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  • Physical Chemistry  (24)
  • 1
    Electronic Resource
    Electronic Resource
    Very low-pressure pyrolysis (VLPP) of t-butylmethyl ether (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 631-641 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of t-butylmethyl ether has been studied using the VLPP technique. The recommended Arrhenius parameters for the molecular elimination, reaction (1), are A(800°K) = 101 3, 9 sec-1 and Ea (800°K) = 59.0 ± 1.0 kcal/mole. No radical reactions occur under the conditions used. These parameters are in good agreement with earlier experimental work and with theoretical estimates of both A and E.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060503
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  • 2
    Electronic Resource
    Electronic Resource
    The decomposition of dimethyl peroxide and the rate constant for CH3O + O2 → CH2O + HO2 (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 31-53 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of dimethyl peroxide (DMP) was studied in the presence and absence of added NO2 to determine rate constants k1 and k2 in the temperature range of 391-432°K: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{rcl} {{\rm DMP}} & \stackrel{1}{\longrightarrow} & {2{\rm MeO}} \\ {{\rm MeO + DMP}} & \stackrel{2}{\longrightarrow} & {{\rm MeOH + CH}_{\rm 2} {\rm O} + {\rm MeO}} \\ \end{array} $$\end{document} The results reconcile the studies by Takezaki and Takeuchi, Hanst and Calvert, and Batt and McCulloch, giving log k1(sec-1) = (15.7 ± 0.5) - (37.1 ± 0.9)/2.3 RT and k2 ≈ 5 × 104M-1· sec-1. The disproportionation/recombination ratio k7b/k7a = 0.30 ± 0.05 was also determined: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{rcl} {{\rm MeO} + {\rm NO}_2 (+ {\rm M})} \stackrel{7a}{\longrightarrow} & {{\rm MeONO}_{\rm 2} (+ {\rm M})} \\ {{\rm MeO} + {\rm NO}_2} \stackrel{7b}{\longrightarrow} & {{\rm CH}_{\rm 2} {\rm O} + {\rm HONO}} \\ \end{array} $$\end{document}When O2 was added to DMP mixtures containing NO2, relative rate constants k12/k7a were obtained over the temperature range of 396-442°K: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{rcl} {{\rm CH}_{\rm 3} {\rm O} + {\rm O}_2} \stackrel{12}{\longrightarrow} & {{\rm CH}_2 {\rm O} + {\rm HO}_{\rm 2}} \\ \end{array} $$\end{document} A review of literature data produced k7a = 109.8±0.5M-1·sec-1, giving log k12(M-1·sec-1) = (8.5 ± 1.5) - (4.0 ± 2.8)/2.3 RT, where most of the uncertainty is due to the limited temperature range of the experiments.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550090105
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  • 3
    Electronic Resource
    Electronic Resource
    Kinetics of the I2-catalyzed isomerization of allyl chloride to cis- and trans-1-chloro-1-propene. The stabilization energy of the chloroallyl radicalThis work was supported in part by Grant No. 00353-07 of the Environmental Protection Agency, Air Pollution Control Administration. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 155-167 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The I2-catalyzed isomerization of allyl chloride to cis- and trans- l-chloro-l-propene was measured in a static system in the temperature range 225-329°C. Propylene was found as a side product, mainly at the lower temperatures. The rate constant for an abstraction of a hydrogen atom from allyl chloride by an iodine atom was found to obey the equation log [k,/M-1 sec-1] = (10.5 ± 0.2) -; (18.3 ± 10.4)/θ, where θ is 2.303RT in kcal/mole. Using this activation energy together with 1 ± 1 kcal/mole for the activation energy for the reaction of HI with alkyl radicals gives DH0 (CH2CHCHCl—H) = 88.6 ± 1.1 kcal/mole, and 7.4 ± 1.5 kcal/mole as the stabilization energy (SE) of the chloroallyl radical. Using the results of Abell and Adolf on allyl fluoride and allyl bromide, we conclude DH0 (CH2CHCHF—H) = 88.6 ± 1.1 and DH0 (CH2CHCHBr—H) = 89.4 ± 1.1 kcal/ mole; the SE of the corresponding radicals are 7.4 ± 2.2 and 7.8 ± 1.5 kcal/mole. The bond dissociation energies of the C—H bonds in the allyl halides are similar to that of propene, while the SE values are about 2 kcal/mole less than in the allyl radical, resulting perhaps more from the stabilization of alkyl radicals by α-halogen atoms than from differences in the unsaturated systems.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050114
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  • 4
    Electronic Resource
    Electronic Resource
    Termolecular reactions of alkali metal atoms with O2 and OH (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1567-1574 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Calculations of low-pressure limit, third-order rate constants are presented for the association reactions A + O2 + N2 and A + OH + N2 (A = Li, Na, K) over the temperature range 200-2000 K and a comparison is made with the available experimental data.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550161210
