title: Hydrogen peroxide decomposition on manganese oxide (pyrolusite): kinetics, intermediates, and mechanism.
abstract: The objective of this study is the kinetic interpretation of hydrogen peroxide decomposition on manganese oxide (pyrolusite) and the explanation of the reaction mechanism including the hydroperoxide/superoxide anion. The decomposition of hydrogen peroxide on manganese oxide at pH 7 was represented by a pseudo first-order model. The maximum value of the observed first-order rates constants (k(obs)) was 0.741 min(-1) at 11.8 of [H(2)O(2)]/[triple bond MnO(2)] when [H(2)O(2)]/[triple bond MnO(2)] were ranged from 58.8 to 3.92. The pseudo first-order rate constants (kMnO(2)) approximated as the average value of 0.025 (min mM)(-1) with a standard deviation of 0.003 at [H(2)O(2)]/[triple bond MnO(2)] ranged from 39.2 to 11.8. When [H(2)O(2)]/[triple bond MnO(2)] was 3.92, the rate constants (kMnO(2)) was 0.061 (min mM)(-1) as maximum. Oxygen production showed that the initial rates increased with decreasing [H(2)O(2)]/[triple bond MnO(2)] and the total amounts of oxygen was slightly less than the stoichiometric value (0.5) in most experiments. However, oxygen was produced at more than 0.5 in low [H(2)O(2)]/[triple bond MnO(2)] (i.e. 3.92 and 9.79). The relative production of hydroperoxide/superoxide anion implied that the production increased with low [H(2)O(2)]/[triple bond MnO(2)], and the existence of anions suggested that the mechanism includes propagation reactions with intermediates such as hydroperoxide/superoxide anion in solution. In addition, both [H(2)O(2)] decomposition and the production of anion were accelerated in alkaline solution. Manganese ion dissolved into solution was negligible in neutral and alkaline conditions, but it greatly increased in acidic conditions.
authors.affiliation: Department of Chemical Engineering, Hanyang University, Seoul 133-791, Republic of Korea.
authors.forename: Si-Hyun
authors.initials: SH
authors.lastname: Do
authors.forename: Bill
authors.initials: B
authors.lastname: Batchelor
authors.forename: Hong-Kyun
authors.initials: HK
authors.lastname: Lee
authors.forename: Sung-Ho
authors.initials: SH
authors.lastname: Kong
mesh_terms: D003124:Colorimetry; D006861:Hydrogen Peroxide / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D017895:Manganese Compounds / Q000737:chemistry*; D010087:Oxides / Q000737:chemistry*
chemical_list: D017895:Manganese Compounds; D010087:Oxides; C027424:manganese oxide; D006861:Hydrogen Peroxide