Studies in mass spectrometry. Part XXXII. The kinetic approach to mass spectrometry

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Abstract
Experimental results have shown that, for a number of compounds investigated, the relative ion abundances at the collector are a function of the time, t2, taken to reach the collector from the source. Experimental support for the ‘instrument constant,’ introduced by Bursey and McLafferty, is given. Extrapolation to the source value of [A+]/[M+](from the measured collector value of [A+]/[M+] for the reaction M+→ A+) is impossible with any accuracy where accelerating voltages higher than 8 kV cannot be used. However, in the substituent effects investigated, changes in [A+]/[M+] between source and collector are probably sufficiently similar from compound to compound not to necessitate modification of the steady-state theory on that account alone. It is emphasised that this result is related to important contributions to recorded M+ intensities from ions with insufficient energies to decompose, and it then follows that [A+]/[M+] is a function of the rates of competing unimolecular decompositions.

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