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  • Physical Chemistry
  • 1975-1979  (115)
  • 1979  (115)
  • 1
    Electronic Resource
    Electronic Resource
    Erratum (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 103-104 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110106
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  • 2
    Electronic Resource
    Electronic Resource
    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    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.550110201
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  • 3
    Electronic Resource
    Electronic Resource
    Neighboring group participation of polar β substituents in the gas-phase pyrolysis of 2-substituted ethyl chlorides (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 109-115 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of 2-dimethylaminoethyl chloride in the temperature range of 360-400°C and the pressure range of 60-271 mmHg is a homogeneous, unimolecular, first-order reaction giving dimethylvinyl amine and hydrogen chloride. 2-Methoxyethyl chloride pyrolysis in the temperature range of 450-490°C and the pressure range of 53-110 mmHg by a similar unimolecular, first-order reaction yields methylvinyl ether and hydrogen chloride. These reactions were carried out in a seasoned reaction vessel and in the presence of a propene inhibitor. The methylvinyl ether decomposes slowly into other products at the temperature of pyrolysis. The rate constants are given by the Arrhenius equations(a) 2-dimethylaminoethyl chloride: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{ - 1}) = (13.22 \pm 0.17) - (203.7 \pm 2.1)kJ/mol/2.303RT $$\end{document}(b) 2-methoxyethyl chloride: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{ - 1}) = (14.06 \pm 0.53) - (244.7 \pm 7.1)kJ/mol/2.303RT $$\end{document}The effects of polar β substituents in the 2 position of ethyl chloride are discussed in terms of anchimeric assistance and electron-withdrawing deactivation in these elimination reactions. The present results are consistent with the heterolytic nature of the four-centered cyclic transition state for the gas-phase pyrolysis of alkyl halides.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110202
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism for the iodination of methylmalonic acid (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 131-145 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction\documentclass{article}\pagestyle{empty}\begin{document}$ CH\left({CH_3 } \right)\left({COOH} \right)_2 + I_2 \rightleftharpoons CI(CH_3)\left({COOH} \right)_2 + H^ + + I^ - $\end{document} was followed spectrophotometrically at 353 nm and 470 nm at 25°C under various conditions of pH and methylmalonic acid concentration. The equilibrium constant for the reaction is 0.11 ± 0.02. An iterative technique was used to integrate postulated rate equations. Agreement between experimental and calculated absorbance versus time curves was generally better than 0.005 A (approximately 5% of maximum) at both wavelengths for a mechanism where the rate-determining step is formation of an enolate (k = 1.63 Θ 10-4 ± 0.03 Θ 10-4 sec-1). The enolate may be rapidly transformed to the enol or enol carboxylate anion depending on the pH. All three forms are rapidly iodinated. The mechanism of general base catalysis is supported by rate increases proportional to base concentration in buffer solutions. The bases, acetate ion, chloracetate ion, sulfate ion, dichloracetate ion, and water, follow a Brønsted relationship with β = 0.7.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110205
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics of oxidation of some amino acids by KMNO4 in a moderately concentrated H2SO4 medium in the presence and absence of Ag+ (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 165-173 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of glycine, alanine, phenylalanine, serine threonine, aspartic, and glutamic acid by acid permanganate were investigated to elucidate the mechanism of the reactions. The rate law was found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{ - d[Mn\left({VII} \right)]}}{{dt}} = k_0 [a\min oacid][Mn\left({VII} \right)] $$\end{document} The reactions were found to be acid catalyzed, and the kinetic data indicate the participation of the water molecules in the rate-determining step as a proton-abstracting agent from the substrate, as per Bunnett's hypothesis. As Ag+ was found to catalyze these reactions, the oxidation of glycine and glutamic acid was studied, and the rate law was found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{ - d\ln [Mn\left({VII} \right)]}}{{dt}} = \frac{{Kk_c^{''} [a\min oacid][Ag^ +]}}{{1 + K[a\min oacid] = K[Ag^ +]}}$$\end{document} A probable mechanism consistent with the observed results is discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110208
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  • 6
    Electronic Resource
    Electronic Resource
    Competitive chlorination-dehydrochlorination of 1,1,1,2-C2H2Cl4 (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 117-124 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The competitive photochlorination and chlorine photosensitized dehydrochlorination of 1,1,1,2-C2H2Cl4 have been studied over the temperature range of 349.4-404.5 K after less than 1% conversion. The results are discussed and a value of \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_{4A} (\sec ^{ - 1}) = (11.6\pm 0.6) - (16,400\pm 1000)/4.58T $$\end{document} is proposed for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CCl}_{\rm 3} {\rm CHCl}\mathop \to \limits^{(4{\rm A)}} {\rm CCl}_{\rm 2} {\rm CHCl + Cl} $$\end{document} This result, combined with existing thermochemical data, indicates that there is no evidence of an activation energy for the addition of a Cl atom on the most chlorinated carbon in trichloroethylene: in that case the selectivity of the addition of Cl on the less chlorinated carbon should not depend on temperature.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110203
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  • 7
    Electronic Resource
    Electronic Resource
    Pressure saturation of SO2(3B1 0,0,0) lifetimes (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 125-130 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lifetime data have been obtained for the decay of SO2(3B1 0,0,0) at 25°C over the pressure range of 1-762 torr. The 3B1 state was populated by direct absorption to eliminate any possible complications in interpretation due to the participation of excited-singlet manifolds. At pressures greater than about 10 torr, the measured lifetimes are longer than predicted from low-pressure Stern-Volmer parameters. This deviation can be interpreted in terms of Freed's theory on collisionally induced intersystem crossing and provides unequivocal evidence to support earlier speculations that the lengthening of the lifetimes at high pressures is due to saturation in depopulation of the 3B1 state.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110204
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  • 8
    Electronic Resource
    Electronic Resource
    Mechanistic details of the Belousov-Zhabotinsky oscillations. II. The organic reaction subset (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 155-164 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Our previous mechanistic model for the Belousov-Zhabotinsky reaction has been revised to include a more realistic set of reactions for the oxidation pathways of the organic intermediates. A few other rate constants have also been modified to include new information. The revised mechanism reproduces the essential experimental observations, although the periods of oscillation are somewhat too long and oscillations cease at malonic acid concentrations about ten times greater than the observed lower limit. However, the essential features of the mechanism are clearly understood.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110207
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  • 9
    Electronic Resource
    Electronic Resource
    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    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.550110301
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  • 10
    Electronic Resource
    Electronic Resource
    The kinetics and mechanism of n-butyraldehyde photolysis in the vapor phase at 313 nm (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 219-237 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis was investigated at 313 nm wavelength, 253-529 K temperatures, and 4 × 10-11-2 × 10-9 mol·photon/cm2·sec light intensities by determining the quantum yields of 20 reaction products. Primary quantum yields for the seven primary processes and rate constant ratios, rate constants, and Arrhenius parameters for secondary processes were derived on the basis of the suggested reaction scheme. The dependence of the quantum yields of the four major primary processes on experimental conditions was established.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110302
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