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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Reaction kinetics and catalysis letters 21 (1982), S. 283-287 
    ISSN: 1588-2837
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Abstract Окисление сульфаниловой кислоты до соответствующего азокси-производного с помощью пероксомонофосфорной кислоты (PMPA) было исследовано в водном растворе. Наблюдаемая зависимость pH—скорость с профилем колокола интерпретировалась на основе протонирования аминогруппы, ионизации PMPA в различные частицы и подбирая соответствующий закон скорости. Механизм окисления заключает в себе нуклеофильную атаку азота на электрофильный пероксокислород.
    Notes: Abstract Oxidation of sulfanilic acid to the corresponding azoxy derivative by peroxomonophosphoric acid (PMPA) has been studied in aqueous medium. The observed bell-shaped pH-rate profile has been rationalized on the basis of protonation of the amino group and ionization into different PMPA species and a suitable rate law has been proposed. The mechanism of oxidation involves the nucleophilic attack of nitrogen on the electrophilic peroxo oxygen.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of dimethyl sulfoxide (DMSO) oxidation by peroxomonophosphoric acid (PMPA) in aqueous medium at 308 K and I = 0.4 mol/dm3 follow the rate expressions In the pH range from 0 to 2, where k1 and k2 are 5.092 × 10-1 dm3/mol sec and ≃ 0, respectively; in the pH range from 4 to 7, where k2 = 8.127 × 10-3 and k3 = 2.90 × 10-3 dm3/mol sec; and in the pH range from 10 to 13.6, where k4 ≃ 0, and k5 = 3.08 × 10-2 dm3/mol sec.The reaction is interpreted in terms of mechanisms involving an electrophilic and a nucleophilic attack of the peroxomonophosphoric acid species, respectively, in acid and alkaline regions, on the sulfur atom of the sulfoxide molecule giving rise to SN2-type transition states followed by oxygen-oxygen bond fission to form the products.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 977-984 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyridiniumchlorochromate (PCC) oxidizes aniline and substituted anilines except nitro anilines smoothly in chlorobenzene-nitrobenzene mixtures in the presence of dichloroacetic acid. The reaction has unit dependence on each of the aniline, PCC, and dichloroacetic acid concentrations. Electron-releasing substituents accelerate the reaction, whereas electronwithdrawing groups retard the reaction, and the rate data obey Hammett's relationship. The reaction constant ρ is -3.75. Azobenzene and p-benzoquinone have been obtained as products. The observed experimental data have been rationalized in terms of the formation of an intermediate complex involving PCC-amine undergoing a rapid decomposition to products.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 85-96 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of dimethyl, dipropyl, and diphenyl sulfides by pyridinium chloro chromate in chlorobenzene-nitrobenzene mixtures are reported. The rate data show Michaelis-Menten behavior. The oxidation process is catalyzed by the organic acids like dichloro and trichloro acetic acids. The rate-determining step appears to be a unimolecular decomposition of a complex of the reactants.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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