MEASUREMENTS OF EQUILIBRIA AND REACTIVITY OF CLUSTER IONS AT ATMOSPHERIC-PRESSURE - REACTIONS OF CL-(CHCL3)0-2 WITH CH3BR AND CH3I

被引:33
作者
GILES, K [1 ]
GRIMSRUD, EP [1 ]
机构
[1] MONTANA STATE UNIV,DEPT CHEM,BOZEMAN,MT 59717
关键词
D O I
10.1021/j100109a012
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Measurements by the kinetic ion mobility mass spectrometer (KIMMS) of (i) equilibrium constants for the clustering reactions X-(CHCl3)i-1 + CHCl3 half arrow right over half arrow left X-(CHCl3)i, where X- = Cl- and Br- and i = 1 or 2, (ii) single ion mobilities for the ions Cl-(CHCl3)0-2 and Br-(CHCl3)0-1, and (iii) rate constants for the S(N)2 nucleophilic displacement reactions of a distribution of chloride cluster ions, Cl-(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 investigation 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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页码:1318 / 1323
页数:6
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