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Author Jarvis, G. K. ♦ Mayhew, C. A. ♦ Tuckett, R. P.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword ENVIRONMENTAL SCIENCES ♦ CHEMISTRY ♦ CARBON COMPOUNDS ♦ ATMOSPHERIC CHEMISTRY ♦ CHEMICAL REACTIONS ♦ NITROGEN OXIDES ♦ CATIONS ♦ OZONE ♦ MASS SPECTROMETERS ♦ IONIZATION ♦ ALKENES ♦ ETHYLENE ♦ FLUORINE ♦ NUMERICAL DATA
Abstract The bimolecular rate coefficients and ion products for the reactions of H{sub 3}O{sup +}, NO{sup +}, O{sub 2}{sup +}, H{sub 2}O{sup +}, N{sub 2}O{sup +}, O{sup +}, CO{sub 2}{sup +}, CO{sup +}, N{sup +}, and N{sub 2}{sup +} with three fluoroalkenes (C{sub 2}F{sub 4}, C{sub 3}F{sub 6}, and 2-C{sub 4}F{sub 8}) and three fully saturated perfluorocarbons (C{sub 2}F{sub 6}, C{sub 3}F{sub 8}, and n-C{sub 4}F{sub 10}) at 300 K are reported. All six perfluorocarbons are found to be unreactive with NO{sup +}. C{sub 2}F{sub 6} is also unreactive with O{sub 2}{sup +}, H{sub 2}O{sup +}, and N{sub 2}O{sup +}, and C{sub 3}F{sub 8} and n-C{sub 4}F{sub 10} are also unreactive with O{sub 2}{sup +}. C{sub 3}F{sub 6} is the only perfluorocarbon studied that reacts with H{sub 3}O{sup +} at a measurable rate. All the other reactions take place at or close to the collisional rate, the exceptions being the reactions of N{sub 2}O{sup +} with C{sub 2}F{sub 4} and C{sub 3}F{sub 8}, and CO{sub 2}{sup +} with C{sub 2}F{sub 4} and C{sub 2}F{sub 6}, for which the experimental rate coefficients show marked departures from the collisional values. It is proposed that most of the reactions proceed through a complex intermediate resulting in electrophilic attack by the ion on the perfluorocarbon. This mechanism generally takes precedent over `long-range` (formal) charge transfer. This work is of possible relevance to atmospheric ion-chemistry and plasma processes. 39 refs., 1 fig., 2 tabs.
ISSN 00223654
Educational Use Research
Learning Resource Type Article
Publisher Date 1996-10-24
Publisher Place United States
Journal Journal of Physical Chemistry
Volume Number 100
Issue Number 43


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