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  • Physical Chemistry  (61)
  • Wiley-Blackwell  (61)
  • American Chemical Society
  • 2020-2024
  • 1980-1984
  • 1970-1974  (61)
  • 1972  (61)
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Verlag/Herausgeber
  • Wiley-Blackwell  (61)
  • American Chemical Society
Erscheinungszeitraum
  • 2020-2024
  • 1980-1984
  • 1970-1974  (61)
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  • 1
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 37-48 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The rate of the isotope exchange reaction between iron(II) and iron(III) perchlorates has been measured in a solvent mixture containing a 3:2 mole ratio of water to dimethyl sulfoxide over the temperature range from 25° to -98°C. In this temperature range, the reactants can diffuse together faster than they can undergo isotope exchange. The activation enthalpy and entropy for the acid-independent reaction were 6.0 ± 1.2 kcal/mole and -38 ± 17 cal/deg mole, respectively. Below -22°C, the acid-dependent exchange reaction did not contribute significantly to the exchange. In liquid media at -112° and -117°C and in a solid glass at -136°C, no isotope exchange was observed over the period of a calculated half-life for the reaction. At these temperatures, the rate at which the reactants diffuse together is slower than the calculated rate of isotope exchange. In a solid glass at -196°C, no isotope exchange was observed over the period of one week.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 307-314 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Effects of deuterium substitution in propylene on the relative rates of H(D) atom abstraction from and addition to the olefin, and on the orientation of H(D) atom addition, have been studied in the gas phase at room temperature. Effects of isotopic substitution of the olefinic hydrogen atoms on abstraction could not be observed, but abstraction is reduced five- to tenfold by deuteration of the methyl group. Deuteration of either olefinic position enhances the rate of addition to the substituted carbon atom. Disproportionation-combination ratios for deuterium-substituted propyl radicals are not greatly different from those for unsubstituted radicals, the largest effect being for C3D7 radicals, for which the overall kd/kc is reduced 10-15%.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 315-324 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The position of abstraction by H atoms from ethylene, propylene, butene-1, and cis- and trans-butene-2 and the rates of abstraction relative to addition have been measured at 25°C. Only allylic abstraction was observed. From ethylene, abstraction relative to addition was ≤3×10-4. For propylene, butene-1, cis-butene-2, and trans-butene-2, abstraction occurred on 0.2%, 1.6%, 1.5%, and 0.9% of the reactive encounters, if dis-proprotionation-combination ratios for allyl and alkyl radicals are similar to those for alkyl-alkyl pairs.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 293-306 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The vibrational excitation of HF and DF and the energy transfer efficiencies for various collision partners were investigated over the temperature and pressure ranges of 1400°K to 4100°K and 0.1 to 0.3 atm, respectively. The extent of excitation was determined as a function of time by continuously monitoring the infrared emission intensity at the center of the 1-0 vibration-rotation band of the molecule. Collisional efficiencies of HF, N2, O2, F, Cl, and DF in relaxing HF and of DF, HF, and N2 in relaxing DF are reported. A comparison with relaxation data for pure HF taken at lower temperature suggests that long-range attractive forces are mechanistically of major importance in the relaxation process. The relatively high efficiency of atomic chlorine in relaxing HF, i.e., (τP)HF-HF/(τP)HF-C1 ≥ 5 at 3000°K is discussed in terms of our previous result for atomic fluorine, i.e., (τP)HF-HF/(τP)HF-F = 18.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 325-330 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Secondary kinetic isotope effects occur in radical additions to deuterated olefins. Substitution of a deuterium at a carbon undergoing an sp2 to sp3 hybridization-change during reaction, Cβ in eq. (1), leads to an inverse isotope effect of 3-5% (kH/kD = 0.95-0.97). The effect at a carbon going from an olefinic to a radical center, Cα in eq. (1), generally has been assumed to be negligible, since a nominal sp2 hybridization is maintained throughout reaction. Using new, sensitive instrumentation for radioactivity determination and a recently developed quench correction technique, we now find that there is a small, normal isotope effect (kH/kT 1) associated with a change from olefin to radical. Specifically, when R· is the polystyryl radical, X is phenyl, and the α-C bears a tritium, kH/kT = 1.04. This result is discussed in relation to recent data on cycloaddition reactions.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 331-338 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: In polychloro-2,2-difluoropropanes, where a large inductive effect results in relatively low reactivity to chlorination, the presence of additional chlorine causes an increased reactivity of the hydrogens geminal to the chlorine and a reduced reactivity of the remote (third carbon) hydrogens. The ways in which resonance, inductive effect, and steric crowding interact in the rates of chlorination of polar molecules are discussed.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 8
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 339-343 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Measurements of the D(R—NO) bond strength in some C-nitrosocompounds have been made using an electron impact method. The appearance potential of the radical ion (R+) has been determined, the D(R—NO) bond energy being obtained from the relation \documentclass{article}\pagestyle{empty}\begin{document}$$D{\rm (R} - {\rm NO) = }AP{\rm (R}^{\rm + } {\rm)} - IP({\rm R}.)$$\end{document} The values obtained are: D(C6H5—NO) = 41 kcal/mole, D(t-C4H9—NO) = 34 kcal/mole, D(t-C5H11—NO) = 36 kcal/mole and D(i-C3H7—NO) = 36.5 kcal/mole. These values are in good agreement with the numerous estimations of Benson and coworkers and confirm that the C—N bond strength in C-nitrosocompounds is very much less than in nitrocompounds or in amines.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 9
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 345-362 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A general computational method for obtaining complete solutions of time-dependent kinetic equations has been developed and applied to free radical-initiated reactions of alkanes with oxygen. The method has been applied to the low-temperature, peroxide-initiated oxidations of isobutane and isopentane. Using available independently measured and estimated values for the rate constants and activation parameters for each of the 20 proposed reaction steps for the oxidation of isobutane, the rates and products have been calculated for both the liquid phase and gas phase in the range of 100°-155°C. The calculated rates and products of oxidation agree with published experimental values. The oxidation of isopentane was examined by a 32-reaction model. The rate constants were estimated using values for the appropriate rate steps in the oxidation of n-butane and isobutane. The calculation of the oxidation rate and products agree with our experiments.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 10
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The pyrolysis of ethyl acetate has been studied by the very low-pressure pyrolysis (VLPP) technique. The results obtained agree well with the previously determined high-pressure Arrhenius parameters where log k∞ = 12.6 - 48.0/θ. The rate constants given by these parameters have also been shown to be consistent with the predictions of the RRK and RRKM theories and demonstrate the applicability of the technique to the study of thermal decompositions.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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