Mechanistic studies of anodic oxidation of hydrocarbons using spectroelectrochemical methods
Mechanistic studies of anodic oxidation of hydrocarbons using spectroelectrochemical methods
The highly sensitive technique of modulated specular reflectance spectroscopy was used in conjunction with conventional electrochemical methods to obtain a complete mechanistic and kinetic analysis of the anodic oxidation of the methylbenzenes in acetonitrile. The technique made it possible for the first time to physically distinguish between an ece and disproportionation mechanism. The rate constants and absorption spectra of the transient cation radical, free radical, and carbonium ion, as well as their extinction coefficients were provided both by direct analysis of the modulated reflectance spectra and by digital simulation of the adsorbance-time transients using new and highly efficient simulation programs. Modulated reflectance spectroscopy was also used for the first time in the recording of infrared spectra of an electrochemically generated species, the thianthrene cation radical, during electrolysis. In addition, the technique was used to study the adsorption and desorption of indole from acetonitrile at a platinum electrode.Polymer bound reagents were used for the first time directly in electrochemical reactions. Solution free intermediates were trapped by the polymer bound reagents, and many useful advantages in using such agents in electrochemistry immediately became obvious: yields were markedly increased, workup was reduced to a minimum, and general applications to large scale processes seem to be a simple matter.
University of Southampton
1979
Pons, Bobby Stanley
(1979)
Mechanistic studies of anodic oxidation of hydrocarbons using spectroelectrochemical methods.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The highly sensitive technique of modulated specular reflectance spectroscopy was used in conjunction with conventional electrochemical methods to obtain a complete mechanistic and kinetic analysis of the anodic oxidation of the methylbenzenes in acetonitrile. The technique made it possible for the first time to physically distinguish between an ece and disproportionation mechanism. The rate constants and absorption spectra of the transient cation radical, free radical, and carbonium ion, as well as their extinction coefficients were provided both by direct analysis of the modulated reflectance spectra and by digital simulation of the adsorbance-time transients using new and highly efficient simulation programs. Modulated reflectance spectroscopy was also used for the first time in the recording of infrared spectra of an electrochemically generated species, the thianthrene cation radical, during electrolysis. In addition, the technique was used to study the adsorption and desorption of indole from acetonitrile at a platinum electrode.Polymer bound reagents were used for the first time directly in electrochemical reactions. Solution free intermediates were trapped by the polymer bound reagents, and many useful advantages in using such agents in electrochemistry immediately became obvious: yields were markedly increased, workup was reduced to a minimum, and general applications to large scale processes seem to be a simple matter.
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Published date: 1979
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Local EPrints ID: 458412
URI: http://eprints.soton.ac.uk/id/eprint/458412
PURE UUID: dee0b2b9-c156-462a-9c99-4624a6ee4044
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Date deposited: 04 Jul 2022 16:48
Last modified: 04 Jul 2022 16:48
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Author:
Bobby Stanley Pons
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