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  • Artikel  (114)
  • Physical Chemistry  (114)
  • Wiley-Blackwell  (114)
  • American Meteorological Society
  • Blackwell Publishing Ltd
  • Springer Nature
  • Springer Science + Business Media
  • 2015-2019
  • 1985-1989  (114)
  • 1960-1964
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  • 1986  (114)
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  • Chemie und Pharmazie  (114)
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  • Artikel  (114)
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  • Wiley-Blackwell  (114)
  • American Meteorological Society
  • Blackwell Publishing Ltd
  • Springer Nature
  • Springer Science + Business Media
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  • 2015-2019
  • 1985-1989  (114)
  • 1960-1964
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  • Chemie und Pharmazie  (114)
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  • 1
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180101
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  • 2
    Digitale Medien
    Digitale Medien
    Hydrogen abstraction by hydrocarbon radicals. I. Interactions between 1-phenyl ethyl radicals and 1-phenyl ethanol as well as benzyl alcohol (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 31-40 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Hydrogen abstraction by 1-phenylethyl radicals (ṘH) from phenylmethyl-carbinol (HROH) and benzyl alcohol (H2R′OH) has been studied in the liquid phase at 120°C. 1-Phenylethyl radicals have been generated by thermal decomposition of azo-bis-1-phenyl ethane and the formation of ethylbenzene (RH2), acetophenone (RO), and 2,3-di-phenyl butane (R2H2) has been monitored during the reaction.In order to optimize the experimental conditions, a mechanism has been assumed for the various pathways of the disappearance of ṘH and by using estimated rate parameters a presimulation was performed.The relative rate constants obtained are: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\frac{{k_{\rm H} }}{{\sqrt {{\rm 2}k_t } }} = 1.4{\rm } \times {\rm }10^{ - 4} {\rm L}^{1/2} {\rm mol}^{ - 1/2} {\rm s}^{ - 1/2} } & {{\rm for}} & {{\rm HROH}} \\ \end{array} $$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\frac{{k_{\rm H} }}{{\sqrt {{\rm 2}k_t } }} = 1.0{\rm } \times {\rm }10^{ - 4} {\rm L}^{1/2} {\rm mol}^{ - 1/2} {\rm s}^{ - 1/2} } & {{\rm for}} & {{\rm H}_{\rm 2} {\rm R'OH}} \\ \end{array} $$\end{document} where kH refers to the hydrogen abstraction while kt is the combination rate coefficient of the radicals ṘH.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180104
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  • 3
    Digitale Medien
    Digitale Medien
    A reevaluation of low temperature experimental rate data for the reactions of O atoms with methane, ethane, and neopentane (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 59-82 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The experimental data for the reactions of oxygen atoms with methane, ethane, and neopentane at temperatures below ca. 600 K have been reexamined. In the case of CH4 and C2H6 reactions, detailed computer models have been assembled to test the assumptions regarding stoichiometries that were made in the original studies in order to derive elementary rate coefficients from the experimentally observed reaction rates. It was found in both cases that the measurements are especially sensitive to secondary reactions not taken into account and impurities in the reagent alkane. Because the original reports did not include sufficient experimental details, it is not now possible to correct their results quantitatively. However, it appears, qualitatively, that the values for the O + CH4 and O + C2H6 rate coefficients were overestimated by factors of approximately 2 to 3 in the 250-400 K temperature range, with the error increasing as T decreases. Although the experimental results for the O + neopentane reaction are not as sensitive to the same kinds of complications, a comparison of the low-temperature measurements with those for the O + ethane reaction suggests that the previously recommended rate coefficients, based on the data of Herron and Huie, are probably also too high by a factor of 2 to 3.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180107
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  • 4
    Digitale Medien
    Digitale Medien
    Determination of absolute rate data for the reactions of atomic sodium, Na(32S1/2), with CH3F, CH3Cl, CH3Br, HCl, and HBr as a function of temperature by time-resolved atomic resonance spectroscopy (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 83-98 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We present a kinetic study of the reactions of ground-state sodium atoms with the molecules CH3F, CH3Cl, CH3Br, HCl, and HBr at elevated temperatures (537-966 K). Na(32S1/2) was generated by the pulsed irradiation of various sodium halide vapors and monitored by time-resolved atomic resonance absorption of the unresolved D-lines at λ = 589 nm [Na(32PJ) ← Na(32S1/2)] in the “single-shot mode.” The photoelectric signals were amplified without distortion, captured, and digitized in a transient recorder interfaced to a microcomputer for data analysis. Absolute second-order rate constants were measured at various temperatures in each case, yielding the following Arrhenius parameters (kRX = A exp(-E/RT), errors 1σ): which constitute, to the best of our knowledge, the first direct measurements of these quantities. The reaction between Na and HBr demonstrated anomalous behaviour which is discussed in terms of potential surfaces that have been calculated previously for this type of collisional process. The data are compared with analogous results for Na + CF4, CF3Cl, and CF3Br and with single-temperature measurements on diffusion flames.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180108
