Udupa, K.S. (1971) Studies on the electrode process with special reference to reduction of organic compounds. PhD thesis, Banaras Hindu University.
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Electrochemical reduction of organic compounds is elegant methods of preparative organic chemistry and quite a number of interesting reactions could be achieved by their adoption. The factors which determine the rate and course of electro-reduction of organic compounds are mainly electrode potential, nature and condition of electrode, concentration of reducible substance, temperature, adsorption behavior of reactants and products, stirring and catalysts. Electro-reduction of six compounds viz., nitro urea, nitro guanidine, carbon dioxide, glucose, guinoline and o-phenanthroline have been described employing measurement of polarization, current efficiency and physical methods. In organic reduction reactions, in which the reducing species are mostly neutral molecule, rotation of the cathode helps to achieve greater transport and maintain saturation of the electrolyte with the reactants. Rotation of the cathode lowers the thickness of the diffusion layer and therefore facilitates better contact between the electrode and the organic molecule and raises the value of limiting current density. The effect of rotation of the cathode has been tried for the reduction of nitro urea, nitro guanidine and glucose and it has been found that the reduction can be carried out under high current densities without affecting the current efficiency. Polarisation studies have also been carried out and the behavior has been explained. Study of the adsorption behavior of reactants and products is necessary to explain the electrode processes of organic compounds. Such study could be quantitatively made on mercury because of its reproducible surface and definite area. In this work, adsorption behavior of o-phenanthroline at a mercury electrode both in aqueous and non-aqueous media has been studied. The construction detail of the capillary electrometer and the apparatus for measuring the double layer capacity have also been described. The specific adsorption of chloride anions and its effect on the competitive adsorption with o-phenanthrolinium cation has been calculated using the space filling model. The orientation of the adsorbed o-phenanthroline molecules have been explained on the basis of strong –electron interactions of the organic molecule with the electrode. It has been observed that the cathode dissolves under cathodic polarization in the presence of certain organic compounds. In the present study, a new concept based on the well known potential-pH diagram (Pourbaix diagram) has been evolved to explain the dissolution of the metal under cathodic conditions. The result of four systems in which the dissolution of cathode occurs has been explained on the basis of the new concept.
| Item Type: | Thesis (PhD) |
|---|---|
| Uncontrolled Keywords: | Electrode process; organic compounds |
| Subjects: | Electroorganic |
| Divisions: | UNSPECIFIED |
| Depositing User: | Dr. N Meyyappan |
| Date Deposited: | 12 Jun 2012 07:39 |
| Last Modified: | 12 Jun 2012 07:39 |
| URI: | http://cecri.csircentral.net/id/eprint/2813 |
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