Low-reactive free radicals inhibiting nonbranched chain processes of additionстатья
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Дата последнего поиска статьи во внешних источниках: 20 января 2016 г.
Аннотация:A kinetic study is made of the processes whereby low-reactive free radicals (o-CH3C6H4CH2Ó4;
HÓ4; HĊ=O; CH2=C(CH3)ĊH2 and CH2=CHĊHOH) can inhibit nonbranched chain addition of reactive
free radicals at O=O, C=O, and C=C double bonds in liquid homogeneous binary systems (a saturated and
an unsaturated components). Increasing the concentration of the unsaturated component (source of
low-reactive free radicals) over an optimum (giving the maximal chain propagation rate) causes progressive inhibition of the chain reaction; this phenomenon may be involved in self-regulation of such processes in nature, returning them to a steady state. The heat effects are compared for the overall reactions of dissociation of simple alkylperoxyl (exothermic) and alkoxyl (endothermic) free radicals in the gas phase. The energy aspects are considered for the key radical–molecular gas-phase reactions. Quasi-steady-state treatment provides rate equations (with one to three parameters to be directly determined) that describe the nonmonotonic dependence (with a maximum) of the rate of molecular 1:1 adduct formation on the concentration of the unsaturated component.
Keywords: free radical, competition, inhibition, nonbranched chain processes