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  • 1
    Electronic Resource
    Electronic Resource
    The formation of C3H3 (propynyl) radicals in the reaction of CH2(1A1) with acetylene (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1103-1110 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Results obtained from the photolysis of ketene with acetylene strongly support the formation of C3H3 radicals in the title reaction. Stationary state studies are interpreted in terms of the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm C}_3 {\rm H}_{\rm 4}^{\rm *} \buildrel3\over\rightarrow{\rm C}_3 {\rm H}_3^ \cdot + {\rm H}^ \cdot$$\end{document} with a rate constant (109.8 s-1) which is compared to RRKM predictions. In pulsed laser induced decomposition experiments, recombination products involving C3H3 have been detected (some for the first time) and their formation modeled using step (3) with the same rate constant.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160905
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  • 2
    Electronic Resource
    Electronic Resource
    The kinetics of the Diels-Alder addition of cyclopentadiene to acetylene and the decomposition of norbornadiene (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 319-329 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reactions have been investigated in a static system. The addition of acetylene to cyclopentadiene (CPD) results in formation of norbornadiene (BCH), cycloheptatriene (CHT), and toluene (T), while BCH decomposition produces CPD, C2H2, CHT, and T. Kinetic studies, comprising both product-time evolution and initial pressure variation, support a mechanism These reactions are almost certainly homogeneous and molecular in nature. Least mean square analysis of the data yield for temperatures of 525-656°K, log k-1 (1./mole·s)=7.51±0.05- (24.19±0.15 kcal/mole)/RT ln 10, and for temperatures of 584-630°K, \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 (s^{ - 1}) = 14.78 \pm 0.10 - (51.37 \pm 0.29\,kcal/mole)/RT\ln 10 $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 (s^{ - 1}) = 14.90 \pm 0.11 - (51.36 \pm 0.30\,kcal/mole)/RT\ln 10 $$\end{document}
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070302
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  • 3
    Electronic Resource
    Electronic Resource
    The photochemistry of methyl cyclobutyl ketone. Part 2. Temperature dependence and the acetyl radical decomposition (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 997-1013 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Following earlier room-temperature studies, gaseous mixtures of methyl cyclobutyl ketone (MCK) diluted in argon have been photolyzed at temperatures up to 205°C. Experiments have been carried out at a variety of pressures (up to ca. 2 atm) at wavelengths of 313 nm (steady state conditions) and 308 nm (pulsed photolysis). The results are consistent with a mechanism dominated by radical-radical reactions involving acetyl, methyl, and cyclobutyl radicals. Acetyl radical processes predominate at lower temperatures while methyl radical reactions are more important at high temperatures.The results are interpreted via kinetic modelling of a mechanism in which a key role is played by the acetyl radical decomposition reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ ({\rm M} +)\,{\rm CH}_{\rm 3} {\rm CO}\mathop {\longrightarrow}\limits^{\rm 3} {\rm CH}_{\rm 3} + {\rm CO\, (+ M)} $$\end{document} Values for k3 have been obtained and its temperature and pressure dependence are fitted by RRKM theory and a weak-collisional activation model to yield \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(}k_3 ^\infty /{\rm s}^{ - 1}) = 13.3 - 17.5{\rm\, kcal\, mol}^{{\rm - 1}} /RT\ln 10 $$\end{document} This high-pressure limiting Arrhenius equation is consistent with other studies in the same temperature range, but is difficult to reconcile with higher temperature investigations.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550191105
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetics of the gas-phase reaction between iodine and trifluorosilane and the bond dissociation energy D(F3Si—H) (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 101-110 
    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 investigated in the temperature range 667-715K. The only reaction products were trifluorosilyl iodide and hydrogen iodide. The rate law \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d\left[{{\rm I}_2} \right]}}{{dt}} = \frac{{k\left[{{\rm I}_2} \right]^{1/2} \left[{{\rm F}_3 {\rm SiH}} \right]}}{{1 + k\prime \left[{{\rm HI}} \right]/\left[{{\rm I}_2} \right]}} $$\end{document} was obeyed over a wide range of iodine and trifluorosilane pressures. This expression is consistent with an iodine atom abstraction mechanism and for the step \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm I}^ \cdot + {\rm F}_3 {\rm SiH}\mathop {\longrightarrow}\limits^1 {\rm F}_3 {\rm Si}^\cdot + {\rm HI} $$\end{document} log k1(dm3/mol·sec) = (11.54 ± 0.17) - (130.5 ± 2.2 kJ/mol)/RT In 10 has been deduced. From this the bond dissociation energy D(F3Si—H) = (419 ± 5) kJ/mol (100.1 kcal/mol) is obtained. The kinetic andthermochemical implications of this value are discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100108
