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Origin of adduct ions in the electron‐capture mass spectrum of tetracyanoethylene
Author(s) -
Culbertson J. A.,
Sears L. J.,
Knighton W. B.,
Grimsrud E. P.
Publication year - 1992
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210270320
Subject(s) - tetracyanoethylene , ion , chemistry , mass spectrum , adduct , electron ionization , mass spectrometry , ion source , analytical chemistry (journal) , photochemistry , organic chemistry , chromatography , ionization
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.