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  • 1
    Electronic Resource
    Electronic Resource
    The addition of methyl radicals to tetrafluoroethylene (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 571-580 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of methyl radicals to tetrafluoroethylene in the gas phase has been studied over the temperature range 80-180°C, using a material balance method. \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CH}_{\rm 3} + {\rm C}_2 {\rm F}_{\rm 4} \to {\rm CH}_3 {\rm C}_2 {\rm F}_4 $$\end{document}Arrhenius parameters of 1011.95±0.23 (mole-1 cm3 sec-1) and 5.7 ± 0.4 (kcal/mole) have been measured for the addition reaction.Electrophilic reagents such as O or CF3 appear to react almost equally readily with ethylene and tetrafluoroethylene but methyl radicals add much more rapidly to tetrafluoroethylene than to ethylene, the difference in reactivity being principally due to an activation energy difference of ∼2 kcal/mole.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010607
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  • 2
    Electronic Resource
    Electronic Resource
    Hydrogen-abstraction reactions from organosilicon compounds. The reactions of methyl, trideuteromethyl, trifluoromethyl, and ethyl radicals with tetramethylsilane (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 339-351 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The following Arrhenius parameters have been determined for the hydrogen-abstraction reactions: R + (CH3)4Si → RH + (CH3)3SiCH3 TextRTemp. (°K)E (kcal/mole)Log A (mole-1 cc sec-1)Log k(400°K) (mole-1 cc sec-1)CF3330-4337.23 ± 0.0911.90 ± 0.057.95CH3396-47610.23 ± 0.3611.55 ± 0.185.68CD3396-49610.36 ± 0.1211.84 ± 0.066.20C2H5423-52211.40 ± 0.4811.88 ± 0.225.68The activation energies are in keeping with the strengths of the bonds formed during the reaction. By comparison with the activation energies for the analogous reactions of neopentane it is estimated that D((CH3)3SiCH2—H) ≃ 97 kcal/mole.The A factors for the above series of reactions fall within the range predicted by transition-state theory for this type of process and the validity of previous results of Kerr, Slater, and Young is seriously in doubt.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010306
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  • 3
    Electronic Resource
    Electronic Resource
    Hydrogen abstraction reactions from organosilicon compounds. The reactions of methyl, trifluoromethyl, and ethyl radicals with trichlorosilane (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 371-380 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Arrhenius parameters have been determined for the hydrogen-abstraction reactions: R + SiHCl3 + RH + SiCl3 TextRTemp (°K)E(kcal/mole)Log A(mole-1 cc sec-1)Log k(400°K) (mole-1 cc sec-1)CF3323-4615.98 ± 0.0611.77 ± 0.038.50CH3333-4434.30 ± 0.0810.83 ± 0.044.48C2H5314-4135.32 ± 0.0711.54 ± 0.048.63The trend in activation energies ECH3 〈 EC2H5 〈 ECF3 is interpreted as indicating a polar effect in the reaction of CF3 with SiHCl3 and the similar reactivities of all three radicals appear to be due to the high exothermicity of the reactions.The A Factors for the reactions are normal for hydrogen abstraction reactions of free radicals. The previous results of Kerr, Slater, and Young for CH3 abstracting an H atom from SiHCl3 have been amended.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010403
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  • 4
    Electronic Resource
    Electronic Resource
    Bond energies in chloroethanes and chloroethyl radicals (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 3-9 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C—Cl and C—C bond energies in the chloroethanes and C—H, C—Cl, and C—C bond energies in the chloroethyl radicals are calculated from known heats of formation of chloroethanes and chloroethylenes and known C—H bond energies in chloroethanes.The results obtained show a dependence of bond energy on the isomeric structure of the molecules and radicals and on the type of bond broken (primary, secondary, or tertiary). Heats of formation and bond energies estimated from group property additivity rules are in close agreement with experimental values.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010103
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  • 5
    Electronic Resource
    Electronic Resource
