ermodynamics in Materials Engineering

Mat E 212 - Course Notes

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

Reaction Equilibria
and an introduction to Ellingham Diagrams

A simple chemical reaction

A B 2C
State I
1A

Intermediate state
1B

G GII GI
2GC G A GB
State II

n A A nB B nC C

2C

Reaction coordinate

nA 1
nB 1

nA

nA

nB n A

nC 0

21 n A

nC 2 n A nB

For any intermediate state: G n A A nB B nC C

n A A n A B 21 n A C

2 2n A
21 n A

Consider only the mixing of A and B

A B 2C
State I
1A

Intermediate state
1B

G GII GI
2GC G A GB
State II

n A A nB B nC C

2C

Reaction coordinate

nA 1
nB 1

nA

nA

nB n A

nC 0

21 n A

nC 2 n A nB

For any intermediate state: G n A A nB B nC C

n A A n A B 21 n A C

2 2n A
21 n A

Consider only the mixing of A and B

G

State I
1A

1B

GB

X AG A X B GB

GI

A B

For 1 mole A
and 1 mole B
(UNMIXED)

A+B

For 1 mole A
and 1 mole B
(MIXED)

G A
X AG A X B GB TS mix
X AG A X B GB RT X A ln X A X B ln X B

XB

Gibbs free energy along reaction coordinate

A B 2C
State I
1A

GB
A B

Intermediate state
1B

n A A nB B nC C

State II
2C

Reaction coordinate

GI

n AG A nB GB nC GC

G A
A+B
mixed

G GII GI
2GC G A GB

GII 2GC
n A A nB B nC C

Equilibrium State

G
0
n A

A simple chemical reaction

A B 2C
State I
1A

G GII GI
2GC G A GB

Intermediate state
1B

State II

n A A nB B nC C

2C

G n A A nB B nC C n A A n A B 21 n A C
Recall:

i Gi RT ln ai

G n A G A RT ln a A n A GB RT ln aB 21 n A GC RT ln aC
Find
minimum
along
reaction
coordinate:

n AG A n AGB 21 n A GC RT n A ln a A n A ln aB 21 n A ln aC

G
G A GB 2GC RT ln a A ln aB 2 ln aC 0
n A
G
G RT ln a A ln aB 2 ln aC

A condition of equilibrium
A B 2C
State I
1A

Intermediate state
1B

n A A nB B nC C

G GII GI
2GC G A GB
State II
2C

G RT ln a A ln aB 2 ln aC
a A aB

G RT ln
2
aC

aC2

G RT ln
a A aB

G RT ln K

K is defined as an
Equilibrium Constant

Temperature dependence
G RT ln K
G

K exp
RT

Note that:

G H TS
G H

S
T
T

G
H

2
T
T

H
R ln K 2
T
T
ln K H

T
RT 2

H
T1 T

T1

R ln K H

ln K
H

1
T
R

Temperature dependence
ln K
H

1
T
R
H

ln K
H

>

<

t
o
Ex
En
d

1/ T

m
er

ic

ot
he
rm
ic

K decreases
with temperature.

K increases
with temperature.

A simple reaction
1
M ( s ) O2 MO( s )
2

pO2

O2 Ar

MO

pO2

Furnace control T

A simple reaction
1
M ( s ) O2 MO( s )
2
1
Ag ( s ) O2 AgO( s )
2
G 30540 66.11T
H

>

Recall:

ln K
H

1
T
R

ln K
H

<

t
o
Ex

m
er

ic

En
do
th
er
m
ic

1/ T

A simple reaction
1
M ( s ) O2 MO( s )
2

H 0

G
aCz
x y
K exp
RT a A aB

1
1/ 2
po 2
If K decreases with increasing T,
pO2 must increase with increasing T.

G RT ln

1
pO2

1
G RT ln p O2
2

1
2

H 30540

Here:

(Exothermic)

K decreases as T increases.

t
o
Ex

ln K
H

<

1/ T

m
er

ic

A simple reaction
1
M ( s ) O2 MO( s )
2

G H TS
G RT ln K
1

G RT ln p O2
2

G H TS
These are tabulated.
(See Table A-1, p.582.)

An example
1
Fe( s ) O2 FeO( s )
2

G 263700 64.35T

G 0

0
O
e
F
=

/2O 2
1
Fe+

K
ng
i
s
p O2
rea
Inc asing
re
I nc

G 0
at this
temperature.

1
G RT ln pO2
2

pO2 1 atm

The pO2 scale

1
G RT ln pO2
2

For any constant pO2:

pO2 1 atm

0
O
e
F
=

/2O 2
1
Fe+

R ln pO2 T
2

pO2 1
pO2 1

Combined reactions
G 528.8 0.130T (kJ )
G 564.8 0.174T ( kJ )
G 18.0 0.022T (kJ )

2 Fe O2 2 FeO
2CO O2 2CO2
FeO CO Fe CO2
0

Fe+CO 2
FeO+CO=

G
O
e+
F
2

O
Fe
2
=

+O
O
2C

CO
2
=
2

The Ellingham-Richardson diagram

2 Fe O2 2 FeO

G 527,400 128.7T ( J )

G 126,052 30.76T (cal )

The Ellingham-Richardson diagram

2 Fe O2 2 FeO

G 527,400 128.7T ( J )
G 126,052 30.76T (cal )

G RT ln K

At T=1000C:

K exp
RT

G 126,052 30.761273
86,895 (cal / mol )

2
aFeO
K 2
aFe aO2

1
K
pO2

pO2

G
1

exp
K
RT

86895 cal / mol

exp
(1.987cal / K mol )(1273K )
1.2110 15

The Ellingham-Richardson diagram

2 Fe O2 2 FeO

G 527,400 128.7T ( J )

Con
s

t an t

pO

G 126,052 30.76T (cal )

pO2 10 15

The Ellingham-Richardson diagram

2 Fe O2 2 FeO
What if we establish EQ at 1000C and then raise the temperature to 1500C?
The EQ value of pO2 will increase, and the reaction is forced to the left.
Con
s

t an t

pO

pO2 10 9

pO2 10 15