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  • 1970-1974  (113)
  • 1890-1899
  • 1972  (61)
  • 1971  (52)
  • Physical Chemistry  (113)
  • 1
    Electronic Resource
    Electronic Resource
    Gas and liquid phase kinetics of the unimolecular isomerization of 1-chloro-4-bromobicyclo[2.2.0]hexane: The radical stabilization energy of an α-bromine atom (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 159-168 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase isomerization of 1-chloro-4-bromobicyclo[2.2.0]hexane to 2-chloro-5-bromohexa-1,5-diene have been measured in a static system over the temperature range of 135-215°C, with a variation in the total pressure from 0.6 to 400 torr. For these conditions the rate constants are well represented by the Arrhenius equation: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log (}k{\rm /sec}^{ - {\rm 1}} {\rm)} = {\rm (13}{\rm .2} \pm {\rm 0}{\rm .2)} - (34.5 \pm 0.4)/\theta$$\end{document} where θ = 2.303RT kcal/mole. Transition state estimates for the biradical mechanism for the isomerization of bicyclo[2.2.0]hexanes are shown to be in good agreement with these Arrhenius parameters. By comparison of the activation energy with that for the isomerization of bicyclo[2.2.0]hexane and 1,4-dichlorobicyclo[2.2.0]hexane, the radical stabilization energy of an α-bromine atom is shown to be 1.0 ± 1.8 kcal/mole. Rates are also reported in the liquid phase at temperatures of 155°C and 175°C with diphenyl ether, nitrobenzene, and dimethylsulfoxide as solvents. The observed rate constants are all faster (by a factor of 1.1-1.7) than those measured in the gas phase and display no correlation between rate and solvent polarity.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040204
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  • 2
    Electronic Resource
    Electronic Resource
    The SO2-sensitized phosphorescence of biacetyl vapor in photolyses at 2650 and 2875 Å. The intersystem crossing ratio in sulfur dioxide (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 175-189 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quantum yields of the triplet sulfur dioxide (3SO2)-sensitized phosphoresence (Φsens) in biacetyl (Ac2) have been determined in experiments over a wide range of pressures of SO2 and Ac2. Excited singlet sulfur dioxide (1SO2) was generated using 2650-Å and 28757hyphen;Å light. The values of Φsens were dependent on the [SO2]/[Ac2] ratio, as anticpated theoretically. However, in runs at a fixed [SO2]/[Ac2] ratio, the measured Φsens values were dependent on the total pressure. This theoretically unexpected effect is probably largely the result of biacetyl triplet diffusion with deactivation at the cell wall. Treatment of the quantum yield data in terms of the complete mechanism gave new estimates of the following rate functions: 1SO2 + SO2 → (2SO2) (1), 1SO2 + SO2 → 3SO2 + SO2 (2), k2/(k1 + k2) = 0.082 ± 0.003 (2650 Å), 0.095 ± 0.005 (2875 Å) 3SO2 + Ac2 → SO2 + 3Ac2 (9a), 3SO2 + Ac2 → SO2 + Ac2 (9b), k9a + k9b = (8.4 ± 2.1) × 1010 (2650 Å), (8.1 ± 3.0) × 1010 l./mole-sec (2875 Å) 3SO2 → SO2 + hvp (6), k6 = (7.3 ± 1.3) × 101 sec-1.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040206
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  • 3
    Electronic Resource
    Electronic Resource
    Rates of reaction of allyl radicals: A reassessment (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 273-276 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Values of the rate constants for allyl-radical abstraction from toluene and allyl-radical recombination have been recalculated in the light of recent data on butene-1 decomposition. The rate of recombination is in good agreement with that found by Van den Bergh and Callear [13] and the cross-combination ratio for the allyl + methyl system has a “normal” value of almost 4. It is concluded that allyl radicals behave like alkyl radicals in respect of their rates of reaction with other radicals.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040304
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  • 4
    Electronic Resource
    Electronic Resource
    A flash photolysis-resonance fluorescence kinetics study of ground-state sulfur atoms. II. Rate parameters for reaction of S(3P) with C2H4 (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 383-394 
