CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 3/29/2013

1
SOLUTION THERMODYNAMICS:
THEORY
The purpose of this chapter is to express the theoretical foundation for
applications of thermodynamics to gas mixtures and liquid solutions.
Separation processes of multicomponent gases and liquids in chemical,
petroleum and pharmaceutical industries commonly undergo composition
changes, transfer of species from one phase to another and chemical
reaction.Thus compositions become essential variables, along with
temperature and pressure.
This chapter introduce new property, i.e. chemical potential which facilitate
treatment of phase and chemical reaction equilibria; partial properties which
are properties of individual species as they exist in solution; and fugacity
which provide treatment for real gas mixtures through mathematical
formulation.
Another solution properties known as excess properties, is the deviation
from ideal solution property.
2
FUNDAMENTAL PROPERTY RELATION
THE CHEMICAL POTENTIAL AND PHASE
EQUILIBRIA
PARTIAL PROPERTIES


3
The most important property relation is that of Gibbs free energy change.
Gibbs energy:
Multiplied by n and differentiated eq. (6.3):

Enthalpy:

Multiplied by n, differentiated

The first Tds relation or Gibbs equation:


Combine eq. (2.11a) and (6.1):


Combine eq. (6.3a) and (6.4) to yield:



4
( ) ( ) ( ) d nU Td nS Pd nV = (6.1)
G H TS (6.3)
( ) ( ) ( ) ( ) d nG d nH Td nS nS dT =
H U PV + (2.11)
( ) ( ) ( ) d nH Td nS nV dP = +
(6.4)
( ) ( ) ( ) d nG nV dP nS dT = (6.6)
( ) ( ) ( ) ( ) d nH d nU Pd nV nV dP = + +
(6.3a)
(2.11a)
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 3/29/2013
2
Equation (6.6) relates the total Gibbs energy of any closed system to
temperature and pressure.
An appropriate application is to a single phase fluid in a closed system
wherein no chemical reactions occur. For such a system the composition
is necessarily constant, and therefore



The subscript n indicates that the numbers of moles of all chemical species
are held constant.
For more general case of a single phase, open system, material may pass
into and out of the system, and nG becomes a function of the numbers of
moles of the chemical species present, and still a function of T and P.


where n
i
is the number of moles of species i.



5
( ) ( )
, , T n P n
nG nG
nV and nS
P T
c c ( (
= =
( (
c c

(A)
( )
1 2
, , , ,..., ,...
i
nG g P T n n n =
Total differential of nG is



The summation is over all species present, and subscript n
j
indicates that
all mole numbers except the ith are held constant.
The derivative in the final term is called the chemical potential of species i
in the mixture. It is define as



With this definition and with the first two partial derivatives [eqn. (A)]
replaced by (nV) and (nS), the preceding equation [eqn. (B)] becomes


Equation (11.2) is the fundamental property relation for single phase fluid
systems of variable mass and composition.



6
( )
, ,
i
i P T nj
nG
n

( c

(
c

(11.1)
( )
( ) ( )
, , , ,
i
i i T n P n P T nj
nG nG nG
d nG dP dT dn
P T n
( c c c ( (
= + +
( ( (
c c c
(B)
( ) ( ) ( )
i i
i
d nG nV dP nS dT dn = +
(11.2)
For special case of one mole of solution, n = 1 and n
i
= x
i
:


This equation relates molar Gibbs energy to T, P and {xi}.


For special case of a constant composition solution:


Although the mole numbers n
i
of eq. (11.2) are independent variables, the
mole fractions x
i
in eq. (11.3) are not, because
i
x
i
= 1. Eq. (11.3) does
imply


Other solution properties come from definitions; e.g., the enthalpy, from
H = G + TS.Thus, by eq. (11.5),



7
i i
i
dG VdP SdT dx = +

(11.3)
dG VdP SdT = (6.10)
( )
1 2
, , , ,..., ,...
i
G G P T x x x =
, P x
G
S
T
c | |
=
|
c \ .
, T x
G
V
P
c | |
=
|
c \ .
(11.5)
(11.4)
, P x
G
H G T
T
c | |
=
|
c \ .
For a closed system consisting of two phases in equilibrium, each individual
phase is open to the other, and mass transfer between phases may occur.
Equation (11.2) applies separately to each phase:





where superscripts o and | identify the phases.
The presumption here is that equilibrium implies uniformity of T and P
throughout the entire system.
The change in the total Gibbs energy of the two phase system is the sum
of these equations.

