Chapter 4 Solutions

What is a solution?
A solution in thermodynamics refers to a system with more than one
chemical component that is mixed homogeneously at molecular level.

Solutions in thermodynamics include mixtures in liquid, solid and gas states.

Homogeneous (single phase), multicomponent
1

4.1 Definitions of important composition variables in solution

Molar Fraction

Xi =

ni
ntot

Atomic Percentage

Weight Fraction

Concentration

with

ntot = ni
i

at% = 100% Xi
wi =

Wi
Wtot

n
Ci = i
V

with

Wtot = Wi
i

or sometimes

Ci =

Wi
V

 Extensive and intensive properties

A property of a system is intensive it may be defined to have a value at a point
in the system.
For example, temperature, pressure, density
A property of a system is extensive if it is the system as whole.
For example, volume, H, G
Extensive properties can be expressed as integrals of intensive properties over
the extent of system.

Two questions about solutions

1. Can the components be mixed and form a homogeneous phase?
Oil/water

Ethanol/water

Salt (NaCl)/water

2. How about the properties of solutions

4.2 Definition of Partial Molal Properties

4.2.1 Definition
The state function V is a function not only of T and P but also of the number of
moles of each component in the system,
V ' = V '(T , P, n1 , n2 ,..., nc )

Thus,

V '
V '
V '
dV ' =
dT
dP
dn1
+
+

T P ,nk
P T ,nk
n1 T , P ,n2 ,...,nk

V '
V '
+
dn
+
...
+
dnc

2
n
n

2 T , P ,n1 ,n3 ,...,nk

c T , P ,n1 ,n2 ,...,nc1

or

c
V '
V '
V '
+
+
dV ' =
dT
dP
dnk

T P ,nk
P T ,nk
k =1 nk T , P , n n
j
k

The coefficient of each of the changes in number of moles can be written:

V '
Vk =

n
k T , P ,n j nk
_

Partial molal volume

k = 1, 2,,c

unit is volume/mole.
5

 An analogous definition can be devised for any of the extensive properties of

the system.
Using B for any of the properties U, S, V, H, G. Then , for a change in
temperature, pressure and chemical content, the change in the properties, B, is
c

dB ' = MdT + NdP + Bk dnk

k =1

The partial molal B for component k is the corresponding coefficient of dnk

B '
Bk =

n
k T , P ,n j nk
_

k = 1, 2,,c

4.2.2 Chemical Potential

G '
S ' dT + V ' dP +
dG ' =
dnk

n
k =1
k T , P , n j
c

_
G '
=
Gk
k =

nk T , P ,n
j

k is referred as chemical potential.

It is the coefficient of each compositional variable.
Putting energy together, the potential differentials
_

dV ' = V ' dT V ' dP + Vi dni

_

dG ' =
S ' dT + V ' dP + Gi dni =
S ' dT + V ' dP + i dni

4.2.3 Consequences of definition of partial molal properties

Considering a process in which the temperature and pressure are held constant,
the system is formed by adding n1 moles of component n1, n2 moles of
component n2,, until a final state consisting of a homogeneous mixture of all
the components at the initial temperature and pressure is achieved. At any step
during the process, we have

dV 'T , P = Vk dnk
k =1

This is the first consequence.

For the process under consideration, visualize the addition of all c components
simultaneously in the proportions found in the final mixture. Thus, during the
process the intensive properties (T, P and the set of Xk values) remain fixed
and each of the terms is constant. In this case, integration is straightforward.

=
V'

nk _

=
Vk dnk

Vk

0
=
k 1=
k 1
c

nk

dnk

V ' = Vk nk
k =1

 This conclusion, that the total volume for the system is the weighted sum of the
partial molal volumes, can be extended without complication to any extensive
property:
c

B ' = Bk nk
k =1

Accordingly, the second consequence of the definition of partial molal

properties is the most rudimentary requirement of any strategy for assigning a
part of a total property to each of the components and that is that the sum of the
contributions must add up to the whole.
For the Gibbs free energy, we have
c

G ' = nk k
k =1

10

 The third consequence is the Gibbs-Duhem equation.

