Time-resolved observation of the formation of CF{sub 2}O and CFClO in the CF{sub 2}Cl + O{sub 2} and CFCl{sub 2} + O{sub 2} reactions. The unimolecular elimination of Cl atoms from CF{sub 2}ClO and CFCl{sub 2}O radicals

Journal Article · Thu Feb 20 04:00:00 EST 1992 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/j100183a046· OSTI ID:554989

Wu, Fuxiang; Carr, R W ^[1]

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1. Univ. of Minnesota, Minneapolis, MN (United States)

The unimolecular elimination of chlorine atoms from CF{sub 2}ClO and CFCl{sub 2}O radicals has been observed at 238 and 298 K, and at 4-20 Torr total pressure by measurement of the rate of formation of the carbonyl halide product in real time. The fragment ion (CFO){sup +} was found to be specific for the detection of CF{sub 2}O and CFClO and was monitored by time-resolved mass spectrometry in flash photolysis of mixtures of CF{sub 2}ClBr or CFCl{sub 3} with O{sub 2} and NO. These two Cl atom elimination reactions were verified to be very facile, even at low temperatures. The rate constants were estimated by regression analysis of experimentally measured formation curves of CF{sub 2}O and CFClO, and decay curves of CF{sub 2}ClO{sub 2} and CFCl{sub 2}O{sub 2} were determined in the same experiments. The estimated 298 K rate constants are (6.4 {+-} 1.4) x 10{sup 4} s{sup {minus}1} for CF{sub 2}ClO and (1.2 {+-} 0.4) x 10{sup 5} s{sup {minus}1} for CFCl{sub 2}O. 30 refs., 4 figs., 6 tabs.

• Sponsoring Organization: USDOE
• OSTI ID: 554989
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 4 Vol. 96; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
54 ENVIRONMENTAL SCIENCES
ATMOSPHERIC CHEMISTRY
CHEMICAL REACTION KINETICS
CHLOROFLUOROCARBONS
OXIDATION
TEMPERATURE RANGE 0065-0273 K
TEMPERATURE RANGE 0273-0400 K