Peroxide catalytic decomposition

Initiation efficiency (e) was estimated with taking into account of peroxide catalytic decomposition with two radicals formation accordingly to the expression (8) ... 

Manganese(IV) oxide is a dark-brown solid, insoluble in water and dilute acids. Its catalytic decomposition of potassium chlor-ate(V) and hydrogen peroxide has already been mentioned. It dissolves slowly in alkalis to form manganates(lW), but the constitution of these is uncertain. It dissolves in ice-cold concentrated hydrochloric acid forming the complex octahedral hexachloromangan-ate(IV) ion ... 

The radicals are then involved in oxidations such as formation of ketones (qv) from alcohols. Similar reactions are finding value in treatment of waste streams to reduce total oxidizable carbon and thus its chemical oxygen demand. These reactions normally are conducted in aqueous acid medium at pH 1—4 to minimize the catalytic decomposition of the hydrogen peroxide. More information on metal and metal oxide-catalyzed oxidation reactions (Milas oxidations) is available (4-7) (see also Photochemical technology, photocatalysis). 

Propellant. The catalytic decomposition of 70% hydrogen peroxide or greater proceeds rapidly and with sufficient heat release that the products are oxygen and steam (see eq. 5). The thmst developed from this reaction can be used to propel torpedoes and other small missiles (see Explosives and propellants). An even greater amount of energy is developed if the hydrogen peroxide or its decomposition products are used as an oxidant with a variety of fuels. 

Decomposition of diphenoylperoxide [6109-04-2] (40) in the presence of a fluorescer such as perylene in methylene chloride at 24°C produces chemiluminescence matching the fluorescence spectmm of the fluorescer with perylene was reported to be 10 5% (135). The reaction follows pseudo-first-order kinetics with the observed rate constant increasing with fluorescer concentration according to = k [flr]. Thus the fluorescer acts as a catalyst for peroxide decomposition, with catalytic decomposition competing with spontaneous thermal decomposition. An electron-transfer mechanism has been proposed (135). 

Concentration Effects. The reactivity of ethyl alcohol—water mixtures has been correlated with three distinct alcohol concentration ranges (35,36). For example, the chromium trioxide oxidation of ethyl alcohol (37), the catalytic decomposition of hydrogen peroxide (38), and the sensitivities of coUoidal particles to coagulation (39) are characteristic for ethyl alcohol concentrations of 25—30%, 40—60%, and above 60% alcohol, respectively. The effect of various catalysts also differs for different alcohol concentrations (35). 

The early work of Kennerly and Patterson [16] on catalytic decomposition of hydroperoxides by sulphur-containing compounds formed the basis of the preventive (P) mechanism that complements the chain breaking (CB) process. Preventive antioxidants (sometimes referred to as secondary antioxidants), however, interrupt the second oxidative cycle by preventing or inhibiting the generation of free radicals [17]. The most important preventive mechanism is the nonradical hydroperoxide decomposition, PD. Phosphite esters and sulphur-containing compounds, e.g., AO 13-18, Table la are the most important classes of peroxide decomposers. 

The rate of peroxide decomposition and the resultant rate of oxidation are markedly increased by the presence of ions of metals such as iron, copper, manganese, and cobalt [13]. This catalytic decomposition is based on a redox mechanism, as in Figure 15.2. Consequently, it is important to control and limit the amounts of metal impurities in raw rubber. The influence of antioxidants against these rubber poisons depends at least partially on a complex formation (chelation) of the damaging ion. In favor of this theory is the fact that simple chelating agents that have no aging-protective activity, like ethylene diamine tetracetic acid (EDTA), act as copper protectors. 

Glutathione-peroxidase (GSH-Pxase) is an enzyme found in erythroqrtes and other tissues that has an essential selenocysteine residue involved in the catalytic decomposition of reactive oxygen species. In the erythrocyte, hydrogen peroxide is the principle reactive oxygen species available. 

The second pathway is seen distinctly at mercury and graphite electrodes. These electrodes are quite inactive in the catalytic decomposition of H2O2. Moreover, at them the potential where the peroxide is reduced further is more negative than the potential where it is formed from oxygen. Hence, within a certain range of not too negative potentials, the reaction can occur in such a way that the hydrogen peroxide formed accumulates in the solution. 

Release of enough energy dining catalytic decomposition of 65% peroxide to evaporate all water present and formed, and subsequent liability of ignition of combustible materials. 

