Hydroperoxide oxidation decomposition

Particle size, morphology, and structure have strong influence on the activities of catalysts, so it is important to develop a simple but effective method to be capable of controlling the particle size and even the microstructure of nanoparticles. Several preparation methods, including impregnation-reduction method (formaldehyde was used as the reducing agent) [38], hydroperoxide oxidation decomposition method [39-41], and the modified polyol method [42-44], were attempted in our laboratory. 

Thermally induced homolytic decomposition of peroxides and hydroperoxides to free radicals (eqs. 2—4) increases the rate of oxidation. Decomposition to nonradical species removes hydroperoxides as potential sources of oxidation initiators. Most peroxide decomposers are derived from divalent sulfur and trivalent phosphoms. 

The question about the competition between the homolytic and heterolytic catalytic decompositions of ROOH is strongly associated with the products of this decomposition. This can be exemplified by cyclohexyl hydroperoxide, whose decomposition affords cyclo-hexanol and cyclohexanone [5,6]. When decomposition is catalyzed by cobalt salts, cyclohex-anol prevails among the products ([alcohol] [ketone] > 1) because only homolysis of ROOH occurs under the action of the cobalt ions to form RO and R02 the first of them are mainly transformed into alcohol (in the reactions with RH and Co2+), and the second radicals are transformed into alcohol and ketone (ratio 1 1) due to the disproportionation (see Chapter 2). Heterolytic decomposition predominates in catalysis by chromium stearate (see above), and ketone prevails among the decomposition products (ratio [ketone] [alcohol] = 6 in the catalytic oxidation of cyclohexane at 393 K [81]). These ions, which can exist in more than two different oxidation states (chromium, vanadium, molybdenum), are prone to the heterolytic decomposition of ROOH, and this seems to be mutually related. 

IR spectrophotometry, 661, 662 TEARS assay, 667 hydroperoxide oxidation, 692 Upid hydroperoxides, 977-8 decomposition, 669 DNA adducts, 978-84 protein adducts, 984-5 ozone adducts, 734 ozonide reduction, 726 ozonization characterization, 737, 739 peroxydisulfate reactions, 1013, 1018 Alkali metal ozonides, 735-7 Alkaline peroxide process, pulp and paper bleaching, 623... 

Tricyclic trioxanes, synthesis, 282, 283 Tricyclohexylgermyl hydroperoxide, thermal decomposition, 822-3 Triethylsilane, oxidation, 807-8 Triethylsilyl hydrotrioxide... 

DOT CLASSIFICATION 8 Label Corrosive SAFETY PROFILE Poison by inhalation. A corrosive irritant to the eyes, skin, and mucous membranes. With the appropriate conditions it undergoes hazardous reactions with formic acid, hydrogen fluoride, inorganic bases, iodides, metals, methyl hydroperoxide, oxidants (e.g., bromine, pentafluoride, chlorine trifluoride, perchloric acid, oxygen difluoride, hydrogen peroxide), 3-propynol, water. When heated to decomposition it emits toxic fumes of POx. 

The importance of alkylperoxy radicals as intermediates had long been realized (see Sect. 2) and their subsequent reaction to yield the alkyl-hydroperoxide or decomposition products such as aldehydes and alcohols had been reasonably successful in describing the mechanism of the autocatalytic oxidation of alkanes. However, even though 0-heterocycles (which cannot be derived from intermediate aldehydes) had been found in the products of the oxidation of n-pentane as early as 1935 [66], the true extent of alkylperoxy radical isomerization reactions has been recognized only recently. Bailey and Norrish [67] first formulated the production of O-heterocycles in terms of alkylperoxy radical isomerization and subsequent cyclization in order to explain the formation of 2,5-dimethyl-tetrahydrofuran during the cool-flame oxidation of n-hexane. Their mechanism was a one-step process which involved direct elimination of OH. However, it is now generally formulated as shown in reactions (147) and(I67)... 

The oxidation reactions of 2,4,5-triphenylimidazole (lophine) have received considerable attention. With chromic acid it gives benzamide and benzanilide, but even more interest has centred on its involvement in the phenomenon of chemiluminescence. Some of this material has been discussed earlier (Sections 4.06.3.6, 4.07.1.2.1 and 4.07.1.2.3). The oxidative decomposition of lophine in the presence of air is accompanied by the emission of light, and it is the excited singlet state of the diaroylarylamidine (12 Scheme 2) which is the light emitter. The radical (46) derived from oxidation of lophine with aqueous ferricyanide and ethanolic KOH forms a hydroperoxide with hydrogen peroxide with consequent luminescence. When 2,4,5-tri- and 1,2,4,5-tetra-phenylimidazoles are oxidized in dilute methanol solution in the presence of methylene blue, the dibenzoylbenzamidine is also formed under circumstances in which hydroperoxides cannot be intermediates (B-76MI40701). 

ZDDPs, and also metal dithiocarbonates, act as oxidation inhibitors by peroxide decomposition in a manner which does not produce radicals, thus removing a major initiation source. It seems likely that ZDDPs are sources of DDPAs (dialkyldithio-phosphonic acids) and it is this which is responsible for either ionic decomposition of the hydroperoxide or decomposition by electron transfer, Reaction (3.4) [56] ... 

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