The Electrochemistry of Inorganic Difluoramino Compounds. II. Solution Chemistry and Electrochemical Reduction of Difluoramine

Abstract

The mechanism of the electrochemical reduction of difluoramine has been studied in water, protonic organic solvents, and aprotic solvents. In water and protonic solvents, such as alcohols, difluoramine undergoes a diffusion-controlled, four-electron reduction to ammonia. In aprotic solvents, such as acetonitrile and dimethyl sulfoxide, the reduction product is ammonia, but the reaction is not completely diffusion controlled. In these systems, ammonia is formed by reaction of the electrode products with the solvent. The effect of added proton donors has been studied. In aprotic systems, the mechanism of the reaction is affected by repulsion of negatively charged intermediate species at the electrode surface. The effect of the nature of the supporting electrolyte on the repulsion phenomenon has been studied. The half-wave potential of difluoramine was found to vary with the solvent used, and the values observed are correlated with the strength of solvation of HNF2.n the first paper of this series,' the mechanism of the

Electrochemical Behavior of Chloramines on the Rotating Platinum and Gold Electrodes

“…From these facts it can be concluded that the first mechanism is more probable. That mechanism resembles the one proposed by Ward et al 21 for NHF 2 reduction on a mercury electrode.…”

Organic polarography

“…Polarographic behavior of difluoramine, HNF2, was measured in water and protonic solvents (1391) and the technique was used to detect the difluoroamide anion, NF2~(855). The hydrogen wave was measured in presence of weak bases (1126).…”