28384-48-7Relevant articles and documents
Effect of Organic Solvents on the Rate of Oxidation of Sulfoxides with Peroxy Acids
Dutka, V. S.,Dutka, Yu. V.,Midyana, G. G.,Pal’chikova, E. Ya.
, p. 329 - 334 (2020/04/27)
Abstract: The reaction of sulfoxides with peroxy acids in various organic media was studied. The reaction mechanism involves the rapid formation of a sulfoxide-–peroxy acid intermediate which decomposes in the second stage to form carboxylic acid and the corresponding sulfone. The second stage is the rate-limiting step. The reaction medium significantly affects the rate of oxidation. The calculated activation parameters of the oxidation process indicate a compensation effect in the investigated reaction. Correlations between the main physicochemical parameters of solvents and the effective rate constants (k) of dimethyl sulfoxide oxidation with peroxy acids were found. Depending on the reaction conditions, the main factors affecting the k values are specific and nonspecific solvation of the reactants and structural factors.
Liquid chromatographic simultaneous determination of peroxycarboxylic acids using postcolumn derivatization
Effkemann,Pinkernell,Neumueller,Schwan,Engelhardt,Karst
, p. 3857 - 3862 (2007/10/03)
The first liquid chromatographic method with postcolumn derivatization for the simultaneous determination of peroxycarboxylic acids is described. Aliphatic peracids with chain lengths from C2 to C12 are separated by HPLC on a reversed-phase C18 column with acetonitrile/water gradient elution. For improved peak shape, tetrahydrofuran and acetic acid are added to the aqueous eluent. After chromatographic separation, the peroxycarboxylic acids react with 2,2′-azino-bis(3-ethylbenzothiazoline)-6-sulfonate, a popular substrate for the enzyme peroxidase. Iodide traces are added as catalyst. The oxidation product, a green radical cation, is determined using a UV/ visible detector in four characteristic regions of the visible and near-infrared spectrum in the range 405-815 nm. The advantages of the new method are detection limits in the low micromolar range, negligible matrix interferences, high reproducibility, and the possibility for simultaneous determination of several peroxycarboxylic acids.
Formation and Thermal Decomposition of Butyl-Substituted Peroxyacyl Nitrates: n-C4H9C(O)OONO2 and i-C4H9C(O)OONO2
Grosjean, Daniel,Grosjean, Eric,Williams, Edwin L.
, p. 1099 - 1105 (2007/10/03)
The butyl-substituted peroxyacyl nitrates n-C4H9C(O)OONO2 and i-C4H9C(O)OONO2 have been synthesized in the liquid phase, prepared in-situ in the gas phase by sunlight irradiation of aldehyde-NO mixtures, measured by electron capture gas chromatography, and characterized in a number of gas-phase and liquid-phase tests. Gas-phase yields as a fraction of initial NO were 0.39 for the n-butyl isomer and 0.20 for the isobutyl isomer. The corresponding gas-phase aldehyde oxidation mechanisms are outlined. Thermal decomposition in the presence of excess NO yielded n-butanal and isobutanal as the major carbonyl products. Thermal decomposition rates at ambient temperature and atmospheric pressure are comparable to that of PAN , with k298 = 1.8E-4 s-1 for n-C4H9C(O)OONO2 and 2.4E-4 s-1 for i-C4H9C(O)OONO2. Emission data for precursor hydrocarbons indicate C4H9C(O)OONO2/PAN ambient concentration ratios of 0.19 in urban air. Atmospheric implications for the formation and removal of C4H9C(O)OONO2 are briefly discussed.
