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Zeitschrift für Physikalische Chemie

International journal of research in physical chemistry and chemical physics

Editor-in-Chief: Rademann, Klaus

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Volume 229, Issue 10-12


Reaction of the CF3 Radical with Various Cations (Ar+, Xe+, O2+, NO+, CO2+, C2F5+)

Nicholas S. Shuman / Justin P. Wiens / Jordan C. Sawyer / Shaun G. Ard / Oscar Martinez Jr. / Thomas M. Miller / Albert A. Viggiano
Published Online: 2015-10-02 | DOI: https://doi.org/10.1515/zpch-2015-0595


The kinetics of reactions of the trifluoromethyl radical (CF3) with several simple cations (Ar+, Xe+, O2+, NO+, CO2+, C2F5+) are studied via the variable electron and neutral density attachment mass spectrometry (VENDAMS) technique. CF3 is produced via dissociative electron attachment to CF3I, resulting in radical concentrations that are smaller than produced using pyrolysis methods, but better quantified. Rate constants and product branching fractions are reported, with typical uncertainties of ∼ 30%. Three of the reactions, Ar+, O2+, and C2F5+ proceed near the calculated collisional rate constant, while the other reactions are between 10% – 30% efficient. The inefficiency of the reactions of Xe+ and CO2+ can be explained by the reactions strictly obeying spin-conservation. The reaction of Ar+ yields predominantly (90%) CF2+ via dissociative charge transfer, with a minor channel to CF3+. The reaction of C2F5+ yields predominantly CF3+ with a second channel (∼ 25%) yielding C2F4+ and CF4, the only example here of a bond-breaking and bond-making reaction. For the other four reactions, only charge transfer to yield CF3+ is observed. Rate constants for these same ions with CF3I are also reported and found to be rapid with a variety of products formed.

Keywords: Radical; Cation; Reaction Kinetics; Ion-molecule; Ion-radical; Fluorocarbon; Rate Constant

About the article

Accepted: 2015-04-25

Received: 2015-03-17

Published Online: 2015-10-02

Published in Print: 2015-10-28

Citation Information: Zeitschrift für Physikalische Chemie, Volume 229, Issue 10-12, Pages 1691–1707, ISSN (Online) 2196-7156, ISSN (Print) 0942-9352, DOI: https://doi.org/10.1515/zpch-2015-0595.

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