Direct measurement of absolute rates of hydrogen abstraction by tert-butoxy radicals. A flash photolysis electron spin resonance study

Wong, S. K.

doi:10.1021/ja00499a031

Cited by 37 publications

(18 citation statements)

References 2 publications

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“…The Arrhenius parameters for these four substrates were also measured. A brief comparison of the techniques and results has been given [3]. In general, both sets of results are considerably higher than those reported, measured or estimated, in the past.…”

Section: Introductionmentioning

confidence: 84%

“…Experimental details of flash photolysis electron spin resonance (FPESR) have been given in [3]. The [R-1, values were determined from the timedependence traces of the ESR signal in FPESR, as in [3, Fig.…”

Section: Methodsmentioning

confidence: 99%

“…by probing the product radicals encouraged us to consider the same probe. Reactions (1)-(8) were included [3] in the reaction scheme to study the hydrogen abstraction by BOto obtain rate constants.…”

Section: Methods and Reaction Schemementioning

confidence: 99%

“…The most powerful techniques commonly used, such as optical flash photolysis and ESR spectroscopy, are all failing. However, two recent reports describe the measurement of the absolute rate constants of hydrogen abstraction reactions of tert-butoxy radicals [2,3]. Scaiano and his co-workers [2] used a nanosecond laser flash photolysis technique and optical absorption spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

“…For the substrate diphenylmethanol, the product radical by hydrogen abstraction was directly monitored to obtain the rate constant, and for all other substrates (a total of 18) the reaction with diphenylmethanol served as a probe. Wong [3], on the other hand, used a flash photolysis ESR technique to directly monitor the product radicals for each substrate (a total of four: cyclopentane, anisole, methyl tert-butyl ether, and methanol). The Arrhenius parameters for these four substrates were also measured.…”

Section: Introductionmentioning

confidence: 99%

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ChemInform Abstract: AN INDIRECT MEASUREMENT OF THE ABSOLUTE RATE CONSTANT OF THE SELF‐REACTION OF TERT‐BUTOXY RADICALS

Wong¹

1981

Chemischer Informationsdienst

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No reliable rate constant is available for the self-reaction of tert-butoxy radicals. We have set up a competition between hydrogen abstraction and self-reaction of tert-hutoxy radicals in a flash photolysis electron spin resonance study to extract this information. Experimental values of hydrogen abstraction product radical concentrations under various hydrogen donor concentrations were then compared with theoretically calculated values with different values of 2k4 to obtain the best fit. Hydrogen donors such as cyclopentane, anisole, methyl tert-butyl ether, and methanol were chosen for the study. A value of (1.3 f 0.5) X 109M-1 sec-l for the rate constant of the self-reaction of tert-butoxy radicals has been determined a t 293°K.

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Section: Introductionmentioning

confidence: 84%

Section: Methodsmentioning

confidence: 99%

Section: Methods and Reaction Schemementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

ChemInform Abstract: AN INDIRECT MEASUREMENT OF THE ABSOLUTE RATE CONSTANT OF THE SELF‐REACTION OF TERT‐BUTOXY RADICALS

Wong¹

1981

Chemischer Informationsdienst

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Peroxides and Peroxide Compounds, Organic Peroxides

Sánchez

Myers

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Organic peroxides are compounds possessing one or more oxygen–oxygen bonds that are thermally and photolytically sensitive to facile homolytic cleavage. Thermal decomposition rates are affected by the structure of the organic peroxide and the decomposition conditions. The initially formed free radicals from the oxygen–oxygen bond homolysis are reactive intermediates which quickly undergo a variety of subsequent reactions to form stable products. Thermolysis of organic peroxides is used commercially to initiate free‐radical reactions, eg, halogenation, vinyl monomer polymerization, unsaturated resin cure, polyolefin cross‐linking and rheology modification. Many organic peroxides also undergo reactions in which free radicals are not involved, eg, heterolyses, hydrolyses, reductions, and rearrangements. This article reviews the physical and chemical properties, synthetic methods, and the principal commercial uses of organic peroxides of the following classes: hydroperoxides, dialkyl peroxides, α‐oxygen‐substituted hydroperoxides and dialkyl peroxides, ozonides, peroxyacids, diacyl peroxides, and alkyl peroxyesters. Class discussions cover the broad structural variation that is possible, including organomineral and polymeric derivatives when appropriate. Emphasis is placed on the relationship between peroxide structure and reactivity (thermal stability). Physical hazards associated with organic peroxide manufacture, handling, storage, transportation, and use are discussed. An overview of health hazards associated with handling of organic peroxides is presented.

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The Decomposition of Alkyl Nitrites and the Reactions of Alkoxyl Radicals

Heicklen

1988

Advances in Photochemistry

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Direct measurement of absolute rates of hydrogen abstraction by tert-butoxy radicals. A flash photolysis electron spin resonance study

Cited by 37 publications

References 2 publications

ChemInform Abstract: AN INDIRECT MEASUREMENT OF THE ABSOLUTE RATE CONSTANT OF THE SELF‐REACTION OF TERT‐BUTOXY RADICALS

ChemInform Abstract: AN INDIRECT MEASUREMENT OF THE ABSOLUTE RATE CONSTANT OF THE SELF‐REACTION OF TERT‐BUTOXY RADICALS

Peroxides and Peroxide Compounds, Organic Peroxides

The Decomposition of Alkyl Nitrites and the Reactions of Alkoxyl Radicals

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