Chemical Engineering

Thermodynamics II

CHE 435
(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 thermodynamics text

Grading
Assignments/Tests = 30 marks
Examination = 70 marks
 Fundamental Property Relations

OBJECTIVE:
The inter-relations of the thermodynamic
properties are expressed in mathematic forms (as
much as reasonably possible) in other to obtain
expressions or magnitudes of unknown properties,
using the known or given properties. This is the
singular objective in this section.
 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
Four thermodynamic properties (U, H, A, G) are
collectively called thermodynamic potentials.
 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=- (9)
𝜕T V 𝜕V T
Similarly, from the fundamental group, dG = − S dT + V dP
𝜕G 𝜕G
S=- and V= (10)
𝜕T P 𝜕P T
Simple Ways To Determine These Expressions

Consider the illustration and statement provided

below (obtained from the 4 Fundamental Groups),
G P H

T S

A V U
Great People Have Studied
Under Very Able Teachers
Simple Ways To Determine These Expressions

Consider the patterns drawn on the diagrams below

G P H G P H

T S T S

A V U A V U

𝜕𝐻 𝜕U
T= and T=
𝜕S P 𝜕S V
Simple Ways To Determine These Expressions

Consider the patterns drawn on the diagrams below,

G P H G P H

T S T S

A V U A V U

𝜕U 𝜕A
P=- and P=-
𝜕V S 𝜕V T
Simple Ways To Determine These Expressions

Consider the patterns drawn on the diagrams below,

G P H G P H

T S T S

A V U A V U

𝜕A 𝜕G
S=- and S=-
𝜕T V 𝜕T P
Simple Ways To Determine These Expressions

Consider the patterns drawn on the diagrams below,

G P H G P H

T S T S

A V U A V U

𝜕H 𝜕G
V= and V=
𝜕P S 𝜕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
equate 1 and 3 and then substitute for dS
𝜕h
dh = CP dT + dP = T dS + V dP
𝜕P T

𝜕S 𝜕S
= T dT + dP + V dP
𝜕T p 𝜕P T

collect like terms

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

𝜕S
At constant P, CP − T dT = 0
𝜕T P
𝜕S
hence CP = T
𝜕T P
 Example
For the functions x = x(y, w), y = y(z, w), z = z(x, w)
𝜕x 𝜕y 𝜕z
demonstrate that = 1 at constant w
𝜕y w 𝜕z w 𝜕x w

Solution
x = x(y, w)
𝜕x 𝜕x
dx = dy + dw ……1
𝜕y w 𝜕w y
𝜕y 𝜕y
dy = dz + dw ….…2
𝜕z w 𝜕w z
𝜕z 𝜕z
dz = dx + dw ….…3
𝜕x w 𝜕w x
substitute eqn. 2 in 1
𝜕x 𝜕y 𝜕y 𝜕x
dx = dz + dw + dw
𝜕y w 𝜕z w 𝜕w z 𝜕w y

𝜕x 𝜕y 𝜕x 𝜕y 𝜕x
= dz + + dw
𝜕y w 𝜕z w 𝜕y w 𝜕w z 𝜕w y

………4
substitute eqn. 3 in 4
𝜕x 𝜕y 𝜕z 𝜕z
dx = dx + dw
𝜕y w 𝜕z w 𝜕x w 𝜕w x

𝜕x 𝜕y 𝜕x
+ + dw
𝜕y w 𝜕w z 𝜕w y
 𝜕x 𝜕y 𝜕z
dx = dx
𝜕y w 𝜕z w 𝜕x w

𝜕x 𝜕y 𝜕z 𝜕x 𝜕y 𝜕x
+ + + dw
𝜕y w 𝜕z w 𝜕w x 𝜕y w 𝜕w z 𝜕w y

rearrange
𝜕x 𝜕y 𝜕z
1 − dx
𝜕y w 𝜕z w 𝜕x w

𝜕x 𝜕y 𝜕z 𝜕x 𝜕y 𝜕x
= + + dw
𝜕y w 𝜕z w 𝜕w x 𝜕y w 𝜕w z 𝜕w w
At constant w, (dw = 0)
i.e.
𝜕x 𝜕y 𝜕z
1 − dx = 0
𝜕y w 𝜕z w 𝜕x w

hence
𝜕x 𝜕y 𝜕z
1 − =0
𝜕y w 𝜕z w 𝜕x w

so
𝜕x 𝜕y 𝜕z
=1
𝜕y w 𝜕z w 𝜕x w
 Exercise
Given that h = h(T, P) and S = S(T, P).
Show that
𝜕V
dh = CP dT + [V - T ] dP and
𝜕T P
𝑑𝑇 𝜕V
dS = CP - dP
𝑇 𝜕T P
 MODULE TWO

CHEMICAL POTENTIAL,
PARTIAL PROPERTIES
AND FUGACITY
 CHEMICAL POTENTIAL, PARTIAL
PROPERTIES AND FUGACITY

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 experience migration/change in phases when
subjected to different operating
conditions/processes.
 CHEMICAL POTENTIAL, PARTIAL
PROPERTIES AND FUGACITY
• Chemical potential connotes tendency of a system
to give/release particles.
• It is the energy associated with the release of
particles in a multicomponent system.

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

chemical potential to that of lower chemical
potential.
• Chemical potential helps to predict the movement
direction of molecules/components.
 CHEMICAL POTENTIAL, PARTIAL
PROPERTIES AND FUGACITY
• For example, benzoic acid molecules in benzene
distribute themselves in between the two clear
layers of benzene and water
• Addition of Ether to the brown solution of (Water
+ Iodine) gives an upper brown layer of (Ether +
Iodine) and lower layer of colourless Water, due to
chemical potential.
• Consider Ca(OH)2 + CO2 CaCO3 + H20
-879 -394 -1129 -237 kJ/mol
Determine the direction of the reaction in attaining
equilibrium.
 Introduction
For a constant mole (n) system involving no chemical
reaction
d nG = nv dP − ns dT (1)
[ i.e G= f (P, T) n = constant]
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 (since 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
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 canonical 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 all 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 also applicable to open
systems where the change is from a transfer of
matter.
• They are also applicable to closed systems where
the 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