Chlorination of Phenols: Kinetics and Formation of Chloroform
- 22 January 2002
- journal article
- research article
- Published by American Chemical Society (ACS) in Environmental Science & Technology
- Vol. 36 (5), 884-890
- https://doi.org/10.1021/es010076a
Abstract
The kinetics of chlorination of several phenolic compounds and the corresponding formation of chloroform were investigated at room temperature. For the chlorination of phenolic compounds, second-order kinetics was observed, first-order in chlorine, and first-order in the phenolic compound. The rate constants of the reactions of HOCl with phenol and phenolate anion and the rate constant of the acid-catalyzed reaction were determined in the pH range 1−11. The second-order rate constants for the reaction HOCl + phenol varied between 0.02 and 0.52 M-1 s-1, for the reaction HOCl and phenolate between 8.46 × 101 and 2.71 × 104 M-1 s-1. The rate constant for the acid-catalyzed reaction varied between 0.37 M-2 s-1 to 6.4 × 103 M-2 s-1. Hammett-type correlations were obtained for the reaction of HOCl with phenolate (log(k) = 4.15−3.00 × Σσ) and the acid-catalyzed reaction of HOCl with phenol (log(k) = 2.37−4.26 × Σσ). The formation of chloroform could be interpreted with a second-order model, first-order in chlorine, and first-order in chloroform precursors. The corresponding rate constants varied between k > 100 M-1 s-1 for resorcinol to 0.026 M-1 s-1 for p-nitrophenol at pH 8.0. It was found that the rate-limiting step of chloroform formation is the chlorination of the chlorinated ketones. Yields of chloroform formation depend on the type and position of the substituents and varied between 2 and 95% based on the concentration of the phenol.Keywords
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