    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 were measured over an ethylene concentration range of 7, a total pressure of 50 to 400 torr, and a flash intensity range of 10. At 298°K, the bimolecular rate constant was found to be invariant over this range of variables and had a measured value of 4.96 × 10-13 cm3 molec-1 s-1. Over the temperature range of 218° to 442°K, the rate data could be fit to a simple Arrhenius equation of the form \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = (7.13 \pm 0.74) \times 10^{ - 12} {\rm exp}\left({\frac{{{\rm - 1}{\rm .58} \pm {\rm 0}{\rm .08 kcal/mole}}}{{RT}}} \right)$$\end{document} Units are cm3 molec-1 s-1. The dependence of the measured value of k1 on the concentration of the reaction product ethylene episulfide is discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040403
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  • 5
    Electronic Resource
    Electronic Resource
    The rate of the gas phase iodination of cyclobutane. The heat of formation of the cyclobutyl radicalThis work was supported, in part, by Grant No. AP 00353-07 of the Environmental Protection Agency, Air Pollution Control Administration. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 487-495 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase iodination of cyclobutane was studied spectrophotometrically in a static system over the temperature range 589° to 662°K. The early stage of the reaction was found to correspond to the general mechanism \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} {\rm RH} + {\rm I} \cdot \mathop {{\rm \rightleftharpoons}}\limits^1 {\rm R} \cdot + {\rm HI} \\ {\rm R} \cdot + {\rm I}_{\rm 2} \mathop {{\rm \rightleftharpoons}}\limits^2 {\rm R} - {\rm I} + {\rm I} \cdot \\ \end{array}$$\end{document} where the Arrenius parameters describing k1 are given by log k1/M-1 sec-1 = 11.66 ± 0.11 - 26.83 ± .31/θ, θ = 2.303RT in kcal/mole. The measured value of E1, together with the fact that E-1 = 1 ± 1 kcal/mole, provides ΔHf,2980(c-C4H7.) = 51.14 ± 1.0 kcal/mole, and the corresponding bond dissociation energy, D(c-C4H7—H) = 96.8 ± 1.0 kcal/mole. A bond dissociation energy of 1.8 kcal/mole higher than that for a normal secondary C—H bond corresponds to one half of the extra strain energy in cyclobutene compared to cyclobutane and is in excellent agreement with the recent value of Whittle, determined in a completely different system. Estimates of ΔHf0 and entropy of cyclobutyl iodide are in very good agreement with the equilibrium constant K12 deduced from the kinetic data. Also in good agreement with estimates of Arrhenius parameters is the rate of HI elimination from cyclobutyl iodide.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040503
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  • 6
    Electronic Resource
    Electronic Resource
    The photolysis of N2O at 2139 Å and 1849 Å (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 497-512 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of chemical difference was utilized to accurately determine the relative importance of all the reaction steps in the direct photolysis of N2O at 2139 Å (25° and 250°C) and 1849 Å (25° C), as well as in the Hg6(1P1)-sensitized photolysis of N2O at 1849 Å (25°C). In all cases, the primary process is predominantly, if not exclusively, \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (1)}} & {{\rm N}_{\rm 2} {\rm O} + hv{\rm or H}_{\rm g} 6(^1 P_1) \to {\rm N}_{\rm 2} + {\rm O(}^{\rm 1} D{\rm)}} \\\end{array}$$\end{document} Experiments with trace amounts of C3H6 added showed a slight, but not significant, difference in product ratios (N2 and O2). From these experiments the quantum yield of O(3P) from all possible sources was estimated as 0.02 ± 0.02. Experiments with excess N2 at 1849 Å indicated that O(1S) was not produced in the direct photolysis. The O(1S) yield is probably zero, and certainly 〈0.05. The O(1D) atom can react with N2O via \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} \begin{array}{*{20}c} {{\rm (2)}} & {{\rm O(}^{\rm 1} D{\rm)} + {\rm N}_{\rm 2} {\rm O} \to {\rm N}_{\rm 2} + {\rm O}_2 } \\\end{array} \\ \begin{array}{*{20}c} {{\rm (3)}} & {{\rm O(}^{\rm 1} D{\rm)} + {\rm N}_{\rm 2} {\rm O} \to 2{\rm NO}} \\\end{array} \\ \end{array}$$\end{document} The ratio k2/k3 was found to be 0.69 ± 0.05 in all cases. When combined with other data from our laboratory, the average value is 0.65 ± 0.07. This represents the value for translationally energetic O(1D) atoms. When excess He was added to remove the excess translational energy, k2/k3 rose to 0.83 ± 0.06, which is in reasonable agreement with the value of 1.01 ± 0.06 found in another laboratory. We conclude that for O(1D) atoms with no excess thermal energy, k2/k3 = 0.90 ± 0.10.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550040504
