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

Abstract

Theoretical studies were carried out to investigate the thermal decomposition of ethyl dithiocarbonates (xanthate) using Hartree–Fock 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 ΔS, enthalpy change ΔH, free energy G, pre-exponential factor A, rate k at 623K, and variation of rate k with temperatures from 498–623K at temperature intervals of 25K. 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.