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics of the gas-phase reaction between iodine and monosilane and the bond dissociation energy D(H3Si—H)A preliminary account of this work has appeared in Ref. [1]. (1981)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 503-514 
    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 investigated in the temperature range of 494-545 K. During the early stages of reaction the only observed products were silyl iodide and hydrogen iodide. Initial rates were found to obey the rate law over a wide range of initial iodine and monosilane pressures. Secondary reactions, most probably of SiH3I with I2, became more important as the reaction progressed. However, provided [SiH4]0/[I2]0 〉 20, these secondary processes had a negligible effect on the kinetics, and an integrated rate expression could be used. These kinetics are consistent with an iodine atom abstraction chain mechanism, and for the step has been deduced. From this the bond dissociation energy D(SiH3—H) = 378 ± 5 kJ/mol (90 kcal/mol) is obtained. The kinetic and thermochemical implications of this value, especially to the pyrolysis of monosilane, are discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550130508
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  • 6
    Electronic Resource
    Electronic Resource
    Kinetics of the gas-phase reaction between iodine and monogermane and the bond dissociation energy D(H3Ge—H)A preliminary account of this work has appeared in [1] (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 547-560 
    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 investigated in the temperature range of 403-446 K. Monoiodogermane and di-iodogermane together with hydrogen iodide were the main products, although at high conversions at least one other product was formed. GeH3I is clearly the primary product. Initial rates were found to obey the rate law \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{{\rm d[I}_{\rm 2} {\rm]}}}{{{\rm dt}}} = \frac{{k[{\rm I}_{\rm 2}]^{1/2} [{\rm GeH}_{\rm 4}]}}{{1 + k'[{\rm HI}]/[{\rm I}_2]}} $$\end{document} over a wide range of initial iodine and monogermane pressures. Secondary reactions (of GeH3I with I2) affect the subsequent kinetics, although at sufficiently high initial reactant ratios ([GeH4]0/[I2]0 ≥ 100) an integrated rate equation fits the data with the same rate constants as the initial rate expression.The observed kinetics are consistent with an iodine atom abstraction chain mechanism, and for the step \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm I}^{\rm .} + {\rm GeH}_4 \mathop {\hbox to 24pt{\rightarrowfill}} {\hskip-16pt ^{{\rm1}}}{\hskip1em} {\rm \dot GeH}_{\rm 3} + {\rm HI} $$\end{document} log k1 (dm3/mol·s) = (11.03 ± 0.13) - (52.3 ± 1.0 kJ/mol)/RT ln 10 has been deduced. From this the bond dissociation energy D(GeH3—H) = 346 ± 10 kJ/mol (82.5 kcal/mol) is obtained. The significance of this value, together with derived values for Ge-Ge and Ge-C bond strengths, is discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150605
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  • 7
    Electronic Resource
    Electronic Resource
    The kinetics of secondary reactions in the iodination of monogermane. The effect of iodine substitution on the Ge—H bond dissociation energy (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 561-568 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study has been made both of secondary reactions occurring during the reaction of I2 with GeH4, and of the direct reaction between I2 and GeH3I. Both these studies show that the abstraction reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm I}^ \cdot + {\rm GeH}_{\rm 3} {\rm I} \to {\rm \dot GeH}_{\rm 2} {\rm I + HI} $$\end{document} occurs about 30 times faster than the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm I}^ \cdot + {\rm GeH}_{\rm 4} \to {\rm \dot GeH}_{\rm 3} {\rm + HI} $$\end{document} in the temperature range of 425-446 K. This information is used to show that iodine substitution weakens Ge-H bonds by 14.4 ± 2.5 kJ/mol and that D(H2IGe—H) = 332 ± 10 kJ/mol (79.3 kcal/mol). Possible reasons for the effects of halogen substituents on Ge—H and Si—H bond strengths are discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150606
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