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  • Physical Chemistry  (30)
  • Wiley-Blackwell  (30)
  • 1980-1984  (11)
  • 1970-1974  (19)
  • 1940-1944
  • 1980  (11)
  • 1974  (19)
  • 1940
  • 1
    Electronic Resource
    Electronic Resource
    The pyrolysis of 2-nitrosoisobutane and the bond dissociation energies of nitroso compounds (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 813-828 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Study of the reaction by very-low-pressure pyrolysis (VLPP) in the temperature range of 550-850°K yields for the high-pressure Arrhenius parameters \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }\,k_{\rm 1} = (15.6 \pm 0.5) - (36.0 \pm 1.0)/\theta {\rm \,(sec}^{{\rm - 1}})$$\end{document} where θ = 2.303RT in kcal/mole. These in turn yield for the high-pressure second-order recombination of tBu + NO, k-1 = (3.5 ± 1.7) × 109 1./mole·sec at 600°K. For the competing reaction l./mole·sec and E4 ≥ 4.2 kcal/mole. The bond dissociation energy DHo (tBu-NO) was determined to be (39.5 ± 1.5) kcal/mole, both from the equilibrium constant and from the activation energy of reaction (1), obtained from RRKM calculations. A ‘free-volume’ model for the transition state for dissociation is consistent with the data. A limited study of the system at 8-200 torr showed an extremely rapid inhibition by products and a very complex set of products.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060605
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  • 2
    Electronic Resource
    Electronic Resource
    Atmospheric photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 231-240 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Atmospheric photodissociation rate coefficients and photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate were calculated as a function of altitude from their measured visible and near ultraviolet photoabsorption cross sections at 298 K. The lifetime of methyl nitrite is nearly independent of altitude and is approximately 2 min. From 0 to 50 km the lifetime of nitromethane varies from 10 to 0.5 hr, while that of methyl nitrate changes from 5.3 to 0.09 days, respectively.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120404
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  • 3
    Electronic Resource
    Electronic Resource
    A flash photolysis-resonance fluorescence study of the reaction of atomic hydrogen with molecular oxygen H + O2 + M → HO2 + M (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 401-416 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the technique of flash photolysis-resonance fluorescence, absolute rate constants have been measured for the reaction H + O2 + M → HO2+M over a temperature range of 220-360°K. Over this temperature range, the data could be fit to an Arrhenius expression of the following form: \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm Ar}} = (6.75{\rm } \pm {\rm }1.1){\rm } \times {\rm }10^{ - 33} \exp {\rm }[685{\rm } \pm {\rm }128{\rm cal/mole]/}RT$$\end{document} The units for kAr are cm6/mole-s. At 300°K the relative efficiencies for the third-body gases Ar:He:H2:N2:CH4 were found to be 1.0:0.93:3.0:2.8:22. Wide variations in the photoflash intensity at several temperatures demonstrated that the reported rate constants were measured in the absence of other complex chemical processes.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060310
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  • 4
    Electronic Resource
    Electronic Resource
    A computational analysis of the alkane pyrolysis mechanism: Sensitivity analysis of individual reaction steps (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 605-621 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The previously reported extensive mechanism for the pyrolysis of propane and n-butane around 800 K is reexamined in the light of a recent reevaluation of the rate constant data base, and the sensitivity of model simulations to variations in the rate parameters is studied. The pyrolysis rates of butane and the product distribution of propane remain in good agreement with the available experiments, while the rate of propane and the product distribution of butane now show significant differences. The linear sensitivity analysis of the reaction matrix demonstrates an intimate coupling between initiation, hydrogen abstraction, radical decomposition, and recombination reactions as primarily responsible for the overall behavior of the mechanism. The role of unsaturated radicals in the self-inhibition of the pyrolysis process is quantitatively established. The study of the sensitivity coefficients for butane product formation has permitted pinpointing those specific reaction steps in the mechanism which are most likely responsible for the remaining discrepancies between model and experiment. This particular example demonstrates the usefulness of sensitivity calculations for the isolation of reactions for which improvements in rate parameter values are needed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120903
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  • 5
    Electronic Resource
    Electronic Resource
    A study of the collisional quenching of O(21D2) by the noble gases employing time-resolved attenuation of atomic resonance radiation in the vacuum ultraviolet (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 77-87 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electronically excited oxygen atoms O(21D2) have been generated by the pulsed irradiation of ozone in the Hartley-band continuum and monitored photoelectrically in absorption by time-resolved attenuation of atomic resonance radiation at λ = 115.2 nm [O(31D2°) → O(21D2)]. Collisional quenching of the excited atom has been investigated for all the noble gases, and the first absolute values for the second-order deactivation rate constants are reported. The resulting rate data are discussed in terms of a curve-crossing mechanism based on existing spectroscopic data for the noble gas oxides. The absolute rate constants are compared with previous relative rate data for the deactivation of O(21D2) by the noble gases.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060108
