Measurement of the OH reaction rate constants for CH{sub 3}CH{sub 2}OH, CF{sub 3}CF{sub 2}CH{sub 2}OH, and CF{sub 3}CH(OH)CF{sub 3}

Journal Article · Thu Apr 15 04:00:00 UTC 1999 · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory

DOI:https://doi.org/10.1021/jp983961x· OSTI ID:347656

Tokuhashi, Kazuaki; Nagai, Hidekazu; Takahashi, Akifumi; Kaise, Masahiro; Kondo, Shigeo; Sekiya, Akira; Gotoh, Yoshihiko ^[1]; Takahashi, Mitsuru; Suga, Atsuo ^[2]

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1. National Inst. of Materials and Chemical Research, Tsukuba, Ibaraki (Japan)
2. Research Inst. of Innovative Technology for the Earth, Tokyo (Japan)

Fully halogenated chlorofluorocarbons (CFCs) cause depletion of the stratospheric ozone layer as well as global warming. Partially fluorinated alcohols are important in relevance with potential substitutes of CFCs. The OH reaction rate constants have been measured for CF{sub 3}CH{sub 2}OH, CF{sub 3}CF{sub 2}CH{sub 2}OH, and CF{sub 3}CH(OH)CF{sub 3} over the temperature range 250--430K. Kinetic measurements have been carried out using the discharge flow, laser photolysis, and flash photolysis methods, combined respectively with the laser-induced fluorescence technique to monitor the OH radical concentrations. The influence of impurities contained in the sample of CF{sub 3}CF{sub 2}CH{sub 2}OH has been investigated by means of sample purification using gas chromatography. No sizable effect of impurities was found on the measured rate constants of these three fluorinated alcohols. The Arrhenius rate constants have been determined from the respective kinetic data as {kappa}(CF{sub 3}CH{sub 2}OH) = (2.00 {+-} 0.37) {times} 10{sup {minus}12} exp[{minus}(890 {+-} 60)/T], {kappa}(CF{sub 3}CF{sub 2}CH{sub 2}OH) = (1.40 {+-} 0.27) {times} 10{sup {minus}12} exp[{minus}(780 {+-} 60)/T], and {kappa}(CF{sub 3}CH(OH)CF{sub 3}) = (6.99 {+-} 1.56) {times} 10{sup {minus}13} exp[{minus}(990 {+-} 70)/T] cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. A method of predicting the OH reaction rate constants for fluorinated alcohols, hydrofluorocarbons, alkanes, and alcohols has been proposed.

• OSTI ID: 347656
• Journal Information: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 15 Vol. 103; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

Related Subjects

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION
54 ENVIRONMENTAL SCIENCES
AIR POLLUTION
ALCOHOLS
ALKANES
ATMOSPHERIC CHEMISTRY
CHLOROFLUOROCARBONS
GREENHOUSE EFFECT
HYDROXYL RADICALS
MATERIAL SUBSTITUTION
ORGANIC FLUORINE COMPOUNDS
OZONE LAYER