hence, we see that the gaseous species corresponding to the higher heat of reaction (more

positive H) will increase in relative importance as the temperature is raised. Now, as a fair
approximation, the values of So for the reactions forming the two species are equal.
Consequently, the partial pressures of the species will approach each other as the temperature
becomes very large. In figure 2.1 we have plotted the logarithms of the pressures against 1/T.
Obviously we may state, as a general rule for a mixture of vapor species in equilibrium with a
common condensed phase, that whatever species is in relatively smalll abundance at low
temperatures will gain in relative abundance as the temperature is raised.

in the case of monomeric and dimeric acetic acid vapor in equilibrium with the liquid,
Homonomer > Hodimer. Hence, the vapor is principally dimer at low temperatures, and the
fraction of monomer increases with the temperature. However, it is more commonly observed
that low molecular weight species predominate inn saturated vapor at low temperatures, and
polymeric species increase in importance with increasing temperature. For example, at low
temperatures the main gaseous species in equilibrium with solid molybdenum trioxide is
Mo3O9. but as the temperature is increased the proportions of Mo4O12 and Mo5O15 steadily
increase. Thus, if one seeks a gaseous system containing a large variety of molecular species
of complex structure, it is usually advisable to go to the highest possible temperature at which
the saturated system can still exist.

qualitative data

thermodynamic reasoning can be applied even to qualitative data. As an example we shall

cite the development of practical syntheses of praktis bis(trifluoromethyl)disulfide,
CF3SSCF3, and trifluoromethanethiol, CF3SH,. It was known that the following two reactions
proceed spontaneously.
CF3SH + CF3SCl CF3SSCF3 + HCl (2.17)
CF3SSCF3 + 2 HCl + Hg 2 CF3SH + HgCl2 (2.18)

If we double eq. (2.17) and add Eq.(2.18), we obtain

2 CF3SCl + Hg CF3SSCF3 + HgCl2 (2.19)
and if we simply add Eqs. (2.17) and add Eq.(2.18), we obtain

CF3SCl + Hg + HCl CF3SH + HgCl2 (2.20)

now the latter two reactions, inasmuch as they are additive combinations of spontaneous
reactions, are themselves spontaneous reactions. This fact was recognized by Cullen and
Dhaliwal, who showed that the latter reactions were useful synthetic methods for A
CF3SSCF3 and CF3SH, respectively.