Electro‐Oxidation of Organic Compounds I: Oxidation of Benzaldehydes at the Dropping Mercury Electrodes
| Autor: | Petr Zuman, W. James Bover |
|---|---|
| Rok vydání: | 1975 |
| Předmět: |
Geminal diol
Polarography Renewable Energy Sustainability and the Environment Inorganic chemistry Substituent Electrolyte Condensed Matter Physics Photochemistry Surfaces Coatings and Films Electronic Optical and Magnetic Materials Ion chemistry.chemical_compound Reaction rate constant chemistry Materials Chemistry Electrochemistry Hydroxide Acid–base reaction |
| Zdroj: | Journal of The Electrochemical Society. 122:368-377 |
| ISSN: | 1945-7111 0013-4651 |
| DOI: | 10.1149/1.2134217 |
| Popis: | Benzaldehydes substituted in the meta and para positions with both electron‐donating and electron‐withdrawing substituents react with hydroxide ions and form geminal diol anions in a reaction . The height of the anodic waves, recorded with d‐c and pulse polarography, decreases with decreasing pH in the shape of a dissociation curve. This has been interpreted as due to the electro‐oxidation of the anion preceded by the above acid base equilibrium. The source of the second oxygen in the electrolytic formation of benzoic acids in alkaline media is thus the hydroxide ion. Based on the shape of the dissociation curve, oxidation of the dianion seems improbable. Under the assumption that the acid‐base reaction behaves like a volume reaction, values of rate constants for the anion formation and cleavage were calculated. Half‐wave potentials of anodic waves are a linear function of Hammett substituent constants σ. |
| Databáze: | OpenAIRE |
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