8
( ) ( ) ( )
i i
i
d nG nV dP nS dT dn
o o o o o
= +

( ) ( ) ( )
i i
i
d nG nV dP nS dT dn
| | | | |
= +

( ) ( ) ( ) ( ) ( ) ( )
i i i i
i i
d nG d nG nV nV dP nS nS dT dn dn
o | o | o | o o | |
( ( + = + + + +


CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 3/29/2013
3

When each total system property is expressed by an equation of the form,


the sum is


Because the two phase system is closed, eq. (6.6) is also valid. Comparison
of the two equations shows that at equilibrium,


The changes dn
i
o
and dn
i
|
result from mass transfer between the phases;
mass conservation therefore requires


9
( ) ( ) nM nM nM
o |
= +
( ) ( ) ( )
i i i i
i i
d nG nV dP nS dT dn dn
o o | |
= + +

0
i i i i
i i
dn dn
o o | |
+ =

( ) 0
i i i i i
dn dn and dn
o | o | o
= =

( ) ( ) ( ) d nG nV dP nS dT = (6.6)
Quantities dn
i
o
are independent; therefore the only way the left side of the
second equation can in general be zero is for each term in parentheses
separately to be zero. Hence,


where N is the number of species present in the system.
For multiple phases (t phases):






Example:A glass of liquid water with ice cubes in it.When the chemical
potential of ice is larger than water, the ice melts (i.e. above 0
o
C).When
chemical potential of water is larger than ice, the water freezes (i.e. below
0
o
C ).Water and ice are in equilibrium when their chemical potential are the
same (i.e. at 0
o
C).


10
( ) 1, 2,...,
i i
i N
o |
= =
( ) ... 1, 2,...,
i i i
i N
o | t
= = = = (11.6)
Multiple phases at the same T and P are in equilibrium when the
chemical potential of each species is the same in all phases.
A chemical species is transported from a phase of larger potential
to a phase of lower potential.
A species exhibits its pure property when no other species exist with it,
i.e. pure component exhibits pure properties.
Species exhibits its partial property when it co-exists with other species in
a mixture or solution.
Partial molar property of a species i in a solution is define as



It is the change of total property nM to the addition of a differential
amount of species i to a finite amount of solution at constant T and P.
Three kinds of properties used in solution thermodynamics are
distinguished by the following symbolism:
Solution properties M, for example: V, U, H, S, G
Partial properties , for example:
Pure species properties M
i
, for example: V
i
, U
i
, H
i
, S
i
, G
i

i M

11
( )
_
, ,
i
i P T nj
nM
M
n
( c

(
c

(11.7)
i M

, , , ,
i i i i i
V U H S G

11
When one mole of water is added to a large volume of water at 25C, the
volume increases by 18cm
3
.The molar volume of pure water would thus
be reported as 18cm
3
mol
-1
.
However, addition of one mole of water to a large volume of pure ethanol
results in an increase in volume of only 14cm
3
.The value 14cm
3
is said to
be the partial molar volume of water in ethanol.
In general, the partial molar volume of a substance i in a mixture is the
change in volume per mole of i added to the mixture.




* The increase in volume is different due to intermolecular forces between molecules, size
and shape of molecules are different in mixture rather than pure species.


12
( )
_
, ,
i
i
P T nj
nV
V
n
( c

(
c

CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 3/29/2013
4
Total thermodynamic properties of a homogeneous phase are functions of T, P,
and the numbers of moles of the individual species which comprise the phase.
Thus, for property M:


The total differential of nM is




where subscript n indicates that all mole numbers are held constant, and
subscript n
j
that all mole numbers except n
i
are held constant.
Because the first two partial derivatives on the right are evaluated at constant
n and because the partial derivative of the last term is given by eq. (11.7), this
equation has the simpler form:




where subscript x denotes differentiation at constant composition.
( )
( ) ( )
, ,
i i
i T x P x
M M
d nM n dP n dT Mdn
P T

c c | | | |
= + +
| |
c c \ . \ .

