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  • Physical Chemistry  (52)
  • Wiley-Blackwell  (52)
  • 1970-1974  (52)
  • 1945-1949
  • 1971  (52)
  • 1
    Electronic Resource
    Electronic Resource
    Rates and mechanism of alkyne ozonationThis paper presents the results of one phase of research carried out at the Jet Propulsion Laboratory, California Institute of Technology, under Contract No. NAS 7-100, sponsored by the National Aeronautics and Space Administration. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 161-173 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates and products of the reactions of ozone with acetylene, methylacetylene, dimethylacetylene, and ethylacetylene have been studied in a long-path infrared cell at 21 ± 1°C. The gas phase reaction gives products formed by cleavage of the carbon-carbon triple bond. A mechanism is proposed that involves formation of a short-lived acid anhydride intermediate, which is energized by virtue of the reaction exothermicity and undergoes unimolecular decomposition. Formation of an α-dicarbonyl was observed in every case, but there is evidence that a side reaction on the walls accounted for that product. The general relationship between alkyne and alkene ozonation is discussed. The rate measurements showed that, unlike the alkenes, the rate of alkyne ozonation is not greatly affected by substitution with simple alkyl groups. The rate constant for C2H2 agrees with earlier work and thus provides additional support for the previously derived high A-factor for acetylene ozonation relative to alkenes.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030208
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  • 2
    Electronic Resource
    Electronic Resource
    Masthead (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971) 
    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.550030301
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  • 3
    Electronic Resource
    Electronic Resource
    The pyrolysis of neopentane at small extents of reaction (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 197-213 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of neopentane, at small extents of reaction, was studied by gas chromatography, in Pyrex reaction vessels between 450° and 530°C and in the initial pressure range 25-200 mm Hg. At initial time, this thermal decomposition can be essentially represented by a homogeneous long-chain radical mechanism. The rate constant of the unimolecular initiation process is approximately given by the expression \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 0} \simeq 10^{13} {\rm exp}\left({\frac{{50,000}}{{RT}}} \right){\rm mole}^{- {\rm 1/2}} {\rm .ml}^{- {\rm 1/2}} {\rm .s}^{- {\rm 1}}$$\end{document} The initial rate constant of the global reaction (order 3/2) is nearly equal to \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 1} + 10^{16.8} {\rm exp}\left({\frac{{82,000}}{{RT}}} \right){\rm s}^{- {\rm 1}}$$\end{document} This reaction is strongly inhibited by propene or isobutene and self-inhibited by the isobutene formed; an interpretation of all these inhibition phenomena of the neopentane pyrolysis is proposed. Our observations and conclusions, which have been summarized in communications during 1968 and 1969, are compared to those of other authors, particularly to the recent ones of Purnell and colleagues [13] and of Taylor and colleagues [14], [15].
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030302
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  • 4
    Electronic Resource
    Electronic Resource
    Multistage reactions, equilibrium, and detailed balancing: A linear algebra approach (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 491-499 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods of linear algebra are applied to (a) the problem of determining whether detailed balancing for some or all stages of a chemical process is implicit from the existence of steady state for some or all of the chemical species involved, and (b) the formulation of general concentration-type equilibrium relationships solely from kinetic considerations and the assumption of full detailed balancing.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030603
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  • 5
    Electronic Resource
    Electronic Resource
    The reactions of O(1D) with ozone and nitrous oxide (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 501-508 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ozone was photolyzed at room temperature in the presence of N2O at 2537 Å and 2288 Å to produce O(1D) atoms. These atoms can react with either O3 or N2O via From the quantum yield of N2, the relative rate constants k6a/k6 and k2/k6 could be obtained, where k6 + k6a + k6b. The former rate constant ratio was found to be 0.37 ± 0.03 at 2537 Å and 0.33 ± 0.03 at 2288 Å, in good agreement with an earlier report from our laboratory. The ratio k2/k6 was found to be 2.6 at 2537 Å, but 4.1 at 2288 Å. The difference in the two numbers, if real, may reflect differences in reactivity due to different amounts of excess translational energy in the O(1D) atom at the two wavelengths.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030604
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  • 6
    Electronic Resource
    Electronic Resource
    Second international symposium on gas kinetics, July 5-9, 1971, University College of Swansea, United Kingdom (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 553-554 
    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.550030608
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  • 7
    Electronic Resource
    Electronic Resource
