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Kinetics and equilibria of ion-molecule association reactions : studied using temperature variable high pressure ion sources

By Richard Thomas Gallagher


Interest in termolecular association reactions of the type shown below, stems from their\ud importance in the chemistry of planetary atmospheres, gas-cooled nuclear reactors and\ud gas-phase cluster ions. This study is concerned with evaluating the rate constants of such\ud X+ + X + M ------> X2+ + M k3 (1)\ud reactions as both a function of temperature and of the third body M. The values of the third\ud order rate constant k3 are expressed conventionally in terms of k3 = CT-m where T is the\ud temperature and C and m are constants characteristic of the reaction which depend also on the\ud nature of M. Literature now shows a general measure of agreement on values of C and m in\ud several studies for which X=M, however, inconsistent values have been reported on the M=He system. This thesis describes an investigation of the two systems X=N2, CO and M= the\ud reactant or a rare gas.\ud Experiments were conducted in a conventional high pressure ion source and a pulsed drift\ud ion source fitted to an updated Kratos MS9 mass spectrometer.\ud Results obtained for the one component studies show good agreement with other literature\ud values for the temperature dependence, m. In general, for both N2 and CO systems, He was\ud found to have the same efficiency as the parent molecule as a third body at 300K, but the\ud temperature dependence of k3 is markedly lower. Ar was found to behave very similarly to the\ud parent molecule in both systems. For the CO system, although good agreement is found for the\ud temperature dependence result with literature, there is still an uncertainty of about a factor of 2\ud in the room temperature values of k3

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