An energetic explanation of the kolbe electrosynthesis

✍ Scribed by K. Sasaki; K. Uneyama; S. Nagaura

• Book ID: 103062141
• Publisher: Elsevier Science
• Year: 1966
• Tongue: English
• Weight: 318 KB
• Volume: 11
• Category: Article
• ISSN: 0013-4686
• DOI: 10.1016/0013-4686(66)87065-2

✦ Synopsis

The product distribution of the Kolbe electrolysis, which varies with the kind of carboxylic acid electrolysed, has been considered from the thermochemical standpoint. Approximating the bond dissociation energy of the carboxylic hydrogen, D(RCOO-II), to be 115 Kcal/mol, the heat of reaction for various possible elementary processes of the Kolbe reaction has been calculated. It has been concluded that the easiness of the elimination of a carbon dioxide from a carboxylate-free radical has an important effect on the resultant distribution of the products. Olel?n and ester may be expected for the case where the rate of decarboxylation is not large enough.

R&am~&La distribution des produits de 1'6lectrolyse de Kolbe, qui varie avec l'acide carboxylique &ctrolyd, eat envisaged du point de we thermochimique. Dans l'approximation attribuant 115 Kcal/mol it l'energie de liaison de l'hydrogene carboxylique de D(RCOO-II), la chaleur de r&&ion de divers processus Cl6mentairea possibles darts la reaction de Kolbe peut etre calculee. L'on en conclut que l'aisance avec laquelle s'blimine COO d'un radical libre carboxylate a un effet important sur la distribution resultante des prod&s. Quand le taux de decarboxylation n'est pas suiBsamment grand, l'on peut attendre une production d'olefine et d'ester.