Methods are presented for rapidly estimating the entropies and heat capacities of free radicals from the known So and CE of structurally similar compounds. The methods consist of estimating the differences due to changes in mass, vibration frequencies, spin, symmetry, and changes in rotational barriers. Tables of contributions to So and CE by different frequencies over the temperature range 300-1500ยฐK are presented to facilitate the tabulation of the above differences. Conjugated radicals, such as benzyl and allyl, are included. I t is shown that the greatest uncertainties in the estimates arise from uncertainties in the barriers to rotation in the radicals.
The results are applied to kinetic data on the pyrolysis of branched hydrocarbons and the reverse reactions of radical recombination. Major discrepancies exist in these data which can be nearly reconciled by postulating improbably high rotational barriers of 8 kcal for CH, rotation in isopropyl and t-butyl radicals.
It is shown that radical thermochemistry can be fitted into group schemes and tables of groups values are given for the rapid estimation of A H ! , So, and C; for different organic radicals, including those containing sulfur, oxygen, and nitrogen.