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  • 7
    Electronic Resource
    Electronic Resource
    A Kinetic study of the reaction of nitrogen dioxide with tetrafluoroethylene (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 575-589 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of NO2 with C2F4 was studied at 30°, 68°, 114°, and 157°C by in situ monitoring the infrared absorption bands of the products. The major primary products of the reaction are O2NCF2CFO and FNO. Smaller amounts of CF2O (and presumably NO) are also produced. There was no evidence for other primary products, though they may have been produced in minor amounts. The rate laws for the production of both O2NCF2CFO and CF2O are first order in both [NO2] and [C2F4]. CF2O production is at least partly heterogeneous as demonstrated by packing the quartz reaction vessel with Pyrex beads and by using a Monel cell. The homogeneous rate constant obtained from the high-temperature results gives a rate constant of 3.4 × 108 exp (minus;17000/RT) M-1sec-1 for CF2O production. Actually these Arrhenius parameters represent lower limits, since the heterogeneous reaction may still be playing a significant role. The production rate of O2NCF2CFO is not much affected by changing the nature of the surface or the surface to volume ratio. However the reaction may be heterogeneous, since the rate constant for its formation of 1.3 × 104 e×p (-7500/RT) M-1sec-1 has an abnormally low pree×ponential factor. E×periments in the presence of NO indicate that the mechanism for O2NCF2CFO formatlon is \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} \begin{array}{*{20}c} {(11)} & {{\rm NO}_{\rm 2} + {\rm C}_{\rm 2} {\rm F}_{\rm 4} \to {\rm O}_{\rm 2} {\rm NCF}_{\rm 2} {\rm CF}_{\rm 2} } \\ \end{array} \\ \begin{array}{*{20}c} {(12)} & {{\rm O}_{\rm 2} + {\rm NCF}_{\rm 2} {\rm CF}_{\rm 2} + {\rm NO}_{\rm 2} \to {\rm O}_{\rm 2} {\rm NCF}_{\rm 2} {\rm CFO} + {\rm FNO}} \\ \end{array} \\ \end{array}$$\end{document} The intermediate can also react with NO: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(13)} & {{\rm O}_{\rm 2} {\rm NCF}_{\rm 2} {\rm CF}_{\rm 2} + {\rm NO} \to {\rm O}_{\rm 2} {\rm NCF}_{\rm 2} {\rm CF}_{\rm 2} {\rm NO}} \\ \end{array}$$\end{document} with k13/k12 = 1.3.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040602
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  • 8
    Electronic Resource
    Electronic Resource
    Arrhenius parameters for the reactions CH3. + C4H10 → CH4 + C4H9. and C2H5. + C4H10 → C2H6 + C4H9. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 657-666 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Study of n-butane pyrolysis at high temperature in a flow system allows measurement of the sum of the rate constants of the initiation reactions \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} \begin{array}{*{20}c} {(1)} & {{\rm C}_{\rm 4} {\rm H}_{{\rm 10}} \to {\rm 2C}_{\rm 2} {\rm H}_{\rm 5} ^{\rm .} } \\ \end{array} \\ \begin{array}{*{20}c} {(2)} & {{\rm C}_{\rm 4} {\rm H}_{{\rm 10}} \to {\rm CH}_{\rm 3} ^{\rm .} } \\ \end{array} + {\rm C}_{\rm 3} {\rm H}_{\rm 7} ^{\rm .} \\ \end{array}$$\end{document} and of the Arrhenius parameters of the reactions \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} \begin{array}{*{20}c} {(3)} & {{\rm CH}_{\rm 3} ^{\rm .} + {\rm C}_{\rm 4} {\rm H}_{{\rm 10}} \to {\rm CH}_{\rm 4} + {\rm C}_{\rm 4} {\rm H}_{\rm 9} ^{\rm .} } \\ \end{array} \\ \begin{array}{*{20}c} {(4)} & {{\rm C}_{\rm 2} {\rm H}_{\rm 5} ^{\rm .} + {\rm C}_{\rm 4} {\rm H}_{{\rm 10}} \to {\rm C}_{\rm 2} {\rm H}_{\rm 6} } \\ \end{array} + {\rm C}_{\rm 4} {\rm H}_{\rm 9} ^{\rm .