Dissociative Chlorination of Nitrogen Oxides and Oxy Anions in Molten Sodium Chloride-Aluminum Chloride Solvents.

摘要

Nitrosyl cation has been found to undergo reversible one-electron reduction-oxidation in molten NaCl-AlCl3 mixtures (175 C) at vitreous C electrodes. The NO(+) ion half-wave potential in normal pulse voltammograms occurs at E(1/2) about +1.86 V vs. Al reference electrode in NaAlCl4 (NaCl saturated) and a diffusion coefficient for NO(+) ion in acidic melts (AlCl3 rich) is estimated to be 1.8 x 10 to the -5th power sq cm/sec (175 C). Nitrite ion reacts with fused NaCl-AlCl3 mixtures to produce high yields of NO(+) ion, which is separable from the solvent phase as nitrosyl chloride. Nitryl ion, nitrogen dioxide, and nitrate ion are reduced in these molten salts, to varying extents, whereas nitrous oxide and nitric oxide remain unaffected in 24 hr. Possible mechanisms are discussed for these dissociative chlorination processes. (Author)