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  • 101
    Electronic Resource
    Electronic Resource
    Erratum (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 719-720 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180609
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  • 102
    Electronic Resource
    Electronic Resource
    Acetaldehyde oxidation in the negative temperature coefficient regime: Experimental and modeling results (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 655-688 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acetaldehyde oxidation has been studied in experiments at temperatures of 553 and 713 K carried out in a low pressure, static reactor and in numerical modeling calculations using a detailed chemical kinetic reaction mechanism. The results of the experimental study were used to construct and validate the reaction mechanism, which was then used to examine acetaldehydeoxidation in the negative temperature coefficient regime between 550 and 900 K. This mechanism was also tested against independent measurements of acetaldehyde oxidation carried out by Baldwin, Matchan, and Walker. The overall rate of reaction and the properties of the negative temperature coefficient regime were found to be sensitive to the competition between radical decomposition reactions and the addition of molecular oxygen to acetyl and methyl radicals, including particularly \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} + {\rm O}_2 + {\rm M = CH}_{\rm 3} {\rm O}_{\rm 2} + {\rm M} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm CO} + {\rm M = CH}_{\rm 3} {\rm + CO} + {\rm M} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} {\rm CO} + {\rm O}_{\rm 2} {\rm = CH}_{\rm 3} {\rm CO}_{\rm 3} $$\end{document} During these experiments, an upper limit to the rate of decomposition ofCH3O2H was measured at 553 K. Implications of the results for future kinetic modeling of engine knock are discussed.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180606
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  • 103
    Electronic Resource
    Electronic Resource
    Base-catalyzed tritium exchange between tritium-containing heavy water and deuterated chloroform-kinetics and equilibrium (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 739-755 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We develop a kinetic model for the exchange of tritium and deuteriumbetween tritium-containing heavy water and deuterated chloroform in a two-phase liquid system, catalyzed by hydroxide ion (sodium hydroxide). For the exchange reaction yielding tritiated chloroform andheavy water, the measured equilibrium constant is 0.518 at 25-45°C, independent of temperature. The rate constant (for the controlling step, deuteron abstraction from chloroform) is 0.22 L/mol s at 25°C, 0.72 at 35°C, and 2.0 at 45°C, corresponding to an activation energy of 87 kJ/mol. Comparison is made with literature data, and effects of mass transfer on the apparent rate constant are discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180703
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  • 104
    Electronic Resource
    Electronic Resource
    Kinetic analysis of the disproportionation of aqueous glyoxal (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 757-773 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of disproportionation of 0.015-0.4 mM aqueous glyoxal toglycolic acid were measured at 0.24-75 mM NaOH and constant ionic strength, leading to the empirical rate expression r = (a1[OH-] + a2[OH-]2) [GT]/(1 + a3[OH-]), where [GT] is the total glyoxal concentration. These results were confirmed in bicarbonate/carbonate buffer and at 2-20 mM [GT]. The rate form is in contradiction to earlier work on glyoxal, which suggested a second-order dependence on [OH-], but agrees with the rate equation for phenylglyoxal disproportionation. The kinetic data can be explained by a mechanism postulating the presence of monohydrated and dihydrated forms of glyoxal in equilibrium, with the rate-limiting steps being intramolecular hydride ion transfers to the unhydrated carbonyl carbon of the mono- and divalent anions of glyoxal monohydrate.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180704
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  • 105
    Electronic Resource
    Electronic Resource
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    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.550180801
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  • 106
    Electronic Resource
    Electronic Resource
    Radical steps in diethyl ether decomposition (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 829-836 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of diethyl ether was studied in the temperature range 697.2-760.5 K. The rate constant of reaction (1), and the ratio of the rate constant of reaction (2) to that of (12): were calculated from the amounts of products: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 ({\rm s}^{{\rm - 1}}) = (17.2 \pm 0.6) - (82.4 \pm 2.0{\rm kcal mol}^{{\rm - 1}})/2.3RT $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 /k_{12^{1/2} } ({\rm dm}^{{\rm 3/2}} {\rm mol}^{{\rm - 1/2}}) = (4.1 \pm 0.4) - (11.9 \pm 1.3{\rm kcal mol}^{{\rm - 1}})/2.3RT $$\end{document}
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180803
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  • 107
    Electronic Resource
    Electronic Resource
    The chromatographic retention of H and D atoms on quartz (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 861-869 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chromatographic retention of H and D atoms has been observed in a quartz tube using argon as a carrier gas for D and six different gases for H. The results give equilibrium constants for the reversible adsorption of H and D on quartz as well as the rates of desorption. Self-consistent conclusions can be drawn from the data. The adsorption energy appears to be ca. 50 kJ mol-1 indicating weak chemisorption. The observations are consistent with vibration frequencies on the surface of around 700-900 cm-1 for D. and around 1000-1300 cm-1 for H. It appears that only a fraction of the surface atoms (ca. 10-2) act as adsorption sites.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180806
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  • 108
    Electronic Resource
    Electronic Resource
    Preface (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. vi 
    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.550180902
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  • 109
    Electronic Resource
    Electronic Resource
