Electron attachment and positive ion chemistry of monohydrogenated fluorocarbon radicals

Abstract

Rate coefficients and product branching fractions for electron attachment and for reaction with Ar(+) are measured over the temperature range 300-585 K for three monohydrogenated fluorocarbon (HFC) radicals (CF3CHF, CHF2CF2, and CF3CHFCF2), as well as their five closed-shell precursors (1-HC2F4I, 2-HC2F4I, 2-HC2F4Br, 1-HC3F6I, 2-HC3F6Br). Attachment to the HFC radicals is always fairly inefficient (between 0.1% and 10% of the Vogt-Wannier capture rate), but generally faster than attachment to analogous perfluorinated carbon radicals. The primary products in all cases are HF-loss to yield C(n)F(m-1)(-) anions, with only a minor branching to F(-) product. In all cases the temperature dependences are weak. Attachment to the precursor halocarbons is near the capture rate with a slight negative temperature dependence in all cases except for 2-HC2F4Br, which is ∼10% efficient at 300 K and becomes more efficient, approaching the capture rate at higher temperatures. All attachment kinetics are successfully reproduced using a kinetic modeling approach. Reaction of the HFC radicals with Ar(+) proceeds at or near the calculated collisional rate coefficient in all cases, yielding a wide variety of product ions.

Kinetics of Cations with C2 Hydrofluorocarbon Radicals

“…We measured the kinetics of electron–radical processes − and several cation reactions with the CF 3 , CH 3 , and hydrofluorocarbon radicals . That work was an extension of the variable electron and neutral density attachment mass spectrometry (VENDAMS) technique developed in our laboratory .…”