Rate parameters for reactions of ground-state difluorocarbene and determination of the absolute intensity of the Ã1B1–X1A1absorption bands
- 1 January 1969
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in Transactions of the Faraday Society
- Vol. 65, 1188-1198
- https://doi.org/10.1039/tf9696501188
Abstract
An effective extinction coefficient (to base 10) of 7620 ± 400 l. mole–1 cm–1 at 298°K was derived for the band maximum of CF2 at 249 nm, by measuring the intensity of the Ã(1B1)–X(1A1) system after flash photolysis of NO2 in mixtures containing C2F4 and N2. The oscillator strength of the transition was 0.028 ± 10%. The decay of CF2 was studied in flashed C2F4+ N2 and CF2CFCl + N2 mixtures and rate parameters for the dimerization were recorded: k1=(2.5 ± 0.5)106T½ exp(–200 ± 50/T(°K))l. mole–1 sec–1. An approximate rate constant for reaction of CF2 with CFCl at 298°K is 6(± 5)108 l. mole–1 sec–1. Data for the reaction (2) of CF2 with C2F4 were combined with the value for k1, to obtain k2=(8.7)104T½ exp(–3200 ± 625/T(°K))l. mole–1 sec–1.Keywords
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