Competitive mechanism of the nonbranched radical chain oxidation of hydrogen involving the free cyclohydrotetraoxyl radical [OO•••H•••OO]., which inhibits the chain process

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 nonmonotonic (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.