| | 1 | Author
| Shailesh Phulkar, Balijepalli Sethu, M. Adhava Rao, Heinz-Peter Schuchmann, Clemens Von Sonntag | Requires cookie* | | | Title
| Radiolysis of Tertiary Butyl Hydroperoxide in Aqueous Solution. Reductive Cleavage by the Solvated Electron, the Hydrogen Atom, and, in Particular, the Superoxide Radical Anion  | | | | Abstract
| The reactions o f the solvated electron, the H atom, the OH radical and the superoxide radi cal anion with /-butylhydroperoxide (/-BuOOH) have been studied in aqueous solutions using y-radiolysis and pulse radiolysis to generate these radicals. The solvated electron reacts rapidly with r-BuOOH (k = 5 x 109 dm 3 m ol" 1 s~') yielding /-BuO ' and OH in a ratio o f 4:1. The yield o f r-BuO' has been determined by measuring its fragmentation product, acetone. The H atom reacts more slowly with r-BuOOH (k = 5x 107 dm 3 m o l-1 s"1). There is very little H-abstraction from the methyl and the hydroperoxyl groups (about 3%), the main reac tion again being the scission o f the hydroperoxyl function with a branching ratio /-BuO'/'OH o f about unity. The OH radical reacts with /-BuOOH considerably more slowly (k = 8 x 107 dm3 m o l" 1 s ' 1) than with /-butanol (k = 5 X 108 dm3 m o l-1 s"1) with an approximate preference o f 8:1 o f ab stracting a methyl hydrogen over a hydroperoxyl hydrogen atom. The carbon-centered radical undergoes y-cleavage (k ~ 102 s"1) thereby reforming an OH radical. The resulting chain reac tion is rather short (maximum yield G (2-methyl-1,2-epoxypropane), 26 x 10"7 mol / ' at low dose rate) due to H-abstraction at the hydroperoxyl function o f r-BuOOH by the OH radical. The superoxide radical anion also reacts with /-BuOOH by cleaving the hydroperoxyl func tion. Its reactivity is, however, rather low (k = 5 dm3 m ol" 1 s"1). | | | |
Reference
| Z. Naturforsch. 45b, 1425—1432 (1990); received May 9 1990 | | | |
Published
| 1990 | | | |
Keywords
| /-Butyl Hydroperoxide, Solvated Electron, H Atom, Superoxide Radical, Hydroxyl Radical, Pulse R adiolysis, Chain Reaction | | | |
Similar Items
| Find | | | DEBUG INFO
| | | | | TEI-XML for
| default:Reihe_B/45/ZNB-1990-45b-1425.pdf | | | | Identifier
| ZNB-1990-45b-1425 | | | | Volume
| 45 | |
|
