Enthalpies (?H�f 298), entropies, heat capacities and carbon - hydrogen bond dissociation energies are reported for a number of C7 and C8 branched alkane hydrocarbons.  ?H�f 298 and C�H BDEs are calculated using isodesmic reactions selected for similar bonding environments on both sides of the reaction. Calculation methods include B3LYP (using the 6-31G(d,p) and 6-311G(2d,2p) basis sets), CBS-QB3, and G3MP2B3 levels of theory. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) level for contributions to entropy and heat capacities. The C�H bond energies on carbons adjacent to different branching structures are found to vary.  Initial reactions of these alkyl radicals  involve association with O2.  Well depths and kinetic analysis of isomerization reactions on peroxy radicals resulting from reactions of oxygen molecule association to the carbon radical on the branched alkanes are evaluated and compared for several of the systems.

Thermochemistry and bond dissociation energies of C7 and C8 branched alkanes and radical reactions with oxygen

245th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.