A kinetic model for chemical events occurring within the high pressure electron capture mass spectrometer (HPECMS) ion source is developed which includes four different pathways by which unconventional negative ions can be produced. These routes to unusual ions include reactions of gas phase free radicals, surfaceassisted reactions, ion-electron and ion-ion recombination reactions, and ion-wall neutralization. The model developed here provides a diagnostic tool useful for the elucidation of unusual HPEC spectra. Such spectra for two environmentally important classes of compounds are explained by use of the model. These compound classes include the trifluoroacetic derivatives of polycyclic aromatic amines, which have been shown to be present in materials derived from liquified coal, and the derivatives of hexachlorocyclopentadiene, which are used as pesticides. It is shown in this study that several processes, in addition to electron capture, can be operative in the typical HPECMS ion source, and that these processes can be used advantageously for the generation of informative and sensitive mass spectral signals.

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High‐pressure Electron Capture Mass Spectrometry (HPECMS) has demonstrated extraordinarily high chemical specificity and sensitivity in the analysis of numerous compounds of environmental and biomedical interest. In the application of this technique, however, difficulties in the form of unexpected EC mass spectra and unexplainable variations of sensitivity are often noted. In this review article, two distinct sets of processes that determine the nature of the ions produced in an HPEC ion source are reviewed and discussed. The first set of gas‐phase processes comprises the electron capture mechanism, leading to simple fragment and molecular anions. The second set of processes is imposed by physical realities of the typical HFEC ion source, These secondary processes can have large effects on the sensitivity of HPECMS to various types of EC‐active compounds and can lead to the production of unexpected ions in HPEC mass spectra. It will be shown that the successful use of HPECMS is greatly facilitated by an understanding of all of the above interactive factors. The scope of this review is limited to the processes that will be important only under the relatively pristine ion source conditions that are typically established for the trace analysis of EC‐active compounds introduced in very small quantities by capillary‐column gas chromatography. © 1996 John Wiley & Sons, Inc.

The high-pressure electron-capture (HPEC) mass spectrum of tetracyanoethylene (TCNE) is dominated by unexpected hydrogen atom and hydrocarbon radical adduct ions when methane is used as the buffer gas. The origin of these unexpected ions was investigated by three separate mass spectrometric experiments: the electron-capture (EC) rate constant of TCNE was determined and integrated into a previously developed kinetic model of HPEC ion source events; electron impact mass spectra of TCNE were obtained following exposure of the ion source surfaces to irradiated methane and irradiated carbon dioxide; and TCNE was determined by gas chromatographic introduction into the HPEC ion source with multiple ion monitoring. All of these experiments suggest that the reactions leading to the major adduct ions observed in the HPEC mass spectrum of TCNE are initiated by alteration of TCNE on the walls of the ion source rather than in the gas phase.