Chemical Engineering

Thermodynamics II

CHE 415
(2 Units)

Dr. Ayoola Ayodeji

 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 = Q rev + Wrev
From the second law, Q rev = 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)

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
Simple Ways To Determine These Expressions

Consider the statement and diagram provided thus,

G P H

T S

A V U
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Note: Obtained from the 4 Fundamental Groups
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
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
CHEMICAL POTENTIAL
AND
PARTIAL PROPERTIES
 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.
 Introduction
For a single-phase fluid in a closed system involving
no chemical reaction
d nG = nV dP ns dT (1)
becomes
(nG)
= nV (2)
P T,n

and
(nG)
= - nS (3)
T P,n
 Introduction
For an open system, n may not be constant.
That is, nG becomes a function of the numbers of moles
of the chemical species present.
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) ()
d(nG) = dP + dT +
P T,n T P,n ,,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, .
That is,
(nG)
= (6)
ni P,T,n
j

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

 d nG = nV dP ns dT + dn (7)
Equation (7) is the fundamental property relation for
single-phase fluid systems of variable mass and
composition.

For One mole of solution (nT = 1 and ni = = )
1
dG = VdP SdT + d (8)
That is, molar Gibbs energy is expressed in terms of
its canonical variables
G = G(T, P, 1, 2, . )
One can infer that
G
V= (9)
P T,
 G
S=- (10)
T P,
Other solution properties come from the definitions.
For example,
Enthalpy, H = G + TS becomes
G
H=GT (11)
T P,
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

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 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 + i=1(ni )S,V,j d
S V
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
+ i=1( )S,V,j d
ni
By definition, chemical potential ( )

= ( ),, (12)

Hence,
U U nT
dU = ( )V, ni dS + ( )S, ni dV + i=1 d (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 + i=1 d (14)
Add d(PV) to each side of the equation (14),
nT
dU + d(PV) = T dS - P dV + P dV + V dP + i=1 d
nT
dH = T dS + V dP + i=1 d (15)
Subtract d(TS) from each side of Equation (14),
nT
dU - d(TS) = T dS - P dV T dS S dT + i=1 d
nT
dA = - S dT P dV + i=1 d (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 + i=1 d
nT
dG = V dP S dT + i=1 d (17)
Remarks
Equations 14 - 17 are applicable to closed systems
where the change in the number of moles of one or
more components is caused by a chemical reaction.
They are also applicable to open systems where the
change is from a transfer of matter.
 Other Definitions of Chemical Potential
U
G P H Recall that = ( ),,

T S Similarly, by using Equations 15 -17,
A V U can also be defined in terms of H,
A, G.
That is,
H A G
= ( ),S, = ( ) ,, = ( ) ,P,

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 = nV dP - nS dT + dn (12)
d nG = nV dP - nS dT + dn (13)
where and represent the two phases.
At equilibrium, T and P are constant and change in total
Gibbs energy of the two phase system is

d(nG) = d nG + d nG (14)
hence

d(nG) = d(nV)dP - d(nS)dT +
dn
+ dn (15)
Since the system is closed, Equation (15) can be
compared to Equation (1) to give


dn +
dn =0 (16)
The changes dn and dn result from mass
transfer between the phases.
Applying mass conservation law,
dn = - dn (17)
Hence Equation (16) becomes

(
- )dn = 0 (18 )
Since the quantities d n are independent and
arbitrary, Equation (18) is only valid if
- = 0
that is
= (i= 1, 2, ..N) (19)
where
N = number of species present in the system
For multiple phases
= = (i= 1, 2, ..N) (20)
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.
 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)
+ n dn (21)
P,T,nj
At constant T and P
(nM)
nM = n (22)
n P,T,n
j

(nM)
= (23)
n P,T,n
j
Equation (23) is the partial property of component i in
solution.
Hence substitute (23) in (21)
(nM) (nM)
d(nM) = dP + dT + dn
P T, n T P, n
If expressed in terms of mole fractions, , for a total
mole of 1
M M
dM = dP + dT + d (24)
P T, T P,
substitute (23) in (22)
nM = ( ) (25)
To express Equation (25) in terms of mole fraction
M = ( ) (26)
Equations (25) and (26) show that the
relationship between molar property (M)
and partial molar property (M ).
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: H = U + PV
G = H - TS
U = TS - PV
A = U - TS
Note
i. partial properties are denoted by an overbar,
with a subscript to identify the species (i.e M )

ii. M 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, M (such as V , U , H , S )
 Gibbs/Duhem Equation
Is a general equation that relates M, M , T, P and

Total differentiation of Equation (26) gives

dM = + d (27)
Comparing (27) and (24)
M M
dP + dT + d
P T, T P,
= + d
That is,
M M
dP + dT - = 0 (28)
P T, T P,
Equation 28 is called Gibbs/Duhem Equation
At constant T and P,
= 0 (29)
Writing partial molar property for Gibbs energy,
That is Equation 23 becomes
(nG)
G = (30)
n P,T,n
j

Compare Equation (6) and Equation (30) show that the

Chemical potential ( ) and the partial molar Gibbs
energy (G ) are identical
that is, G (31)
Application of Partial Properties To Binary System

Consider a binary mixture of two liquids with partial

volume VA and VB
From Equation 26
V = A VA + B VB
V = (1 - B )VA + B VB (32)
By differentiation
dV = - ( VA - VB ) dB (33)
Making VA and VB the subjects in Equation 33 and
substitute in Equation 32 give
 V
VA = V - B (34)
B
and
V
VB = V + (1 - B ) (35)
B
or
V
V = VA + B (36)
B
From Equation 36, plot of V against can be
related to straight line graph that gives a slope of

and intercepts of (and )

this is represented in graphical form as

Molar Vol. VB

VA

0 B mole fraction,
Molar Volume (V) vs mole fraction for a binary system
N.B: As B changes, the values of VA and VB change also.
 Example
Use graphical illustration to explain
M
M1 = M + 2 and
1
M
M2 = M - 1
1
Solution
Plot of M vs 1 , for
constant T, P I1 a binary system.
M
The tangent line at
I2 1 intersects the
two edges (1 = 0
and 1) at points I2
and I1 .
0 1 1
Slope of the tangent line can be written in two
forms
M M I2 M I2
= = *
1 1 0 1
and
M I1 I2
= = I1 I2 **
1 10

from *, = M - ***

substitute *** in **
M M
= I1 M + 1
1 1
that is,

= M + (1 - ) #

comparing *** and # with the two given expressions
shows that
= and =
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 B = 0.4, using the following
experimental data at constant pressure for a binary
system.
B 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 B = 0.4,

and can be read by

drawing tangential line at this
point.
= 101.80 cm3 /gmol
0 0.4 B 1 = 106.00 cm3 /gmol