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  • 1975-1979  (4)
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Material
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Year
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  • 1
    Electronic Resource
    Electronic Resource
    Neuere Untersuchungen zum thermischen Zerfall von CO2 (1975)
    Springer
    Colloid & polymer science 253 (1975), S. 332-332 
    Details
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02352086
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    The heat of formation of the acetonyl radical VLPP studies of acetonyl bromide, isopropenylmethylether, and hexanedione-2,5 in a search for acetonyl stabilization energy (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 295-306 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of acetonyl bromide, isopropenylmethylether, and hexanedione-2,5 was studied using the very-low-pressure pyrolysis (VLPP) technique. The acetonyl radical is a product of each reaction. Arrhenius parameters determined are or acetonyl bromide ← acetonyl + Br: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k\left({\sec ^{- 1}} \right) = 16.0 - 62.5/\theta\,{\rm at}\,300^{\rm o} {\rm K} $$\end{document} and for isopropenylmethylether ← acetonyl + CH3: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k\left({\sec ^{- 1}} \right) = 15.8 - 66.3/\theta\,{\rm at}\,300^{\rm o} {\rm K} $$\end{document} These lead to values of acetonyl stabilization energy (SE) of 0.8 and -4.0 kcal/mol, respectively. Comparison of the pyrolyses of hexanedione-2,5 and 2,5-dimethylhexane indicate a value of SE ∼ 2 kcal/mol. The total of these results is taken, along with previous work, to indicate that 0 ≲ SE ≲ 2 kcal/mol.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100306
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    Paper (German National Licenses)
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  • 3
    Electronic Resource
    Electronic Resource
    Thermal gas-phase decomposition of chloroethylenes. II. Vinyl chloride (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 651-662 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal gas-phase decomposition of vinyl chloride has been studied behind shock waves over the temperature range of 1350-1900°K and the density range of 7 × 10-7-1.5 × 10-3 mol/cm3 (at 1600°K) in mixtures of C2H3Cl highly diluted with argon. The ultraviolet absorption of C2H3C was recorded at 230 nm as a function of time. The decomposition proceeds via molecular elimination of HCl. The unimolecular dissociation rate is pressure dependent at all but the highest pressures applied. Application of modified HKRR theory results in the rate expression \documentclass{article}\pagestyle{empty}\begin{document}$$ k_\infty = 10^{14.0 \pm 0.2}\, {\rm exp}[= (290 \pm 12){\rm kJ}/{\rm mol}/RT]\,{\rm s}^{- 1},\,\quad 1400^ \circ {\rm K} \le T \le 1800^ \circ {\rm K} $$\end{document} for the limiting high pressure rate constant, and in a collision efficiency of \documentclass{article}\pagestyle{empty}\begin{document}$$ \beta _c = \frac{{k_0 ({\rm experiment})}}{{k_{\rm 0} {\rm (theoretical, strong collisions})}} \cong 0.04,\quad {\rm for M} = {\rm Ar},T = 1600^ \circ {\rm K} $$\end{document} derived from the limiting low-pressure rate constant.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550090413
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    Paper (German National Licenses)
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  • 4
    Electronic Resource
    Electronic Resource
    The very low-pressure pyrolysis of phenyl ethyl ether, phenyl allyl ether, and benzyl methyl ether and the enthalpy of formation of the phenoxy radical (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 161-178 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A value of the enthalpy of formation of the phenoxy radical in the gas phase, ΔH°,298K (φO·, g) = 11.4 ± 2.0 kcal/mol, has been obtained from the kinetic study of the unimolecular decompositions of phenyl ethyl ether, phenyl allyl ether, and benzyl methyl etherTrivial names for ethoxy benzene, 2-propenoxy (allyloxy) benzene, and α-methoxytoluene, respectively at very low pressures. Bond fission, producing phenoxy or benzyl radicals, respectively, is the only mode of decomposition in each case. The present value leads to a bond dissociation energy BDE(φO - H) = 86.5 ± 2 kcal/mol,1 kcal = 4.18674 kJ (absolute) in good agreement with recent estimates made on the basis of competitive oxidation steps in the liquid phase. A comparison with bond dissociation energies of aliphatic alcohols, BDE(RO - H) = 104 kcal/mol, reveals that the stabilization energy of the phenoxy radical (17.5 kcal/mol) is considerably greater than the one observed for the isoelectronic benzyl radical (13.2 kcal/mol). Decomposition of phenoxy radicals into cyclopentadienyl radicals and CO has been observed at temperatures above 1000°K, and a mechanism for this reaction is proposed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550090202
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    Paper (German National Licenses)
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