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Arrhenius Parameters for the Reaction of Trifluoromethyl Radicals with Cyanogen Chloride

DOI: 10.1039/f19817700253

Source and publish data:

Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases p. 253 - 260 (1981)

Update date:2022-08-11

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Authors:

Cosa, FernandoCosa, Fernando

Oexler, Elena V.Oexler, Elena V.

Staricco, Eduardo H.Staricco, Eduardo H.

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Article abstract of DOI:10.1039/f19817700253

The reaction of CF3 radicals with ClCN has been studied over a wide temperature range, 268-693 K, using CF3 radicals generated by the photolysis of CH3I.Over the range 408-473 K, CF3COCF3 was also used as a CF3 radical source.The radicals react with ClCN by addition followed by decomposition of the adduct and by chlorine abstraction: .The Arrhenius plot for this reaction is strongly curved.Using data from the low- and high-temperature regions, the following expressions for the rate constants for addition reaction (1) and chlorine abstraction (3) relative to CF3 recombination have been obtained: .The combination of E1 with the difference E-1-E2, which can be estimated, gives an upper limit for ΔH03 from which an approximate value of ΔH0f(CN) of 393.4 kJ mol-1 or less has been obtained.

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