} \\ \end{array}$$\end{document} Established data for k1/k2 allow estimation of k1 for 951°K and this, with recent thermochemical data, yields the result log k-1 (l.mole s-1) = 8.5, in remarkable agreement with a recent measurement [20] but over si×ty times smaller than conventional assumption. The product k3k4 (l.2mole-2s-2) is found to be associated with the Arrhenius parameters log (A3A4) = 21.90 ± 0.6 and (E3 + E4) = 38.3 ± 2.7 kcal/mole. These values are much higher than would be e×pected on the basis of low temperature estimates. Independent evaluation gives log A4 = 10.5 ± 0.4 (l.mole-1s-1) and E4 = 20.1 ± 1.7 kcal/mole, hence log A3 = 11.4 ± 0.8 (l.mole-1s-1) and E3 = 18.2 ± 3.2 kcal/mole. These values are shown to be entirely consistent with a wide range of results from pyrolytic studies, and it is argued that they further confirm the view that Arrhenius plots for alkyl radical-alkane metathetical reactions are strongly curved, in part due to tunneling and, appreciably, to other as yet unidentified effects. Since there is published evidence that metathetical reactions involving hydrogen atoms show even greater curvature, it is suggested that this may be a characteristic of many metathetical reactions.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550040606
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  • 9
    Electronic Resource
    Electronic Resource
    Masthead (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
    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.550040101
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  • 10
    Electronic Resource
    Electronic Resource
    Iron (II) and iron (III) isotope exchange in water-dimethyl sulfoxide mixturesAbstracted in part from the Ph.D. Thesis of Marian S. Henry, University of Minnesota, December 1970. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 37-48 
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    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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    URL: http://dx.doi.org/10.1002/kin.550040103
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  • 11
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    Electronic Resource
    The pyrolyses of tri- and tetramethylethylene in the presence of nitric oxide (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 49-60 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolyses of trimethylethylene and tetramethylethylene have been investigated in the presence and absence of nitric oxide. It appears that apart from a unimolecular split, e.g., a disproportionation reaction such as may play an important role in initiation. Nitric oxide had no effect on H2 production, which is probably a molecular process. There was similar behavior of both compounds in the presence of NO, indicating that the olefinic hydrogen atom does not play a decisive role. Other aspects of the mechanisms are discussed.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550040104
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  • 12
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    Electronic Resource
    The decomposition of chemically activated n-butane, isopentane, neohexane, and n-pentane and the correlation of their decomposition rates with radical recombination rates.Abstracted in part from the Ph.D. Thesis of W. L. Hase, New Mexico State University, 1970.The National Science Foundation is gratefully acknowledged for financial support (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 1-35 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The total decomposition rates of the chemically activated alkanes n-butane, n-pentane, isopentane, and neohexane were measured using an internal comparison technique. Chemical activation was by the C—H insertion reaction of excited singlet-state methylene radicals. A total of ten rate constants ranging from 4.6 × 105 to 2.3 × 107 sec-1 were measured for these alkanes at different excitation energies. These rates correlate via RRKM theory calculations with thermal A-factors in the range of 1016.1 to 1017.1 sec-1 for free rotoractivated complex models and in the range of 1016.4 to 1017.8 sec-1 for vibrator-activated complex models. It was found that high critical energies for decomposition, “tight” radical models, and activated complex models with free internal rotations were required to correlate the decomposition rates of these alkanes with estimated alkyl radical recombination rates. The correlation is just barely possible even for these favorable extremes, indicating that there may be a basic discrepancy between the recombination rate and decomposition rate data for alkanes.
