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  • 1
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 271-275 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Decomposition of 1-phenylethyl-hydroperoxide has been studied in the presence of 2,6-di-tert-butyl-4-methyl-phenol inhibitor in ethylbenzene and chlorobenzene both in oxygen and nitrogen. The oxygen consumption and the inhibitor concentrations were measured against the initial inhibitor concentrations. Two methods were applied for the determination of the rate coefficients of the reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm HROOH + InH}\mathop {\hbox to 30pt{\rightarrowfill}}\limits^{k_1 } {\rm HRO}^{\rm .} + {\rm In}^{\rm .} + {\rm H}_{\rm 2} {\rm O} $$\end{document} Its value is about 3 × 10-4L × mol-1 × S-1, at 120°C. However, large experimental errors we deal with, the existence of a reaction yielding radicals, presumably an interaction between hydroperoxide and inhibitor molecules, can be established emphasizing the importance of measurements carried out with various initial concentrations of the inhibitor.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 249-263 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Absolute rate constants for the addition of the 2-cyano-2-propyl radical to 26 alkenes CH2=CXY at 315 K were determined in solution by time-resolved electron-spin-resonance spectroscopy. They vary with the alkene substituents from 30 M-1 s-1 to 7′010 M-1 s-1. For styrene the temperature dependence is given by log k/M-1 s-1 = 7.7 - 26.1/Θ where Θ = 2.303 RT in kJ/mol. An analysis of the substituent effects in terms of polar and enthalpic factors reveals a dominant influence of the overall reaction enthalpy. © 1993 John Wiley & Sons, Inc.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 913-920 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Absolute rate constants for the addition of the 2-hydroxy-2-propyl radical to 18 substituted alkenes (CH2 = CXY) were determined at (296 ± 1) K in 2-propanol by time-resolved electronspin-resonance spectroscopy. With alkene substitution the rate constants vary by more than 6 orders of magnitude. For 3,3-dimethyl-but-1-ene the temperature dependence is given by log k/M-1 · s-1 = 6.4 minus;; 19.1/Θ where Θ = 2.303 RT in kJ/mol-1. As shown by a good correlation with the alkene electron affinities, log k296/M-1 · s-1 = 6.46 + 1.71 · EA/eV (r = 0.930), 2-hydroxy-2-propyl is a very nucleophilic radical, and its addition rates are highly governed by polar effects. © 1993 John Wiley & Sons, Inc.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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