Formation of Organic Nitrates Mechanism of the Process

Abstract

The analysis of the literature, including our works, was carried out, on the basis of which this review article was prepared. Previously, the direct (radiochemical) method proved the participation of nitrate ion in the anodic process - the oxygen evolution reaction (OER). Of interest was the possibility of accepting NO3 radicals formed during electrolysis by other anion-radical particles. Salts of acetic and propionic acids were chosen as model objects. It was found that during electrolysis of acetate-nitrate (system 1) and propionate-nitrate (system 11) mixtures, the pH of the medium significantly affects the selectivity of the reactions. In an acidic medium during electrolysis of both systems at high potentials, nitrate ion acts as a source of active oxygen, which is used to form molecular oxygen and destructively oxidizes alkyl groups. In a weakly alkaline solution, during the electrolysis of an equimolar mixture of system 1, ethane is formed, the current output (CO) of which drops sharply and reaches a value of ~30%, and a small amount of oxygen. A significant part of the current is spent on the oxidation of CH3 particles with the formation of carbon dioxide (CO~60%) and water. In a weakly alkaline solution, the process of system 11 differs from system 1 and is interesting in that during the electrolysis of an equimolar mixture of propionate and nitrate, products of the interaction of nitrate radicals and propionate particles are formed with the formation of organic nitrates. Based on the analysis of the data obtained by a set of methods, a mechanism for the formation of organic nitrates is proposed.