Beginning compute the differential of B,
c

dB ' = d ( Bk nk )
k =1

Since the differential of the sum of the differentials, differentiating the

product yields
_
_

=
dB ' Bk dnk + nk d Bk

k =1
c

=
dB '

dn + nk d Bk

k
k
=
k 1=
k 1

11

=
dB '

dn + nk d Bk

k
k
=
k 1=
k 1

The first summation is equal to the left side of the equation.

c

dB ' = Bk dnk
k =1

Accordingly, the second summation must be zero.

c

Gibbs Duhem equation

n d B
k

k =1

=0

This equation demonstrates that the partial molal properties are not all
independent.
For example, for a two-component solution,
_

n1d V1 + n2 d V2 =
0

12

4.3 Molar quantities

4.3.1 Definition
A molar quantity refers to an extensive thermodynamic variable that has been
divided by the total number of moles in the system.
_

B'
ntot

V'
ntot

B=

For example, molar volume

V=

It is frequently useful to normalize the description of properties of mixtures

and express them on the basis of one mole of the solution formed,
c

dB '
d=
B =
ntot

B
k =1

ntot
_

Thus,

dnk
=

B
k =1

dX k

B = X k Bk
k =1

13

4.3.2 Relation between partial properties and total properties

Two-component system
c

B = X k Bk

k =1

=
B BA X A + BB X B
as
then

d B = Bk dX k

k =1

=
d B BA dX A + BB dX B
1
XA + XB =

dX A = dX B
_

We have

_
_
dB
= BB BA
dX B

14

_
_

dB
= BB BA
dX B
_

_
_

_
_

dB
dB
=
BA
dX B
dX A

BB =
BA +

_
_

d
B
(1 X )
B= BA X A + BA
A

dX A

_
_
_

_
d
B
d
B
X B

= BA X A + BA
A
A

dX A
dX A

=
B BA X A + BB X B

_
_

= BA ( X A + 1 X A )

dB
dB
+ XA
dX A
dX A

_
_

= BA (1 X A )
_
_

dB
dX A
_

_
_

Hence BA = B + (1 X A ) d B = B X B d B
dX A
dX B

BB = B + (1 X B )

dB
dX B
15

Related to real systems, we have

_
_

VA = V + (1 X A )

_
_

dV
dV
=V X B
dX A
dX B
_

A = G + (1 X A )

_
_

dG
dG
= G X B
dX A
dX B

16

4.3.3 Graphic interpretation

a. Free Energy

_
_

A = G + (1 X A )
_
_

A= G X B

_
_

dG
dG
= G X B
dX A
dX B

dG
dX B
_

B = G + (1 X B )

dG
dX B
_

=
G XA XAXB
AXA

dG
dX B
_

B X B = G X B + X B (1 X B )
_
_

= G X B+XAXB

dG
dX B

G( X B )

dG
dX B

Thus,=
G A X A + B X B
17

b. Volume
For example, the partial molar volumes can be obtained from the molar volume
_
_

V A= V X B

dV
dX B

_
_

V B = V + (1 X B )

dV
dX B

This figure illustrates the intercept rule as applied to the molar volume of a
binary A-B solution. It also graphically illustrates the different terms that appear
in the expressions for the molar volumes in equations presented above.
_

V (XB)

V (XB)

18

The importance to notice the different way of chemical potentials are obtained.
G '

i T , P ,n n

i =

_
_

A= G X B

dG
dX B

19

4.4 Mixing Process

4.4.1 Volume change
nA moles of pure A is mixed with nB moles of pure B. Before mixing, the
combined volume of the two component is simply
_

nA VA0 + nB VB0

where
and are the molar
volumes of pure A and B,
respectively.

