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Title: A mechanistic study of some redox reactions of nitrogen (III)
Author: Emeish, Samir Salem Said
ISNI:       0000 0001 3447 3736
Awarding Body: University of London
Current Institution: Royal Holloway, University of London
Date of Award: 1977
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Oxidation of nitrogen(III) by chlorite, periodate and chlorate is reported in this work. The introduction reviews the reported, assumed and proposed reactivities of non-metallic oxyanions in aqueous acid solutions in general and the reactants studied in the present investigation in particular. Mechanistic studies of the reactions, N(III)/C1(III) and N(III)/I(VII) are reported for the first time. Nitrite and chlorite react under mildly acid conditions (pH ∼ 4) in the molar ratio of 2:1. The rate equation is represented by, Rate = [NO 2-]1.5[ClO2-] 0.5[H+]1.5(k + k'[Cl-]). The reaction between nitrite and periodate has been studied in aqueous hydrochloric acid solution (pH ∼ 0). Its rate equation is represented by, Rate = k[HNO 2]0.5[H5IO6][H+]Cl -][Br-]. The rate of reaction is particularly catalysed by traces of Br-. This observation may nominate the reaction as the simplest method that may be used for the quantitative estimation of traces of Br- present in chlorides. In a rather differently oriented study, the reaction between N(III)/C1(V) has been studied in water/dioxan solutions. The specific rate constant for the reaction increases as the dielectric constant of the medium decreases, a result which agrees with the mechanism suggested by other workers. The ionization constants of nitrous acid in similar water-dioxan mixtures are also reported.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Inorganic Chemistry