In a printed circuit board etching line using copper(II) chloride solution, 45 wt% hydrogen peroxide solution was used to recover the copper salts. The peroxide header tank became contaminated with trace amounts of the etching solution, and catalytic decomposition of the peroxide led to a pressure burst of the tank. 

Spillage of a weak (5%) aqueous peroxide solution onto cotton waste led, after some time, to ignition. This probably involved concentration of the peroxide by evaporation/absorption of the water, the heat insulating effect of the fibrous mass preventing heat loss as oxidation proceeded, and possibly the presence of trace metals in the waste promoting catalytic decomposition. 

Catalytic Decomposition of Hydrogen Peroxide by Ferrous Ions... 

The catalysis of hydrogen peroxide decomposition by iron ions occupies a special place in redox catalysis. This was precisely the reaction for which the concept of redox cyclic reactions as the basis for this type of catalysis was formulated [10-13]. The detailed study of the steps of this process provided a series of valuable data on the mechanism of redox catalysis [14-17]. The catalytic decomposition of H202 is an important reaction in the system of processes that occur in the organism [18-22]. 

The catalytic decomposition of hydrogen peroxide under the action of the Fe2+/Fe3+ ions includes the following steps (H20, T = 298 K, acidic medium) [14—17] ... 

As in the case with catalytic decomposition of hydrogen peroxide, radical generation by the reaction of metal ions with hydroperoxide consists of several steps. In an aqueous solution, first ROOH is substituted in the internal coordination sphere of the ion followed by the transfer of an electron from the ion to ROOH accompanied by the subsequent cleavage of hydroperoxide to RO and OH, for example,... 

Howell, O.R. (1923) The catalytic decomposition of sodium hypochlorite by cobalt peroxide. Proceedings of the Royal Society, 104A, 134. 

A large quantity of discoloured (and peroxidised) turpentine was heated with fuller s earth to decolourise it, and it subsequently exploded. Fuller s earth causes exothermic catalytic decomposition of peroxides and rearrangement of the terpene molecule. 

Our approach utilized the metals gold, platinum, then later gold, platinum, and nickel electroplated in succession because the catalytic decomposition of hydrogen peroxide reaction we tested was most efficiently catalyzed with platinum.After fabrication of the nanowires they were freed by removing the conductive silver backing with nitric acid and the sacrificial template with a strong base, sodium hydroxide. Then nanorods were washed with deionized water and ultracentrifuged to achieve a neutral pH. 

One of the potential applications of catalytically driven motors is in microelec-tromechanical devices (MEMS). Catchmark capitalized on the concept of the platinum-gold nanorods by designing gold gears (150 /rm in size) with platinum spots on the teeth (Fig. 3.4) to produce the first rotating devices driven by the catalytic decomposition of hydrogen peroxide. 

Here we presented two general aspects of the interactions between superoxide and metal centers. One is the catalytic decomposition of superoxide by non-heme metal centers (Scheme 9) and the role of the ligand structure in it, and another is the reversible binding of superoxide to the heme metal center and the nature of the product metal(lll)-peroxo species (Scheme 17). In both cases through the same redox reaction steps a metal(III)-peroxo species is formed as the intermediate (Scheme 9), in the catalytic cycle, or the product of stoichiometric reaction (Scheme 17). The crucial difference is in the protonation step. If the protonation of peroxo species is followed by efficient release of hydrogen peroxide (and not 0-0 bond cleavage,... 

The quantity of hydrogen peroxide found was not equivalent to the acid sorption. Catalytic decomposition might be responsible for this. The formation of peroxide-like substances when moist air and acid reacted on carbon was deducted by Lamb and Elder (114), Kolthoff (20), and King (33) from the positive potassium iodide-starch test and, in my laboratory, from the reaction with titanyl ions. 

Hydrazine hydrate is used as a reducing agent in synthetic and analytical reactions and as a solvent for many inorganic compounds. It also is used with methanol as a propellant for rocket engines. Another apphcation is catalytic decomposition of hydrogen peroxide. 

The catalytic decomposition of hydrogen peroxide at the surface of platinum foil investigated by Bredig and Tetelow (Zeit. Elehtro-chem. XII. 581, 1906) was found to obey a unimolecular law and the seat of the reaction was shown to be the thin saturated layer at the surface of the metal. 

However, the solutions are fairly stable when stored in clean vessels and protected from light, because reaction (6) is slow, as well as the oxidation of water but, dust, metal ions, and organic traces can catalyze the reactions the effervescence of H2O2 in contact with traces of hemoglobin is a well-known illustration of the catalytic disproportionation of the peroxide. The decomposition of concentrated solutions induced by impurities can be explosive. 

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