A study of ion-molecule reactions in the Xe+ plus acetone system by flow technique mass spectrometry

Flow reactor technique mass spectrometry was used to study the reaction of Xe+ ions with acetone and the subsequent transformation of the product ions at a buffer gas (He) pressure of 1.1 Torr. A kinetic scheme describing the evolution of the ionic composition of the most abundant ionic constituents (up to the fourth generation) has been determined. The values of rate constants and branching ratios of the key reactions involved in the scheme have been evaluated from experimental kinetic dependences. The main channel of the Xe+ + acetone reaction (which occurs practically at each collision) is the production of the CH3CO+ fragment as the exothermicity of the charge transfer is higher than the dissociation threshold of the ground state acetone cation. The formation of a 2.5% fraction of the molecular ion via a parallel channel indicates that the production of an electronically-excited, long-lived state of the acetone cation takes place. The competition of association and particle-rearrangement processes in the reactions of the CH3CO+ ion and its CH3CO+(CH3)(2)CO cluster with acetone was also studied. It was found that channels in which a rearrangement of particles takes place (the production of protonated acetone for CH3CO+ and the protonated acetone dimer for CH3CO+(CH3),CO) are slower than the association process at 1.1 Torr. Total effective rate constants (involving all the channels) for these ions are approximately several 10(-10) cm(3) s(-1) units and the rate constant for the cluster ion is about 40% smaller. The production of slowly reacting C3H6O+ ions with an increase of acetone concentration was observed. Their structure may be ascribed to the enolic acetone cation (CH2COHCH3+). The only pathway for the loss of the ion in an exoergic reaction with acetone is the association process. The product of the process, i.e. the non-protonated ionic dimer of acetone, was also observed in the mass spectra.