + d nG (20)
hence
d(nG) = d(nV)dP - d(nS)dT + σ𝑖 𝜇𝑖 𝛼 dn𝑖 α
+ σ𝑖 𝜇𝑖 β dn𝑖 β (21)
Since the system is closed, Equation (21) can be
compared to Equation (1) to give
σ𝑖 𝜇𝑖 𝛼 dn𝑖 α + σ𝑖 𝜇𝑖 β dn𝑖 β = 0 (22)
The changes dn𝑖 α and dn𝑖 β result from mass
transfer between the phases.
Applying mass conservation law,
dn𝑖 α = - dn𝑖 β (23)
Hence Equation (22) becomes
𝛼
σ𝑖(𝜇𝑖 - 𝜇𝑖 β )dn𝑖 α = 0 (24)
Since the quantities d n𝑖 α are independent and
arbitrary, Equation (24) is only valid if
𝜇𝑖 𝛼 - 𝜇𝑖 β = 0
that is
𝜇𝑖 𝛼 = 𝜇𝑖 β (i= 1, 2, ……..N) (25)
where
N = number of species present in the system
For multiple phases
𝜇𝑖 𝛼 = 𝜇𝑖 β = ………… 𝜇𝑖 𝜋 (i= 1, 2, ……..N) (26)
Remark: Thus multiple phases at the same T and P
are in equilibrium when the chemical potential of
each species is the same in all phases.
 Chemical Potential of a Single Phase
Pure Substance
For a single phase of a pure substance,
From d nG = nV dP − ns dT + σ𝑖 𝜇𝑖 dn𝑖
At constant T and P,
G = σ𝑖 n𝑗 𝜇𝑖
G=n𝜇 (a pure substance)
OR
𝐆
𝝁 = = 𝐠ത
𝐧
𝝁 Is the same as the gibbs function per mole
Example: An isolated system consists of two phases,
A and B. Each phase has two same substances, 1
and 2, and the phases are partition by a freely
moving thin wall permeable by substance 2 only. If
dSU,V = 0 at equilibrium, establish the necessary
equilibrium conditions.
Solution
Assumption:
Q = 0, W = 0, KE = 0, PE = 0
At equilibrium,
dSU,V = 0,
dSU,V = dSA + dSB = 0 …………^^^
nT
From eqn. (14) dU = T dS - P dV + σi=1 𝜇𝑖 d𝑛𝑖
dUA = TA dSA - PA dVA + μ1A dn1A + μA
2 dn A
2 ……*
Also
dUB = TB dSB - PB dVB + μ1B dn1B + μB2 dnB2 …..…**
Substance 1 does not flow,
so μ1A dn1A = μ1B dn1B = 0 (since dn1𝐴 = dn1B = 0)
For a rigid and insulated container,
dV = 0, i.e. dVB = - dVA
dU = 0, i.e. dUB = - dUA
Make dSA and dSB subjects of the formula in Eqn.
…...* and …...**, to give
dUA PA μA
dSA = + dVA - 2
dnA
2
TA TA TA
And
dUB PB μB
dSB = + dVB - 2
dnB2
TB TB TB
Substitute the last two Eqn. in
dSU,V = dSA + dSB = 0
i.e. dSU,V = dSA + dSB = 0
dUA PA μA
dSU,V = + dVA - 2
dnA
2
TA TA TA
dUB PB μB
+ + dVB - 2
dnB2 = 0
TB TB TB
hence
dUA dUB PA PB μA μB
+ + dVA + dVB - 2
dnA
2 -
2
dnB2
TA TB TA TB TA TB
=0
That is,
dUA dUA PA PB μA μB
- + dVA - dVA - 2
dnA
2 +
2
dnA
2 = 0
TA TB TA TB TA TB
So
1 1 PA PB
dUA { - } + dVA { - }
TA TB TA TB
μA μB
- dnA {
2 T
2
- 2
} = 0
A TB
Since dUA , dVA and dnA
2 are variable (i.e. ≠ 0)
Hence at equilibrium,
𝑻𝑨 = 𝑻𝐁
𝐏𝑨 = 𝐏𝑩
𝛍𝑨𝟐 = 𝛍𝐁𝟐
 Partial Molar Properties
A partial property is a property of a component in
solution or when mixed with other components.
Also, it is the rate at which any property (e.g U, S, A)
of a solution changes with respect to the number of
moles of any component in the solution at constant
Temperature, Pressure and composition of the
other components.
It can be determined from the slope of a plot of
property versus number of moles of a component
in solution at constant Temperature and Pressure.
For a molar thermodynamic property, M, that varies with
respect to T, P and n
nM = f(P, T, n1 , n2 , …………….. nn )
Total differential
𝜕(nM) 𝜕(nM)
d(nM) = dP + dT
𝜕P T, n 𝜕T P, n
𝜕(nM)
+ σ𝑖 dn𝑖 (27)
𝜕n𝑖 P,T,n
j

