Pulse radiolysis with conductometric detection: Two approaches to absolute dosimetry

Schuchmann, Heinz‐Peter; Deeble, David J.; Phillips, Glyn O.; Sonntag, Clemens von

doi:10.1016/1359-0197(91)90122-i

Cited by 7 publications

(6 citation statements)

References 6 publications

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“…In conductometry, dimethyl sulfoxide dosimetry allows us to determine yields accurately, but the dose remains unknown. In principle, this can also be determined accurately, 34 but this method is laborious and has not be done here, since the dose can be estimated to an accuracy of ±25% from the positioning of the cell and dosimetry by optical detection. For the purpose of the information to be drawn from Fig.…”

Section: Methodsmentioning

confidence: 99%

OH-Radical-induced chain scission of chitosan in the absence and presence of dioxygen

Ulański

Sonntag

2000

J. Chem. Soc., Perkin Trans. 2

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Section: Methodsmentioning

confidence: 99%

OH-Radical-induced chain scission of chitosan in the absence and presence of dioxygen

Ulański

Sonntag

2000

J. Chem. Soc., Perkin Trans. 2

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“…In its first step [reaction (19)] it hydrolyses with a rate constant of 1.7 × 10 3 dm 3 mol Ϫ1 s Ϫ1 . 14 The second step is much slower [reaction (20), k = 3.9 dm 3 mol Ϫ1 s Ϫ1 ]. Apparently, following the first rapid decay processes, the HX-elimination slows down.…”

Section: General Considerations Regarding the Mechanistic Features Of...mentioning

confidence: 99%

The reaction of the OH radical with pentafluoro-, pentachloro-, pentabromo- and 2,4,6-triiodophenol in water: electron transfer vs. addition to the ring

Fang

Schuchmann

Sonntag

2000

J. Chem. Soc., Perkin Trans. 2

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The OH-radical-induced dehalogenation of pentafluorophenol (F 5 C 6 OH), pentachlorophenol (Cl 5 C 6 OH), pentabromophenol (Br 5 C 6 OH) and 2,4,6-triiodophenol (I 3 H 2 C 6 OH) in water has been studied by pulse radiolysis in basic solution where these compounds are deprotonated and hence slightly water soluble. Hydroxyl radicals react with these phenolates both by electron transfer and by addition. Electron transfer yields hydroxide ions and the corresponding phenoxyl radicals (X 5 C 6 O ؒ and I 3 H 2 C 6 O ؒ ); these were also generated independently, to the exclusion of OH-adduct radicals, by reacting the phenolates withHydroxyl radical addition to the pentahalophenolates is followed by rapid halide elimination, giving rise to hydroxytetrahalophenoxyl radical anions (X 4 O Ϫ C 6 O ؒ ). The latter exhibit absorption maxima near those of the pentahalophenoxyl radicals. This prevents a proper determination of the relative importance of the two processes by optical detection. However, these two processes distinguish themselves by their behaviour with respect to the stoichiometry and kinetics of the production of ionic conducting species. In basic solution, electron transfer causes a conductivity increase due to the formation of OH Ϫ whereas addition followed by HX elimination and deprotonation of the X 4 OHC 6 O ؒ radical results in a conductivity drop. The evaluation of the conductivity change at 8 µs after the radiolytic pulse has ended, reveals that about 27%, 53%, 73%, and 97% of the OH radicals react by electron transfer with F

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“…13 For dosimetry, N 2 O-saturated 10 Ϫ2 mol dm Ϫ3 thiocyanate solution was used for optical detection, 14, 15 taking Gε[(SCN) 2 Ϫ ] = 5.28 × 10 Ϫ4 m 2 J Ϫ1 at 480 nm. 15 For conductometric detection, N 2 O-saturated 10 Ϫ2 mol dm Ϫ3 dimethyl sulfoxide solution 2 at pH 4 was used as dosimeter, taking 16 At elevated methanesulfinate concentrations, the increased ؒ OH-scavenging capacity 17 has been taken into account.…”

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confidence: 99%

OH-Radical-induced oxidation of methanesulfinic acid. The reactions of the methanesulfonyl radical in the absence and presence of dioxygen

Flyunt

Makogon

Schuchmann

et al. 2001

J. Chem. Soc., Perkin Trans. 2

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Pulse radiolysis with conductometric detection: Two approaches to absolute dosimetry

Cited by 7 publications

References 6 publications

OH-Radical-induced chain scission of chitosan in the absence and presence of dioxygen

OH-Radical-induced chain scission of chitosan in the absence and presence of dioxygen

The reaction of the OH radical with pentafluoro-, pentachloro-, pentabromo- and 2,4,6-triiodophenol in water: electron transfer vs. addition to the ring

OH-Radical-induced oxidation of methanesulfinic acid. The reactions of the methanesulfonyl radical in the absence and presence of dioxygen

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