13
( )
1 2
, , , ,..., ,...
i
nM T P n n n = M
( )
( ) ( ) ( )
, , , ,
i
i i T n P n P T nj
nM nM nM
d nM dP dT dn
P T n
( c c c ( (
= + +
( ( (
c c c

(11.9)
13
Because n
i
= x
i
n,

Moreover,

When dn
i
and d(nM) are replaced in Eq. (11.9), it becomes



The terms containing n are collected and separated from those containing
dn to yield



The left side of this equation can be zero if each term in brackets be zero
too.Therefore,



14
i i i
dn x dn ndx = +
( ) d nM ndM Mdn +
( )
, ,
i i i
T x P x i
M M
ndM Mdn n dP n dT M x dn ndx
P T

c c | | | |
+ = + + +
| |
c c \ . \ .

, ,
0
i i i i
T x P x i i
M M
dM dP dT M dx n M x M dn
P T
( c c ( | | | |
+ =
| | ( (
c c \ . \ .

, ,
i i
T x P x i
M M
dM dP dT Mdx
P T

c c | | | |
= + +
| |
c c \ . \ .
(11.10) i i
i
M x M

=
(11.11)
Multiplication of eq.(11.11) by n yields the alternative expression:


Equations (11.11) and (11.12) are known as summability relations, they
allow calculation of mixture properties from partial properties.
Differentiate eq. (11.11) yields:


Comparison of this equation with eq. (11.10), yields the Gibbs/Duhem
equation:


For changes at constant T and P,
15
i i
i
nM n M

=

(11.12)
, ,
0
i i
T x P x i
M M
dP dT x d M
P T

c c | | | |
+ =
| |
c c \ . \ .

0
i i
i
x d M

i
i i i
i i
dM x d M M dx

= +

(11.13)
(11.14)
Partial properties have all characteristics of properties of individual species
as they exist in solution.Thus, they may be assigned as property values to
the individual species.
Partial properties, like solution properties, are functions of composition.
In the limit as a solution becomes pure in species i, both M and
approach the pure species property M
i
.


For a species that approaches its infinite dilution limit, i.e., the values as its
mole fraction approaches zero, no general statements can be made.Values
come from experiment or from models of solution behavior. By definition,
16
i M

1 1
lim lim
i i
i i
x x
M M M

= =
0
lim
i
i i
x
M M

CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 3/29/2013
5
Equations for partial properties can be summarized as follows:
Definition:


which yields partial properties from total properties.
Summability:


which yields total properties from partial properties.
Gibbs/Duhem:


which shows that the partial properties of species making up solution
are not independent of one another.

17
( )
_
, ,
i
i P T nj
nM
M
n
( c

(
c

i i
i
M x M

=
(11.11)
, ,
i i
T x P x i
M M
x d M dP dT
P T

c c | | | |
= +
| |
c c \ . \ .
(11.13)
(11.7)
For binary solution, the summability relation, eq.(11.11) becomes


Differentiation of eq. (A) becomes


When M is known as a function of x
1
at constant T and P, the appropriate
form of the Gibbs/Duhem equation is eq. (11.14), expressed as


Because x
1
+ x
2
= 1, dx
1
+ dx
2
= 0 dx
1
= - dx
2
. Substitute eq. (C) into eq.
(B) to eliminate dx
2
gives

1 1 2 2
0 x d M x d M

+ =
18
1 1 2 2
M x M x M

= + (A)
1 1 1 1 2 2 2 2
dM x d M M dx x d M M dx

= + + +
(B)
(C)
1 2
1
dM
M M
dx

=
(D)
18
Two equivalent forms of eq. (A) result from elimination separately of x
1

and x
2
:






In combination with eq. (D) becomes




Thus for binary systems, the partial properties are calculated directly from
an expression for the solution property as a function of composition at
constant T and P.

2 1
1
dM
M M x
dx

=
19
( ) ( )
( ) ( )
1 2 2 1
2 1 2 2 1 1 1 2
1 2 1 2 2 1 1 2 1 2
1 2 1 2 1 1 2 2
1 1
1 1
and
x x x x
M x M x M M x M x M
M M x M x M M x M M x M
M M x M M M x M M M



= =
= + = +
= + = +
= = +
1 2
1
dM
M M x
dx

= +
(11.15)
(11.16)
19
Eq. (C), the Gibbs/Duhem equation, may be written in derivative forms:









When are plotted vs. x
1
, the slopes must be of opposite sign.
20
1 2
1 2
1 1
0
d M d M
x x
dx dx

+ =
1 2 2
1 1 1
dM x dM
dx x dx

=
(E)
(F)
2 1 1
1 2 1
dM x dM
dx x dx

=
(G)
1
2
and M M

CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 3/29/2013
6
Moreover,



Similarly,




Thus, plot of vs. x
1
become horizontal as each species
approaches purity.

