A. Al-Ajlouni, B. Gould
Mar 19, 1999
Citations
0
Influential Citations
8
Citations
Journal
Inorganic Chemistry
Abstract
Trioxodinitrate (N2O32-), prepared as its sodium salt (Angeli's salt, Na2N2O3) by nitrosation of hydroxylamine using isopropyl nitrate and sodium ethoxide, reacts with a variety of inorganic oxidants. Observed stoichiometries for both le- and 2e- reagents at pH values above 4 generally point to conversion mainly to nitrite with both types. Kinetic acidity patterns, pertaining to media where the uninegative ion, HN2O3- (pKA = 9.3) predominates, indicate that oxidations by both I2 and I3- proceed through the dinegative ion, N2O32-, but that oxidations by I(V) involve HIO3 and the monoprotonated reductant. Oxidations with both Cl(I) and I(VII) proceed by multiple paths involving several protonation levels, with the acidity profile for the latter (Figure 1) being unusually complex. It is proposed that oxidations by HOCl proceed by Cl+ transfer, that iodate and periodate utilize oxygen transfer, and that the le- oxidants employ a pair of outer-sphere transactions of which the first is rate-determining. The mos...