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  • 101
    Electronic Resource
    Electronic Resource
    Studies by the electron cyclotron resonance (ECR) technique. XII. Interactions of thermal-energy electrons with the molecules CHF3, CHClF2, and CHCl2F (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1215-1223 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the ECR technique the electron scavenging properties of the halomethanes CHF3, CHClF2, and CHCl2F were investigated. A brief discussion is given on the evaluation of experimental data for inefficient polar scavengers. Absolute attachment rate constants were obtained from the decrease of the cyclotron resonance signal upon addition of the above scavengers. For the molecules CHF3 and CHCl2F the activation energies for the capture processes are given. Possible capture mechanisms are discussed.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550101204
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  • 102
    Electronic Resource
    Electronic Resource
    The kinetics of ClO formation in the flash photolysis of chlorine-oxygen mixtures (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1233-1244 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The production of ClOO and ClO radicals following the flash photolysis of chlorine + oxygen mixtures has been studied. For the mechanism the following kinetic parameters were measured: k3K = 1.3 × 1010 l2/mol2·sec; k2/k3 = 17; and k3/∊(ClOO; 250 nm) = 9.7 × 105 cm/sec. Then k3 = 5.9 × 109 l/mol·sec, k2 = 1.0 × 1011 l/mol·sec, and ∊(ClOO; 250 nm) = 6.1 × 103 l/mol·cm. From limits established for the equilibrium constant K, ΔH°f (ClOO) = 94 ± 2 kJ/mol.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550101206
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  • 103
    Electronic Resource
    Electronic Resource
    The participation of aromatic neighboring groups in gas-phase elimination reactions (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 923-929 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase pyrolysis of 2-chloroethylbenzene and p-methoxy-2-chloroethylbenzene was studied in a static system over the temperature range of 411°-471°C and a pressure range of 39-202 mm Hg. The reactions in seasoned vessels, with the propene inhibitor always present, were homogeneous, first-order, and unimolecular. The rate constants are given by the Arrhenius equation for 2-chloroethylbenzene: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{- 1}) = (13.07 \pm 0.35) - (220.9 \pm 4.6){\rm kJ/mol/2}{\rm .303}RT $$\end{document} and for p-methoxy-2-chloroethylbenzene: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{- 1}) = (13.81 \pm 0.34) - (228.4 \pm 4.6){\rm kJ/mol/2}{\rm .303}RT $$\end{document} The presence of phenyl substituents in the β position of ethyl chloride has been found to provide anchimeric assistance in these elimination reactions.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100903
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  • 104
    Electronic Resource
    Electronic Resource
    The gas-phase pyrolysis of alkyl nitrites VI. t-Amyl nitritePart V, Int. J. Chem. Kinet., 9, 567 (1977). (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 931-943 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of decomposition of tert-amyl nitrite (t-AmONO) has been studied in the absence (120°-155°C) and presence (160°-190°C) of nitric oxide. In the absence of nitric oxide for low concentrations of tert-amyl nitrite (∼10-4M) and small extents of reaction (∼1%), the first-order homogeneous rates of acetone formation are a direct measure of reaction (1) since k3a ≫ k2(NO): The rate of acetone formation is unaffected by the addition of large amounts of carbon tetrafluoride or isobutane (∼1 atm) but is completely suppressed by large amounts of nitric oxide (1 atm 120°-155°C).The rate of reaction (1) is given by k1 = 1016.3±0.1 10-40.3±0.1/θ sec-1. Since (E1 + RT) and ΔH°1 are identical, both may be equated with D(t-AmO - NO) = 40.9 ± 0.1 kcal/mol and E2 = 0 ± 0.1 kcal/mol. The thermochemistry leads to the result that ΔH°f (t-AmO) = -26.6 ± 1 kcal/mol. From ΔS°1 and A1, k2 is calculated to be 1010.5±0.2 M-1·sec-1.Although the addition of nitric oxide completely suppresses acetone formation at lower temperatures, it reappears at higher temperatures. This is a result of reaction (3a) now competing with reaction (2), thus allowing k3a to be determined. The rate constant for reaction (3a) is given by k3a = 1014.7 ± 0.2 10-14.3 ± 1/θ sec-1. There are two possible routes for the decomposition of the tert-amyloxyl radical: The dominating process is (3a). From the result at 160°C that k3a/k3b = 80, we arrive at the result k3b = 1015.0-18.7/θ sec-1.In addition to the products accounted for by the radical split (1), methyl-2-but-1-ene and methyl-2-but-2-ene are produced as a result of the six-centre elimination of nitrous acid (5): The ratio k5a/k5b was 0.35. Unlike tert-butyl where the rates of the two paths were comparable [(l) and (5)], here the total rate of the elimination process was only 0.5% that of the radical split (1). The reason for this is not clear.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100904
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  • 105
    Electronic Resource
    Electronic Resource
    Quenching of biacetyl (3Au) molecules by near-resonant and off-resonant collisional partners (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1225-1232 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Laser-induced time-resolved phosphorescence has been used to evaluate the quenching of gaseous biacetyl (3Au) molecules by various molecules at 25°C. The quenching of biacetyl (3Au) molecules by biacetyl itself was not detectable under our experimental conditions, and a pressure-independent lifetime of 1.70 ± 0.08 msec was found. The bimolecular rate constants (units of l/mol·sec) for quenching of the 3Au molecules by cis-2-pentene, trans-2-pentene, cis-1,3-pentadiene, trans-1,3-pentadiene, and oxygen were found to be (3.3 ± 1.9) × 103, (4.0 ± 0.2) × 104, (3.9 ± 0.1) × 108, (1.3 ± 0.1) × 108, and (5.2 ± 0.4) × 108, respectively.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550101205
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