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  • 1
    Electronic Resource
    Electronic Resource
    Kinetics of the isomerization reaction of cholest-5-en-3-one catalyzed by trichloroacetic acid in aprotic solvents of low dielectric constant (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 875-891 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The isomerization reaction of cholest-5-en-3-one has been studied in a solution of cyclohexane using trichloroacetic acid as catalyst. At the same time a general reaction scheme is proposed to be valid for all the cases assayed in which the monomer form of the acid is considered as the only effective catalyst. The experimental results agree with these hypotheses and with the calculation of the individual rate constant together with the reaction order with respect to the catalyst. Semiquantitative studies have been carried out with other catalysts and solvents, confirming the validity of the reaction scheme. The thermodynamic activation parameters have also been calculated, and a comparative study was made with the results of the evaluation of the reaction when it takes place in amphiprotic solvents. A reaction mechanism is proposed based on all the kinetic information obtained.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140807
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  • 2
    Electronic Resource
    Electronic Resource
    Pseudo-phase ion-exchange model for micellar catalysis in the acid hydrolysis of vinyl ethers (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 269-276 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the perchloric acid hydrolysis of aqueous ethyl and butyl vinyl ethers at 25.0°C, in the presence of micellar aggregates [anionic, sodium dodecyl sulfate (SDS); cationic, cetyl trymethyl ammonium bromide (CTAB); and nonionic, polyoxyethylen—23—dodecanol, (Brij 35)], has been studied. Negligible effects were observed in the cases of cationic and nonionic micelles. Anionic micelles produce an enhancement in the reaction velocity, and the rate constants go through maxima with increasing SDS concentration. These maxima disappear in the presence of excess sodium perchlorate. All these facts are interpreted quantitatively by means of the pseudo-phase ion-exchange model.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160309
    Library Location Call Number Volume/Issue/Year Availability
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    Paper (German National Licenses)
    Fulltext
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