At constant T and P
𝜕(nM)
nM = σ n𝑖 (28)
𝜕n𝑖 P,T,n
j

𝜕(nM)
= 𝑀𝑖 (29)
𝜕n𝑖 P,T,n
j
Equation (29) is the partial property of component i in
solution.
Hence substitute (29) in (27)
𝜕(nM) 𝜕(nM)
d(nM) = dP + dT + σ𝑖 𝑀𝑖 dn𝑖
𝜕P T, n 𝜕T P, n
If expressed in terms of mole fractions, 𝑥𝑖 , for a total
mole of 1
𝜕M 𝜕M
dM = dP + dT + σ𝑖 𝑀𝑖 d𝑥𝑖 (30)
𝜕P T, 𝑥 𝜕T P, 𝑥
substitute (29) in (28)
nM = σ𝑖(𝑛𝑖 𝑀𝑖 ) (31)
To express Equation (31) in terms of mole fraction
M = σ𝑖(𝑥𝑖 𝑀𝑖 ) (32)
Equations (31) and (32) show that the
relationship between molar property (M)
and partial molar property (M𝑖 ).
Both equations are referred to as
summability relations.
That is, thermodynamic properties (such as H, U, V,
G, A, S) can be expressed in their partial molar
properties
For example: H𝑖 = U𝑖 + PVഥ𝑖
Gഥ𝑖 = H𝑖 - TSഥ𝑖
U𝑖 = TSഥ𝑖 - PVഥ𝑖
A𝑖 = U𝑖 - TSഥ𝑖
Note
i. partial properties are denoted by an overbar,
with a subscript to identify the species (i.e M𝑖 )

ii. M𝑖 can be partial specific property if mass is

considered or partial molar property if mole is
considered.
iii. the kinds of properties used in solution
thermodynamics are:
solution properties, M (such as V, U, H, S)
partial properties, M𝑖 (such as Vഥ𝑖 , U𝑖 , H𝑖 , Sഥ𝑖 )
 Gibbs/Duhem Equation
Is a general equation that relates M, M𝑖 , T, P and 𝑥ഥ𝑖

Total differentiation of Equation (32) gives

dM = σ𝑖 𝑥𝑖 𝑑𝑀𝑖 + σ𝑖 𝑀𝑖 d𝑥𝑖 (33)
Comparing (33) and (30)
𝜕M 𝜕M
dP + dT + σ𝑖 𝑀𝑖 d𝑥𝑖
𝜕P T, 𝑥 𝜕T P, 𝑥
= σ𝑖 𝑥𝑖 𝑑𝑀𝑖 + σ𝑖 𝑀𝑖 d𝑥𝑖
That is,
𝜕M 𝜕M
dP + dT - σ𝑖 𝑥𝑖 𝑑𝑀𝑖 = 0 (34)
𝜕P T, 𝑥 𝜕T P, 𝑥
Equation 34 is called Gibbs/Duhem Equation
At constant T and P,
σ𝑖 𝑥𝑖 𝑑𝑀𝑖 = 0 (35)
Writing partial molar property for Gibbs energy,
That is Equation 29 becomes
𝜕(nG)
Gഥ𝑖 = (36)
𝜕n𝑖 P,T,n
j

Compare Equation (6) and Equation (36) show that the

Chemical potential (𝜇𝑖 ) and the partial molar Gibbs
energy (Gഥ𝑖 ) are identical
that is, 𝜇𝑖 ≡ G𝑖 (37)
Application of Partial Properties To Binary System