20

Dividing this premixing volume by ntot = nA + nB, gives the molar volume
before mixing,
_

_
_
nA V + nB VB0
0
= X A VA + X B VB0
nA + nB
0
A

This represents the dashed line.

_

21

 When A and B are mixed, forming a solution, the change in volume upon
mixing can be written as
_

V mix= V ( X B ) ( X A V + X B VB0 )
Where

0
A

is the molar volume after mixing.

4.4.2 Change in other functions

Similarly we can have:
_

H mix= H ( X B ) ( X A H + X B H B0 )
0
A

G mix= G ( X B ) ( X A G + X B GB0 )
0
A

22

H mix

is equal to the heat exchange with environment upon mixing a total one
mole of pure component A and B.
At concentration of XB,
when Hmix is negative, heat is released, the mixing is exothermic.
when Hmix is positive, heat is absorbed, the mixing is endothermic.

XB
exothermic

endothermic

23

The value of
will occur or not.

is an important quantity as its sign determines whether mixing

A negative Gibbs free energy of mixing means that there is a thermodynamic

driving force for mixing and the pure components when brought in contact will
spontaneously form a solution.
A positive Gibbs free energy of mixing means that the components are
immiscible and will not form a solution when brought together, but rather a
two phase dispersion of a pure A phase mixed with a pure B phase.

24

It is possible to apply the intercept rule to a plot of the molar Gibbs free energy
of mixing.
Start from
_
_

dG
dX B

A= G X B
_

dG d ( X A G + X B G + G mix )
=
dX B
dX B
0
A

0
B

d (G X B G + X B G + G mix )
dX B
0
A

0
A

0
B

=
GA0 + GB0 +
_

d G mix
dX B
_

=
A X A GA0 + X B GB0 + G mix X B ( GA0 + GB0 +

d G mix
)
dX B

d G mix
G
+

X
=
mix
A
B
dX B
_

Thus,

0
A

or

A GA0 =
G mix X B

d G mix
dX B
25

4.4.3 Activity of component k

It is defined as

k k0 =
k =
RT ln ak
Where ko is the chemical potential of k in its reference state.
Where ak is the activity of k in its reference state.
Note: when k = k0, ak =1
Another convenient measure of solution behavior, is the activity coefficient
of component k, k

ak = k X k
Note: when ak = Xk, k = 1

26

4.5 Examples of solutions

4.5.1 Ideal solution

ak = X k

RT ln ak =
RT ln X k
Gk =
k =
_

G mix=

G = RT X k ln X k

k
k
k 1=
k 1
=

G '
S ' dT + V ' dP +
dG ' =
dnk

n
k =1
k T , P , n j
c

G '
S ' =

T P ,nk

_
G '

G '
S '
Gk

Sk =
=

=

=

=
k

T
T n

T P ,nk
nk T , P ,n j
nk T P ,nk T , P ,n j
k T , P ,n j P ,nk

P ,nk
_

( RT ln X k )
k
S k =

=
R ln X k

T
T

P ,nk

P ,nk
_

=
R X k ln X k
X S =

mix
k
k
=
k 1=
k 1

27

Mixtures obeying these relations, regardless of solids, liquid, or gas, are in

general called ideal solutions.

28

29

4.5.2 Regular solution

For a regular solution,
1. The entropy of mixing is the same as that for an ideal solution:
_

Sk =
R ln X k
2. The enthalpy of solution is not zero, but is a function of composition
_

H k =
H k ( X 1 , X 2 ,...)
The simplest regular solution model contains a single adjustable parameter in its
description of heat of mixing,
Thus Gmix= aX 1 X 2 + RT ( X 1 ln X 1 + X 2 ln X 2 )

30

31

4.5.3 A two parameter regular solution model

=
Gmix X 1 X 2 (a1 X 1 + a2 X 2 ) + RT ( X 1 ln X 1 + X 2 ln X 2 )
32