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  • 6
    Electronic Resource
    Electronic Resource
    Reaction of excited iodine atoms with methyl iodide: Rate constant determinations (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 297-308 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction I(2P1/2) + CH3I → I2 + CH3 has been reevaluated taking into account both collisional deactivation of excited iodine atoms and loss of I2 by I2 + CH3 → I + CH3I. The reevaluation is based upon data obtained (R. T. Meyer), J. Chem. Phys., 46, 4146 (1967) from the flash photolysis of CH3I using time-resolved mass spectrometry to measure the rate of I2 formation. Computer simulations of the complete kinetic system and a closed-form solution of a simplified set of the differential equations yielded a value of 6(± 4) × 106 1./mole-sec for the excited iodine atom reaction in the temperature region of 316 to 447 K. A slight temperature dependence was observed, but an activation energy could not be evaluated quantitatively due to the small temperature range studied. An upper limit for the collisional deactivation of I(2P1/2) with CH3I was also determined (2.4 × 107 1./mole-sec).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060302
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  • 7
    Electronic Resource
    Electronic Resource
    Arrhenius parameters for reactions of oxygen atoms with the fluorinated ethylenesThis paper was presented at the Seventh International Symposium on Fluorine Chemistry at Santa Cruz, California, July 1973. (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 443-452 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Competitive studies of the reactions of ground-state oxygen atoms, generated by mercury-photosensitized decomposition of nitrous oxide, have been carried out with ethylene and all the fluoroethylenes using 2-(trifluoromethyl)-propene as reference compound. From measurements at 25°C and 150°C relative rate constants have been determined and used to calculate the Arrhenius parameters shown in the following table: TextOlefin\documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{A_{{\rm olefin}} }}{{A_{{\rm 2TFMP}} }}$$\end{document}ΔERef\documentclass{article}\pagestyle{empty}\begin{document}$$\frac{{A_{{\rm olefin}} }}{{A_{{\rm C}_{\rm 2} {\rm H}_{\rm 4} } }}$$\end{document}ΔEC2H4CH2—CH21.10-1.18(1.0)(0)CH2—CHF1.030.840.942.02CH2—CF20.711.490.652.67CHF—CHF (cis-)1.231.921.123.10CHF—CHF (trans-)1.400.791.271.97CF2—CHF1.060.000.961.22CF2—CF20.86-3.220.78-2.04ΔERef = Eolefin - E2TFMP and ΔEC2H4 = Eolefin - EC2H4. Units are kJ/mole.The results are compared with corresponding data for other atoms and radicals, and discussed in terms of the electronic changes produced in the double bond by fluorine substitution, and in relation to the nature of the transition state.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060314
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  • 8
    Electronic Resource
    Electronic Resource
    The kinetics of nucleophilic substitution processes in the alkyl halides. Part B - analysis of experimental data (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 467-479 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nucleophilic substitution reactions in the alkyl halides, RX + Y- → RY + X-, proceeding in polar media are considered on the basis of the theory presented in Part A. It is shown that the solvent reorganization energy is the main part of the activation energy for this processes. According to calculations performed, the values of the solvent reorganization energy equal ∼2.5-3 eV for H2O and ∼ 1.8-2.3 eV for acetone. From experimental data on the kinetic isotope effect, an estimate for the splitting of nonadiabatic terms and for the slope of the potential curve v′ of the intermolecular interaction between halide ion and methyl halide near transition configuration is made. Further, the parameter v′ is used for calculating the activation entropy of substitution reactions in the methyl halides. Theoretical activation energies and activation entropies agree with experimental values. In the framework of theory presented an interpretation of change of Ea and the preexponential factor with the type of alkyl halide is given.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060403
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  • 9
    Electronic Resource
    Electronic Resource
    The kinetics of nucleophilic substitution processes in the alkyl halides. Part A - theory (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 457-466 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Activation energies for substitution reactions of the type AC + B → A + CB, occurring in polar media and characterized by an abrupt change of the term along two coordinates have been calculated within the framework of the quantum-mechanical theory of chemical reactions. In the case of nonadiabatic processes, the transmission coefficient and activation energy for these reactions are expressed in terms of characteristic parameters of the medium (reorganization energy, effective frequency of solvent fluctuation polarization) and the potential energy curves for intermolecular interactions between the reactants (AC and B) and between the products (A and BC).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060402
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  • 10
    Electronic Resource
    Electronic Resource
    Rate constants for the bimolecular self-reactions of ethyl, isopropyl, and tert-butyl radicals in solution. A direct comparison (1974)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 453-456 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A competitive method involving the direct measurement of radical concentrations by EPR spectroscopy has been used to show that in solution at 25°C the rate constants for the bimolecular self-reactions of ethyl, isopropyl, tert-butyl, cyclopentyl, and trichloromethyl are all approximately equal, as had been indicated previously by direct measurement of the rate constants for decay of these radicals.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550060315
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