Kinetics, Product Analysis and Mechanism of the Reduction of Chlorate by Chloride and Phenol in Aqueous Acidic Solution
A detailed study of the kinetics and product analysis of the reaction between chlorate and chloride in the range of 1.00-3.00 M hydrogen and chloride ion at 3.00 M ionic strength in the presence of varying amounts of phenol in aqueous solution at 25.0°C is reported. A linear set of rate parameters, each parameter being first order in chlorate, is proposed as representing three parallel paths for the reduction of chlorate. Evidence presented indicates that phenol acts to scavenge reactive intermediates formed from the acid-dependent interaction between chlorate and chloride ion and also enters into a direct rate determining bimolecular reductive step of chlorate. Both o- and p-chlorophenols have been semi-quantitatively determined as reaction products along with the qualitative determination of oxidation products with phenol. An increase in the direct interaction between phenol and chlorate results in the oxidized phenolic compounds, whereas the chloride interaction results in the formation of chlorine intermediates that produce chloro-phenolic compounds. An increase in the direct interaction between phenol and chlorate results in increased formation of oxidized phenolic compounds. Increased formation of chlorophenolic compounds parallels an increase in the generation of chlorine containing intermediates such as dichlorine dioxide.
E. B. Grimley and H. L. Collier, "Kinetics, Product Analysis and Mechanism of the Reduction of Chlorate by Chloride and Phenol in Aqueous Acidic Solution," Journal of Inorganic and Nuclear Chemistry, vol. 39, no. 10, pp. 1827-1834, Elsevier, Feb 1977.
The definitive version is available at http://dx.doi.org/10.1016/0022-1902(77)80209-1
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