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Kinetic isotope effects from reactions of muonium atoms in water with various ketones, and acetaldehyde: Contrasts with hydrogen atoms

TitleKinetic isotope effects from reactions of muonium atoms in water with various ketones, and acetaldehyde: Contrasts with hydrogen atoms
Publication TypeJournal Article
Year of Publication1997
AuthorsStadlbauer, JM, Venkateswaran, K, Walker, DC
JournalCanadian Journal of Chemistry-Revue Canadienne De Chimie
Volume75
Pagination74-76
Date PublishedJan
Type of ArticleArticle
ISBN Number0008-4042
KeywordsACETONE, ADDITION-REACTIONS, AQUEOUS-SOLUTIONS, CONSTANTS, hydrogen atom reactions, KETONES, kinetic isotope effects, muon spin rotation, muonium atoms, radical formation
Abstract

This paper presents data showing that in dilute aqueous solutions of butanone, 3-pentanone, cyclohexanone, di-tert-butyl ketone, and acetaldehyde the addition reaction of muonium atoms occurs with a rate constant close to 1 x 10(8) M-1 s(-1). The same value was obtained previously for acetone. Thus the reaction rate is virtually independent of the group attached to the C=O, be it a methyl, methylene, tert-butyl, or even a hydrogen atom. This is in sharp contrast to the reactivity of ordinary H-1 atoms, whose rate constants are much slower and dependent on adjacent groups. In fact muonium and H-1 react by different mechanisms, to form different products, so their rate ratio represents a complex kinetic isotope effect.

URL<Go to ISI>://A1997XD81000011