Copper ions-hydrogen peroxide, oxidation

It was found that the value of F, is markedly increased by ions which are effective catalysts of oxidation reactions of peroxydisulphate. These are silver(I) copper(n), and iron(III). Cobalt(II) and nickel(II) ions, although they are good catalysts for the decomposition of hydrogen peroxide, exert their effect merely as inert electrolytes in the induced reaction. Therefore it can be concluded that, in this process, activation of the rather less reactive 8203 is more important than that of hydrogen peroxide . ... 

In the manufacture of printed circuit boards, the unwanted copper is etched away by acid solutions of cupric chloride (Equation 1.1). As the copper dissolves, the effectiveness of the solution tails and it must be regenerated. The traditional way of doing this is to oxidize the cuprous ion produced with acidified hydrogen peroxide. During the process the volume of solution increases steadily and the copper in the surplus liquor is precipitated as copper oxide and usually landfilled. 

Metal ions play an important role in several of these oxidative reactions as well as in biological dioxygen metabolism. As an example, copper(II) acetate and hydrogen peroxide have been used to produce a stable oxidizing agent, hydroperoxy copper(II) compound. The same oxidation system is also obtained from copper(II) nitrate and hydrogen peroxide (Eq. 1) [103] but requires the neutralization of ensuing nitric acid by potassium bicarbonate to maintain a pH 5. 

The flow-cell design was introduced by Stieg and Nieman [166] in 1978 for analytical uses of CL. Burguera and Townshend [167] used the CL emission produced by the oxidation of alkylamines by benzoyl peroxide to determine aliphatic secondary and tertiary amines in chloroform or acetone. They tested various coiled flow cells for monitoring the CL emission produced by the cobalt-catalyzed oxidation of luminol by hydrogen peroxide and the fluorescein-sensitized oxidation of sulfide by sodium hypochlorite [168], Rule and Seitz [169] reported one of the first applications of flow injection analysis (FTA) in the CL detection of peroxide with luminol in the presence of a copper ion catalyst. They... 

The luminol reaction has been used for the determination of oxidizing agents such as hydrogen peroxide, for enzymes such as peroxidase and xanthine oxidase, and for metal ions such as copper or cobalt that catalyze this CL reaction [24],... 

Haapakka and Kankare have studied this phenomenon and used it to determine various analytes that are active at the electrode surface [44-46], Some metal ions have been shown to catalyze ECL at oxide-covered aluminum electrodes during the reduction of hydrogen peroxide in particular. These include mercu-ry(I), mercury(II), copper(II), silver , and thallium , the latter determined to a detection limit of <10 10 M. The emission is enhanced by organic compounds that are themselves fluorescent or that form fluorescent chelates with the aluminum ion. Both salicylic acid and micelle solubilized polyaromatic hydrocarbons have been determined in this way to a limit of detection in the order of 10 8M. 

In contrast to the flavin-dependent monoamine oxidases, SSAO/VAP-1 has evolved to hydroxylate a tyrosine residue in the active site which is further oxidized to the quinone state by oxygen in the presence of copper ion releasing hydrogen peroxide [28-30]. The primary amine in the substrate (R-NH2, Scheme 1) forms a Schiff-base with the quinone carbonyl group, which through a series of steps ultimately releases the aldehyde product. 

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