Size effects on cation heats of formation. III. Methyl and ethyl substitutions in group IV XH₄, X = C, Si, Ge, Sn, Pb.

The heats of formation of alkyl-substituted XH4 (X = C, Si, Ge, Sn, Pb) ΔfH(M(+)) = IEad(M) + ΔfH (M) molecular ions have often never been measured or are not known to better than 10 or 20 kJ/mol. The present study on these Main Group IV compounds adopts a graphical approach that relates cation heats of formation to cation size. A study of methyl substitution in XH4 is followed by a similar examination of heat of formation data on ethyl substitution in methane, silane, germane, stannane, and plumbane. The results provide tests of the validity of this graphical method as well as its use as a predictive tool for determining cation and neutral heats of formation. Suggestions are made of the need to investigate or reinvestigate the ionization energies and/or the heats of formation of several of the molecules studied. Results and conclusions are tabulated.