Topic:
Thermochemistry and Oxidation Reactions of Small Sulfur Hydrocarbons

Abstract:
Thermochemical properties and elementary reaction pathways for the association of O2 with HC•=S, CH3S•, and CH3S(=O)C•H2 radicals are analyzed.

CBS-QB3, G3MP2, and density functional methods are utilized to estimate ?Hf,298, S298, and Cp(T) for reactants and transition states. Isodesmic working reactions are applied to evaluate enthalpies of formation. Contributions to the entropy and the heat capacity from translation, vibration, and external rotations are calculated using the rigid-rotor-harmonic-oscillator approximation based on the B3LYP/6-311++G(d,p) structures. Hindered internal rotational contributions to entropies and heat capacities are calculated by summation over the energy levels found using the internal rotor potential from B3LYP/6-31G(d,p) calculation level.

Rate constants for the chemical activation and dissociation reactions are estimated as a function of temperature and pressure using quantum RRK analysis for k(E) and master equation for pressure fall-off.  Data are compared with the available experiment results.

Seminar Series Coordinators:
Dr. Zeyuan Qiu       zeyuan.qiu@njit.edu             973-596-5357
Dr. Sergiu Gorun    sergiu.m.gorun@njit.edu       973-569-6595