    Experimental study of the D + H2 (v = 1) reaction by CARS spectroscopy (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 919-935 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions D + H2 (v = 0, 1) → HD (v = 0, 1) + H have been studiedin a discharge flow reactor by CARS-spectroscopy. For H2(v = 0) molecules a rate constant of (4, 0 ± 1, 0) 10-16 cm3 s-1 is obtained at 310 K from measured HD (v = 0, 1) product yields. Keeping the degree of vibrational excitation of H2in the microwave discharge in the range of 1% from the increase of the HD (v = 0, 1) CARS signals a rate of k2a, b = (1, 0 ± 0, 4) 10-13cm3 s-1 is derived. The total consumption of H2 (v = 1) in the presence of D atoms gives a rate k2 = (1, 9 ± 0, 2) 10-13 cm3 s-1 at 310 K. The resultsare discussed in regard to previous measurements and theoretical treatments.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180904
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  • 110
    Electronic Resource
    Electronic Resource
    Molecular beam scattering studies of the reaction D + H2 (v = 0) and D + H2 (v = 1) → HD + H (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 949-959 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction D + H2 → HD + H has been investigated in two molecular beam scattering experiments. Angular and time-of-flight distributions have been measured for the initial vibrational ground state (v = 0) at a most probable collision energy of Ecm = 1.5 eV and for the first vibrational excited state (v = 1) at Ecm = 0.28 eV with the same apparatus. Results for the ground-state experiment are compared with quasiclassical trajectory calculations(QCT) on the LSTH-hypersurface transformed into the laboratory system and averaged over the apparatus distributions. The agreement isquite satisfactory. At this high collision energy the HD products are no longer scattered in a backward direction but in a wide angular region concentrated about θ = 90° in the center-of-mass system. The absolute reactive cross section has been determined and the agreement with the theoretical value from QCT calculations is within the experimental error. The high sensitivity of the experiment to different properties of the doubly differential cross section has also been demonstrated. A preliminary evaluation of the experiment with initial vibrational excitation (v = 1) shows that the HD-product molecules are preferably backward scattered and the change of internal energy is small supporting the concept of a reaction which is adiabatic with respect to the internal degrees of freedom.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550180906
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  • 111
    Electronic Resource
    Electronic Resource
    Importance of enolate anions in the high-pressure kinetics of nitroalkanes and nitroaromatics (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1205-1214 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We review and systematize experimental evidence concerning the extreme high-pressure kinetics of condensed phase nitroalkanes and nitroaromatics. This systematization suggests that enolate aci anions of the nitroalkanes and enolate aci-quinone anions of the nitroaromatics are important in the initial high-pressure kinetics of such systems. Kinetic data from experiments which observed the effect of: (1) small amounts of chemical additives, (2) substitution for protons, (3) difference in chemical isomer, (4) exposure to ultra-violet light, and (5) application of very high pressure can all be rationalized within the framework of our hypothesis. We suggest a static high-pressure ultra-violet absorption spectroscopy experiment on nitromethane that would test the proposed hypothesis.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181009
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  • 112
    Electronic Resource
    Electronic Resource
    An FTIR spectroscopic study of the kinetics and mechanism for the NO2-initiated oxidation of tetramethyl ethylene at 298 K (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1235-1247 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechansim for the NO2-initiated oxidation of tetramethyl ethylene (TME) have been studied using the FTIR spectroscopic method in mixtures containing NO2 and TME (0.1-1.0 Torr) and N2—O2 (700 Torr) at 298 ± 2 K. While TME decayed according to -d[TME]/dt = kobs[NO2][TME], NO2 exhibited a complex kinetic behavior. Furthermore, values of kobs were dependent on [O2]. Among the products were (CH3)2CO and at least three NO2-containing compounds. These results indicate the formation of a nitro-alkylperoxy radical via reactions (1), (-1), and (2), and its subsequent reactions leading to the observed products. The [O2]-dependence of kobs yielded k1 = (1.07 ± 0.15) × 10-20 cm3 molecule-1 S-1 and k-1/k2 = (3.54 ± 0.61) × 1018 molecule cm-3.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181103
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  • 113
    Electronic Resource
    Electronic Resource
    Gas phase thermal isomerization of 4-acetyl-5-methyl-isoxazole (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1333-1340 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase thermal isomerization of 4-acetyl-5-methyl-isoxazole affords 3-cyano-2,4-pentanedione as the only product in good agreement with previous proposed isomerization mechanism for isoxazoles. On the other hand, kinetic parameters and MO theoretical calculations do not agree with those previously reported. An alternative reaction mechanism which explains this fact is discussed.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181205
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  • 114
    Electronic Resource
    Electronic Resource
    Room temperature rate constants for the reaction of OH with selected chlorinated and oxygenated hydrocarbons (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1355-1371 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study was conducted to measure the hydroxyl radical rate constants using a relative rate procedure in which the photolysis of methyl nitrite was the source of OH. During the course of this study, the OH rate constant was measured for a number of chlorinated solvents for which measurements have not previously been reported or for which there are few reliable measurements.Room temperature OH rate constants are presented for six chlorinated hydrocarbons (allyl chloride, benzyl chloride, chlorobenzene, epichlorohydrin, trichloroethylene, and vinylidene chloride) and four oxygenated hydrocarbons (acrolein, methacrolein, methyl ethyl ketone, and propylene oxide). Also included are OH rate constants for alkanes (ethane, propane, isobutane, and cyclohexane), alkenes (trans-2-butene and isoprene), and aromatic hydrocarbons (benzene, toluene, o-, m-, and p-xylene). Rate constants for compounds not previously reported include vinylidene chloride (1.49 ± 0.21 × 10-11 cm3 molecule-1 s-1) and benzyl chloride (2.96 ± 0.15 × 10-12 cm3 molecule-1 s-1). The analysis for chlorinated hydrocarbons included a correction for possible chlorine atom reactions.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550181207
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