Thermodynamics in Materials Engineering

Mat E 212 - Course Notes

R. E. Napolitano
Department of Materials Science & Engineering
Iowa State University



Nonideal mixing and the Regular Solution Model
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-1
Recall our general expressions for the Gibbs free energy of a binary solution phase.
The Gibbs free energy vs composition
m B B A A
G G X G X G A + + =
0 0
m m B B A A
S T H G X G X G A A + + =
0 0
( )
B B A A m B B A A
X X X X RT H G X G X G ln ln
0 0
+ + A + + =
B B A A
X X G + =
i i i
X a =
|
|
.
|

\
|
A
=
RT
H
m
i
exp
X
B
X
A

m
G A
0
A
G
0
B
G
A

or in terms of the partial molar quantities:

i i i
a RT G ln
0
+ =
where:
and is the partial molar enthalpy of mixing.
m H A
The Ideal Solution
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-2
For an ideal solution, the enthalpy of mixing is zero.
( )
B B A A B B A A
X X X X RT G X G X G ln ln
0 0
+ + + =
B B A A
X X G + =
i i i
X a =
|
|
.
|

\
|
A
=
RT
H
m
i
exp
or in terms of the partial molar quantities:
i i i
a RT G ln
0
+ =
where:
For , we see that .
0 = A m H
1 =
i

Ideal mixing
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-3
Lets examine a simple example. Consider an unmixed binary system (below left). Now
consider the randomly mixed condition (below right). The enthalpy of mixing is given by:
1 2 State State
m
H H H = A
State 1 State 2
If each particle has no preference regarding which type of particle resides in its
nearest neighbor shell (i.e. the energy of A-A, A-B, B-B pairs are equal), the mixing
is said to be ideal.
Pair potentials
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-4
For any pair of particles, we can express the potential energy as a function of the distance
between the two particles. Generally, there will be a net repulsion at short distances and a net
attraction at long distances.
x
E
The minimum in energy represents the most likely (i.e. average) distance between the two
particles and the average pair potential.
E
BB
Pair potentials
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-5
Generally, the potential associated with each type of particle (or atom) pair will be different.
x
E
The minimum in energy represents the most likely (i.e. average) distance between the two
particles and the average pair potential.
E
BB
E
AA
A
Pair potentials
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-6
Now we compare the A-A and B-B potentials with the A-B potential.
x
E
Here we see that, in general, the equilibrium distances and the associated potentials are
different for each pair type. (Note that E
AB
=E
BA
.)
E
BB
E
AA
B
E
AB
A
Ideal Mixing
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-7
x
E
E
AA
= E
BB
= E
AB
For the case of ideal mixing, we assume that mixing is random and that all three pair
potentials are identical. Thus, the enthalpy change associated with mixing is equal to zero.
Thus, the change in the total interaction enthalpy associated with MIXING is zero.
Nonideal mixing
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-8
If the potentials for the different pairs are not equal, then the mixing will generally NOT be
random and (even if it is random) the enthalpy of mixing will depend on the differences in the
pair potentials.
x
E
There are many ways to compute the enthalpy of mixing based on these pair potentials. Here,
we will examine a few of the simplest.
E
BB
E
AA
A B
E
AB
A simple solution model
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-9
Assumptions:
- we neglect the differences in equilibrium interparticle distances
- we assume that mixing is random
- we account only for nearest neighbor interactions
- we assume that all pair potentials are equal to that for the equilibrium pair distance.
x
E
Therefore, the enthalpy of mixing is computed as a function of only {E
AA
, E
BB
, E
AB
}.
E
BB
E
AA
B
E
AB
A
A simple solution model
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-10
State 1 State 2
Number of A-A bonds broken = n
AA
= 4
Number of B-B bonds broken = n
BB
= 4
Number of A-B bonds created = n
AB
= 8
In this case, the enthalpy change =
( )
BB BB AA AA AB AB m
E n E n E n H + = A
BB AA AB m
E E E H 4 4 8 = A
In general:
A simple solution model
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-11
( )
BB BB AA AA AB AB m
E n E n E n H + = A
For a randomly mixed solution, the number of A-B pairs created per mole of solution is given by:
B A AB
zX X N n
0
=
For every A-B bond created, one A-A and one B-B bond must be broken:
BB AA AB
n n n + =
AB BB AA
n n n
2
1
= =
|
.
|

\
|
+ = A
BB AB AA AB AB AB m
E n E n E n H
2
1
2
1
( )
(

+ = A
BB AA AB AB m
E E E n H
2
1
Substitution yields:
( )
(

+ = A
BB AA AB B A m
E E E X zX N H
2
1
0
Note that the quantity in
brackets is simply the
energy of the mixed pair
minus the average energy
of the unmixed pairs.
A simple solution model
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-11
For a randomly mixed solution, we must now determine the number of A-B
pairs created per mole of solution:
( )
(

+ = A
BB AA AB AB m
E E E n H
2
1
( )
(

+ = A
BB AA AB B A m
E E E X zX N H
2
1
0
The number of atoms
The number of A atoms
The number of nearest
neighbors around A atoms
The number of B-atom nearest
neighbors around A atoms
AB
n =
0
N =
A
X N
0
=
z X N
A 0
=
B A
zX X N
0
=
A simple solution model
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-12
( )
(

+ = A
BB AA AB B A m
E E E X zX N H
2
1
0
x
E
E
BB
E
AA
E
AB
What governs the
enthalpy of mixing in
this simple model is just
the difference between
the A-B potential and the
average of the the A-A
and B-B potentials.
E
Lets look at this
more closely.
A simple solution model
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-13
( )
(

+ = A
BB AA AB B A m
E E E X zX N H
2
1
0
E
AB
E
0
E
AA
E
BB
c

E
AA
+E
BB
2

c

If c is positive, the
enthalpy of mixing is
positive.

If c is negative, the
enthalpy of mixing is
negative.
A simple solution model
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-14
( ) ( )
B B A A BB AA AB B A B B A A
X X X X RT E E E X zX N G X G X G ln ln
2
1
0
0 0
+ +
(

+ + + =
m
H A
m
S TA
m
G A
( )
B B A A B A B B A A
X X X X RT X X G X G X G ln ln
0 0
+ + O + + =
Because AH
m
is a function only of composition, we introduce a constant, O, and write:
This is known as the
regular solution model.
The excess Gibbs free energy
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-15
For the regular solution model, the excess Gibbs free energy depends only on X
B
, T, and O.
m
H A
m
S TA
m
G A
m
S A
For the RS Model, AH
m
may be positive or negative but does not vary with temperature.
The excess Gibbs free energy
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-16
For a positive AH
m
, the regular solution model can predict immiscibility in a given phase.
m
H A
m
S TA
mix
G A
T
1
T
2

>
T
3

>
Phase diagram predictions using the RS model
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
19-16
HW#9 (Teams):

1. Use the regular solution model
for two phases and indicated
parameters to compute the
highlighted phase diagrams
(left).
2. Develop a 3-phase model that
shows a peritectic invariant in
the binary phase diagram.

For both problems, submit:
(a) Your code
(b) The phase diagram(s)
(c) Representative G(X) curves