21
1 1
1 2
1 1
1 1
lim 0 Provided lim is finite
x x
d M d M
dx dx


| |
| =
|
\ .
2 2
2 1
1 1
1 1
lim 0 Provided lim is finite
x x
d M d M
dx dx


| |
| =
|
\ .
1
2
and M M

Figure 11.1 (a) shows a representative plot of M
vs. x
1
for a binary system.
The tangent line shown extend across the figure,
intersecting the edges (at x
1
= 1 and x
1
= 0) at
points label I
1
and I
2
.
Two equivalent expressions can be written for
the slope of this tangent line:



The first equation is solved for I
2
; it combines
with the second to give I
1
.



Comparison of these expression with eqs.
(11.16) and (11.15) show that


The tangent intercepts give directly the values of
the two partial properties.

22
Describe a graphical interpretation of eqs. (11.15) and (11.16).

Solution:
2
1 2
1 1 1
and
dM M I dM
I I
dx x dx

= =
( ) 2 1 1 1
1 1
and 1
dM dM
I M x I M x
dx dx
= = +
1 2 1 2
and I M I M

= =
The limiting values are indicated by Fig.
11.1 (b).
For the tangent line drawn at x
1
= 0
(pure species 2), and at the
opposite intercept,

For the tangent line drawn at x
1
= 1
(pure species 1), and at the
opposite intercept,

23
1 1
M M

=
2 2
M M


=
2 2
M M

=
1 1
M M


=
The need arises in a laboratory for 2000 cm
3
of an antifreeze solution
consisting of 30 mole % methanol in water.What volumes of pure
methanol and of pure water at 25
o
C (298.15K) must be mixed to form the
2000 cm
3
of antifreeze, also at 25
o
C (298.15K)? Partial molar volumes for
methanol and water in a 30 mole % methanol solution and their pure
species molar volumes, both at 25
o
C (298.15K), are

24
( )
( )
3 -1 3 -1
1 1
3 -1 3 -1
2 2
Methanol 1 : 38.632 cm mol 40.727 cm mol
Water 2 : 17.765 cm mol 18.068 cm mol
V V
V V

= =
= =
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 3/29/2013
7
Solution:
Equation (11.11) is written for the molar volume of the binary antifreeze solution,
and known values are substituted for the mole fractions and partial volumes:




Because the required total volume of solution is V
t
= 2000 cm
3
, the total number
of moles required is


Of this, 30% is methanol, and 70% is water:



The total volume of each pure species is V
i
t
= n
i
V
i
; thus,


i i
i
V x V

=
25
( )( ) ( )( )
1 1 2 2
3 -1
0.3 38.632 0.7 17.765
24.025 cm mol
V x V x V

= +
= +
=
2000
83.246 mol
24.025
t
V
n
V
= = =
25
( )( )
( )( )
1
2
0.3 83.246 24.974 mol
0.7 83.246 58.272 mol
n
n
= =
= =
( )( )
( )( )
3
1
3
2
24.974 40.727 1017 cm
58.272 18.068 1053 cm
t
t
V
V
= =
= =
i i
n x n =
1 2 and V V

Values of for the
binary solution
methanol(1)/water(2) at 25
o
C
(298.15K) are plotted in Fig.
11.2 as functions of x
1
.
The line drawn tangent to the
V vs x
1
curve at x
1
= 0.3
illustrates the graphical
procedure by which values of
may be obtained.
The curve becomes
horizontal at x
1
= 1 and the
curve for becomes
horizontal at x
1
= 0 or x
2
= 1.
The curves for
appear to be horizontal at
both ends.

26
1 2
, and V V V

1 2
and V V

1
V

1 2
and V V

2
V

For the tangent line drawn at x

1
= 0 (pure species 2), and at the opposite
intercept,
For the tangent line drawn at x
1
= 1 (pure species 1), and at the opposite
intercept,

1 1
V V

=
2 2
V V


=
2 2
V V

=
1 1
V V


=
The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is
represented by the equation


where H is in Jmol
-1
. Determine expressions for as a functions
of x
1
, numerical values for the pure species enthalpies H
1
and H
2
, and
numerical values for the partial enthalpies at infinite dilution
27
( )
1 2 1 2 1 2
400 600 40 20 H x x x x x x = + + +
1 2
and H H

