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  • 1
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the pyrolysis of 1-Chloro-1, 1-difluoroethane in the presence of chlorine (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 497-504 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first stage thermal reactions of CF2CICH3 in the presence of chlorine have been studied between 554 and 614 K. These are and \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CF}_{\rm 2} {\rm CICH}_{\rm 3} {\rm + CI}_{\rm 2} \to {\rm CF}_{\rm 2} {\rm CICH}_{\rm 2} {\rm CI + HCI} $$\end{document} Rate equations derived from a radical mechanism are shown to fit the experimental results. Values of Arrhenius parameters for the decomposition of the CF2ClCH2. radical and its reactions with Cl2 and Cl are given.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180408
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  • 2
    Electronic Resource
    Electronic Resource
    Pyrolysis of 1-chloro-1,1-difluoroethane in the absence and in the presence of CCl4 and mixtures of CCl4 + HCl (1985)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 157-165 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal dehydrochlorination CF2ClCH3 → CF2 = CH2 + HCl has been studied in a static system between 637 and 758 K. It is a homogeneous, molecular first-order reaction and its rate constant is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} {\rm }(k,{\rm s}^{ - {\rm 1}}) = - (53,400 \pm 100)/4.576{\rm T + (12}{\rm .21} \pm {\rm 0}{\rm .03)} $$\end{document} This reaction has also been studied in the presence of CCl4 and mixtures of CCl4 and HCl between 585 and 662 K. It is then accelerated and the initial rate increase is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ v = d[{\rm CF}_{\rm 2} {\rm = CH}_{\rm 2} ]/dt = k' \left( {1 + k'' {\textstyle{{{\rm [HCl]}} \over {{\rm [CF}_{\rm 2} {\rm ClCH}_{\rm 3} {\rm ]}}}}} \right)^{{\raise0.5ex\hbox{$\scriptstyle 1$}\kern-0.1em/\kern-0.15em\lower0.25ex\hbox{$\scriptstyle 2$}}} [{\rm CF}_2 {\rm ClCH}_3 ]^{{\raise0.5ex\hbox{$\scriptstyle 3$}\kern-0.1em/\kern-0.15em\lower0.25ex\hbox{$\scriptstyle 2$}}} $$\end{document} with log10 (k′, L½ /mol½ · s) = -(41,650 ± 180)/4.576T + (10.84 ± 0.06) and log10 k″ = (7900 ± 180)/4.576T - (0.59 ± 0.06). A radical chain mechanism is shown to be consistent with these latter results.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550170204
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  • 3
    Electronic Resource
    Electronic Resource
    Pyrolysis of CH2ClCH3: Considerations about its molecular nature (1992)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 671-677 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Numerical integrations of a hypothetical radical chain reaction model have been performed for the pyrolysis of CH2ClCH3 which is known to be molecular. Analyses of the modelling results have led to a better understanding of the participation (or nonparticipation) of “dead” radicals in the self-inhibition of the radical chain reaction. Attention is focused on the fact that apparently slow elementary reactions still may have to be taken into account in a pyrolysis mechanism when they produce “dead” radicals which can accumulate. © John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550240707
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetics of the thermal reactions of bicyclo[4.2.2]deca-3,7-diene and endo-and exo-5-vinylbicyclo[2.2.2]oct-2-ene in the gas phase (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 251-257 
    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 reactions of bicyclo[4.2.2]deca-3,7-diene (BDD) and endo- and exo-5-vinylbicyclo[2.2.2]oct-2-ene (endo- and exo-VBO) have been studied in the gas phase. The temperature range was 459-526 K for BDD, 476-563 K for endo-VBO, and 513-578 K for exo-VBO. The initial pressures were varied from 2 to about 40 torr. These compounds isomerize to cis-1,2,4a,5,8,8a-hexahydronaphtalene (HHN) and into each other, and decompose to 1,3-butadiene (BD) + cyclohexa-1,3-diene (CHD). The reactions are homogeneous and first order. Their rate constants (in s-1) are given by: where the superscripts represent the reagents and the subscripts the products. The heats of formation and the entropies of endo-VBO, exo-VBO, and BDD are estimated.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140305
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the addition of 1,3-butadiene to cyclohexa-1,3-diene in the gas phase (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 259-267 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reactions of 1,3-butadiene (BD) with cyclohexa-1,3-diene (CHD) have been studied in a static system between 437 and 526 K. The pressures of BD and CHD were varied from 61 to 397 torr and from 50 to 93 torr, respectively. The percentages of consumed BD and CHD were always kept lower than 14%. The reactions - in the order of importance - are All the reactions are homogeneous and of the first order with respect to the reagents. Their rate constants (in L/mol·s) are given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} \log _{10} k_{{\rm HHN}} = - (25,370 \pm 70)/4.576T + (7.02 \pm 0.03) \\ \log _{10} k_{{\rm KNDO}} = - (24,840 \pm 50)/4.576T + (6.58 \pm 0.02) \\ \log _{10} k_{{\rm BDD}} = - (25,530 \pm 50)/4.576T + (6.61 \pm 0.02) \\ \log _{10} k_{{\rm EXO}} = - (26,760 \pm 50)/4.576T + (7.06 \pm 0.02) \\ \end{array} $$\end{document} A thermochemical analysis of a biradical mechanism is in agreement with these results.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550140306
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  • 6
    Electronic Resource
    Electronic Resource
    Pyrolysis of 1,1,1-Trichloroethane in the absence and the presence of added HCl and/or CCl4 (1989)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 575-591 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction has been studied in a static quartz reaction vessel between 587 and 658 K at pressures between 40 and 152 torr. The dehydrochlorination is the only significant reaction and is autoaccelerated by the produced HCl. Numerical modelling indicates that the Rice-Herzfeld mechanism, generally used for describing the pyrolysis of halogenated ethanes, has to be completed in the case of CC13CH3 with additional transfer reactions converting “dead” radicals into chain carriers and vice-versa. The numerical simulation fits the experimental results, in the absence as well as in the presence of different amounts of added HCl. The dehydrochlorination is also accelerated by the addition of CCl4, which can be explained in terms of additional elementary steps involving · CCl3 radicals.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550210708
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