Reduction potentials nitrogen

Amine—borane adducts have the general formula R3N BX where R = H, alkyl, etc, and X = alkyl, H, halogen, etc. These compounds, characterized by a coordinate covalent bond between boron and nitrogen, form a class of reducing agents having a broad spectmm of reduction potentials (5). 

Table 11.4 Standard reduction potentials for nitrogen species in acidic aqueous solution (pH 0, 25°C)...

Tlic power of these various concepts in codifying and rationalizing the redox chemistry of the clcineiUs is ilhislraled for Ihe case of nitrogen in tbe present section Standard reduction potentials and plots of volt equivalents against oxidation state fur odicr elements are presented in later chapters... 

Figure 11.8 Oxidation states of nitrogen showing standard reduction potentials in volts (a) in acid solution at pH 0, and (b) in basic solution at pH 14.

Chen KC, Chen JJ, Houng JY (2000) Improvement of nitrogen removal efficiency using immobilized microorganisms with oxidation-reduction potential monitoring. J Ind Microbiol Biotechnol 25 229-234... 

Peroxynitrous acid is a powerful oxidizing agent with estimated one- and two-electron reduction potentials of ° (ONOOH, H+/"N02, HjO) = 1.6-1.7 V and ° (ONOOH, H /N02 , H2O) = 1.3-1.4 V, respectively . In addition, it was reported that, upon protonation, ONOO can undergo decomposition via homolytic 0—0 cleavage to generate nitrogen dioxide radical ("NO2) and hydroxyl radical ( OH) in approximately 30% yields... 

The reduction potentials of some pyrazines and their benzo-fused analogs have been summarized as part of an ESR study of the electron-transfer interaction between nitrogen heterocycles and -Bu4N BH4 <1995JOM(494)123>. 

Although much of the biological literature focuses on nitrosating reactions of nitric oxide, chemically nitric oxide is a moderate one-electron oxidant, making formation of nitroxyl anion feasible under physiological conditions. The reduction potential to reduce nitric oxide to nitroxyl anion is +0.39 V, whereas it requires +1.2 V to oxidize nitric oxide to nitrosonium ion. Nitrosating reactions of nitric oxide are often mediated by conversion of nitric oxide to another nitrogen oxide species or by direct reaction with transition metals (Wade and Castro, 1990). 

The two positive oxidation states of P (+ 5 and + 3) are both more stable than their nitrogen equivalents, and phosphoric acid has no oxidant properties apart from those given by the hydrated protons produced from it in aqueous solution. A dilute solution of phosphoric acid will provide a sufficiently high concentration of hydrated protons to oxidize any metal to its most stable state, providing the reduction potentials for the metal ion/metal couple are negative. 

For the monocyclic complexes 1-7, oxidation to Ni(III) occurs at +0.90-+0.93 V and reduction to Ni(I) at -1.46--1.55 V vs SCE. However, in the macropolycyclic ligand complexes 9-14, oxidation and reduction occur at + 1.25-+1.60 V and at -0.94-—1.40 V vs SCE, respectively. That is, electrochemical oxidation of Ni(II) complex to Ni(III) species is easier for the monocyclic complexes, whereas electrochemical reduction to Ni(I) is easier for the macropolycyclic complexes. The anodic shifts in both oxidation and reduction potentials for Ni(II) macropolycyclic complexes in part may be attributed to the tertiary nitrogen donors of the ligands. 

---