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  • 1975-1979  (5)
  • Physical Chemistry  (5)
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  • 1
    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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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Very-low-pressure pyrolysis (VLPP) of group IV (A) tetramethyls: Neopentane and tetramethyltin (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 529-542 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of neopentane was studied using the very-low-pressure pyrolysis (VLPP) technique at temperatures from 1000 to 1260 K. The derived Arrhenius parameters \documentclass{article}\pagestyle{empty}\begin{document}$$ {log k(sec}^{{ - 1}} {) = 17}{.3 - 80}{.8/}\theta { at 1000 K } $$\end{document} are consistent with δHf0(t-butyl) = 8.4 kcal/mol. Using the above A factor, data on the decomposition of tetramethyltin yield DH0(Sn(CH3)3 - CH3) = 69 ± 2 kcal/mol.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110506
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  • 3
    Electronic Resource
    Electronic Resource
    The very-low-pressure pyrolysis (VLPP) of n-propyl nitrate, tert-butyl nitrite, and methyl nitrite. Rate constants for some alkoxy radical reactions (1975)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 7 (1975), S. 725-737 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of n-propyl nitrate and tert-butyl nitrite at very low pressures (VLPP technique) is reported. For the reaction the high-pressure rate expression at 300°K, log k1 (sec-1) = 16.5 - 40.0 kcal/mole/2.3 RT, is derived. The reaction was studied and the high-pressure parameters at 300°K are log k2(sec-1) = 15.8 - 39.3 kcal/mole/2.3 RT. From ΔS1,-10 and ΔS2,-20 and the assumption E-1 and E-2 ⋍ 0, we derive log k-1(M-1·sec-1) (300°K) = 9.5 and log k-2 (M-1·sec-1) (300°K) = 9.8. In contrast, the pyrolysis of methyl nitrite and methyl d3 nitrite afford NO and HNO and DNO, respectively, in what appears to be a heterogeneous process. The values of k-1 and k-2 in conjunction with independent measurements imply a value at 300°K for of 3.5 × 105 M-1·sec-1, which is two orders of magnitude greater than currently accepted values.In the high-pressure static pyrolysis of dimethyl peroxide in the presence of NO2, the yield of methyl nitrate indicates that the combination of methoxy radicals with NO2 is in the high-pressure limit at atmospheric pressure.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550070509
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  • 4
    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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  • 5
    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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