    The rate of addition of hydrogen atoms to olefins: Isobutane and ethylene (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 69-87 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reactions have been investigated in a fast flow system at pressures of about 2 torr and temperatures between 12 and 132°C. The following Arrhenius equations are derived for reaction (2) where the units of k2 are l/mole sec and of E2, cal/mole, and the limits are the 95% confidence limits assuming random errors.These equations are in good agreement with those which can be derived from previous investigations.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010108
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  • 6
    Electronic Resource
    Electronic Resource
    Pressure Effects in the Solvolysis of Benzyl Chlorides (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 113-126 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of solvolysis of benzyl chloride and of substituted benzyl chlorides have been measured in an acetone-water mixture (acetone mole fraction 0.147) at pressures ranging from atmospheric to 1 kbar. Pressure studies have also been made for p-methyl benzyl chloride in various acetone-water mixtures. Measurements have also been made of the partial molar volumes of the reactants. The plots of log k against pressure are fitted to a second-degree polynomial in P, and values of ΔV
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010111
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  • 7
    Electronic Resource
    Electronic Resource
    Kinetics and rate constants for the reaction of tri-n-butylgermanium hydride with methyl iodide and carbon tetrachloride. The combination of methyl and trichloromethyl radicals in solution.Issued as NRCC No. 10642. (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 315-323 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the photoinitiated reductions of methyl iodide and carbon tetrachloride by tri-n-butylgermanium hydride in cyclohexane at 25°C have been studied and absolute rate constants have been measured. Rate constants for the combination of CH3ċ and CCl3ċ radicals are equal within experimental error and are also equal to the values found for the self-reactions of most non-polymeric radicals in low viscosity solvents, i.e. ∼1-3 × 109 M-1 sec-1.Rate constants for hydrogen atom abstraction by CH3ċ and CCl3ċ radicals are both ∼1-2 × 105 M-1 sec-1. Tri-n-butyltin hydride is about 10-20 times as good a hydrogen donor to alkyl radicals as is tri-n-butylgermanium hydride.The strength of the germanium-hydrogen bond, D(n-Bu3Ge-H) is estimated to be approximately 84 kcal/mole.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010304
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  • 8
    Electronic Resource
    Electronic Resource
    Kinetics of the reaction of cyclopentane with trichloroethylene (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 325-337 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermally and radiation initiated chain reaction between trichloroethylene and cyclopentane to produce 1,1-dichlorovinylcyclopentane and hydrogen chloride have been investigated in the temperature range 250-360°C at high pressure in the gas phase. The rate governing step in the chain is (k3 = 3.3 × 109 exp -(4800/RT) cc mole-1 sec -1). The rate of the unimolecular decomposition of trichloroethylene is 1.4 × 1014 exp -(61,200/RT) sec-1.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010305
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  • 9
    Electronic Resource
    Electronic Resource
    Studies of cage reactions III. A test over a wide temperature range (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 357-359 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010308
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  • 10
    Electronic Resource
    Electronic Resource
    The photolysis of pentafluoroacetoneThis work was supported by a grant from the National Scienc Foundation, GP-8069. (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 413-425 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of pentafluoroacetone has been investigated in the 3130 Å region, from room temperature to 360°C. The ΦCO varies from 0.7 to 0.9 over this range, and the decomposition is represented by CF2HCOCF3 → CF2H + CO + CF3. The disproportionation/combination ratio for CF3 and CF2H (→ CF3H + CF2) radicals is found to be 0.09. Arrhenius parameters for hydrogen atom abstraction from the ketone are log10A = 12.7 (units are mole-1 cc sec-1) and E = 14.3 kcal mole-1 for CF2H, and log10A = 12.1 and E = 11.8, for CF3 radicals. At low pressures HF elimination reactions are observed from the vibrationally excited fluoroethanes, C2F5H* and C2F4H2*, formed in the system. A rough estimate of the activation energy for the process C2F5H → C2F4 + HF of 60-65 kcal mole-1 is made.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010407
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