Thermodynamics Lecture 14 Reactions between gases and pure condensed phases

In some ways, we can think of evaporation as a reaction between a condensed

phase and a gas.

A(s) = A(g)
Greaction = Gsublimationo + RTlnPA .

At equilibrium, Greaction = 0, so RTlnPA = -Gsublimationo . or

lnPA = -Gsublimationo /RT = lnXA + lnPtot
The composition of the gas phase in equilibrium with A will be at least partially
controlled by the vapor pressure of A.

We can have a slightly more complicated situation if a reactive gas species can
react with a condensed metal to form a condensed compound. The most common
example of such a reaction is oxidation. For silicon

Si(s) + O2(g) = SiO2(s)

Greaction = GSiO2 – GSi – GO2 = 0 at equilibrium

Since both Si and SiO2 are pure condensed phases, they are in their standard states.
Therefore

GSiO2 = GSiO2o
GSi = GSio
The oxygen gas may not be in its standard state.

GO2 = GO2o + RT lnPO2

Then Greaction = GSiO2o - GSio - GO2o - RT lnPO2 = Greactiono - RT lnPO2

At equilibrium Greaction = 0 ,

so RT lnPO2 = Greactiono = RT lnXO2 + RT lnPtot

Note that this is just like the vaporization reaction, except for the sign change,
because the gas species is being consumed in the reaction instead of produced in the
reaction.

If we neglect the cp terms, then

RT lnPO2 = Hreactiono -T Sreactiono ,
That is, this should be a straight line with a slope of -Sreactiono .

This is what is plotted on the Ellingham diagram (Figure 12.13 in Gaskell).