Rate constants for the reactions of chloride monoxide radical (ClO) and organic molecules of environmental interest

Water Sci Technol. 2023 Apr;87(8):1925-1944. doi: 10.2166/wst.2023.114.

Abstract

ClO plays a key role in the UV/chlorine process besides Cl, Cl2 - , and OH. In many experiments, ClO proved to be the main reactant that destroyed the organic pollutants in advanced oxidation process. About 200 rate constants of ClO reactions were collected from the literature, grouped together according to the chemical structure, and the molecular structure dependencies were evaluated. In most experiments, ClO was produced by the photolytic reaction of HClO/ClO-. For a few compounds, the rate constants were determined by the absolute method, pulse radiolysis. Most values were obtained in steady-state experiments by competitive technique or by complex kinetic calculations after measuring the pollutant degradation in the UV/chlorine process. About 30% of the listed rate constant values were derived in quantum chemical or in structure-reactivity (QSAR) calculations. The values show at least six orders of magnitude variations with the molecular structure. Molecules having electron-rich parts, e.g., phenol/phenolate, amine, or sulfite group have high rate constants in the range of 108-109 mol-1 dm3 s-1. ClO is inactive in reactions with saturated molecules, alcohols, or simple aromatic molecules.

MeSH terms

  • Chlorides
  • Chlorine / chemistry
  • Kinetics
  • Oxidation-Reduction
  • Phenol
  • Ultraviolet Rays
  • Water Pollutants, Chemical* / chemistry
  • Water Purification* / methods

Substances

  • Chlorides
  • Chlorine
  • Phenol
  • Water Pollutants, Chemical