Phase Diagrams

Thermodynamics in Materials Engineering
Mat E 212 - Course Notes

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

An Introduction to Binary Phase Diagrams
A binary phase diagram is a thermodynamic map, indicating the most stable (i.e. equilibrium) phases and
phase compositions for any average binary composition at a selected temperature.
Mat E 212 - Thermodynamics in Materials Engineering - R.E. Napolitano
Binary Phase Diagrams
Multiple invariants can give binary phase diagrams a more complex appearance. However, they can always be
broken down into the individual invariant reactions.
Multiple invariants
In summary, the auxiliary functions express the intercepts as functions of P,V,S, and T.
Auxiliary Functions

U = ++V
cU
cV
|
\

|
.
|

+ =U + PV

H U + PV

U = u+ S
cU
cS
|
\

|
.
|

u =UTS

A UTS

U = O + S
cU
cS
|
\

|
.
|
+V
cU
cV
|
\

|
.
|

O =U+ PV TS

GU+ PV TS
These functions provide useful conditions for equilibrium under certain constraints.
Auxiliary Functions

H U + PV

A UTS

GU+ PV TS

dA = dUTdS SdT

= TdS PdV
( )
TdS SdT

= SdT PdV

dH = dU+ PdV +VdP

= TdS PdV
( )
+ PdV +VdP

= TdS +VdP

dG= dU+ PdV +VdP TdS SdT

= TdS PdV
( )
+ PdV +VdPTdS SdT

= SdT +VdP
Realizing that there may be other sources of energy
Other sources of energy

dG= SdT +VdP+
cG
ce
1
|
\

|
.
|
de
1
+
cG
ce
2
|
\

|
.
|
de
2
+
cG
ce
3
|
\

|
.
|
de
3
+ ...
where these may be electrical, magnetic, chemical, etc.
Chemical Potential
Considering the chemical energy, we realize that there will be an energy contribution from
each component in the material.

dG= SdT +VdP+
cG
cn
1
|
\

|
.
|
dn
1
+
cG
cn
2
|
\

|
.
|
dn
2
+
cG
cn
3
|
\

|
.
|
dn
3
+ ...+
cG
cn
C
|
\

|
.
|
dn
C
where C is the number of components in the system.
|
|
.
|
\
|
i
i
n
G
c
c

dG = SdT +VdP +
i
dn
i
i=1
C
We now define the chemical potential for the i

th
component as
and the Gibbs free energy becomes:
For any binary solution

i

cG
cn
i
|
\

|
.
|
dn
i

dG = SdT +VdP +
i
dn
i
i=1
C
0 1
X
B
(mole fraction)

A
0
B
G
0
A
G
) (
B
X G
G
i
b
b
s

f
r
e
e

e
n
e
r
g
y

B B A A
X X + =
Our Strategy
Recall that the Gibbs free energy is related to the experimentally measurable quantity of heat
capacity:
We are interested in G(T,P,n
1
,n
2
,n
C
). In Materials Science, we are often interested in constant
pressure (i.e. 1 atm). Therefore, the problem is reduced to quantifying the Gibbs free energy
as a function of temperature and composition.

G T,n
1
,n
2
,...n
C
( )
= H T,n
1
,n
2
,...n
C
( )
TS T,n
1
,n
2
,...n
C
( )

G(T) = G
ref
+ c
p
dT
T
ref
T
}
T
c
p
T
dT
T
ref
T
}
The problem is that the above relationship gives G for a particular composition. We could choose to
measure the heat capacity for many compositions, and compute G(T,n
i
) using the above relation. A
more reasonable (and more useful) approach is to use reference compositions for which we
measure the heat capacity and compute a reference value of G(T). We then compute the free energy
for a mixture or solution of the reference components by combining the appropriate reference
free energies and then adding the energy associated with mixing. This free energy of mixing must
include all enthalpic and entropic contributions

G(T, n
1
, n
2
,...n
C
) =
n
i
N
G
i
0
(T)
i=1
C
+ AG
mix
(T, n
1
, n
2
,...n
C
)
Our Strategy
For convenience, we introduce a different composition variable, the mole fraction, X:

X
i

n
i
N

X
i
i=1
C
=
n
i
N
i=1
C
=
1
N
n
i
=
1
N
N
( )
i=1
C
=1
thus
For example, in the simple case of a binary solution (C=2):

G(T, X
A
, X
B
) = X
A
G
A
0
(T) + X
B
G
B
0
(T) + AG
mix
(T, X
A
, X
B
)

G(T, X
B
) = G(T, X) = 1 X
( )
G
A
0
(T) + XG
B
0
(T) + AG
mix
(T, X)
Furthermore, because X
A
=1-X
B
, we can reduce the composition to a single variable, X=X
B
.

