Electrochemical studies of surface oxidations on metal electrodes
Electrochemical studies of surface oxidations on metal electrodes
The anodic behaviour of a mercury electrode in solutionsof halides and barbiturates and that of a nickel.electrode in alkaline solution have been investigated further using potentiostaticpulse techniques, cyclic voltammetry and steady-state methods.The formation of mercurous halide surface films on amercury drop electrode in an acidic and a neutral medium were shown to occur by a two dimensional nucleation and layer by layer growth mechanism with the incorporation of new material into the lattice as the slow step. It has been shown that the formation of such films may be used as a concentration procedure in analytical chemistry and that the halides can be analysed singly and in a mixture with the concentration range 2 x 10-5- 10-3M by cathodic stripping voltammetry. Similar studies for barbiturates in a borax buffer showed that they form insoluble surface films of their mercury compounds on the electrode. The kinetics and mechanisms for the formation of these layers varies with the barbiturate. In particular the behaviour of 5,5'-disubstituted barbiturates differed from those barbiturates not fully substituted at the 5-position, with the former only a monolayer is formed while with the latter a multilayer formation is observed. It was found possible to analyse individual barbiturates in the concentration range of 10-3M - 10-5M, but their analysis in mixtures was not possible. The anodic behaviour of a nickel electrode in alkaline aqueous and t-butanol-water systems were studied using a massive nickel disc electrode and nickel disc electrodes prepared by the electrodeposition of nickel onto a copper or a graphite disc substrate from a Watt's bath. Electro deposited nickel electrodes were prepared under conditions where microrough surfaces were likely to result and the effects of various parameters on the electrodeposition were studied. It has been shown that the apparent current densities for the oxidation of alcohols are markedly increased by the use of such microrough electrodes. Preparative scale oxidation of alcohols on a large electrodeposited nickel electrode resulted in high yields of the corresponding acids.
University of Southampton
1979
Manandhar, Krishna
(1979)
Electrochemical studies of surface oxidations on metal electrodes.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The anodic behaviour of a mercury electrode in solutionsof halides and barbiturates and that of a nickel.electrode in alkaline solution have been investigated further using potentiostaticpulse techniques, cyclic voltammetry and steady-state methods.The formation of mercurous halide surface films on amercury drop electrode in an acidic and a neutral medium were shown to occur by a two dimensional nucleation and layer by layer growth mechanism with the incorporation of new material into the lattice as the slow step. It has been shown that the formation of such films may be used as a concentration procedure in analytical chemistry and that the halides can be analysed singly and in a mixture with the concentration range 2 x 10-5- 10-3M by cathodic stripping voltammetry. Similar studies for barbiturates in a borax buffer showed that they form insoluble surface films of their mercury compounds on the electrode. The kinetics and mechanisms for the formation of these layers varies with the barbiturate. In particular the behaviour of 5,5'-disubstituted barbiturates differed from those barbiturates not fully substituted at the 5-position, with the former only a monolayer is formed while with the latter a multilayer formation is observed. It was found possible to analyse individual barbiturates in the concentration range of 10-3M - 10-5M, but their analysis in mixtures was not possible. The anodic behaviour of a nickel electrode in alkaline aqueous and t-butanol-water systems were studied using a massive nickel disc electrode and nickel disc electrodes prepared by the electrodeposition of nickel onto a copper or a graphite disc substrate from a Watt's bath. Electro deposited nickel electrodes were prepared under conditions where microrough surfaces were likely to result and the effects of various parameters on the electrodeposition were studied. It has been shown that the apparent current densities for the oxidation of alcohols are markedly increased by the use of such microrough electrodes. Preparative scale oxidation of alcohols on a large electrodeposited nickel electrode resulted in high yields of the corresponding acids.
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Published date: 1979
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Local EPrints ID: 462412
URI: http://eprints.soton.ac.uk/id/eprint/462412
PURE UUID: af109342-3cfe-48b9-b01c-f6cf0603786f
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Date deposited: 04 Jul 2022 19:07
Last modified: 04 Jul 2022 19:07
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Author:
Krishna Manandhar
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