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  • Physical Chemistry  (13)
  • Wiley-Blackwell  (13)
  • 1970-1974  (13)
  • 1950-1954
  • 1973  (13)
  • 1950
  • 1
    Electronic Resource
    Electronic Resource
    A flash photolysis-resonance fluorescence kinetics study of the reactions of ground-state sulfur atoms. V. Rate parameters for the reaction of S(3P)with cis-2-butene and tetramethylethylene (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 841-857 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate parameters for the reaction of ground-state atomic sulfur, S(3P), with the olefins cis-2-butene and tetramethylethylene have been determined over a temperature range of ∽280°K. A major finding of this study was that the rate constants for both reactions showed negative temperature dependencies. When k is expressed in the form of an Arrhenius equation, this necessarily leads to negative activation energies: k1 = (4.68 ± 0.70) × 10-12 exp (+0.23 ± 0.09 kcal/mole)/RT (219°-500°K) k2 = (4.68 ± 1.70) × 10-12 exp (+1.29 ± 0.23 kcal/mole)/RT (252°-500°K) Units are cm3 molec-1s-1. When a threshold energy of 0.0 kcal/mole is assumed for reaction (2), the temperature dependence of the preexponential term has a value of T-2. Making the usual simplifying assumptions, neither collision theory nor transition state theory leads to a preexponential factor with a strong enough negative temperature dependence. A comparison of these results with those derived from studies of the reactions of atomic oxygen, O(3P), with the same olefins shows that in both studies simple bimolecular processes were being examined. Also discussed are the possible experimental and theoretical ramifications of these new results.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050511
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  • 2
    Electronic Resource
    Electronic Resource
    A flash photolysis resonance fluorescence kinetics study of ground-state sulfur atoms. III. Rate parameters for reaction of S(3P) with ethylene episulfide (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 149-153 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants for the reaction of S(3P) with ethylene episulfide were measured over a C2H4S concentration range of 5, a total pressure of 20-200 tort, and a flash intensity range of ˜4. Over this range of variables, the bimolecular rate constant was found to be invariant. Because of limitations imposed by the physical properties of the reactant C2H4S, temperature variations were necessarily held to the range 298-355°K. The bimolecular rate constant was found to be invariant over this limited temperature range, having a value of (4.47 ± 0.26) × 10-11 cm3 molec.-1 sec-1. The possible influence of this reaction in studies of the S(3P)-ethylene system are discussed.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050113
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  • 3
    Electronic Resource
    Electronic Resource
    A flash photolysis-resonance fluorescence kinetics study of ground-state sulfur atoms. IV. Rate parameters for reaction of S(3P) with propene and 1-butene (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 375-384 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the technique of flash photolysis-resonance fluorescence, absolute rate constants have been measured for the reaction of S(3P) with propene and 1-butene. Variations in experimental conditions included the following: temperature (215-500°K); total pressure a factor of 10; olefin concentration, a factor of 6; flash intensity (S atom concentration), a factor of 10. It was found that over these variations in the experimental conditions only the temperature had a measureable effect on the bimolecular rate constant. The derived Arrhenius rate expressions for the reactions (2) and (3) were as follows: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = \left( {6.03 \pm 0.72} \right) \times 10^{ - 12} \exp \left( {\frac{{ - 0.38 \pm 0.09kcal/mol}}{{RT}}} \right) $$\end{document} temperature range 214-500°K \documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 = \left( {7.41 \pm 1.15} \right) \times 10^{ - 12} \exp \left( {\frac{{ - 0.36 \pm 0.09kcal/mol}}{{RT}}} \right) $$\end{document} Units are cm3 molec-1 s-1.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050308
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  • 4
    Electronic Resource
    Electronic Resource
    Electronically excited oxygen atoms, O(21D2). A time-resolved study of the collisional quenching by the gases H2, D2, CH4, NO, NO2, N2O, and C3O2 using atomic absorption spectroscopy in the vacuum ultraviolet (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 819-831 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Time-resolved atomic absorption spectroscopy in the vacuum ultraviolet has been employed to monitor electronically excited oxygen atoms, O(21D2), following their genera-tion by the flash photolysis of ozone in the Hartley band region. We report the first values for the absolute second-order rate constants describing the removal of the excited atom on collision with the molecules H2, D2, CH4, NO, NO2, N2O, and C3O2. Where possible, these data are considered within the context of restrictions arising from spin and orbital symmetry and are further discussed in tems of previously reported relative rate data derived from indirect measurements. Consideration is given to the importance of these rate con-stants in discussing processes taking place in the earth's atmosphere and in systems giving rise to chemical laser action.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050509
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  • 5
    Electronic Resource
    Electronic Resource
    Very low-pressure pyrolysis. VIII. The decomposition of Di-t-amyl peroxideThis work was supported in part by Contract No. F44620-71-C-0103 with the Air Force Office of Scientific Research. (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 55-65 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The very low-pressure pyrolysis (VLPP) technique has been applied to the pyrolysis of di-t-amyl peroxide (DTAP) over the temperature range 523-633°K. VLPP yields a low-pressure rate constant, kuni The conversion of kuni to k∞ which must be made to calculate the Arrhenius parameters, is accomplished via the RRKM theory. The transition state model used in the RRKM calculations was based on a transition state model which accurately reproduced the VLPP data for di-t-butyl peroxide for which the Arrhenius parameters are well known. For the decomposition of DTAP it was found that log k∞(300°K) = 15.8 - 36.4/θ, where θ = 2.303RT, in kcal/mole, and the units of k∞, are sec-1.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050106
