Selected ion flow tube studies of the reactions of H 3O +, NO +, and O 2+ with some organosulphur molecules

Abstract

We report the results of a selected ion flow tube (SIFT) study of the reactions of H 3O +, NO +, and O 2 + with eight organosulphur molecules, M. If we assume that all the exothermic proton transfer reactions of H 3O + occur at the collision rate (i.e. the rate coefficients, k, are equal to the collisional rate coefficient, k c ), it is seen that the k for most of the NO + and O 2 + reactions also are equal to or close to k c . However, the reaction of H 3O + with one of the chosen reactants, CS 2, is known from our previous SIFT study to be slightly endothermic, and therefore it proceeds more slowly than the collisional rate. The ionic product of seven of the H 3O + reactions is only the protonated parent molecule MH +, but in one reaction, that of thiolacetic acid CH 3COSH, elimination of an H 2S molecule occurs in a fraction of the collisions. The NO + reactions mostly proceed via charge transfer, producing the parent molecular ion M +, but the reaction with ethanthiol is unusually complicated, with four processes occurring in parallel (charge transfer, H − and SH − transfer, and ion-molecule association), and the reaction with thiolacetic acid occurs exclusively and rapidly via SH − transfer. The O 2 + reactions proceed by dissociative charge transfer, often with the production of three or more ionic fragments of the parent molecular ion. Sample mass spectra obtained using our SIFT method of analysis of the vapours emitted by cut onion and crushed garlic are presented and discussed, noting the presence of some organosulphur molecules and other organic species.