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  • 1985-1989  (2)
  • 1
    Electronic Resource
    Electronic Resource
    The kinetics and the mechanism of the thermal reaction between sulfurtetrafluoride (SF4) and trifluoromethylhypofluorite (CF3OF) (1985)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 43-53 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal reaction between SF4, and CF3OF has been studied between 142°C and 185°C. The reaction was found to be homogeneous and the only products formed are equimolecular amounts of SF6 and CF3O2CF3 and smaller amounts of CF3OSF5. The reaction mechanism was not affected by the total pressure, the oxygen pressure, or by the buildup of products. The experimental data can be explained by the following mechanism: The rate constants can be expressed as \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{lr} k_1 = (4.58 \pm 0.30) \times 10^7 \,{\rm exp( - 18900} \pm {\rm 1000}\,{\rm cal/}RT)M^{ - 1} \,{\rm s}^{{\rm - 1}} \\ k_2 = (3.88 \pm 0.30) \times 10^9 \,{\rm exp( - 9800} \pm {\rm 1000}\,{\rm cal/}RT)M^{ - 1} \,{\rm s}^{{\rm - 1}} \end{array} $$\end{document}
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550170106
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    The kinetics and the mechanism of the thermal gas-phase reaction between NO2 and 1,1-dichlorodifluoroethylene, CF2CCl2 (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 907-917 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase reaction between NO2 and CF2CCl2 has been investigated in the temperature range from 50 to 80°C. The reaction is homogeneous. Three products are formed: O2NCF2CCl2NO2 and equimolecular amounts of CINO and of O2NCF2C(O)Cl. The rate of consumption of the reactants is independent of the total pressure, the reaction products, and added inert gases and can be represented by a second-order reaction: \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm NO}_{\rm 2}]}}{{dt}} = - 2\frac{{d[{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}]}}{{dt}} = k[{\rm NO}_{\rm 2}][{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}] $$\end{document}However, the distribution of the products is influenced by the pressure of the present gases, which favor the formation of the dinitro-compound in a specific way. The effect of CF2CCl2 is the greatest. In the absence of added gases, the ratio of O2NCF2CCl2NO2 to that of O2NCF2C(O)Cl is proportional to (CF2CCl2 + γP products).The experimental results can be explaned by the following mechanism: P and X represent the products and the added gases: \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm NO}_{\rm 2}]}}{{dt}} = - 2\frac{{d[{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}]}}{{dt}} = k_1 [{\rm NO}_{\rm 2}][{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2}] $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1 = 3.16 \pm 0.5 \times 10^6 \exp ( - 10500 \pm 1000{\rm cal/}RT){\rm M}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm \gamma }_{{\rm CF}_{\rm 2} {\rm CCI}_{\rm 2} } :{\rm \gamma }_P :{\rm \gamma }_{{\rm C}_{\rm 2} {\rm F}_{\rm 5} {\rm CI}} :{\rm \gamma }_{{\rm CCL}_{\rm 3} } :{\rm \gamma }_{{\rm CF}_{\rm 4} } :{\rm \gamma }_{{\rm N}_{\rm 2} } = 1:0.22:0.15:0.14:0.054:0.015 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm \gamma }_{{\rm NO}_{\rm 2} } 〈 0.01 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 = 1.4 \pm 0.3 \times 10^8 {\rm s}^{{\rm - 1}} $$\end{document}
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180810
    Library Location Call Number Volume/Issue/Year Availability
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    Paper (German National Licenses)
    Fulltext
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