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• W2058903326 endingPage "604" @default.
• W2058903326 startingPage "597" @default.
• W2058903326 abstract "The reactions of SO˙–4 with several substituted benzenes having the general formula, C6H5–nXnY (where X = F, Cl or Br and Y = CH3, CH2Cl, CHCl2, CF3 or OCH3), have been investigated in aqueous solution by pulse radiolysis. The transient absorption spectra exhibit maxima at 315–330 nm and additional peaks at 270–290 nm with chlorotoluenes and weak peaks around 400 nm with chlorobenzene and 3-chlorofluorobenzene. Only in the case of 3-chloroanisole is the observed spectrum different, exhibiting two distinct peaks at 290 and 475 nm. The second-order rate constants for the reaction of SO˙–4 range from about 108 for 2-chlorobenzotrifluoride to 1010 dm3mol–1s–1 for 3-chloroanisole. It is concluded from the Hammett treatment (ρ+=– 1.6) that the reaction mechanism involves both direct electron transfer and addition–elimination reactions. The intermediate radical cation is hydrolysed to give the corresponding ˙OH adduct absorbing at 315–330 nm except in the case of 3-chloroanisole where it is stabilized. The formation of a benzyl-type radical by direct H abstraction by SO˙–4 from the CH3 group and/or deprotonation of the radical cation is an additional process whose extent is determined by the relative position of the CH3 group, the order being para > ortho≈meta with monochlorotoluenes. The transient species absorbing around 400 nm is assigned to the phenoxyl-type radical. The differences in reaction mechanism between SO˙–4 and ˙OH attack are discussed." @default.
• W2058903326 created "2016-06-24" @default.
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• W2058903326 date "1994-01-01" @default.
• W2058903326 modified "2023-09-25" @default.
• W2058903326 title "Pulse radiolysis study of the reactions of SO˙–4 with some substituted benzenes in aqueous solution" @default.
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• W2058903326 doi "https://doi.org/10.1039/ft9949000597" @default.
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