NEGATIVE ION-MOLECULE REACTIONS IN SULFURYL HALIDES

The negative ion-molecule reactions in sulfuryl chloride, sulfuryl fluoride, and sulfuryl chloride fluoride are described. Their mass spectra have been determined as a function of pressure and time at different ionization energies. In SO2CI2the most abundant primary ion is Cl-. It reacts with SO2CI2forming the secondary ions CI3-and SO2CI-. SO2CI-reacts with the neutral leading to the formation of CI3-. Other secondary ions are formed in relatively small amounts. Equilibrium studies made it possible to estimate the heat of formation of CI3-as -71.8 kcal/mol-1. In sulfuryl fluoride SO2F3-is formed by two different processes: a three-body attachment reaction of F-with SO2F2and the reaction of F2-with SO2F2leading to SO2F3-and F. In sulfuryl chloride fluoride the primary ions F-and Cl-react with SO2C1F leading to the formation of SO2F-. Rate studies were made by varying both pressure and time, and rate constants were obtained for most of the principal reactions. © 1979, American Chemical Society. All rights reserved.