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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 307-314 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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%.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 315-324 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 3 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 293-306 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 9 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 325-330 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 1 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 331-338 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 3 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 339-343 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 3 Tab.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 345-362 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1013-1029 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dark reaction of NOx and H2O vapor in 1 atm of air was studied for the purpose of elucidating the recently discussed unknown radical source in smog chambers. Nitrous acid and nitric oxide were found to be formed by the reaction of NO2 and H2O in an evacuable and bakable smog chamber. No nitric acid was observed in the gas phase. The reaction is not stoichiometric and is thought to be a heterogeneous wall reaction. The reaction rate is first order with respect to NO2 and H2O, and the concentrations of HONO and NO initially increase linearly with time. The same reaction proceeds with a different rate constant in a quartz cell, and the reaction of NO2 and H218O gave H18ONO exclusively. Taking into consideration the heterogeneous reaction of NO2 and H2O, the upper limit of the rate constant of the third-order reaction NO + NO2 + H2O → 2HONO was deduced to be (3.0 ± 1.4) × 10-10 ppm-2-min-1, which is one order of magnitude smaller than the previously reported value. Nitrous acid formed by the heterogeneous dark reaction of NO2 and H2O should contribute significantly to both an initially present HONO and a continuous supply of OH radicals by photolysis in smog chamber experiments.
    Additional Material: 5 Ill.
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