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Bimolecular self-reactions of phenyl-substituted phenoxyl radicals studied by flash photolysis

✍ Scribed by I. V. Khudyakov; P. P. Levin; V. A. Kuzmin; C. R. H. I. De Jonge

Publisher: John Wiley and Sons
Year: 1979
Tongue: English
Weight: 757 KB
Volume: 11
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550110403

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✦ Synopsis

Rate, equilibrium, and thermodynamic data for reaction (1) of 2,6-diphenyl-4R-phenoxyl radicals, where R=OCH3 (I), Ph (11), OCzHs (III), O-n-ClSH37 (IV), and 2,6-dicyclohexyl-4-phenylphenoxyl radical (V),

in various solvents are obtained. The k l values of radicals I t,o V are within (5.5 f 1.0) X 107-(1.4 f 0.3) X 10gM-l.sec-l in propanol. The solvent effect on k l for radicals I and I1 was studied. The dimerization of radical I is diffusion-controlled in all solvent studies. The dimerization of radical I1 is viscosity-dependent but not diffusion-controlled. Plots of k l against ET have a V shape. Specific solvent-solute interactions are seeming to be responsible for numerical k l values of radicals I and 11. The solvent effect is more pronounced for "slow" dimerization of radicals I1 than for "fast" dimerization of radicals I. The minimum k l values correspond to pyridine and chloroform. The reaction (1) rate strongly depends upon the composition of a chloroform (S)+msolvent binary mixture. Besides reaction (1) the following reactions proceed in binary mixture:

PhO, + PhO, F? D K14 = 0.18 f 0.05 M-l, kls = (2.0 f 1.0) X I@M-'.sec-' (radical I, S-CCL4 mixture) K14 = 0.9 f 0.2M-', k15 = (1.2 f 0.5) X 107M-'-sec-' (radical 11, S-C6H14 mixture) K14 = 0.45 f 0.10M-', k15 = (9.0 f 2.0) X 106M-'-sec-l (radical 11, S-CCL4 mixture)

In all cases k16 << k15. Factors influencing dimerization rates in strongly nonideal mixtures CH30H-CCL4 and CHsOH-CHCls are discussed.

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