December 5, 2001

Reading: Chapter XII

Homework: 12.1, 12.3, 12.5, 12.7
Oxides of Carbon: CO-CO2-C equilibrium:
Consider the following reactions:
C+O2 CO2 -----------------(1)

K1 =

p CO 2
pO 2

2C+O2 2CO ----------------(2)

p2
K 2 = CO
pO 2
And, CO2 + C 2CO ----------------(I)
p2
K I = CO
pCO 2
Lets assume that pO 2 << pCO , pCO 2 .
Then, in a gaseous mixture total pressure equals to 1 atm.
pCO + p CO 2 = 1
KI =

2
2
pCO
p CO
=
p CO 2 1 pCO

2
pCO
+ K I p CO K I = 0

So, pCO =

K I + K I2 + 4 K I

pCO 2 = 1 p CO =

2
2 + K I K I2 + 4 K I
2

Now, G I0 = 170700 174.5T

170700 174.5T
So, K I = exp

8.3144T

Figure 12.15 from Gaskell is a plot of %CO (pCO in 1atm) vs. T. Note that as the T
increases, in a mixture of CO and CO2 in equilibrium with graphite C, the relative
concentration of CO increases. At higher T, there is great amount of CO. This is
consistent with the fact that CO2+C 2CO is an endothermic reaction.
G I0 = H I0 TS I0 = 170700 174.5T
Although we considered reaction (I), we could also have considered the following
reaction:
2CO+O2 2CO2 ------------ (II)
Where (II)=2(1)-(2)
p2
And K II = 2 CO 2
p CO p O 2
Or, pO 2 =

2
pCO
1
2
2
p CO K II

If reactions (I) and (II) are both to be in equilibrium with a total pressure of 1atm, then it
follows that

pO 2 =

2 + K I K I2 + 4 K I
K I + K + 4K I
2
I

1
K II

2
p CO 2 2 + K I K I + 4 K I
If the ratio
, with pCO + p CO 2 = 1 , carbon will no longer be
>
pCO
K I + K I2 + 4 K I
present. In such a case, reaction equilibrium (I) is not maintained. However, reaction (II)
p
continues to hold. This shows that above a certain value of CO 2 ration, no carbon is
pCO
present. Then the only reaction equilibrium of interest would be
2CO+O2 2CO2 ------------ (II)
2
G II0 p CO
1
2
With K II = exp
= 2
RT pCO pO 2

And pO 2

2
1 p CO
2
=
2
K II pCO

For the above reaction,

p
G 0 = 2 RT ln CO 2 + RT ln pO 2
p CO
p
Or, G 0 + 2 RT ln CO 2 = RT ln p O 2
p CO
Now, G 0 = 564800 + 173.62T

So, G 0 + 2 RT ln

p CO 2
p
= 564800 + 173.62T + 2 RT ln CO 2
pCO
p CO

p CO 2
, the above is a straight line A+BT. When T=0, the constant A=pCO
564800. This is point C in Figure 12.16.

For a given