Consider a binary mixture of two liquids with partial

volume VA and VB
From Equation 32
V = 𝑥A VA + 𝑥B VB
V = (1 - 𝑥B )VA + 𝑥B VB (38)
By differentiation
dV = - ( VA - VB ) d𝑥B (39)
Making VA and VB the subjects in Equation 39 and
substitute in Equation 38 give
 𝜕V
VA = V - 𝑥B (40)
𝜕𝑥B
and
𝜕V
VB = V + (1 - 𝑥B ) (41)
𝜕𝑥B
or
𝜕V
V = VA + 𝑥B (42)
𝜕𝑥B
From Equation 42, plot of V against 𝒙𝑩 can be
related to straight line graph that gives a slope of
𝝏𝐕
and intercept of 𝐕𝐀
𝝏𝒙𝐁
This is represented in graphical form as
Molar Vol. VB

VA

0 𝑥B mole fraction, 𝑥
Molar Volume (V) vs mole fraction for a binary system
N.B: As 𝑥B changes, the values of VA and VB change also.
 Example 1
Use graphical illustration to explain
𝜕M
M1 = M + 𝑥2 and
𝜕𝑥1
𝜕M
M2 = M - 𝑥1 for a binary system.
𝜕𝑥1
Solution
Plot of M vs 𝑥1 , for
constant T, P I1 a binary system.
M
The tangent line at
I2 𝑥1 intersects the
two edges (𝑥1 = 0
and 1) at points I2
and I1 .
0 𝑥1 1
Slope of the tangent line can be written in two
forms
𝜕M M −I2 M −I2
= = *
𝜕𝑥1 𝑥1 − 0 𝑥1
and
𝜕M I1 −I2
= = I1 − I2 **
𝜕𝑥1 1−0
𝝏𝑴
from *, 𝐈𝟐 = M - 𝒙𝟏 ***
𝝏𝒙𝟏
substitute *** in **
𝜕M 𝜕M
= I1 − M + 𝑥1
𝜕𝑥1 𝜕𝑥1
that is,
𝝏𝑴
𝐈𝟏 = M + (1 - 𝒙𝟏 ) #
𝝏𝒙𝟏
comparing *** and # with the two given expressions
shows that
𝐈𝟏 = 𝐌𝟏 and 𝐈𝟐 = 𝐌𝟐
That is, the tangent intercepts give directly the
values of the two partial properties.
These intercepts shift as the point of tangency
moves along the curve.
 Example 2
Determine the partial molar volume of the two
components at 𝑥B = 0.4, using the following
experimental data at constant pressure for a binary
system.
𝑥B 0.0 0.2 0.4 0.6 0.8 1.0
Molar Volume, V, (cm3 /gmol) 89.27 100.57 103.34 102.60 100.21 97.19

solution
V From the plot at 𝑥B = 0.4,

𝐕𝐁 and 𝐕𝐀 can be read by

drawing tangential line at this
point.
𝐕𝐀 = 101.80 cm3 /gmol
0 0.4 𝑥B 1 𝐕𝐁 = 106.00 cm3 /gmol
 Example 3
Determine the partial molar volumes of liquid mixture of
cyclohexane (A) and carbon tetrachloride (B) at 1 atm and 60 deg.C
at 𝑥B = 0.6, using the data below.
𝑥i 0.00 0.04 0.08 0.15 0.30 0.50 0.70 0.85 0.92 0.96 1.00
V 101. 101. 102. 103. 105. 107. 110. 111. 112. 113. 113.64
cm3 /gmol 46 97 48 37 25 72 13 89 71 18

solution
V From the plot at 𝑥B = 0.6,

𝐕𝐁 and 𝐕𝐀 can be read by

drawing tangential line at this
point.
i.e 𝐕𝐀 = 101.7 cm3 /gmol
0 𝑥B 0.6 1 𝐕𝐁 = 113.7 cm3 /gmol
 Example 4
2,000 cm³ of an antifreeze consisting of 30 mol% methanol in
water is to be prepared. What volumes of pure methanol and of
pure water at 25⁰C must be added? Partial molar volumes for
methanol and water in a 30mol% methanol solution and their
molar volumes (at 25⁰C) are given thus:
Methanol (1): vഥ1 = 38.632 cm³/mol v1 = 40.727 cm³/mol
Water (2): v2 = 17.765 cm³/mol v2 = 18.068 cm³/mol
Solution:
Molar solution volume at 30mol% methanol is
𝑉 σ𝑚 ഥ
𝑖 𝑛𝑖 V𝑖
V =
𝑛T
= = σ𝑚 ഥ ഥ ഥ
𝑖 𝑥𝑖 V𝑖 = 𝑥1 V1 + 𝑥2 V2
𝑛T
V = 0.3(38.632) + 0.7(17.765) = 24.025 cm³/mol
 Example 4
For the mixture,
𝑉 2000
𝑛T = = = 83.246 mole
𝑣 24.025
Volume of pure methanol, V1
= 𝑥1 𝑛T v1 = 0.3(83.246)(40.727) = 1017cm³
[n.b. mole of methanol = 0.3(83.246)]
Volume of pure water, V2
= 𝑥2 𝑛T v2 = 0.7(83.246)(18.068) = 1053cm³
 Example 5
20 wt% chloroform solution is obtained by mixing
chloroform, CHCl₃, with acetone, C₃H₆O, in an
insulated mixer at steady state. For every gram of
solution, 9.83 J is removed to keep the system
temperature constant at 14 ⁰C. Determine the
enthalpy of mixing for this solution.
 solution
n1 , h1 Q
n2 , h2 (n1 +n2 ), h