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  • 5
    Digitale Medien
    Digitale Medien
    Rate constants for the decarboxylation of the t-butoxicarbonyl radical and concurring radical terminations directly obtained by kinetic ESR (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 145-158 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Rate constants of various simultaneous reactions of t-butoxicarbonyl and t-butyl radicals generated by photolysis of t-butylpivalate in n-heptane are directly determined by kinetic electron spin resonance. The temperature dependence of the decarboxylation reaction t-BuOĊO → t-Bu. + CO2 obeys log )K/S-1( = 13.8-49.0/θ where θ = 2.303 RT/kJ . mol-1. The self- and cross-termination of the radicals are diffusion limited.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180202
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  • 6
    Digitale Medien
    Digitale Medien
    Masthead (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986) 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180301
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  • 7
    Digitale Medien
    Digitale Medien
    Linearization of second-order reaction data (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 281-286 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reaction data described by the second-order growth function A(t) = A∞(αt) (1 + αt)-1, where A∞ is the ultimate value of the product concentration A(t), can be linearized by plotting a suitable function F(t) against the time (t). The slope of the straight line obtained is (2α), where α is the product of the rate constant (k2) and the initial concentration of either reactant, with the result that k2 can be determined without knowledge of Aϰ. Optimal determination of the parameter α requires that data taking be limited to the interval 0 ≤ t ≤ T, where (αT) is approximately 4.0. Numerical data derived from an experiment on the exchange of lead by zinc ions in the enzyme carbonic anhydrase are analyzed to illustrate the method. The effects of small errors in the initial concentrations and of small deviations from second-order kinetics are briefly discussed.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180302
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  • 8
    Digitale Medien
    Digitale Medien
    Effects of nonionic, cationic, and anionic micelles on the kinetics of the complexation reaction of nickel (II) with pyridine-2-azo-p-dimethylaniline (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 609-621 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The stopped-flow technique has been used to study the effect of cationic (CTAN), nonionic (Triton X-100), andanionic (SDS) micelles on the rate of the reaction between nickel(II) ion and the ligand pyridine-2-azo-p-dimethylaniline (PADA) at 20.0°C and ionic strength 0.03 mol dm-3. The complex formation reaction is markedly inhibited by both CTAN and Triton X-100 micelles. The kinetic dataare found to conform to a reaction mechanism which implies only partitioning of the ligand between water and the micellar phase, the estimated bindingconstant of PADA being significantly larger in the presence of CTAN aggregates. Anionic micelles strongly speed the complexation reaction, Which occurs in the micellar phase with the same rate and the same mechanism as in water. The extent of binding of PADA to anionic micelles is similar to that found for the cationic micellar aggregates.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180602
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  • 9
    Digitale Medien
    Digitale Medien
    Erratum (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 719-720 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180609
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  • 10
    Digitale Medien
    Digitale Medien
    Kinetics and mechanism of the oxidation of primary alcohols by sodium N-chloroethylcarbamate (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 689-699 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The oxidation of primary alcohols by sodium N-chloroethylcarbamate in acid solution, results in the formation of corresponding aldehydes. The reaction is first order with respect to the oxidant and alcohol. The rate increases with an increase in acidity. The oxidation of α,α-dideuterioethanol exhibited a primary kinetic isotope, kH/kD = 2.11 at 298 K. The value of solvent isotope effect k(H2O)/k(D2O) = 2.23 at 298 K. Addition of ethyl carbamate does not affect the rate. (EtOC(OH)NHCl)+ has been postulated as the reactive species. Plots of (log k2 + Ho) against (Ho + log[H+]) are linear with the slope, φ, having values from 1.78-1.87. This suggested a proton abstraction by water in the rate-determining step. The rates of oxidation of alcohols bearing both electron-withdrawing and electron-donating groups are more than that of methanol. A concerted mechanism involving transfer of a hydride ion from the C—H bond of the alcohol tothe oxidant and removal of a proton from the O—H group by a water molecule has been proposed.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180607
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