Characterisation and quantitative determination of (hydro)peroxides formed in the radiolysis of dioxygen-containing systems and upon ozonolysis

Abstract Organic (hydro)peroxides, ROOR and ROOH, were generated either radiolytically in oxygenated aqueous solutions ( OH+RH→R +H 2 O; R +O 2 →ROO ; 2 ROO →ROOR+O 2 ; ROO +HO 2 /O 2 − +H + →ROOH+O 2 ) or by ozonolysis (R 2 C=CR 2 +O 3 +H 2 O→R 2 C=O+R 2 C(OH)OOH). Their pseudo-first-order kinetics with molybdate-activated iodide allows us to characterise a given peroxide, since the half-lives vary by more than seven orders of magnitude. Some (hydro)peroxides do not react under these conditions, e.g. dimethylperoxide, but the very reactive ones, e.g. formic peracid, do not even require molybdate catalysis. For the reactive ones, including H 2 O 2 , HPLC with post-column reaction is a convenient method for spotting a (hydro)peroxide in the chromatogram and for its quantitative determination. Recommendations are given how to use this assay for the determination of mixtures of (hydro)peroxides of different reactivity.