Chloroform (1), CHCl₃ MW1 = 119.39

Acetone (2), C₃H₆O MW2 = 58.08
For 100g of solution,
n1 = 20/119.39 = 0.1675 mol CHCl₃
n2 = 80/58.08 = 1.3774 mol C₃H₆O
nT = n1 +n2 = 0.1675 + 1.3774 = 1.5449 mol
According to 1st Law,
n1 h1 + n2 h2 – (n1 +n2 )h – Q = 0
divide by n1 +n2 , – Q/(n1 +n2 ) = h – (x1 h1 + x2 h2 )
x = mole fraction
Δhmix = – Q/nT = -q = h – (x1 h1 + x2 h2 )
since x1 = 0.1675/1.5449 = 0.1084
x2 = 1.3774/1.5449 = 0.8916
Heat of mixing = heat removed per mole of solution
Δhmix = – Q/nT = - q = - 𝑞(x
ො 1 MW1 + x2 MW2 )
= - (9.83)(0.1084x119.39 + 0.8916x58.08)
Δhmix = 636.3 J/mol
 Example 6
5 wt% H2SO4 solution at 60 0F was concentrated to
45 wt% H2SO4 solution by the evaporation of water.
Both the concentrated solution and water vapour
left the evaporator at 180 0F. Using the Enthalpy-
concentration chart for H2SO4-H2O and assume that
the enthalpy of water vapour at 180 0F is 1138
Btu/ib, calculate the rate at which heat was supplied
(in Btu/hr) to the evaporator to process 500 ib/hr of
the feed solution.
 Q
5 wt% soln water vapour m1 , hv
500 ib/hr 45 wt% soln m2 , h0
hf
Solution
Taking material balance for Acid
0.05(500) = 0.45(m2 )
0.05(500)
hence m2 = = 55.56 lb/hr
0.45
The mass rate of water vapour leaving the evaporator
m1 = 500 - 55.56 = 444.44 ib/hr
From the Chart,
Enthalpy of the 5wt% Feed solution at 60 0F
hf = 10 Btu/lb
 Enthalpy of the 45wt% solution at 180 0F
ho = -30 Btu/lb
Enthalpy of water vapour at 180 0F
hv = 1130 Btu/lb (given)
Taking Energy balance of the evaporator
Q = 444.44 hv + 55.56ho - 500hf
= 444.44(1130) + 55.56(-30) - 500(10)
= 495550.4 Btu/hr
Rate of heat supplied = 495550 Btu/hr
 FUGACITY (Introduction)
• Recall, conditions for phase equilibrium are 𝐓𝐀 =𝐓𝐁 ,
𝑨 𝑩
𝐏𝐀 =𝐏𝐁 and 𝝁𝒊 =𝝁𝒊 (i components, A & B = phases).
• If 𝑮 can be calculated, then 𝝁𝒊 can be calculated
(they are the same, at the prevailing condition).
• But it is difficult to obtain correlations for 𝝁𝒊 . Hence
an auxiliary function that is more convenient to
compute than the chemical potential ( 𝝁𝒊 ), but
provide similar or same effect (role), is needed.
• This auxiliary function is called fugacity, f
 FUGACITY
• Characterizes the escaping tendency of a
component.

• Fugacity is a derived thermodynamic property that

has the unit of pressure.

