Micelle-induced change of mechanism in the reaction of muonium with acetone

1996 ◽  
Vol 74 (11) ◽  
pp. 1945-1951 ◽  
Author(s):  
John M. Stadlbauer ◽  
Krishnan Venkateswaran ◽  
Hugh A. Gillis ◽  
Gerald B. Porter ◽  
David C. Walker

Muonium atoms add to the O atom of the carbonyl group of acetone to give the muonated free radical (CH3)2Ċ-O-Mu when the reaction takes place in water or hydrocarbons, but not when the acetone is localized in micelles. Micelles have no effect on the formation of muonated cyclohexadienyl radicals when muonium reacts with benzene under similar conditions. The addition reaction with acetone appears to have been subsumed by a faster alternative reaction in the micellar environment. Evidence is presented for this interpretation rather than for an inhibition of the radical or for a shift in the muon level-crossing resonance spectrum with hydrogen (muonium) bonding, though major shifts are seen for the spectrum of this radical in pure solvents of widely different dielectric constant. It is suggested that muonium's "abstraction" reaction takes over in micelles because significant micelle-induced enhancement effects were previously observed in that type of reaction. The data are consistent with a rate constant for the abstraction reaction of muonium with acetone in micelles of >6 × 108 M−1 s−1. Key words: muonium, kinetic isotope effects, micelle enhancement, H/Mu-addition, H/Mu abstraction.

1974 ◽  
Vol 29 (3) ◽  
pp. 493-496 ◽  
Author(s):  
Peter Potzinger ◽  
Louis C. Glasgow ◽  
Bruno Reimann

The Reaction of Hydrogen Atoms with Silane; Arrhenius Parameters and Kinetic Isotope Effect Relative rate constants were measured for the systems H + C2H4/SiD4 and D + C2D4/SiH4 over a wide temperature range. From the known arrheniusparameter for the reaction H + C2H4 the activation energy EA and the preexponential factor A of the abstraction reactionH + SiD4 → HD + SiD3may be calculated. Values of EA = 3.2 kcal/Mol and A = 4.92 • 1013 cm3 Mol-1 sec-1 were obtained. Upper limits for the kinetic isotope effects are given in the paper


2003 ◽  
Vol 118 (14) ◽  
pp. 6280-6288 ◽  
Author(s):  
A. Fernández-Ramos ◽  
E. Martı́nez-Núñez ◽  
J. M. C. Marques ◽  
S. A. Vázquez

2005 ◽  
Vol 83 (11) ◽  
pp. 1936-1940 ◽  
Author(s):  
Detlef Schröder ◽  
Helmut Schwarz

The gas-phase reactions of methane with the platinum(II) ions PtX+ with X = H, Cl, Br, and CHO are studied by mass spectrometry. The PtX+ ions are generated by electrospray ionization of methanolic solutions of hexachloroplatinic acid and hexabromoplatinic acid, respectively. Small to moderate intramolecular kinetic isotope effects determined for the C—H(D) bond activation of CH2D2 suggest that the activation of methane by gaseous PtX+ cations is subject to thermochemical control by the product channels. In addition, the PtCl2+ cation is also able to activate methane, whereas PtCl3+ is unreactive under the conditions chosen. Key words: gas-phase reactions, mass spectrometry, methane activation, platinum bromide, platinum chloride.


2005 ◽  
Vol 83 (9) ◽  
pp. 1510-1515
Author(s):  
John E Baldwin ◽  
Stephanie R Singer

The gas-phase thermal isomerizations of deuteriocyclopropane to the four possible monodeuterium-labeled propenes have been followed at 435 °C. The observed distribution of products provides estimates of two deuterium kinetic isotope effects, the secondary [Formula: see text] for the carbon–carbon bond cleavage leading to trimethylene diradical reactive intermediates and the primary [Formula: see text] ratio for a [1,2] shift of a hydrogen or deuterium leading from the diradical to a labeled propene. The values determined are [Formula: see text] = 1.09 ± 0.03 and [Formula: see text] = 1.55 ± 0.06. The experimental [Formula: see text] value found agrees well with some, but not all, earlier calculated values and conjectures. Key words: cyclopropane, thermal rearrangement, kinetic isotope effects.


2016 ◽  
Vol 114 (22) ◽  
pp. 3396-3406
Author(s):  
Ichraf Oueslati ◽  
Mariem Hechmi ◽  
Emna Jebari ◽  
Karim Baccari ◽  
Boutheïna Kerkeni

Sign in / Sign up

Export Citation Format

Share Document