1 2
and H H


Solution:
Replace x
2
by 1 x
1
in the given equation for H and simplify:




By equation (11.15),


Then,
Replace x
2
by 1 x
1
and simplify:


By eq. (11.16),


or

2 3
1 1 1
420 60 40 H x x

= +
28
3 3
2 1 1 1 1 1
1
600 180 20 180 60
dH
H H x x x x x
dx

= = + +
3
1 1
600 180 20 H x x =
(A)
2
1
1
180 60
dH
x
dx
=
1 2
1
dH
H H x
dx

= +
3 2
1 1 1 2 1 2
600 180 20 180 60 H x x x x x

=
(B)
3
2 1
600 40 H x

= +
(C)
28
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 3/29/2013
8

A numerical value for H
1
results by substitution of x
1
= 1 in either eq (A) or
(B). Both eqn. yield H
1
= 400 J mol
-1
.

H
2
is found from either eq. (A) or (C) when x
1
= 0.
The result is H
2
= 600 J mol
-1
.

The infinite dilution are found from eq. (B) and (C) when x
1
= 0
in eq. (B) and x
1
= 1 in eq. (C). The results are:



Exercise: Show that the partial properties as given by eqs. (B) and (C)
combine by summability to give eq. (A), and conform to all requirements of
the Gibbs/Duhem equation.


1 2
and H H


29
-
-1 -1
1 2
420 Jmol and H = 640 Jmol H

-
=
29
By eq. (11.8),

and eq. (11.2) may be written as





Application of the criterion of exactness, eq. (6.12),



yields the Maxwell relation,


30
i
i
G

( ) ( ) ( ) i i
i
d nG nV dP nS dT G dn

= +

(11.17)
y
x
M N
y x
| | c c | |
= | |
c c \ .
\ .
(6.12)
, , P n T n
V S
T P
c c | | | |
= | |
c c \ . \ .
(6.16)
( ) ( ) ( )
i i
i
d nG nV dP nS dT dn = +
(11.2)
(11.8)
dz Mdx Ndy = +
Plus the two additional equations:



where subscript n indicates constancy of all n
i
, and subscript n
j
indicates
that all mole numbers except the ith are held constant.
In view of eq. (11.7), the last two equations are most simply expressed:



These equations allow calculation of the effects of P and T on the partial
Gibbs energy (or chemical potential). They are partial property analogs of
eqs. (11.4) and (11.5).

,
i
i
T x
G
V
P

| |
c
| =
| c
\ .
31
( )
, ,
, j
i
i P T n
T n
nV G
P n

| |
( c c
| =
(
| c c

\ .
(11.18) (11.19)
,
i
i
P x
G
S
T

| |
c
| =
| c
\ .
31
Every equation that provides a linear relation among thermodynamic
properties of a constant-composition solution has as its counterpart an
equation connecting the corresponding partial properties of each
species in the solution.
( )
, ,
, j
i
i P T n
P n
nS G
T n

| |
( c c
| =
(
| c c

\ .
An example is based on the equation that defines enthalpy:
H = U + PV
For n moles,

Differentiation with respect to n
i
at constant T, P, and n
j
yields



By eq. (11.7) this becomes


In a constant-composition solution, is a function of P and T, and therefore:




By eqs. (11.18) and (11.19),


These examples illustrate the parallelism that exists between equations for a
constant-composition solution and the corresponding equations for partial
properties of the species in solution.
32
( ) nH nU P nV = +
( ) ( ) ( )
, , , , , , j j j
i i i P T n P T n P T n
nH nU nV
P
n n n
( ( ( c c c
= +
( ( (
c c c

i i i
H U PV

= +
i
G

, ,
i i
i
T x P x
G G
d G dP dT
P T

| | | |
c c
| | = +
| | c c
\ . \ .
i i i
dG V dP S dT

=
Similar to eq. (2.11)
HU+PV
Similar to eq. (6.10)
dG=VdP-SdT
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 3/29/2013
9
Smith, J.M.,Van Ness, H.C., and Abbott, M.M. 2005. Introduction to Chemical
Engineering Thermodynamics. Seventh Edition. Mc Graw-Hill.
http://www.chem1.com/acad/webtext/thermeq/TE4.html
http://mpdc.mae.cornell.edu/Courses/ENGRD221/LECTURES/lec26.pdf
http://science.csustan.edu/perona/4012/partmolvolsalt_lab2010.pdf

33
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303