Theoretical study of the thermochemistry and the kinetics of the SF xCl ( x = 0–5) series

Abstract

A systematic thermodynamic and kinetic study of the entire SF x Cl ( x = 0–5) series has been carried out. High-level quantum chemical composite methods have been employed to derive enthalpy of formation values from calculated atomization and isodesmic energies. The resulting values for the SCl, SFCl, SF 2Cl(C 1), SF 3Cl(C s), SF 4Cl(C s) and SF 5Cl molecules are 28.0, −36.0, −64.2, −134.3, −158.2 and −237.1 kcal mol −1. A comparison with previous experimental and theoretical values is presented. Statistical adiabatic channel model/classical trajectory, SACM/CT, calculations of selected complex-forming and recombination reactions of F and Cl atoms with radicals of the series have been performed between 200 and 500 K. The reported rate coefficients span over the normal range of about 6 × 10 −12 and 5 × 10 −11 cm 3 molecule −1 s −1 expected for this type of barrierless reactions.