December 3, 2001

Reading: Chapter XII

Homework: 12.1, 12.3, 12.5, 12.7
Equilibrium between condensed and gaseous phases:
Specified cases of interest include equilibrium between a metal, its oxide and the gas
phase. Consider equilibrium between M(s), MO(s), and O2(g). In this 3-phase
equilibrium, O2(g) appears only in the gas phase- i.e., there is no condensed O2. However,
M and MO occur both as condensed phases (here assumed to be solids) and the gas
phase- a consequence of the following equilibria:
M(s) M(g)
MO(s) MO(g)
So, G M ( s ) = G M ( g ) = G M0 ( g ) + RT ln p M
0
G MO ( s ) = G MO ( g ) = G MO
( g ) + RT ln p MO

Now, as equilibrium between M(s), MO(s), and O2(g) is established, so must also be
between M(g), MO(g), and O2(g)
So, M(g)+1/2 O2(g) MO(g)
1
G M ( g ) + G O 2 ( g ) = G MO ( g )
2

1
1
0
Or, G M0 ( g ) + RT ln p M + GO0 2 ( g ) + RT ln pO 2 = G MO
( g ) + RT ln p MO
2
2
p MO
1
0
( g ) GM0 ( g ) GO0 2 ( g ) = RT ln K g = RT ln
G 0 ( g ) = G MO
2
p M p O1 /22

1
1
1
0
( g ) + RT ln p MO G M0 ( g ) RT ln p M GO0 2 ( g ) = RT ln 1 / 2 = RT ln p O 2
Or, G MO
2
2
pO 2
0
But, G MO
( g ) + RT ln p MO = G MO ( g ) = G MO ( s )

And G M0 ( g ) + RT ln p M = G M ( g ) = G M ( s )
1
So, G MO ( g ) G M ( g ) GO0 2 ( g ) =
2
1
And G MO ( s ) G M ( s ) GO0 2 ( g ) =
2

1
RT ln pO 2
2
1
RT ln p O 2
2

We will assume M and MO to be pure. So,

G M ( s ) = G M0 ( s ) +

Ptotal

VM ( s )dP

But, VM(s) is small enough that

Ptotal

VM ( s )dP is negligible compared to GM0(s). Thus,

G M ( s ) G M0 ( s )
0
Similarly, G MO ( s ) G MO
( s)

1
1
Thus, G MO ( s ) G M ( s ) GO0 2 ( g ) = RT ln p O 2 is the same as
2
2
1
1
G MO ( s ) G MO ( s ) GO0 2 ( g ) = RT ln p O 2
2
2
The above is G0(s) for the reaction
M(s)+1/2 O2(g) MO(s)
So, G 0 =

1
RT ln p O 2
2

Let us write the above reaction for the consumption of one mole of O2, i.e.,
2M(s)+O2(g) 2MO(s) ---------------(1)
Examples: oxidation of a divalent metal: Ca, Ba, Sr, Mg, Zn, etc.
For a monovalent metal,
2M(s)+1/2 O2(g) M2O(s) ---------------(2)
Then, G 20 = RT ln p O 2 = 2G M0 2O ( s ) 4G M0 ( s ) GO0 2 ( g )
Examples: Oxidation of Na, K, Li, Ag, etc.
For an trivalent metal:
2M(s)+3/2 O2(g) M2O3(s)
And for the consumption of one mole of O2,
4/3M(s)+O2(g) 2/3M2O3(s) ---------------(3)
G30 = RT ln p O 2
Examples: Al, Cr, rare earth metals (Yb, Gd, Sm,)
For a tetravalent metal:
M(s)+O2(g) MO2(s) ---------------(4)

So, G40 = RT ln p O 2
Examples: Hf, Ti, Zr
Now, at any T, G 0 = H 0 TS 0
If it can be assumed that H 0 and S 0 are (approximately) temperature-independent,
then a plot of G 0 vs. T should be a straight line with H 0 as the intercept and - S 0 as
the slope.
0
0
0
Now, S 40 = S MO
2 S M S O 2 for (4)

Or, S 30 = 2 / 3S M0 2O 3 4 / 3S M0 S O0 2 for (3), etc.

0
0
0
0
It can be verified that S MO
2 , S M , S M 2 O 3 << S O 2

Thus, S 0 S O0 2 , the slope is S O0 2

For this reason, plots of G 0 vs. T for a number of oxides are nearly parallel lines. The
intercept (for T=0K) gives H 0 .
0
-50
-100

G0

Ellingham diagram

-150

(KJ/mol) -200