Journal of Physical Chemistry p. 1318 - 1323 (1993)
Update date:2022-08-11
Topics:
Giles, K.
Grimsrud, E. P.
Measurements by the kinetic ion mobility mass spectrometer (KIMMS) of (i) equilibrium constants for the clustering reactions X(1-)(CHCl3)i-1 + CHCl3 ->/<- X(1-)(CHCl3)i, where X(1-) = Cl(1-) and Br(1-) and i = 1 or 2, (ii) single ion mobilities for the ions Cl(1-)(CHCl3)0-2 and Br(1-)(CHCl3)0-1, and (iii) rate constats for the SN2 nucleophilic displacement reactions of a distribution of chloride cluster ions, Cl(1-)(CHCl3)0-2, with CH3Br and with CH3I in nitrogen buffer gas at atmospheric pressure are reported.A unique feature of the present equilibrium and kinetic measurements is that they are obtained from ion mobility measurements and, therefore, are not subject to potential sources of error that can accompany mass spectrometric-based measurements involving aperture sampling of a high-pressure ion source.Another unique feature of the present investigations is that the reactivity of a selected set of cluster ions is determined under physical conditions in which the individual ions are kinetically labile with respect to cluster decomposition and growth.
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