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  • Physical Chemistry  (117)
  • Wiley-Blackwell  (117)
  • American Institute of Physics
  • Elsevier
  • Institute of Physics
  • National Academy of Sciences
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  • 1985-1989
  • 1980-1984  (117)
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  • 1983  (117)
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  • Wiley-Blackwell  (117)
  • American Institute of Physics
  • Elsevier
  • Institute of Physics
  • National Academy of Sciences
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  • 2020-2022
  • 1985-1989
  • 1980-1984  (117)
  • 1970-1974
  • 1965-1969
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Year
  • 1
    Electronic Resource
    Electronic Resource
    Formation of nitrous acid and nitric oxide in the heterogeneous dark reaction of nitrogen dioxide and water vapor in a smog chamber (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1013-1029 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dark reaction of NOx and H2O vapor in 1 atm of air was studied for the purpose of elucidating the recently discussed unknown radical source in smog chambers. Nitrous acid and nitric oxide were found to be formed by the reaction of NO2 and H2O in an evacuable and bakable smog chamber. No nitric acid was observed in the gas phase. The reaction is not stoichiometric and is thought to be a heterogeneous wall reaction. The reaction rate is first order with respect to NO2 and H2O, and the concentrations of HONO and NO initially increase linearly with time. The same reaction proceeds with a different rate constant in a quartz cell, and the reaction of NO2 and H218O gave H18ONO exclusively. Taking into consideration the heterogeneous reaction of NO2 and H2O, the upper limit of the rate constant of the third-order reaction NO + NO2 + H2O → 2HONO was deduced to be (3.0 ± 1.4) × 10-10 ppm-2-min-1, which is one order of magnitude smaller than the previously reported value. Nitrous acid formed by the heterogeneous dark reaction of NO2 and H2O should contribute significantly to both an initially present HONO and a continuous supply of OH radicals by photolysis in smog chamber experiments.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151006
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the reactions of the superoxide ion in solutions. I. Absorption spectra and interaction with solvents and cations (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1045-1056 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absorption spectra of the superoxide ion have been studied in dimethylformamide (DMF) and acetonitrile (AN). It was found that the superoxide ion existed in equilibrium with an ion pair in AN (Keq = 20M-1, Bu4N+ is the cation) and as “free” (solvated) ion in DMF. The addition of DMF caused the destruction of an ion pair in AN. The addition of the proton donors HX (water or ethanol) to the \documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document} solutions in DMF and AN caused the formation of new ion pairs (Bu4N+\documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document})2HX. The equilibrium constants of these ion pairs were determined in DMF and AN.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151008
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  • 3
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of the reactions of the superoxide ion in solutions. III. Kinetics and mechanism of the reaction of the superoxide ion with ethyl acetate in dimethylformamide, acetonitrile, and their mixtures (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1063-1068 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction of the superoxide ion with ethyl acetate have been studied in DMF, AN, and their mixtures. It was shown that the rate constants depend on the ethyl acetate concentration, which indicates the formation of an intermediate in this process. Equilibrium constants for the process of the intermediate formation and the rate constants for its decay have been determined. It is concluded that aprotic solvents affect mainly the stage of the intermediate decay in this reaction.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151010
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetic and equilibrium study of gas-phase interconversions of 1,3,6-cyclooctatriene, 1,3,5-cyclooctatriene and bicyclo[4.2.0]octa-2,4-diene (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1069-1080 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase equilibrium and rate constants for the isomerizations of 1,3,6-cyclooctatriene (136COT) to 1,3,5-cyclooctatriene (135COT) [reaction (1)] and bicyclo[4.2.0]octa-2,4-diene (BCO) to 135COT [reaction (-2)] have been measured between 390 and 490 K and between 330 and 475 K, respectively. The rate constant of reaction (1) obeys the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 1} = 10^{10.93 \pm 0.08} {\rm exp}[- (115.9 \pm 0.7{\rm kJ}/{\rm mol})/RT]{\rm s}^{ - 1}$$\end{document} The corresponding equilibrium constant is