Peroxide decomposition, acid catalyzed radical

Thus, antioxidant effects of nitrite in cured meats appear to be due to the formation of NO. Kanner et al. (1991) also demonstrated antioxidant effects of NO in systems where reactive hydroxyl radicals ( OH) are produced by the iron-catalyzed decomposition of hydrogen peroxide (Fenton reaction). Hydroxyl radical formation was measured as the rate of benzoate hydtoxylation to salicylic acid. Benzoate hydtoxylation catalyzed by cysteine-Fe +, ascorbate - EDTA-Fe, or Fe was significantly decreased by flushing of the reaction mixture with NO. They proposed that NO liganded to ferrous complexes reacted with H2O2 to form nitrous acid, hydroxyl ion, and ferric iron complexes, preventing generation of hydroxyl radicals. 

Fe2+. Because peroxide decomposition was slowest under the same conditions at which benzoic acid decomposition was highest, it is important to consider the efficiency of hydroxyl radical formation from peroxide decomposition. With the surface catalyst, either hydroxyl radical is not readily available to benzoic acid and is scavenged by other species, or the mineral-catalyzed decomposition of hydrogen peroxide involves additional, nonhydroxyl radical-forming pathways for peroxide decomposition. 

The complexity of the peroxide curing system arises from a range of possible side reactions such as /3-cleavage of the oxy radical, addition reaction, polymer scission, radical transfer, dehydrohalogenation, oxygenation, and acid catalyzed decomposition of the peroxide." ... 

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). 

Similar results were obtained for tert-butyl hydroperoxide and perchloric acid in 2-propanol. Thus, it is evident from the decomposition of hydrogen peroxide into free radicals that both heterolytic and homolytic reactions may be catalyzed by hydrogen ions. Further research is needed to investigate proton catalysis in certain homolytic reactions. 

Aliphatic amines have much less effect on the later reactions of the gas-phase oxidation of acetaldehyde and ethyl ether than if added at the start of reaction. There is no evidence that they catalyze decomposition of peroxides, but they appear to retard decomposition of peracetic acid. Amines have no marked effect on the rate of decomposition of tert-butyl peroxide and ethyl tert-butyl peroxide. The nature of products formed from the peroxides is not altered by the amine, but product distribution is changed. Rate constants at 153°C. for the reaction between methyl radicals and amines are calculated for a number of primary, secondary, and tertiary amines and are compared with the effectiveness of the amine as an inhibitor of gas-phase oxidation reactions. 

The results given in this paper show that aliphatic amines do not catalyze the decomposition of peroxides, and compared with their effect at the start of reaction, they have much less effect on the later stages of oxidation, although they appear to retard the decomposition of peracetic acid. The reactions of radicals with aliphatic amines indicate that an important mode of inhibition is most probably by stabilization of free radicals by amine molecules early in the chain mechanism, possibly radicals formed from the initiation reaction between the fuel and oxygen. For inhibition to be effective, the amine radical must not take any further part in the chain reaction set up in the fuel-oxygen system. The fate of the inhibitor molecules is being elucidated at present. 

Transition metals will promote oxidative reactions by hydrogen abstraction and by hydroperoxide decomposition reactions that lead to the formation of free radicals. Prooxidative metal reactivity is inhibited by chelators. Chelators that exhibit antioxidative properties inhibit metal-catalyzed reactions by one or more of the following mechanims prevention of metal redox cycling occupation of all metal coordination sites thus inhibiting transfer of electrons formation of insoluble metal complexes stearic hinderance of interactions between metals and oxidizable substrates (e.g., peroxides). The prooxidative/antioxidative properties of a chelator can often be dependent on both metal and chelator concentrations. For instance, ethylene diamine tetraacetic acid (EDTA) can be prooxidative when EDTAiiron ratios are <1 and antioxidative when EDTAiiron is >1. The prooxidant activity of some metal-chelator complexes is due to the ability of the chelator to increase metal solubility and/or increase the ease by which the metal can redox cycle. 

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