
TY  - JOUR
A1  - Pendlebury, JN 
A1  - Smith, RH 
T1  - Kinetics of oxidation of nitrite by aqueous chlorine
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1973
VL  - 26
IS  - 9
SP  - 1857
EP  - 1861
KW  - 
UR  - https://doi.org/10.1071/CH9731857 
N2  - 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. 
ER  -

