Abstract

AbstractUnimolecular and collision induced decompositions of the major ions of selected polychlorinated biphenyls in the field free region between the magnetic and electric sectors of a reversed Nier‐Johnson instrument were studied. Loss of a single chlorine atom is associated with a wide range of kinetic energy releases but still can be correlated by a single reaction mechanism. Loss of two chlorines is interpreted as a rapid sequential loss from isomerized molecular ions for all but one compound. The decompositions which metastable ions undergo are not always the same as those of high energy ions in the source. Correlations between substituent positions and kinetic energy release can be made for the [M]+·→[MCl]+ and [MCl2]+· processes.

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