Mechanism and kinetics of chlorine dioxide reaction with hydrogen peroxide under acidic conditions

Abstract

The reaction of chlorine dioxide with hydrogen peroxide was studied in a well stirred batch reactor in a pH range of 3.60 to 5.07, which is of interest for commercial chlorine dioxide bleaching of chemical pulp. The reaction rate was determined by following the consumption of chlorine dioxide and hydrogen peroxide and the formation of chlorite. The rate equation was established. It was found that the concentration dependencies of chlorine dioxide, hydrogen peroxide and hydroxide ion were all first‐order. A reaction mechanism compatible with the rate equation was proposed. Since it was found in previous work that chlorite in chlorine dioxide solution by the addition of small amount of hydrogen peroxide potentially led to a decrease in the formation of organically bound chlorine during chlorine dioxide bleaching, two methods were suggested to implement this technique in a bleach plant.

Lignin-Derived Non-Heme Iron and Manganese Complexes: Catalysts for the On-Demand Production of Chlorine Dioxide in Water under Mild Conditions

“…It should be noted that, in addition to the reactions shown in Scheme , catalytic decomposition of ClO 2 by 3 /PAA produces molecular oxygen (4%, PAA as the limiting reagent) through side reactions. These may include oxidation of PAA by ClO 2 analogous to dioxygen formation from the reaction of ClO 2 and hydrogen peroxide in basic solution. , Molecular oxygen and chloride may also form from the reaction of [Mn­(IV)–O] − and ClO 2 via a peroxyhypochlorite adduct [Mn–OOClO] analogous to that postulated for porphyrin systems and the heme enzyme chlorite dismutase. ,, …”

“…These may include oxidation of PAA by ClO 2 analogous to dioxygen formation from the reaction of ClO 2 and hydrogen peroxide in basic solution. 3,39 Molecular oxygen and chloride may also form from the reaction of [Mn(IV)−O] − and ClO 2 via a peroxyhypochlorite adduct [Mn−OOClO] analogous to that postulated for porphyrin systems and the heme enzyme chlorite dismutase.…”

Quantitative description of the chloride effect on chlorine dioxide generation from the ClO2‐HOCl reaction

“…The kinetic experiments were performed in the cuvette of a UV spectrophotometer (Model Milton Roy 1001 Plus) following the procedure established before (Ni and Wang, 1997). The reagents were added to an acetateacetic acid buffer solution with a ionic strength of 0.2 mol/L.…”

IS ALL chlorine dioxide CREATED EQUAL?

“…The data (Ni & Wang, 1996) in Table 9 show shortterm conversion of ClO 2 → ClO 2in the presence of H 2 O 2 . The data (Sterling Pulp Chemicals, 1999) in Table 10 show that when ClO 2 and H 2 O 2 are present in solution in equal concentrations at drinking water pH, the ClO 2 conversion to ClO 2can be as high as 50% of the starting concentration after 2 h. These data confirm that ClO 2 and H 2 O 2 are not compatible oxidants because they react.…”