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  • Physical Chemistry  (11)
  • Wiley-Blackwell  (11)
  • American Chemical Society
  • Elsevier
  • International Union of Crystallography (IUCr)
  • Nature Publishing Group
  • 1980-1984  (11)
  • 1970-1974
  • 1980  (11)
Collection
Keywords
Publisher
  • Wiley-Blackwell  (11)
  • American Chemical Society
  • Elsevier
  • International Union of Crystallography (IUCr)
  • Nature Publishing Group
Years
  • 1980-1984  (11)
  • 1970-1974
Year
  • 1
    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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  • 2
    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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  • 3
    Electronic Resource
    Electronic Resource
    Deactivation of O2(A3Σu+) by O2, O, and Ar (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 501-508 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: O2 in the A3Σu+ state has been prepared in a discharge flow system by recombining oxygen atoms on a nickel surface. The decay of this excited state was followed by observing the emission between 280 and 400 nm. The wall deactivation was observed to approach unit efficiency. Rate constants were determined to be 0.9 × 10-11, 2.9 × 10-13, and 8.6 × 10-16 cm3/molecule sec for the quenching of O2(A3Σu+) by O, O2, and Ar, respectively.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120706
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetics of the diels-alder addition of ethene to cyclohexa-1,3-diene and its reverse reaction in the gas phase (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 253-259 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of ethene to cyclohexa-1,3-diene has been studied between 466 and 591 K at pressures ranging from 27 to 119 torr for ethene and 10 to 74 torr for cyclohexa-1,3-diene. The reaction is of the “Diels-Alder” type and leads to the formation of bicyclo[2.2.2]oct-2-ene. It is homogeneous and first order with respect to each reagent. The rate constant (in l./mol sec) is given by\documentclass{article}\pagestyle{empty}\begin{document}$$ \log _{10} k_a = - (25,970 \pm 50)/4.576{\rm T + }(6.66 \pm 0.02) $$\end{document}The retron-Diels-Alder pyrolysis of bicyclo[2.2.2]oct-2-ene has also been studied. In the ranges of 548-632 K and 4-21 torr the reaction is first order, and its rate constant (in sec-1) is given by\documentclass{article}\pagestyle{empty}\begin{document}$$ \log _{10} k_p = - (57,300 \pm 100)/4.576{\rm T + }(15.12 \pm 0.04) $$\end{document}The reaction mechanism is discussed. The heat of formation and the entropy of bicyclo[2.2.2]oct-2-ene are estimated.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120406
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  • 5
    Electronic Resource
    Electronic Resource
    The thermal unimolecular decomposition of bromocyclobutane (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 339-346 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal unimolecular decomposition of bromocyclobutane has been investigated over the temperature range of 791-1224 K using the technique of very low-pressure pyrolysis (VLPP). HBr elimination is the sole mode of decomposition under the experimental conditions. No evidence could be found for the ring-cleavage pathway to ethylene and vinyl bromide. Assuming a four-center transition state and an Arrhenius A factor the same as that for HCl elimination from chlorocyclobutane, RRKM calculations show that the experimental unimolecular rate constants are consistent with the Arrhenius expression \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\,{\rm sec}^{{\rm - 1}} {\rm )}\, = \,(13.6 \pm 0.3) - (52.0 \pm 1.0)/{\rm \theta }\,$$\end{document} where θ = 2.303RT kcal/mol. The activation energy is higher than that for the open-chain analog, 2—bromobutane. This finding is consistent with the results for the corresponding chloro and iodo compounds.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120505
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  • 6
    Electronic Resource
    Electronic Resource
    Azide mechanisms for the production of NCl metastables (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 741-753 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The production of both the b1Σ+ and a1Δ states of NCl has been observed from the reaction of HN3 with flowing streams of Cl and F atoms. The results suggest that a two-step reaction sequence is responsible for the production of excited NCl, as follows: The rate contant (all products) for the first step is k(F + HN3) 〉 1 × 10-11 cm3/molecule sec. Comparison of this value to results obtained in a previous study of the F + HN3 system yields a value k(F + N3) = 2 × 10-12 cm3/molecule sec. The rate constant for the reaction of chlorine atoms with HN3 was determined to be k(Cl + HN3) 1 × 10-12 cm3/molecule sec. The difference between the Cl + HN3 and F + HN3 rates is interpreted in terms of an addition-elimination mechanism.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550121007
