Abstract
The determination of rate constants by using flow techniques typically is made under pseudo-first-order reaction conditions, whereby rates are derived from semilogarithmic plots of ion intensity versus reactant gas concentration. Reproducible curvature in such plots is often taken as an indication of measurable differences in the reactivity of various ion states. In the present study, curvature is traced to effects arising from the mass flow of the buffer gas. These results, in conjunction with previous investigations, suggest that accurate determination of rate constants using flow techniques requires a judicious selection of flow conditions and reactant gas inlet design with due consideration to the flow tube dimensions.
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