given by the van′t Hoff equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm In K}_{\rm 1}^{\rm 0} = (0.24 \pm 0.04) + (13.78 \pm 0.15{\rm kJ}/{\rm mol})/RT$$\end{document} The strain energy of the 136COT ring is calculated to be 31.7 kJ/mol, based on the known value of 37.2 kJ/mol for 135COT, and ΔHf0(298 K) for gaseous 136COT is 196.3 kJ/mol. The rate constant of reaction (-2) obeys the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm - 2}} = 10^{12.38 \pm 0.23} {\rm exp}[(- 106.9 \pm 1.5{\rm kJ}/{\rm mol})/RT]{\rm s}^{ - 1}$$\end{document} The equilibrium constant for 135COT ⇆ BCO fits the van′t Hoff equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm In K}_{\rm 2}^{\rm 0} = (- 1.20 \pm 0.02) - (0.40 \pm 0.07{\rm kJ}/{\rm mol})/RT$$\end{document} The strain energy of the BCO skeleton is calculated to be 108.3 kJ/mol, and ΔHf0(298 K) for gaseous BCO is 183.3 kJ/mol.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151011
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  • 5
    Electronic Resource
    Electronic Resource
    The azoethane-initiated thermal reaction of isobutene. Heat of formation of the 2-methyl-2-pentyl radical (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1133-1145 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The azoethane-sensitized thermal reaction of isobutene has been studied at 526-565 K. The initial concentrations of azoethane and isobutene were in the ranges of 1.40-10.5 × 10-4 and 6.78-26.6 × 10-4 mol/dm3, respectively. From the initial rates of formation of ethane and 2-methylpentane the heat of formation of the 2-methyl-2-pentyl radical was determined. The result obtained is ±Hf0(2-methyl-2-pentyl) = 0.8 ± 2.0 kcal/mol. The entropy of the radical, obtained from statistical mechanical calculations and experimentally, is S0(2-methyl-2 pentyl) = 92.8 ± 1.5 cal/mol°K. The results support the high heat of formation of the t-butyl radical suggested by different authors.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151103
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  • 6
    Electronic Resource
    Electronic Resource
    Gas-phase thermal isomerization of hexachlorocyclopropane (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1179-1187 
    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 hexachlorocyclopropane to hexachloropropene at 208-283°C is first order and unaffected by changes in the surface-to-volume ratio or by the addition of iodine, tetrachloroethylene, and oxygen. The first-order rate constants fit the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}k({\rm s}^{ - 1}) = (15.74 \pm .022) - (45,660 \pm 526)/4.576T$$\end{document} The reaction was interpreted as an unimolecular process taking place with chlorine atom migration. A comparison of the reactivities of several chlorocyclopropanes is made.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151106
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  • 7
    Electronic Resource
    Electronic Resource
    Shock-tube determination of the rate coefficient for the reaction CN + HCN → C2N2 + H (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1237-1241 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151110
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  • 8
    Electronic Resource
    Electronic Resource
    Announcement (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1244-1244 
    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.550151112
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  • 9
    Electronic Resource
    Electronic Resource
    Pyrolysis of 5-chloropentan-2-one and 4-chloro-1-phenylbutan-1-one. Participation of the carbonyl group (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1275-1282 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of elimination of 5-chloropentan-2-one and 4-chloro-1-phenylbutan-1-one in the gas phase have been determined in a static system, seasoned with allyl bromide, and in the presence of the chain inhibitor propene. The reactions are unimolecular and follow a first-order rate law. The working temperature and pressure ranges were 339.4-401.1°C and 46-117 torr, respectively. The rate coefficients for the homogeneous reactions are given by the following Arrhenius equations: for 5-chloropentan-2-one, log k1(s-1) = (13.12 ± 0.88) - (207.8 ± 11.0)kJ/mol/2.303RT; and for 4-chloro-1-phenylbutan-1-one, log k1(s-1) = (12.28 ± 1.09) - (185.2 ± 12.0)kJ/mol/2.303RT. The carbonyl group at the γ position of the C—Cl bond of haloketones apparently participates in the rate of pyrolysis. The five-membered conformation appears to be a favorable structure for anchimeric assistance of the C=O group in the gas-phase elimination of chloroketones.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151203
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  • 10
    Electronic Resource
    Electronic Resource
    Announcement (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 107-107 
    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.550150110
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