• It is an abstract concept defined to facilitate

certain calculations involved in phase and chemical
equilibrium.
• Fugacity is used for gases or for liquids that can be
described using Equations of State (EOS).
 FUGACITY
For a pure substance at given T and P,
dG = V dP − S dT
At constant T, dG = V dP
and for pure substance, dG = dμ
RT
For an ideal gas, V = (an EOS)
P
RT dP
hence dμ = dP = RT = RT d (ln P)
P P
A function, f, that is like the pressure for a real fluid
(gas or liquid) can be defined in the form
dμ = RT d (ln f)
 FUGACITY
• A plot of μ for an ideal and real gas is shown as a
function of the pressure at constant T.
• f has the units of pressure and as P approaches 0,
the real gas approach the
ideal gas behavior
and f approaches P.

note: P⁰ = 1 atm.
 FUGACITY
RT
For a real gas, V ≠
P
However, a function, f, called fugacity is introduced
so that the change in chemical potential with respect
to P is given by an expression similar to equation.
i.e. dμ = RT d(ln f )
Integrating between a reference state (⁰) and the
state of the system yields
𝑓
μ - μ0 = RT ln ( 0)
𝑓
𝑓
so μ = μ0 + RT ln ( 0)
𝑓
 FUGACITY
Similarly, the fugacity, 𝑓መ𝒊 , of a specie in solution is
defined as
0 𝑓መ𝒊
μ𝑖 - μ𝑖 = RT ln ( መ 0)
𝑓𝒊
0 𝑓መ𝒊
μ 𝑖 = μ𝑖 + RT ln ( መ 0)
𝑓𝒊
For phases A and B in equilibrium,
μ A = μ B,
𝑖 𝑖

Using μ𝑖 A = μ𝑖 B , the above equation becomes

𝑓መ𝑖
A B
0,A 𝑓መ𝑖
μ𝑖 + RT ln ( ) = μ𝑖 0,B + RT ln ( B)
0,A 0,
𝑓መ𝒊 𝑓መ𝑖
 FUGACITY
Rearrange
0,A B
0,A 0,B 𝑓መ𝒊 𝑓መ𝑖
μ𝑖 - μ𝑖 = RT ln (
B ) + RT ln ( A)
0,
𝑓መ𝒊 𝑓መ𝑖

The 1st - 3 terms of the equation are parts of the

0 𝑓መ𝒊
definition of fugacity given as μ𝑖 - μ𝑖 = RT ln ( መ 0)
𝑓𝒊
0,A
0,A 0,B 𝑓መ𝒊
Hence, μ𝑖 - μ𝑖 = RT ln ( 0,B )
𝑓መ𝒊
መ
𝑓𝑖
B
Therefore, 0 = RT ln ( A)
𝑓መ𝑖
෠ A ෠ B
⟹ 𝒇𝒊 = 𝒇𝒊 This forms the criterion for phase
equilibrium in terms of fugacity.
 FUGACITY COEFFICIENT
• If fugacity is an “effective pressure” , that is, the
pressure that gives the right value for the chemical
potential of a real gas. So, the only way we can get
a value for it and hence for µ is from the gas
pressure.
• Thus a relation between the effective pressure (f)
and the measured pressure (P) is needed.
let f = φ p
• φ is defined as the fugacity coefficient.
f
Hence φ =
𝐩
 Exercise1
Determine the partial molar volumes of liquid mixture
of cyclohexane (A) and carbon tetrachloride (B) at 1 atm
and 60 0C at the point 𝑥A = 0.6, using the data below

𝑥A 0.0 0.0 0.0 0.1 0.3 0.5 0.7 0.8 0.92 0.96 1.0
0 4 8 5 0 0 0 5 0
V 101 101 102 103 105 107 110 111 112. 113. 113
cm3 /g .46 .97 .48 .37 .25 .72 .13 .89 71 18 .64
mol
 Exercise2
3,000 cm³ of an antifreeze consisting of 40 mol%
methanol in water is to be prepared. What volumes of
pure methanol and of pure water at 25⁰C must be
added? Partial molar volumes for methanol and water
in a 40mol% methanol solution and their molar
volumes (at 25⁰C) are given thus:
Methanol (1): v1 = 38.632 cm³/mol
v1 = 40.727 cm³/mol
Water (2): v2 = 17.765 cm³/mol
v2 = 18.068 cm³/mol
 Exercise3
For two multicomponent phases in equilibrium in a
solution system, show that:
α β
𝑓෡𝑖 = 𝑓෡𝑖
where,
α, β= different phases in the solution system

i = component in the solution system

𝑓መi = fugacity of component i in the solution
system.