Gallagher, Richard Thomas (1987) Kinetics and equilibria of ion-molecule association reactions : studied using temperature variable high pressure ion sources. PhD thesis, University of Warwick.

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Abstract

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

Item Type:	Thesis (PhD)
Subjects:	Q Science > QC Physics
Library of Congress Subject Headings (LCSH):	Ion-molecule collisions, Ionized gases, Graphite -- Oxidation
Official Date:	November 1987
Dates:	Date Event November 1987 Submitted
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Jennings, Keith R., 1932-
Sponsors:	Science and Engineering Research Council (Great Britain) (SERC) ; Great Britain. Central Electricity Generating Board
Extent:	xx, 121 leaves
Language:	eng

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