Hydrogen peroxide number

Hydrogen peroxide is probably unique in the very large number of reactions by which it is formed. Some of these may be mentioned ... 

A number of per-acids and organic derivatives of hydrogen peroxides are manufactured by Laporte Chemicals Ltd., Luton, England. 

Oxidation. Hydrogen peroxide is a strong oxidant. Most of its uses and those of its derivatives depend on this property. Hydrogen peroxide oxidizes a wide variety of organic and inorganic compounds, ranging from iodide ions to the various color bodies of unknown stmcture in ceUulosic fibers. The rate of these reactions may be quite slow or so fast that the reaction occurs on a reactive shock wave. The mechanisms of these reactions are varied and dependent on the reductive substrate, the reaction environment, and catalysis. Specific reactions are discussed in a number of general and other references (4,5,32—35). 

A number of chemiluminescent reactions may proceed through unstable dioxetane intermediates (12,43). For example, the classical chemiluminescent reactions of lophine [484-47-9] (18), lucigenin [2315-97-7] (20), and transannular peroxide decomposition. Classical chemiluminescence from lophine (18), where R = CgH, is derived from its reaction with oxygen in aqueous alkaline dimethyl sulfoxide or by reaction with hydrogen peroxide and a cooxidant such as sodium hypochlorite or potassium ferricyanide (44). The hydroperoxide (19) has been isolated and independentiy emits light in basic ethanol (45). 

Weak to moderate chemiluminescence has been reported from a large number of other Hquid-phase oxidation reactions (1,128,136). The Hst includes reactions of carbenes with oxygen (137), phenanthrene quinone with oxygen in alkaline ethanol (138), coumarin derivatives with hydrogen peroxide in acetic acid (139), nitriles with alkaline hydrogen peroxide (140), and reactions that produce electron-accepting radicals such as HO in the presence of carbonate ions (141). In the latter, exemplified by the reaction of h on(II) with H2O2 and KHCO, the carbonate radical anion is probably a key intermediate and may account for many observations of weak chemiluminescence in oxidation reactions. 

Actinide Peroxides. Many peroxo compounds of thorium, protactinium, uranium, neptunium, plutonium, and americium are known (82,89). The crystal stmctures of a number of these have been deterrnined. Perhaps the best known are uranium peroxide dihydrate [1344-60-1/, UO 2H20, and, the uranium peroxide tetrahydrate [15737-4-5] UO 4H2O, which are formed when hydrogen peroxide is added to an acid solution of a uranyl salt. 

Fig. 2. Steps in advanced oxidation process (AOPs) involving o2one, hydrogen peroxide, and uv light of 254 nm. ( D) represents the doublet state ( ) represents quantum yield, and the other numbers associated with the reaction arrows are rate constants in units of (Af-s). Dashed arrows indicate...

Titanium Silicates. A number of titanium siUcate minerals are known (160) examples are Hsted in Table 19. In most cases, it is convenient to classify these on the basis of the connectivity of the SiO building blocks, eg, isolated tetrahedra, chains, and rings, that are typical of siUcates in general. In some cases, the SiO units may be replaced, even if only to a limited extent by TiO. For example, up to 6% of the SiO in the garnet schorlomite can be replaced by TiO. In general, replacement of SiO by TiO bull ding blocks increases the refractive indices of these minerals. Ti has also replaced Si in the framework of various zeofltes. In addition, the catalytic activity of both titanium-substituted ZSM-5 (TS-1) and ZSM-11 (TS-2) has received attention (161), eg, the selective oxidation of phenol, with hydrogen peroxide, to hydroquinone and catechol over TS-1 has been operated at the 10,000 t/yr scale in Italy (162). 

Solid Peroxygen Compounds. Hydrogen peroxide reacts with many compounds, such as borates, carbonates, pyrophosphates, sulfates, sihcates, and a variety of organic carboxyHc acids, esters, and anhydrides to give peroxy compounds or peroxyhydrates. A number of these compounds are stable sohds that hydrolyze readily to give hydrogen peroxide in solution. 

The ease of oxidation varies considerably with the nature and number of ring substituents thus, although simple alkyl derivatives of pyrazine, quinoxaline and phenazine are easily oxidized by peracetic acid generated in situ from hydrogen peroxide and acetic acid, some difficulties are encountered. With unsymmetrical substrates there is inevitably the selectivity problem. Thus, methylpyrazine on oxidation with peracetic acid yields mixtures of the 1-and 4-oxides (42) and (43) (59YZ1275). In favourable circumstances, such product mixtures may be separated by fractional crystallization. Simple alkyl derivatives of quinoxalines are... 

Calculate (i) the weight of hydrogen peroxide per L of the original solution and (ii) the volume strength , i.e. the number of millilitres of oxygen at s.t.p. that can be obtained from 1 mL of the original solution. 

A number of 4//-thiopyrans were converted to their corresponding sulfones with hydrogen peroxide in acetic acid 132... 

The use of molybdenum catalysts in combination with hydrogen peroxide is not so common. Nevertheless, there are a number of systems in which molybdates have been employed for the activation of hydrogen peroxide. A catalytic amount of sodium molybdate in combination with monodentate ligands (e.g., hexaalkyl phosphorus triamides or pyridine-N-oxides), and sulfuric acid allowed the epoxidation of simple linear or cyclic olefins [46]. The selectivity obtained by this method was quite low, and significant amounts of diol were formed, even though highly concentrated hydrogen peroxide (>70%) was employed. 

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