Electrochemical oxidation of α-hyponitrate ion and its analytical applications

α-Hyponitrate ion is electrochemically oxidized at mercury electrodes: the reaction proceeds by an initial 1-electron oxidation to give an anion radical which decomposes to give nitrogen oxide and nitrite as the ultimate products. The d.c. polarographic wave of α-hyponitrate (E_{$\text{1}\text{2}$} = -0.325 V vs. SCE) in 0.1 M sodium hydroxide can be used for the determination of α-hyponitrate in the range 0.08–1.3 mM; a.c. polarography (E_p = -0.30 V vs. SCE) is useful in the range 0.075–1.0 mM. Amperometric titration with 0.05 M hexacyanoferrate(III) is suitable for determinations of 5–20 mg of sodium α-hyponitrate. A.c. polarography at pH 11.0 allows α-hyponitrate to be determined in the presence of 50-fold amounts of hydroxylamine.