G(T, X
1
, X
2
,...X
C1
) = X
i
G
i
0
(T)
i=1
C
+ AG
mix
(T, X
1
, X
2
,...X
C1
)
And rewrite our expression for the Gibbs free energy.
Our Strategy
Given that the system is comprised of a set of components for which the heat capacity can be
(or has been) measured, the free energy of each reference state can be computed.

G(T, X) = 1 X
( )
G
A
0
(T) + XG
B
0
(T) + AG
mix
(T, X)

G
A
0
(T) = H
A
0
(T) TS
A
0
(T) = G
A
0
(T
ref
) + c
p(A)
dT
T
ref
T
}
T
c
p(A)
T
dT
T
ref
T
}

G
B
0
(T) = H
B
0
(T) TS
B
0
(T) = G
B
0
(T
ref
) + c
p(B)
dT
T
ref
T
}
T
c
p(B)
T
dT
T
ref
T
}

AG
mix
(T, X) =AH
mix
(T, X) TAS
mix
(T, X)
Our primary challenge then, is to formulate the appropriate description of both the enthalpy of
mixing and the entropy of mixing, i.e. we seek the free energy associated with combining the
reference states into the mixture of interest.
To summarize our approach:
Gibbs
free
energy
X
B

G
B
0
mix
G A
solution
G

X
A
G
A
0
+ X
B
G
B
0

G
A
0
Gibbs Free Energy vs Temperature
G
T
Slope = -S
Gibbs Free Energy vs Temperature
G
T
T
m

X
B

T
1

T
G
Gibbs Free Energy in a binary solution
T
X
B

T
2

G
G
T
X
B

T
3

Gibbs Free Energy vs Composition: the simplest case
G
X
B

G
B
0

G
A
0
The Gibbs free energy of
the unmixed mixture.
X
A
G
A
0
+ X
B
G
B
0
If there are no atom-atom
interactions, then AH
mix
=0.
What about AS
mix
?
Generally, we are interested in AS
mix
as a function of composition.

O(n
A
, n
B
) =
n
A
+ n
B
( )
!
n
A
!n
B
!
1 9 36 84 126 84 126 36 9 1
Entropy of Mixing
( )
! !
!
) , (
B A
B A
B A
n n
n n
n n
+
= O
4-23
Entropy of Mixing
(
|
|
.
|
\
|
+
+
|
|
.
|
\
|
+
=
B A
B
B
B A
A
A
n n
n
n
n n
n
n k ln ln
| |
B B A A
X X X X nk ln ln + =
(Entropy of mixing - per mole of the mixture)
NOTE:
N
o
= Avogadros #
n/ N
o
=#moles =N
N
o
k=R
( )
B B A A mix
X X X X R S ln ln + = A
O = A ln ' k S
mix
| |
B B B A A A B A B A B A
n n n n n n n n n n n n k + + + + + = ln ln ) ( ) ln( ) (
(Now Apply Sterlings approx.)
Now we define the mole
fraction, X
i
=n
i
/n.
| |
B B A A
X X X X NR ln ln + =
( ) | | ! ln ! ln ! ln
B A B A
n n n n k + =
Entropy of Mixing

AS
mix
= R X
A
ln X
A
+ X
B
ln X
B
| |

AS
mix

X
B
Gibbs Free Energy vs Composition
G
X
B

G
B
0

G
A
0

TAS
mix

X
A
G
A
0
+ X
B
G
B
0
TAS
mix

X
A
G
A
0
+ X
B
G
B
0
The
IDEAL
Solution
The Ideal Solution

AS
mix
= R X
A
ln X
A
+ X
B
ln X
B
| |

AH
mix
=0
| |
B B A A B B A A
X X X X RT G X G X G ln ln
0 0
+ + + =
( ) ( ) ( ) | |
B B B B B B A B
X X X X RT G X G X G ln 1 ln 1 1
0 0
+ + + =

AG
mix
=AH
mix
TAS
mix
This is a simple model for G(X
B
) for a single phase.
Comparing G(X) for two phases
G
X
B

