Peroxides in solution

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. 

After reading the article by Kelly on peroxidizables (see Table 13-2 reference), state the minimum hazardous concentrations of peroxides in solution with organic chemicals. 

For a review of free radical mechanisms involving peroxides in solution, see Howard, in Patai The Chemistry of Peroxides Wiley New York, 1983, pp. 235-258. For a review of pyrolysis of peroxides in the gas phase, see Batt Liu. in the same volume, pp. 685-710. See also Chateauneuf Lusztyk Ingold J. Am. Chem. Soc. 1988,110. 2877. 2886. 

Peroxide in solution is necessary to produce fast co-oxidation. When isooctane was used as solvent instead of benzene, a slow and linear oxygen uptake was observed (0.5 mole per mole of indene in 100 hours at 20°C.). This behavior was the result of low solubility in the paraffin of the hydroperoxide, I, which precipitated out and rapidly rearranged to inactive sulfoxides. 

Hydrogen peroxide in solution decomposes slowly at room temperature with liberation of oxygen, but it decomposes rapidly at higher temperatures. The decomposition is accelerated by trace amounts of transition... 

A binder for copper clad laminates contains the prepolymer from BPA/DC and A -(3,5-dimethyl-4-vinylphenyl)maleimide in methylethylketone, an epoxynovolak resin, Zn acetate and tert.butyl peroxide [100], In a similar composition, a prepolymer obtained from epoxide resin, BMI and bis(4-aminophenyl)methane was mixed with BPA/DC, Zn acetate and tert.butyl peroxide in solution [101]. 

Depolymerisation of hyaluronic acid induced by Cu(II) and hydrogen peroxide in solution... 

O Grady et al. [227] studied the reduction and evolution of oxygen on RuO on titanium and reported that the cathodic reaction involves the formation of peroxide in solution. From y 1/2 vs. rotating disk electrodes, the authors concluded that the reaction 02/H202 was in equilibrium at the surface [227], Miles et al. [428] also studied the oxygen electrode reactions on several metal oxides (Ir, Ru, Pd, and Rd)... 

The thermal decomposition of S5mrmetrical dialkyl peroxides such as diisopropyl peroxide in solution has been shown to involve a competition between monomolecular homolysis k ) and an electrocyclic reaction yielding acetone and hydrogen ( h) cf Eq. (5-59) [564]. 

METHYL ETHYL KETONE PEROXIDE see MKA500 METHYL ETHYL KETONE PEROXIDE, in solution u-ith >9% by weight active oxygen (DOT) see MKA500 METHYL ETHYL KETONE SEMICARBAZONE see MKA750... 

Kinetics of thermal decomposition of dialkyl peroxides in solution as well as the gas phase have been reviewed by Molyneux and Frost and Pearson . The decomposition of dialkyl peroxides is moderately free from induced decomposition, compared to other types of peroxides. As seen from Table 65, the first-order rate coefficient increases by about 16 % when the initial peroxide concentration is increased about 5 fold at reasonably high peroxide concentrations. The increase in the rate coefficient is attributed to an induced decomposition where hydrogen atom abstraction generates the radical (I). Further reaction of (I) produces isobutylene oxide and the f-butoxy radical, viz. 

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