A New Generalized Bond Energy/Group Contribution Scheme for Calculating the Standard Heat of Formation of Monomers and Polymers. Part V. Oxygen Compounds

Abstract

The new generalized bond energy scheme has been extended to organic oxygen compounds. About 50 different types of bonds have been identified and their ΔH_f°(g) contributions and atomization energies evaluated by a procedure similar to multilinear regression analysis. Recent thermochemical data (1969-1973) on 145 oxygen compounds and about 80 ring compounds have been employed to test the efficiency of the scheme in predicting the gas phase heats of formation. This was found to be about ±0. 8 kcal/mole, which is quite comparable to the group contribution method of Benson and co-workers involving a much larger number of parameters.

The typical chemical bonds identified and resolved in respect of their bond energies bear good consistency and correlation with bond lengths and force constants measurable independently. Heats of formation and polymerization on about 47 monomer-polymer systems and enthalpies of other polymeric reactions have been predicted and compared with available experimental data.