Competitive Mechanism of the Nonbranched Radical Chain Oxidation of Hydrogen Involving the Free Cyclohydrotetraoxyl Radical [OO…H…OO]~·,which Inhibits the Chain Process

摘要

A nonbranched radical chain mechanism, which does not pass into non-steady-state critical regimes, was proposed for the uncatalyzed oxidation of hydrogen. This mechanism includes competitive reactions with the participation of H~·, HO~·, and HO_2~· free radicals and the inactive cyclohydrotetraoxyl radical HO_4~· stabilized by inner hydrogen bonding, wherein the cyclohydrotetraoxyl radical inhibits the chain process. A simple rate equation, which describes the nonmonotomic (with a maximum) dependence of the rate of the nonbranched chain process of hydrogen peroxide and water formation on the concentration of molecular oxygen, was derived using the quasi-steady-state approximation. The nonchain reaction paths of free-radical hydrogen oxidation were considered. It was assumed that the cyclic free radical HO_4~· can be an intermediate in the series of conversions of biologically harmful energy of cosmic radiation in the upper atmosphere.