Environmental issues hydroperoxides

Hartree-Fock calculations, peracid alkene epoxidation, 48-50 Hazardous materials commercial codes, 621 emergency response, 746-7 environmental hazards, 747, 751-3 labels, 751-3 NIOSH Pocket Guide, 749 occupational hazards, 747-9 safety issues, 744-9 HDL see High-density lipoprotein Heat of formation see Enthalpy of formation HEHP (1-hydroxyethyl hydroperoxide), 605, 638... 

In the development of effective catalytic oxidation systems, there is a qualitative correlation between the desirability of the net or terminal oxidant, (OX in equation 1 and DO in equation 2) and the complexity of its chemistry and the difficulty of its use. The desirability of an oxidant is inversely proportional to its cost and directly proportional to the selectivity, rate, and stability of the associated oxidation reaction. The weight % of active oxygen, ease of deployment, and environmental friendliness of the oxidant are also key issues. Pertinent data for representative oxidants are summarized in Table I (4). The most desirable oxidant, in principle, but the one with the most complex chemistry, is O2. The radical chain or autoxidation chemistry inherent in 02-based organic oxidations, whether it is mediated by redox active transition metal ions, nonmetal species, metal oxide surfaces, or other species, is fascinatingly complex and represents nearly a field unto itself (7,75). Although initiation, termination, hydroperoxide breakdown, concentration dependent inhibition... 

An issue which deserves further mention is the environmentally fiiendly nature of TS-l/H Oj system. It involves the use of a safe silica based catalyst, titanium silicalite, and a reagent, hydrogen peroxide, which yields water as the coproduct. This holds for the in situ route illustrated in Scheme I and also for the epoxidation of propylene with preformed hydrogen peroxide, either used as an aqueous solution (72) or extracted by means of die epoxidation solvent (Scheme 11). Hazardous chemicals, such as chlorine, performic or other organic peracids, are not required in the process. The disposal of chlorinated salts or the recycle of brine (chloroydrin process) and any possible burden resulting from the coproduction of odier chemicals (styrene and r-butanol in the hydroperoxide route) are eliminated. The liquid phase oxidation of isobutane and ethylbenzene with air under pressure and at high temperature, to produce... 

The occurrence of highly-reactive and labile peroxides and hydroperoxides in the atmosphere is another issue of concern in environmental analysis. Peroxides are used in polymer industry as a source of free radicals. Conventional EI-MS of peroxides results in extensive fragmentation, whereas lAMS, e.g., in EGA-IAMS (Sect. 6.4.2) enables molecular profiling of peroxides. Proton-transfer reaction MS (PTR-MS) technique has also been used for kinetics studies of organic peroxy radicals such as CH302, CH3CH202, and C3H,02 [23, 24]. 

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