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics of the gas-phase reaction of cyclopropylcarbinyl iodide and hydrogen iodide. Heat of formation and stabilization energy of the cyclopropylcarbinyl radicalThis work was supported, in part, by Grant No. AP 00353-06 of the National Air Pollution Control Administration, Environmental Protection Agency. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 359-374 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the gas phase reaction \documentclass{article}\pagestyle{empty}\begin{document}$$\Delta - {\rm CH}_{\rm 2} - {\rm I + I} \cdot {\rightleftharpoons}\Delta - {\rm CH}_{\rm 2} \cdot + {\rm I}_{\rm 2}$$\end{document} has been measured spectrophotometrically over the range 480°-550°K. The rate constant fits the equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}k{\rm (M}^{- {\rm 1}} {\rm sec}^{- {\rm 1}} {\rm)} = {\rm (11}{\rm .4} \pm {\rm 0}{\rm .1)} - (16.8 \pm 0.2)/\theta$$\end{document} where θ = 2.303RT in kcal/mole. This result, together with the assumption that the activation energy for the back reaction is 0 ± 1 kcal/mole, allows calculation of DH0298 (Δ—CH2—H) = 97.4 ± 1.6 kcal/mole and ΔH0f 298 (Δ—CH2·) = 51.1 ± 1.6 kcal/mole. These values correspond to a stabilization energy of 0.4 ± 1.6 kcal/mole in the cyclopropylcarbinyl radical.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030406
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  • 6
    Electronic Resource
    Electronic Resource
    Very low-pressure pyrolysis. IV. The decomposition of i-propyl iodide and n-propyl iodideThis work was supported in part by NASA Contract NAS7-472 (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 411-426 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition rate constant of i-PrI under conditions of very low-pressure pyrolysis (VLPP) is completely consistent with the well-known high-pressure Arrhenius parameters and the RRK(M) theory. The decomposition of n-PrI under the same conditions proceeds via two pathways, the anti-Markownikoff dehydroiodination and C—I bond scission. The data, analyzed by taking into account the mutual interaction of the two pathways, is completely consistent with the known Arrhenius parameters for the bond scission step and, when combined with a reasonable A-factor, yields an activation energy for HI elimination which is as predicted for these semi-ion pair transition states.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030504
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  • 7
    Electronic Resource
    Electronic Resource
    Very-low-pressure pyrolysis of nitroso- and pentafluoronitrosobenzene C—NO bond dissociation energiesPresented in part at the Spring Meeting of the American Chemical Society, Los Angeles, California, April 1974. (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 713-724 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The high-pressure absolute rate constants for the decomposition of nitrosobenzene and pentafluoronitrosobenzene were determined using the very-low-pressure pyrolysis (VLPP) technique.Bond dissociation energies of DH0(C6H5—NO) = 51.5 ± 1 kcal/mole and DH0 (C6F5—NO) = 50.5 ± 1 kcal/mole could be deduced if the radical combination rate constant is set at log kr(M-1·sec-1) = 10.0 ± 0.5 for both systems and the activation energy for combination is taken as 0 kcal/mole at 298°K. δHf0(C6H5NO), δHf0(C6F5NO), and δHf0(C6F5) could be estimated from our kinetic data and group additivity. The values are 48.1 ± 1, -160 ± 2, and - 130.9 ± 2 kcal/mole, respectively. C-X bond dissociation energies of several perfluorinated phenyl compounds, DH0(C6F5-X), were obtained from the reported values of δHf0(C6F5X) and our estimated δHf0(C6F5) [X = H, CH3, NO, Cl, F, CF3, I, and OH].
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070508
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  • 8
    Electronic Resource
    Electronic Resource
    Very low-pressure pyrolysis: VI. The decomposition of ethyl acetateThis work was supported in part by the Environmental Protection Agency Grant AP 00353-07, Air Pollution Control Administration. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 265-271 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of ethyl acetate has been studied by the very low-pressure pyrolysis (VLPP) technique. The results obtained agree well with the previously determined high-pressure Arrhenius parameters where log k∞ = 12.6 - 48.0/θ. The rate constants given by these parameters have also been shown to be consistent with the predictions of the RRK and RRKM theories and demonstrate the applicability of the technique to the study of thermal decompositions.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040303
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  • 9
    Electronic Resource
    Electronic Resource
    The absolute rate constant for the metathesis t-C4H9• + DI → C4H9D + I• and the heat of formation of the t-butyl radical (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 969-976 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Arrhenius parameters for the title reaction have been measured in a very-low-pressure pyrolysis apparatus in the temperature range 644-722 K and are given by log k2 (M-1 · sec-1) = 9.68 - 2.12/θ, where θ = 2.303RT in kcal/mol. Together with the published Arrhenius parameters for the reverse reaction from iodination studies, they result in a standard heat of formation of the t-butyl radical of 8.4 kcal/mol, accepting S0(C4H9·) = 72.2 e.u. at 300 K from other kinetic data, and thus confirm the accepted value for ΔHf0(t-C4H9·), at variance with recent investigations which yielded significantly higher values. This value for ΔHf0(t-C4H9·) results in a bond-dissociation energy (BDE) for isobutane of 92.7 kcal/mol.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110904
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  • 10
    Electronic Resource
    Electronic Resource
    Continuity and growth: An editorial (1984)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. i 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550160102
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