
%0 Journal Article
%A Pendlebury, JN 
%A Smith, RH 
%T Kinetics of oxidation of nitrite by aqueous chlorine
%J Australian Journal of Chemistry
%D 1973/09/01
%V 26
%N 9
%P 1857-1861
%K 
%R https://doi.org/10.1071/CH9731857
%U https://www.publish.csiro.au/paper/CH9731857 
%X The kinetics of oxidation of nitrite to nitrate by chlorine in aqueous acid solution (pH 0-1) have been studied using a spectrophotometric stopped flow technique. The rate law is                    -d[Cl2]a/dt =([Cl2][NO2-]/Ka[Cl-]2)(f+g[HNO2])   where [Cl2]a = [Cl2]+[Cl3-] and where Ka is the ionization constant for nitrous acid. At 298.2 K and ionic strength 2.75M, f = 60.8±0.5 mol2 l-2 s-1 and g = (2.35±0.05)x105 mol l-1 s-1: the associated activation energies are 68±3 and 44±2 kJ mol-1 respectively. A mechanism is proposed involving the reversible initial step:                              NO2-+Cl2 &#8596; NO2Cl+Cl-   with the NO2Cl undergoing two parallel subsequent reactions, one a unimolecular decomposition and the other an attack by HNO2 upon NO2Cl.     Oxidation of nitrite by the three halogens, Cl2, Br2, I2, is discussed. 
