Gas-phase chemistry of vanadium oxide cluster cations 3. Reactions with CCl4

R. C. Bell, K. A. Zemski, A. W. Castleman

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Abstract

The reactions of selected vanadium oxide cluster cations with carbon tetrachloride were studied using a triple quadrupole mass spectrometer coupled with a laser vaporization source. The vanadium oxide species VO2+, V2O4-6+, V3O6-8+, V4O8-11+, V5O11-13+, V6O13-15+, and V7O16-18+ demonstrated several pathways for reaction with CCl4. The chloride ion transfer reaction is the dominant reaction pathway for the smaller clusters that contain three or fewer vanadium atoms. For the larger clusters, the abstraction of two chlorine atoms with the transfer of oxygen to the neutral reactant molecule dominates their reactions with CCl4, leading to the production of phosgene. This is consistent with the reactions that occur over the condensed-phase vanadium oxide catalyst for the degradation of carbon tetrachloride to phosgene and carbon dioxide. In addition, oxidation reactions are observed to occur more readily for clusters that contain vanadium atoms with oxidation states lower then +5.

Original languageEnglish (US)
Pages (from-to)1585-1591
Number of pages7
JournalJournal of Physical Chemistry A
Volume103
Issue number11
StatePublished - Dec 1 1999

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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