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  • 7
    Electronic Resource
    Electronic Resource
    An FTIR study of the Cl atom-initiated oxidation of CH2Cl2 and CH3Cl (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 1001-1012 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cl atom-initiated oxidation of CH2Cl2 and CH3Cl was studied using the FTIR method in the photolysis of mixtures typically containing Cl2 and the chlorinated methanes at 1 torr each in 700 torr air. The results obtained from product analysis were in general agreement with those reported by Sanhueza and Heicklen. The relative rate constant for the Cl atom reactions of CH2Cl2 and CH3Cl was determined to be k(Cl +CH3Cl)/k(Cl + CH2Cl2) = 1.31 ± 0.14 (2σ) at 298 ± 2 K.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550121209
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  • 8
    Electronic Resource
    Electronic Resource
    Kinetics of oxidation of butane 2,3-diol by osmium(VIII) (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 225-230 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of butane 2,3-, propane 1,2-, ethane diol and 2-methoxy ethanol in aqueous alkaline medium by Os(VIII) has been studied. The reaction is base catalyzed and shows first-order kinetics in Os(VIII), whereas the order is less than 1 in butane 2,3-diol [BD]. The rate of oxidation is BD 〉 propane 1,2 〉 ethane diol ≈ 2-methoxy ethanol. The change in ionic strength has no effect on the rate of reaction. Activation parameters ΔE, PZ, and ΔS* have been evaluated.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550120403
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  • 9
    Electronic Resource
    Electronic Resource
    Mutual interactions of the methyl and methylperoxy radicals studied by flash photolysis and kinetic spectroscopy (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 949-977 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decadic extinction coefficient of the methyl radical at 216.4 nm and the rate constant for mutual combination were redetermined as: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} \varepsilon (216.4) = (9.5 \pm 0.4) \times 10^3 1./mol\,cm \\ k_2 = (3.2 \pm 0.4) \times 10^{10} 1./mol\sec \\ \end{array} $$\end{document}. The application of the Beer-Lambert law to these measurements was justified experimentally. The absorption spectrum of the methylperoxy radical was characterized as a weak, broad, structureless band, having a maximum at 240 nm with ∊(240) = 1.55 × 103 l./mol cm. The mutual interaction of methylperoxy radicals leads to the generation of methoxy and hydroperoxy radicals as a consequence of the nonterminating interaction\documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} 2{\rm CH}_{\rm 3} {\rm OO}^{\rm .} \to 2{\rm CH3O}^{\rm .} + {\rm O}_{\rm 2} \\ {\rm CH}_{\rm 3} {\rm O}^{\rm .} + {\rm O}_2 \to {\rm HCHO + HOO}^{\rm .} \\ \end{array} $$\end{document}. Each derivative radical may consume a significant fraction of the methylperoxy radicals, and either of these cross interactions may be made predominant by a suitable choice of oxygen pressure. The mutual interaction was studied under both conditions. The overall mechanism was analyzed by a precise computational method, and the rate constant of the total mutual interaction \documentclass{article}\pagestyle{empty}\begin{document}$$ 2{\rm CH3O}^{\rm .} \to {\rm all}\,{\rm products} $$\end{document} was estimated as \documentclass{article}\pagestyle{empty}\begin{document}$$ k_4 = (3.5 \pm 0.3) \times 10^8 1./mol\sec $$\end{document}.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550121206
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  • 10
    Electronic Resource
    Electronic Resource
    Reaction of di-tert-butylnitroxide radicals (1980)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 871-881 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Di-tert-butylnitroxide (DTBN) is the simplest of the stable nitroxide radicals and is only consumed at temperatures higher than 90°C or in the presence of very reactive substrates. The pyrolysis of DTBN in solution gives, at least at low conversion, 2-methyl-2-nitrosopropane and di-tert-butylnitroxide-tert-butyl ether. The reaction involves, as the rate-limiting step, the cleavage of the C—N bond. This reaction takes place with an activation energy of 33 kcal/mol. DTBN is stable in the presence of styrene, aldehydes, hydrogen peroxide, α-methyl-N-ethyl nitrone, phenol, and triphenylmethane. On the other hand, it reacts readily with diethylhydroxylamine, ascorbid acid, ethanethiol, and hexanethiol. For the two former compounds the reaction involves a hydrogen transfer as the rate-determining step, and the reaction proceeds, a low conversion, with simple second-order kinetics. The reaction with the thiols is complex and shows a clear inductiontime.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550121106
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