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  • 1
    Digitale Medien
    Digitale Medien
    CH3 state distributions form the reactions of O(1D) with saturated and chlorinated hydrocarbons (1995)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 8371-8377 
    Details
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: CH3 product state distributions arising from the reaction of O(1D) with CH4, C2H6, C3H8, and i-C4H10 were characterized using resonantly enhanced multiphoton ionization (REMPI). The vibrational distributions in the ν1 symmetric stretch and in the ν2 "umbrella'' mode are noninverted in all cases. The results are compared to statistical adiabatic channel-phase space theory (SACM-PST) calculations. The ν2 excitation is much less excited than statistically expected for the reactions with CH4 and C2H6 but nearly statistical in the case of the heavier hydrocarbons. For all reactions but the one with C2H6, the ν1 excitation is similar to the distribution statistically expected. The CH3 rotational distribution from the reaction of O(1D) with CH4 is much hotter than room temperature as comparison with simulated rotational band contours showed. From the integrated CH3 band intensities, we obtained approximate reaction cross sections for the CH3 channel with a decrease in the order CH3(approximately-greater-than)C2H6(approximately-greater-than)C3H8(approximately-greater-than)i-C4H10. In the reactions of O(1D) with CH3Cl, CH3CH2Cl, and CH3CH2CH2Cl, we observed CH3 as a primary product. CH3–ν1 excitation is small in all cases but ν2 excitation is considerable with even an inverted v=1/v=0 distribution in the case of the reaction with C2H5Cl. The relative reaction cross sections for the CH3 channel decrease in the order CH4(very-much-greater-than)CH3Cl(approximately-greater-than)CH3CH2Cl(approximately-greater-than)CH3CH2CH2Cl. © 1995 American Institute of Physics.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1063/1.468828
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  • 2
    Digitale Medien
    Digitale Medien
    Rate coefficients for the reactions of hydrogen atoms with 1-bromopropane, 2-bromopropane, 1-bromobutane, and 2-bromobutane (1998)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 721-727 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The rate coefficients for the reactions of hydrogen atoms with n-C3H7Br, s-C3H7Br, n-C4H9Br, and s-C4H9Br were determined in a discharge flow-reactor at 298 K and a pressure of 4 mbar. Molecular-beam sampling and subsequent mass-spectrometric detection with electron-impact ionisation was used for the measurement of the bromo-hydrocarbon concentration. The rate coefficients obtained are (in 1010 cm3 mol-1 s-1): 2.3±1.2 for n-C3H7Br, 2.3±1.2 for s-C3H7Br, 2.4±1.2 for n-C4H9Br, and 2.8±1.4 for s-C4H9Br. The results are compared with predictions from bond-energy bond-order (BEBO) calculations, where a reasonable agreement is found. Furthermore, also by BEBO calculations, the relative importance of bromine abstraction as compared to hydrogen abstraction is estimated. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 721-727, 1998
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    An extended mechanism for chemical activation systems (1991)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 825-835 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The classical mechanism of chemically activated unimolecular reactions is extended to interpret experimental results in systems olefin/hydrogen atoms. In the case of a large excess of the latter, one has to take into consideration a second chemical activation of the primarily formed radicals by their recombination with H-atoms to yield chemically activated alkane molecules. The radicals as well as the alkane molecules may decompose, and a method based on the coupling of two steady-state master equations is developed to evaluate the contribution of either of the two reaction paths to the ratio decomposition to stabilization. The treatment proposed is demonstrated for the example cis but-2-ene/excess of thermal hydrogen atoms in the presence of molecular hydrogen as a bath gas at 298 K. It turns out that the step via activated butane is not negligible under these conditions.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550230909
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