Hydrogen peroxide catalytic decomposition

Hemocyanin from molluscan and crustacean sources is able to decompose hydrogen peroxide catalytically (Ghiretti, 1956 Felsenfeld and Printz, 1959). This catalase-like action is due to the presence of copper in the hemocyanin molecule. However, equivalent amounts of copper alone have no effect on the decomposition of HgOj. Among the copper complexes of the amino acid tested, only Cu-arginine is active. 

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). 

Because the reaction takes place in the Hquid, the amount of Hquid held in the contacting vessel is important, as are the Hquid physical properties such as viscosity, density, and surface tension. These properties affect gas bubble size and therefore phase boundary area and diffusion properties for rate considerations. Chemically, the oxidation rate is also dependent on the concentration of the anthrahydroquinone, the actual oxygen concentration in the Hquid, and the system temperature (64). The oxidation reaction is also exothermic, releasing the remaining 45% of the heat of formation from the elements. Temperature can be controUed by the various options described under hydrogenation. Added heat release can result from decomposition of hydrogen peroxide or direct reaction of H2O2 and hydroquinone (HQ) at a catalytic site (eq. 19). 

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. 

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 catalytic activity of PCSs results from their semiconductor properties. The first studies in this field date from 1959—1961. Thus, we have demonstrated catalytic activity of products of the thermal transformation of PAN in the decomposition reactions of hydrogen peroxide, hydrazine hydrate, and formic acid270, 271. There is an indication of catalytic activity of poly(aminoquinone) in the reactions of the hydrogen peroxide decomposition272. ... 

PCSs obtained by dehydrochlorination of poly(2-dilorovinyl methyl ketones) catalyze the processes of oxidation and dehydrogenation of alcohols, and the toluene oxidation207. The products of the thermal transformation of PAN are also catalysts for the decomposition of nitrous oxide, for the dehydrogenation of alcohols and cyclohexene274, and for the cis-tnms isomerization of olefins275. Catalytic activity in the decomposition reactions of hydrazine, formic acid, and hydrogen peroxide is also manifested by the products of FVC dehydrochlorination... 

One of the most used systems involves use of horseradish peroxidase, a 3-diketone (mosl commonly 2,4-pentandione), and hydrogen peroxide." " " Since these enzymes contain iron(II), initiation may involve decomposition of hydrogen peroxide by a redox reaction with formation of hydroxy radicals. However, the proposed initiation mechanism- involves a catalytic cycle with enzyme activation by hydrogen peroxide and oxidation of the [3-diketone to give a species which initiates polymerization. Some influence of the enzyme on tacticity and molecular... 

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. 

Metal-ion catalysis of hydrogen peroxide decomposition can generate perhydroxyl and hydroxyl free radicals as in Scheme 10.26 [235]. The catalytic effects of Fe2+ and Fe3+ ions are found to be similar [235]. It is not necessary for the active catalyst to be dissolved [237], as rust particles can be a prime cause of local damage. The degradative free-radical reaction competes with the bleaching reaction, as illustrated in Scheme 10.27 [237]. Two adverse consequences arise from the presence of free radicals ... 

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. 

Action of chlorine trifluoride causes incandescence [1]. Manganese dioxide catalytically decomposes powerful oxidising agents, often violently. Dropped into cone, hydrogen peroxide, the powdered oxide may cause explosion [2], Either the massive or the powdered oxide explosively decomposes 92% peroxomonosulfuric acid [3], and mixtures with chlorates ( oxygen mixture , heated to generate the gas) may react with explosive violence [4], Cuban pyrolusite can be used in place of potassium dichromate to promote thermal decomposition of potassium chlorate in match-head formulations [5],... 

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,... 

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