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  • Chemistry  (13)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 75 (1963), S. 137-137 
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    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 following gas-phase reactions: were studied by the competitive method with CF3I as the source of radicals. The kinetic parameters obtained in the temperature range 533-613 K and 503-613 K respectively for chlorine atom transfer reactions are given by: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 /k_c ^{1/2} ({\rm cm}^{\rm 3}\, {\rm mol}^{{\rm - 1/2}} s^{ - 1/2}) = (6.19 \pm 0.10) - (16900 \pm 100)/\theta $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 /k_c ^{1/2} ({\rm cm}^{\rm 3}\, {\rm mol}^{{\rm - 1/2}} s^{ - 1/2}) = (6.52 \pm 0.10) - (14890 \pm 100)/\theta $$\end{document} where θ = 2.303 RT (cal mol-1).The Arrhenius A values were calculated for seven chlorine atom transfer reactions (CF2Cl2, CFCl3, CCl4 with CF3 radicals; CF3Cl, CF2Cl2, CFCl3 and CCl4 with CH3 radicals) by using the thermochemical kinetic version of the Transition State Theory (TST).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 1003-1014 
    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 thermal decomposition of 1,1,2,2-tetrafluorocyclopropane (TFC) to 1,1-difluoroethylene and CF2 was studied in the temperature range of 507.0-577.0 K and with a total pressure of 200 to 300 torr of a 1:100 mixture of reactant and C2H4. Also at 557.0 K experiments were made at different total pressures, in the range 2-20 torr with neat TFC and between 20-300 torr with the C2H4/TFC mixture, confirming that the reaction is in the high pressure limit. The reaction is first-order and the rate constants fit the following Arrhenius relationship: \documentclass{article}\pagestyle{empty}\begin{document}$$\log \,k/(s^{ - 1}) = (14.02 \pm 0.16) - (45,150 \pm 200)/4.576T$$\end{document} From this value of the activation energy, the data for the decomposition of chemically activated TFC were revised. The new results yield a minimum energy of the activated molecule of 98 ± 4 kcal/mol and ΔHf°(TFC) = -155.4 ± 7 kcal/mol, while an analysis of the kinetic data yields ΔHf°(TFC) = -159 ± 9 kcal/mol.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 361-367 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: CF3 radicals were generated by the photolysis of perfluoroacetic anhydride. In the presence of pentafluorobenzene, the CF3 radicals react according to the following mechanism: It was found that the addition reaction (3) becomes reversible above ca. 453 K. The addition rate parameters have been revised and they satisfactorily agree with those reported previously.At temperatures higher than 593 K, only true H-abstraction occurs. The rate constant kH for reaction (5) is given by: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log [(k_{\rm H} /k_c^{1/2}){\rm mol}^{- 1/2} \,{\rm cm}^{{\rm 3/2}} \,{\rm s}^{{\rm - 1/2}}]\, = \,(4.34\, \pm \,0.43)\, - \,(59,00\, \pm \,2.62)/\theta $$\end{document} where θ = 2.303 RT kJmol-1 and kc is the rate constant for combination of CF3 radicals. The reactions of CF3 with benzene and pentafluorobenzene are compared.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1351-1356 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of some perfluoroalkyl radicals with carbon tetrachloride have been studied using the photolysis of the corresponding perfluoroalkyl iodide as the free radical source. The Arrhenius parameters, based on the value of 2.3 × 1013 cm3 mol-1 s-1 for the self-combination rate constant of all radicals are: TextReactionlog(A/cm3 mol-1 s-1)E/kcal mol-1CF3 + CCl412.811.3C2F5 + CCl412.811.6n-C3F7 + CCl412.912.0
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1357-1370 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction of CF3 with HCN has been examined over a wide conversion range using CF3I as a thermal and photolytic source of radicals. Quantitative and qualitative results show a significant increase of the specific rate constant for the hydrogen abstraction reaction relative to CF3 recombination when reaction is carried out under ultraviolet irradiation. This “extra” formation of the reaction product, CF3H, has been assigned to the participation of iodine in this system through the formation of a (I-HCN) intermediate. Arrhenius parameters obtained for the addition mechanism of I to HCN do not seem to conform to a single reaction step, on the contrary, they correspond to a more complex reaction scheme.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 619-629 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of CH2(1A1) with 1,1,2,2-tetrafluorocyclopropane was studied at 300 K and at pressures between 9.0 and 365.0 torr. Chemically activated 1-methyl-2,2,3,3-tetrafluorocyclopropane was formed and two competitive reaction paths, namely decomposition and isomerization, were observed. By fitting the experimental results to calculated values from RRKM theory, we estimated the Arrhenius parameters for both reaction processess as well as the heat of formation of 1-methyl-2,2,3,3-tetrafluorocyclopropane. © John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 331-341 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The following reactions: were studied over the temperature ranges 533-687 K, 563-663 K, and 503-613 K for the forward reactions respectively and over 683-763 K, for the back reaction. Arrhenius parameters for chlorine atom transfer were determined relative to the combination of the attacking radicals. The ΔHr°(1) = -3.95 ± 0.45 kcal mol-1 was calculated and from this value the ΔH∮(C2F5Cl) = -2.66.3 ± 2.5 kcal mol-1 and D(C2F5-Cl) = 82.0 ± 1.2 kcal mol-1 were obtained. Besides, the ΔHr°(2) was estimated leading to D(CF2ClCF2Cl) = 79.2 ± 5 Kcal mol-1. The bond dissociation energies and the heat of formation are compared with those of the literature. The effect of the halogen substitutents as well as the importance of the polar effects for halogen transfer processes are discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 321-328 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase photochlorination of perfluorocyclopentene under continuous and intermittent illumination with 4360-Å radiation was studied between 10° and 60°C. The rate constants for the reactions. (3) \documentclass{article}\pagestyle{empty}\begin{document}$$ C_5 F_8 CL + Cl_2 \to C_5 F_8 Cl_2 + Cl $$\end{document} (4) \documentclass{article}\pagestyle{empty}\begin{document}$$ 2C_5 F_8 Cl \to \Pr oducts $$\end{document} were measured as k3 = (1.20 + 0.58) × 108 exp (-6.430 ± 177/RT) l·(mole sec) and k4 = (1.86 ± 0.76) × 107 l·(mole sec).
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 47-56 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of C2F5I with CF3COOH in the temperature range 473-533 K was studied in the gas phase.Evidence is presented that supports a complex mechanism for the formation of C2F5H through the H-atom abstraction reaction from CF3COOH by C2F5 radicals as well as the participation of I(2P½).
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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