The importance of three-body processes to reaction kinetics at atmospheric pressures. III. Reactions of He/sub 2//sup +/ with selected atomic and molecular reactants

For pt.II see ibid., vol.22, p.47-50 (1986). Results are presented from studies of the reactions He/sub 2//sup +/ with five species displaying a wide variation of molecular structures and polarizabilities: Ar, Xe, Ne, O/sub 2/, and CO/sub 2/. Measurements were made in the afterglows of preionized discharges into the reactant gas mixtures diluted in 1-6-atm pressures of helium. Effective rates of reaction were obtained that could be separated into contributions from bimolecular and termolecular channels. The latter generally dominated, showing no evidence of saturation up to 6 atm pressure of diluent. These results continue to confirm earlier reports that the initial capture step in the reaction is not limited by the Langevin rate as usually applied. Such super-Langevin rates appear to be a general phenomenon at high pressures, at least for the reactions of He/sub 2//sup +/. In the most extreme case examined, He/sub 2//sup +/+CO/sub 2/, the effective rate of reaction contributed by all channels was found to exceed Langevin by a factor of five at 6-atm pressure of diluent. >

[1]  J. Pouvesle,et al.  The importance of three-body processes to reaction kinetics at atmospheric pressures--II: Occlusive effects of discharge morphology , 1986 .

[2]  J. Pouvesle,et al.  The importance of three-body processes to reaction kinetics at atmospheric pressures--I: Archetype reactions of He species with N 2 , 1986 .

[3]  C. B. Collins The nitrogen ion laser pumped by charge transfer , 1984 .

[4]  F. W. Lee,et al.  Modeling of ion–molecule reactions at high pressures , 1983 .

[5]  A. Bouchoule,et al.  Modeling of the charge transfer afterglow excited by intense electrical discharges in high pressure helium nitrogen mixtures , 1982 .

[6]  F. W. Lee,et al.  Measurement of the rate coefficients for the bimolecular and termolecular de‐excitation reactions of He(2 3S) with selected atomic and molecular species , 1979 .

[7]  F. W. Lee,et al.  Pressure dependence of the reaction of He2(3Σ) metastable molecules with Ar , 1978 .

[8]  F. W. Lee,et al.  Measurement of the rate coefficients for the bimolecular and termolecular ion–molecule reactions of He2+ with selected atomic and molecular species , 1978 .

[9]  M. Payne,et al.  Charge transfer and Penning ionization of N2, CO, CO2, and H2S in proton excited helium mixtures , 1977 .

[10]  F. W. Lee,et al.  Measurement of the rate coefficients for the bimolecular and termolecular de‐excitation reactions of He(23S) with Ne, Ar, N2, CO, CO2, and CH4 , 1976 .

[11]  F. W. Lee,et al.  Measurement of the rate coefficients for the bimolecular and termolecular charge transfer reactions of He2+ with Ne, Ar, N2, CO, CO2, and CH4 , 1976 .

[12]  J. L. Calvé,et al.  Effets d'additifs sur la postluminescence de He2 dans l'hélium excité par une impulsion intense d'électrons , 1971 .

[13]  D. Bohme,et al.  Flowing Afterglow Studies of the Reactions of the Rare‐Gas Molecular Ions He2+, Ne2+, and Ar2+ with Molecules and Rare‐Gas Atoms , 1970 .

[14]  George Gioumousis,et al.  Reactions of Gaseous Molecule Ions with Gaseous Molecules. V. Theory , 1958 .