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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 94 (1972), S. 5523-5532 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Analytical chemistry 48 (1976), S. 1644-1645 
    ISSN: 1520-6882
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 283-289 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase photolysis of CCl4 in the presence of several alkanes has been used to obtain Arrhenius parameters for the abstraction of hydrogen atoms by the CCl3 radical: The following log k4 values were obtained: TextRHlog k4c-C5H10,\documentclass{article}\pagestyle{empty}\begin{document}$$12.00 \pm 0.21 - \frac{{10,700 \pm 400}}{{2.3RT}}$$\end{document}n-C6H14\documentclass{article}\pagestyle{empty}\begin{document}$$11.81 \pm 0.18 - \frac{{10,800 \pm 300}}{{2.3RT}}$$\end{document}2,3-Dimethylbutane\documentclass{article}\pagestyle{empty}\begin{document}$$10.88 \pm 0.11 - \frac{{8,200 \pm 200}}{{2.3RT}}$$\end{document}c-C7H14\documentclass{article}\pagestyle{empty}\begin{document}$$12.07 \pm 0.43 - \frac{{9,900 \pm 800}}{{2.3RT}}$$\end{document}Methylcyclohexane\documentclass{article}\pagestyle{empty}\begin{document}$$11.75 \pm 0.26 - \frac{{9,900 \pm 500}}{{2.3RT}}$$\end{document}c-C8H16\documentclass{article}\pagestyle{empty}\begin{document}$$12.11 \pm 0.29 - \frac{{9,600 \pm 500}}{{2.3RT}}$$\end{document}The results are compared to those for CH3 and CF3 radicals.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 275-283 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The removal of *UF6 (A state) molecules by selected alkanes has been investigated at 25°C. The following rate constants (units of 1011 l/mol·sec) were evaluated: iso-C4F10, 0.0432 ± 0.0115; n-C4F10, 0.0764 ± 0.020; C2F6, 0.0192 ± 0.0052; CH4, 0.0612 ± 0.0061; C2H6, 3.78 ± 0.60; C3H8, 5.08 ± 0.60; n-C4H10, 5.05 ± 0.78; iso-C4H10, 4.17 ± 1.15; neo-C5H12, 6.59 ± 0.93; CF3—CH3, 0.0385 ± 0.0056; CF2H—CF2H, 0.0729 ± 0.0074; and CF2H—CFH2, 0.149 ± 0.015. The perfluoro-alkane quenching of *UF6 proceeds via a physical mechanism. The other alkane quenching reactions are consistent with a chemical mechanism also contributing in varying degrees which may involve removal of two hydrogens from the alkane.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 483-489 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase photolysis of CF3CCl3 in the presence of several alkanes has been used to obtain Arrhenius parameters for the abstraction of hydrogen atoms by the CF3CCl2 radical: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CF}_{\rm 3} {\rm CCl}_2 + {\rm RH} \to {\rm CF}_{\rm 3} {\rm CCl}_2 {\rm H} + {\rm R}$$\end{document}Activation energies of 9.6 and 8.0 kcal/mole are found for abstraction from secondary and tertiary C-H bonds, respectively. The Arrhenius parameters are compared to those for CCl3 and CF3 radicals.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 107-117 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative intensities of phosphorescence of SO2(3B1) molecules have been determined following the optical excitation of SO2(1B1) molecules by a 2662 Å laser pulse. From a kinetic treatment of these measurements, the intersystem crossing ratio, k2b/(k1b + k2b), was determined; SO2(1B1) + M → SO2(3B1) + M (2b); SO2(1B1) + M → SO2 + M (1b). With M = O2, N2, Ar, CO2, and CO, k2b/(k1b + k2b) = 0.030 ± 0.013, 0.034 ± 0.029, 0.025 ± 0.005, 0.052 ± 0.014, and 0.045 ± 0.028, respectively. These data allow a new, more quantitative evaluation of the extent of involvement of the “excess” triplet SO2 in the 3130 Å-irradiated mixtures of SO2 and CO at high pressures [5, 6]. The new data are also of direct interest in the determination of the theoretical maximum rates of photooxidation of SO2 in the sunlight-irratiated atmosphere of the earth.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of SO2 at 3080 Å, FWHM = 150 Å, and 22°C has been investigated in the presence of cis- and trans-C2F2H2. Quantum yield measurements for the photosensitized isomerization of cis-C2F2H2 to trans-C2F2H2 have been made for a variation in the [SO2]/[cis-C2F2H2] ratio from 0.992 to 253. The results fit a mechanism which is consistent with the SO2(3B1) state being the reactive excited state of sulfur dioxide. A mechanism employing only the SO2(1B1) and SO2(3B1) excited states is quite satisfactory to rationalize the data. A value for the SO2 collisionally induced intersystem crossing efficiency from SO2(1B1) to SO2(3B1) of 0.35 ± 0.14 was estimated while the cis-C2F2H2 efficiency was found to be 0.030 ± 0.012. The rate constant at 22°C for the removal of SO2(3B1) molecules by cis-C2F2H2 was found to be (1.43 ± 0.13) × 10101./mole · sec. A photostationary composition, [cis]/[trans] = 1.0 ± 0.1, was found from prolonged irradiations of SO2 in the presence of the cis and trans isomers.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 8 (1976), S. 935-943 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of SO2 in the presence of cis- and trans-2-pentene has been investigated at 3660 Å and 22°C. Quantum yield measurements of the SO2 photosensitized conversion of one isomer into the other are consistent with a mechanism in which the only participating excited electronic state of SO2 is the SO2(3B1) state. Quantum yield measurements were made for a variation in PSO2/Pisomer reactant ratios of 4.01-283 and 57.5-351 for the cis and trans isomers, respectively. The data are consistent with a mechanism in which a (SO2-olefin)3 collision intermediate is the precursor to the photosensitized isomeric products. The intermediate undergoes unimolecular decay to yield the cis and trans isomers with probabilities of 0.26 ± 0.05 and 0.69 ± 0.04, respectively. Estimates of the quenching rate constants at 22°C for removal of SO2(3B1) molecules by cis- and trans-2-pentene are (0.633 ± 0.125) × 1011 l./mole/sec and (1.00 ± 0.27) × 1011 l./mole/sec, respectively. An experimentally determined photostationary composition, [trans-2-pentene]/[cis-2-pentene] = 2.3 ± 0.1 was in fair agreement with that of 1.7 ± 0.7 as predicted from kinetic data derived in this study.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 125-130 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lifetime data have been obtained for the decay of SO2(3B1 0,0,0) at 25°C over the pressure range of 1-762 torr. The 3B1 state was populated by direct absorption to eliminate any possible complications in interpretation due to the participation of excited-singlet manifolds. At pressures greater than about 10 torr, the measured lifetimes are longer than predicted from low-pressure Stern-Volmer parameters. This deviation can be interpreted in terms of Freed's theory on collisionally induced intersystem crossing and provides unequivocal evidence to support earlier speculations that the lengthening of the lifetimes at high pressures is due to saturation in depopulation of the 3B1 state.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the combination of 1,1-dichloro-2,2,2-trifluoroethyl radicals in the gas phase has been measured by applying the rotating sector technique to the 1,1,1-trichloro-2,2,2-trifluoroethane-cyclohexane photochemical system. The combination rate constant, k5, was found to be 6.6 × 1012 cc mole-1 sec-1. Arrhenius parameters for the reaction, are given by the expression log k4 = 11.81 - (9700/2.3RT).
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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