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  • 6
    Electronic Resource
    Electronic Resource
    The homogeneous gas phase H2—D2 metathesis at room temperature: Reaction induced by specific vibrational excitation (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 93-106 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have demonstrated that reactions for which substantial activation energies are needed can be induced to occur at room temperature via specific vibrational excitation. Indeed, the indications are that the atom-switching reactions for which Ea 〉 25 kcal take place with high probability only when the activation energy is localized in the vibrational mode. In this preliminary report on the utilization of the stimulated Raman effect to generate substantial populations in the critical vibrational states required for the homogeneous atom exchange between H2 and D2, we first summarized the historical development of the concept. The experimental arrangement is then described and the analytical results tabulated; the observed dependence on relative concentrations is semiquantitatively rationalized on the basis of a model proposed in 1964. Independent shock tube and molecular beam investigations were similarly accounted for. Attention is called to the discrepancy between the generally concordant experimental results and the ab initio quantum mechanical calculations of the potential energy surface for 4H atoms.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050109
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  • 7
    Electronic Resource
    Electronic Resource
    Reactions of unsymmetrically substituted allyl radicals with methyl radicals (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 513-522 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Hg(63P1) photosensitized decompositions of 3-methyl-1-butene, 2-methyl-2-butene, 3,3-dimethyl-1-butene, and 2,3-dimethyl-1-butene have been used to generate 1-methylallyl, 1,2-dimethylallyl, 1,1-dimethylallyl, and 1,1,2-trimethylallyl radicals in the gas phase at 24 ± 1°C. From a study of the relative yields of the CH3 combination products, the relative reactivities of the reaction centers in each of these unsymmetrically substituted ambident radicals have been determined. The more substituted centers are found to be the less reactive, and this is ascribed primarily to greater steric interaction at these centers during reaction. Measurement of the ratio of trans- to cis-2-pentene formed from the 1-methylallyl radical, combined with published values for this ratio at higher temperatures, enabled the differences in entropy and heat of formation of the trans- and cis-forms of this radical to be calculated as 0.62 ± 0.85 J mol-1 K-1 and - 0.63 ± 0.25 kJ mol-1, respectively, at 298K. Approximate values of the disproportionation/combination ratios for reaction of CH3 with 1,1-dimethylallyl and 1-methylallyl have been estimated and used to compute rate constants for the recombinations of tert-butyl and isopropyl radicals that are in agreement with recently published data.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050402
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  • 8
    Electronic Resource
    Electronic Resource
    Reaction of methyl radicals with atomic oxygen (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 47-53 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of hydrogen atoms with diazomethane was used as a source of methyl radicals to study the reaction of oxygen atoms with methyl radicals. This investigation verifies directly the earlier results that formaldehyde is a major product and that the rate constant is greater than 3×10-11cm3 molecule-1 sec-1.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050105
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  • 9
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of cyclopropane derivatives. III. Gas-phase unimolecular isomerization of cyclopropyl cyanide to the cyanopropenes (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 137-147 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyclopropyl cyanide isomerizes in the gas phase at 660°-760°K and 2-89 torr to give mainly cis- and trans-crotonitrile and allyl cyanide, with traces of methacrylonitrile. The reactions are first order, homogeneous, and unaffected by the presence of radical-chain inhibitors. The rate constants are given by Overall: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k/{\rm sec}^{ - 1} = (14.58 \pm 0.08) - (242.0 \pm 1.2){\rm kJ}\,{\rm mole}^{ - 1} /2.303RT$$\end{document} cis-Crotonitrile: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k/{\rm sec}^{ - 1} = (14.01 \pm 0.11) - (237.6 \pm 1.4){\rm kJ}\,{\rm mole}^{ - 1} /2.303RT$$\end{document} trans-Crotonitrile: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k/{\rm sec}^{ - 1} = (14.09 \pm 0.07) - (243.7 \pm 0.9){\rm kJ}\,{\rm mole}^{ - 1} /2.303RT$$\end{document} Allyl cyanide: \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k/{\rm sec}^{ - 1} = (14.59 \pm 0.13) - (252.0 \pm 1.8){\rm kJ}\,{\rm mole}^{ - 1} /2.303RT$$\end{document} where the error limits are standard deviations. On the basis of a biradical mechanism, it is deduced that the —CH—CN radical center is resonance stabilized by ca. 30 kJ mole-1. Approximate equilibrium data are given for interconversion of the 1- and 3-cyanopropenes.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050112
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  • 10
    Electronic Resource
    Electronic Resource
    The deuterium isotope effect in disproportionation of CF2D radicals (1973)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 5 (1973), S. 169-171 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550050115
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