Some Ion–Molecule Reactions of H3+ and the Proton Affinity of H2

Abstract

The flowing afterglow technique has been used to study the reactions of H3+ with a number of neutral reactants at thermal energies. Proton transfer was the only primary reaction observed with N2, CO, CO2, N2O, NO, CH4, C2H2, H2O, and NH3. Both proton transfer and dissociative charge transfer were observed with C2H4 and C2H6, while dissociative charge transfer is the exclusive primary process with NO2. Secondary reactions were observed with NO, C2H6, C2H4, and C2H2. Cluster ions were formed between NO+ and NO2 and H2O, between H3O+ and H2O, CO2, and CO, and between NH4+ and NH3 and H2O. Proton transfer was also observed between HN2+ and CO2, N2O, CH4, and H2O, and between HO2+ and H2 and N2. Rate constants were obtained for these reactions and are discussed. Limits could be placed on the proton affinity (P.A.) of H2 from the failure to observe rapid proton transfer to O2 and the observation of proton transfer to N2. These indicate 4.2 < P.A. (H2)< 4.7 eV with a recommended value of 4.4 eV. The technique can be used to measure relative proton affinities of gases.