The thermochemistry of carbon: valence states, heats of sublimation and energies of linkage

The controversy which exists at the present time between the figures 125 and 170 kcal./g.- atom for the latent heat of sublimation of carbon into monatomic vapour in the ground state originates largely from the neglect to take into consideration the energy required to raise the carbon atoms from the ground (3P) state to the lowest tetravalent (5S) electronic configuration corresponding to that in which it is normally found in chemical combination. Consideration of the energies of removal of a hydrogen atom from the methane and ethane molecules and of the energies of reorganization of the resulting radicals leads to the figure 190 ± about 10 kcal. for L2, the heat of sublimation into free atoms in the 5S state. This in turn leads to a satisfactory and unambiguous assignment of values to bond energies (as distinct from dissociation energies) which can now be expressed with an uncertainty of not more than a few kcal. In the light of the valency distinction there remains no sound evidence to maintain the higher value put forward for L1 and 125 kcal. is unquestionably of the right order. There are strong indications that an earlier estimate of 100 kcal. for the energy level of the 5S state above the 3P (ground) state is about 50 % in excess of the true value. The necessity for establishing this branch of thermochemistry on a sound theoretical and experimental footing has long been a very obvious need. The scheme here suggested reconciles points hitherto in apparent conflict, and brings virtually all established experimental knowledge into alignment.