The Kinetics of the Decomposition of Tertiary Hydroperoxides in Solvents^1,2

Solvent and catalytic metal effects on the decomposition of cumene hydroperoxide

“…It is not surprising that the Patel-Teja equation does not work well with the alcohols, octene, and CFM since this equation does not model the types of complexing, such as hydrogen bonding, expected to occur between these solvents and the activated complex (Reichardt, 1979;Spirin, 1969;Swain et al, 1950;Stannett and Mesrobian, 1950). This calculated increase is consistent with experimental observation, but the absolute value of the increase is too low.…”

The Role of Peroxides in the Liquid-Phase Oxidation of Hydrocarbons

“…The kinetic order varies with the initial concentration of the peroxide. there was practically no decomposition over a similar period [18]. An increase in the velocity constant for peroxide decomposition with initial hydroperoxide concentration was also observed for the de composition of tert-butyl hydroperoxide in n-octane [17].…”

Thermolysis and photolysis of 2-ethyl-4-nitro-1(2H)-isoquinolinium hydroperoxide

“…Specifically, the purity of the solvent is vital, since traces of strong acids and metallic complexes can catalyze the O – O bond breakage. Furthermore, the rate of thermolysis was found to be significantly higher in alcoholic and unsaturated solvents than in aromatic or chlorinated hydrocarbon solvents . These results are explained in terms of a radical forming, bimolecular solvent (SH)/hydroperoxide (ROOH) thermolysis of the type: ROOH + SH → RO .…”

“…The decomposition usually begins with the O – O bond homolysis of the hydroperoxide, followed by a chain of reactions involving hydroxyl and alkoxyl radicals . The reaction mechanism, rates and product distribution are readily affected by experimental conditions, such as the concentration of the hydroperoxide, temperature, solvent and radical initiators or inhibitors …”