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Title: Direct rate constant measurements for the reaction of ground-state atomic oxygen with ethylene, 244-1052 K

The rate constant for the reaction of ground-state atomic oxygen with ethylene was determined by using two techniques: flash photolysis-resonance fluorescence (FP-RF, 244-1052 K) and discharge flow-resonance fluorescence (DF-RF, 298-1017 K). Kinetic complications due to the presence of molecular oxygen in the FP-RF experiments at high temperatures (T > 800 K) were overcome by using NO as the photolytic source of the O atoms. The rate constant, k/sub 1/ (T), derived in this study exhibits extreme non-Arrhenius behavior, but it can be successfully fit to the sum of exponentials expression, 244-1052 K, k/sub 1/(T) = (1.02 +/- 0.06) x 10/sup -11/ exp(-753 +/- 17 K/T) + (2.75 +/- 0.26) x 10/sup -10/ exp(-4220 +/- 550 K/T), in units of cm/sup 3/ molecule/sup -1/ s/sup -1/. Additionally, a fit of the results of this work to a simple transition-state theory expression and the comparison of these results with those of other workers are discussed.
Authors:
; ; ; ;
Publication Date:
OSTI Identifier:
6808827
DOE Contract Number:
AC02-76CH00016
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Phys. Chem.; (United States); Journal Volume: 91:6
Research Org:
Brookhaven National Lab., Upton, NY
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ETHYLENE; CHEMICAL REACTIONS; NITRIC OXIDE; PHOTOLYSIS; OXYGEN; GROUND STATES; CHEMICAL REACTION KINETICS; EXPERIMENTAL DATA; FLUORESCENCE; FLUORESCENCE SPECTROSCOPY; HIGH TEMPERATURE; LOW TEMPERATURE; MEDIUM TEMPERATURE; RESONANCE ABSORPTION; VERY HIGH TEMPERATURE; ABSORPTION; ALKENES; CHALCOGENIDES; DATA; DECOMPOSITION; ELEMENTS; EMISSION SPECTROSCOPY; ENERGY LEVELS; HYDROCARBONS; INFORMATION; KINETICS; LUMINESCENCE; NITROGEN COMPOUNDS; NITROGEN OXIDES; NONMETALS; NUMERICAL DATA; ORGANIC COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; PHOTOCHEMICAL REACTIONS; REACTION KINETICS; SPECTROSCOPY 400201* -- Chemical & Physicochemical Properties; 400500 -- Photochemistry