G
B
|

G
A
|

G
A
o

G
B
o
G

G
A
|

G
A
o

G
B
|

G
B
o
G

G
A
|

G
A
o

G
B
|

G
B
o
G

G
A
|

G
A
o

G
B
|

G
B
o
G

G
A
|

G
A
o

G
B
|

G
B
o
G

G
A
|

G
A
o

G
B
|

G
B
o
G

G
A
|

G
A
o

G
B
|

G
B
o
G
WAIT!
There is
another
variable to
consider

G
A
|

G
A
o

G
B
|

G
B
o
Compositional Stability
Suppose we have a particular overall composition, defined by X
B
. Will the system remain
homogeneously mixed at equilibrium?
X
B

G
A
|

G
B
|
B
X
B

G
A
|

G
B
|
B
X
B

G
A
|

G
B
|
Here we consider fluctuations in local composition. Realizing that mass must be conserved, a
local increase in X
B
must be accompanied by a decrease in X
B
elsewhere.
X
B

X
B
+
X
B
-

There is a net
increase in G!

G
A
|

G
B
|
G
Phase Stability
o
|
o+|

G
A
|

G
B
|

G
A
o

G
B
o
Phase Stability
|
G
A
vs T G
B
vs T
G
o
|
X
B

T
Phase Stability
|
G
A
vs T G
B
vs T
G
o
|
X
B

T
Phase Stability
G
A
vs T G
B
vs T
G
o
|
X
B

T
Phase Stability
G
A
vs T G
B
vs T
G
o
|
X
B

T
Phase Stability
G
A
vs T G
B
vs T
G
o
|
X
B

T
Phase Stability
G
A
vs T G
B
vs T
G
o
|
X
B

T
Phase Stability
G
A
vs T G
B
vs T
G
o
|
X
B

T
Phase Stability
|
G
A
vs T G
B
vs T
G
o
|
X
B

T
Phase Stability
G
A
vs T G
B
vs T
G
o
|
X
B

T
Phase Stability
G
A
vs T G
B
vs T
G
o
|
X
B

T
Phase Stability
G
A
vs T G
B
vs T
G
o
|
X
B

T
o
|
A Note on Reference States
G
A
vs T G
B
vs T
G
o
|
X
B

T
o
|
4-12
G
A
vs T G
B
vs T
G
o
|
X
B

T
o
|
4-12
G
A
vs T G
B
vs T
G
o
|
X
B

T
o
|
4-12
G
A
vs T G
B
vs T
G
o
|
X
B

T
o
|
A simple binary phase diagram
G
G
L
G
o
X
B

T
G
G
L
G
o
X
B

T
G
G
L
G
o
X
B

T
G
G
L
G
o
X
B

T
G
G
L
G
o
X
B

T
G
G
L
G
o
X
B

T
G
G
L
G
o
X
B

T
G
G
L
G
o
X
B

T
L
o
G
G
L
G
o
X
B

T
Another simple binary phase diagram
G
|
G
G
L
G
o
X
B

T
G
|
G
G
L
G
o
X
B

T
G
|
G
G
L
G
o
X
B

T
G
|
G
G
L
G
o
X
B

T
G
|
G
G
L
G
o
X
B

T
G
|
+
G
G
L
G
o
X
B

T
G
|
-
G
G
L
G
o
X
B

T
G
|
G
G
L
G
o
X
B

T
G
|
G
G
L
G
o
X
B

T
L
G
|
o
|
o + |
o+L
|+L
G
G
L
G
o
X
B

T
L
Homework #8 (by team) Due Friday 3/9/07
G
|
o
|
o + |
o+L
|+L
1. Create a ppt schematic like this for
your project system. Be as quantitative
as possible with temperature and
composition values.
2. Assume ideal solutions for the solid and liquid phases and write a short
program to compute and plot the binary phase diagram for the Cu-Ni system
over the temperature range from 1080 to 1460 C.
| |
B B A A B B A A
X X X X RT G X G X G ln ln
0 0
+ + + =
( ) ( ) ( ) | |
B B B B B B A B
X X X X RT G X G X G ln 1 ln 1 1
0 0
+ + + =

AG
mix
=AH
mix
TAS
mix

AS
mix
= R X
A
ln X
A
+ X
B
ln X
B
| |

AH
mix
=0
For the ideal solution
2. Assume ideal solutions for the solid and liquid phases and write a short
program to compute and plot the binary phase diagram for the Cu-Ni system
over the temperature range from 1080 to 1460 C.
SUBMIT BOTH OF THESE ITEMS
ELECTRONICALLY (EMAIL)
BY 11am ON FRIDAY, 3/9.

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Thermodynamics in Materials Engineering

Mat E 212 - Course Notes

We now define the chemical potential for the i

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