Quantum mechanical studies of the kinetics, mechanisms and thermodynamics of gas-phase thermal decomposition of ethyl dithiocarbonate (xanthate)

Theoretical studies were carried out to investigate the thermal decomposition of ethyl dithiocarbonates (xanthate) using HartreeFock at the HF/321-G* level and the density functional method with Becke 3 Lee Yang pair DFT/(B3LYP), 6-31G*, 6-31G**, 6-31+G*, MP2 and CCSD in the ab initio method of calculation using Spartan 10. Geometric parameters, such as the bond length, bond angles, dihedral angles, heat of formation, atomic charges and vibrational frequencies, were obtained. The data were used to calculate the thermodynamics parameters, change in entropy Delta S, enthalpy change Delta H, free energy G, pre-exponential factor A, rate k at 623 K, and variation of rate k with temperatures from 498-623 K at temperature intervals of 25 K. It was observed that the values obtained are in good agreement with the experimental values for the ab initio methods, and according to Arrhenius theory, the calculated rate k increases with increasing temperature. (C) 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University.