    Disproportionation-combination ratios of small alkyl radicals formed by the mercury-photosensitized hydrogenation of olefins in the gas phase (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 523-534 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Disproportionation-combination ratios have been obtained for small alkyl radicals produced in the mercury-photosensitized hydrogenation of ethylene, propylene, butene-1, butene-2, and isobutene. For conditions favoring thermalized radicals, kd/kc (ethyl, ethyl) = 0.14, kd/kc (isopropyl, isopropyl) = 0.69, kd/kc (isopropyl, n-propyl) = 0.41, kd/kc (2-butyl, 2-butyl) = 0.77, kd/kc (2-butyl, n-butyl) = 0.45, and kd/kc (t-butyl, t-butyl) = 3.1. The results are consistent with kd/kc (n-propyl, n-propyl) = 0.15 and kd/kc (n-butyl, n-butyl) = 0.14. The general agreement between these disproportionation-combination ratios and those obtained where photolytic radical sources have been used indicates that under appropriate conditions, H atom addition to olefins is a suitable source for the study of thermalized alkyl radicals and may be especially useful for larger alkyl radicals for which clean photolytic precursors are not available.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030606
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  • 8
    Electronic Resource
    Electronic Resource
    Disproportionation-combination ratios of large branched alkyl radicalsThis work was supported by the Office of Naval Research. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 535-551 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The disproportionation-combination reactions of radicals 4,4-dimethylpentyl-2 and 2,4-dimethylpentyl-2, produced by collisional stabilization of the respective chemically activated species, have been studied at 298°K, with and without getter radicals. Use of getters t-C4H9 and C2H5 with 4,4-dimethylpentyl-2, and of iso-C3H7 with 2,4-dimethylpentyl-2 yielded disproportionation-combination ratios ω for parent-getter and t-C4H9-C2H5 cross reactions, and for the mutual reaction of t-C4H9 radicals. The unstabilized hot radicals decompose, and these experiments also yielded values for the high-pressure rate constant ka∞ of 1.70 × 108sec-1 and 2.11 × 107sec-1 for 4,4-dimethylpentyl-2 and 2,4-dimethylpentyl-2, respectively. The results, compared to those for other large alkyl radical systems obtained earlier, suggest that steric effects influence the accessibility of H atoms for transfer.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030607
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  • 9
    Electronic Resource
    Electronic Resource
    Kinetics of the gas phase reaction of methyl benzoate with bromine and iodine: The methoxyl C—H bond strength of methyl estersThis work supported in part by Grant No. 00353-06 from the Environmental Protection Agency, Air Pollution Control Administration. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 509-522 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase reactions of PhCOOCH3 with I2 and Br2 were studied spectrophotometrically in a static system over the temperature ranges 344-359° and 246-303°, respectively. For each system the initial rate was first order in PhCOOCH3 and half order in halogen as the concentration of PhCOOCH3 was varied from 1.4 to 15.2 torr, that of I2 from 6.2 to 26.4 torr, and that of Br2 from 3.0 to 13.6 torr. The rate-determining step is the extraction of a methoxyl hydrogen atom: Empirical assignment of A-factors for k1 lead to \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(k}_{\rm 1} {\rm /M}^{- {\rm 1}} {\rm sec}^{- {\rm 1}} {\rm) = (11}{\rm .5} \pm {\rm 0}{\rm .3)} - (29.9 \pm 0.8)/\theta $$\end{document} for the I2 system, and to \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(k}_{\rm 1} {\rm /M}^{- {\rm 1}} {\rm sec}^{- {\rm 1}} {\rm)} = {\rm (11}{\rm .3} \pm {\rm 0}{\rm .3)} - (14.6 \pm 0.8)/\theta $$\end{document}for the Br2 system, where φ = 2.303RT in kcal/mole. Combined with the assumption that E-1 = 1 ± 1 kcal/mole and 2 ± 1 kcal/mole for HI and HBr, respectively, DH2980 (PhCOOCH2—H) calculated from the two systems shows excellent agreement at 100.2 ± 1.3 kcal/mole and 100.1 ± 1.3 kcal/mole. Using a value of δHf,2980 (PhCOOMe) = -65.6 ± 1.5 kcal/mole obtained from group additivity estimates, δHf,2980 (PhCOOCH2) is calculated to be -16.7 ± 2.0 kcal/mole. Unimolecular decomposition of the Ph(CO)O°CH2 radical was also observed: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Ph}\left( {{\rm CO}} \right){\rm O\dot CH}_{\rm 2} \mathop {\hbox to 20pt{\rightarrowfill}}\limits^3 {\rm Ph\dot CO} + {\rm H}_{\rm 2} {\rm CO} $$\end{document} with a rate constant equal to \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(}k_{\rm 3} {\rm /sec}^{- {\rm 1}} {\rm)} = {\rm (15} \pm {\rm 0}{\rm .5)} - (26 \pm 3)/\theta $$\end{document} The abnormally high methoxyl C—H bond strength is discussed in relation to the bonding in ethers, alkanes, and esters.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030605
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  • 10
    Electronic Resource
    Electronic Resource
    A critical review of the kinetics of the dissociation-recombination reactions of fluorine and chlorineThis work was supported by the Office of Standard Reference Data, N.B.S., and the Naval Ordnance Systems Command ORD 3311 as part of a program to foster production of tables of chemical kinetics. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 39-68 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A critical evaluation of the rates of the dissociation and recombination reactions of fluorine and chlorine is given. Data are presented graphically and in tabular form. The effect of various third bodies is discussed. Rate expressions for specified temperature ranges are recommended, while comparison with theoretical values obtained from the Benson and Fueno theory is made where applicable.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030105
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