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    URL: http://dx.doi.org/10.1002/kin.550040102
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  • 13
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    Electronic Resource
    Kinetics of the formation of cyclobutane from ethylene (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 61-68 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of the thermal reaction of ethylene to form cyclobutane has been measured over the temperature range 723°-786°K and at pressures between 300 and 1300 torr. The equilibrium constant for the system \documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}$${\rm 2C}_{\rm 2} {\rm H}_{\rm 4}\mathop {\leftrightharpoons}\limits_{kf}^{kr} c - {\rm C}_{\rm 4} {\rm H}_{\rm 8}$$\end{document} was calculated both from the initial rate data and from measurements of the equilibrium concentration of cyclobutane. Agreement with the reported thermodynamic quantities for cyclobutane was satisfactory. The initial rate data gave the following epxression for kf: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log }k_f {\rm (1}{\rm .mole}^{ - {\rm 1}} {\rm sec}^{ - {\rm 1}} {\rm)} = {\rm 7}{\rm .84} - \frac{{43800}}{{2.3RT}}$$\end{document} while the measurements of the equilibrium concentration of cyclobutane gave the expression for K, \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log }K{\rm (atm}^{ - {\rm 1}} {\rm)} = - \frac{{45.4}}{{2.3R}} + \frac{{20700}}{{2.3RT}}$$\end{document}.
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    URL: http://dx.doi.org/10.1002/kin.550040105
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  • 14
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    Electronic Resource
    Thermal decomposition of 3-chloro-3-trichloromethyldiazirine in solution (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 229-233 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of 3-chloro-3-trichloromethyldizairine in carbon tetrachloride and iso-octane has been investigated over the temperature range 75-115°C. The products, tetrachloroethylene and nitrogen, are formed quantitatively by a first-order reaction which is probably unimolecular: The results yielded the following Arrhenius equations: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} k({\rm CCl}_{\rm 4} {\rm)} = {\rm 10}^{{\rm 13}{\rm .8} \pm {\rm 0}{\rm .2}} \exp (- 29,200 \pm 200/RT)\sec ^{ - 1} \\ k(iso - {\rm octane)} = {\rm 10}^{{\rm 13}{\rm .8} \pm {\rm 0}{\rm .2}} \exp (- 29,000 \pm 150/RT)\sec ^{ - 1} \\ \end{array}$$\end{document}.
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    URL: http://dx.doi.org/10.1002/kin.550040209
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  • 15
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    Electronic Resource
    A study of the intersystem crossing reaction induced in gaseous sulfur dioxide molecules by collisions with nitrogen and cyclohexane at 27°C (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 191-205 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The quantum yields of the sulfur dioxide triplet (3SO2)-sensitized phosphorescence of biacetyl (Φsens) were determined in experiments with N2-SO2-Ac2 and c-C6H12-SO2-Ac2 mixtures excited at 2875 Å at 27°C. The fraction of the biacetyl triplets which reacts homogeneously by radiative or nonradiative decay reactions was determined in a series of runs at constant [SO2]/[M] and [SO2]/[Ac2] ratios but at varied total pressure. A kinetic treatment of the Φsens results and singlet sulfur dioxide (1SO2) quenching rate constant data gave the following new kinetic estimates: 1SO2 + M → (SO2-M) (1b) 1SO2 + M → 3SO2 + M (2b); for 1SO2-N2 collisions, k2b/(k1b + k2b) = 0.033 ± 0.008; for 1SO2-c-C6H12 collisions, k2b/(k1b ± k2b) = 0.073 ± 0.024; previous studies have shown this ratio to be 0.095 ± 0.005 for 1SO2-SO2 collisions. It was concluded that the inter-system crossing ratio in 1SO2 induced by collision is relatively insensitive to the nature of the collision partner M. However, the individual rate constants for the collision-induced spin inversion of 1SO2 (k2b) and the total 1SO2-quenching constants (k1b + k2b) are quite sensitive to the nature of M: k2b/k2a varies from 0.10 ± 0.03 for M = N2 to 1.11 ± 0.37 for M = c-C6H12, and (k1b + k2b)/(k1a + k2a) varies from 0.29 for M = N2 to 1.44 for M = c-C6H12; k1a and k1b are the rate constants for the reactions 1SO2 - SO2 → (2SO2) (1a) and 1SO2 + SO2 → 3SO2 + SO2 (2a), respectively.
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    Emission studies of the mechanism of gaseous biacetyl photolysis at 3450, 3650, 3880, and 4358 a and 28°C (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 207-227 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The quantum yields of phosphorescence (Φp) of biacetyl have been determined in pure biacetyl, biacetyl-SO2, and biacetyl-c-C6H12 mixtures in experiments using bands of radiation centered at 3450, 3650, 3880, and 4348 Å. It has been shown that the unexpected effect of gas concentration on the quantum yields of the sulfur dioxide triplet-sensitized phosphorescence of biacetyl resulted largely from the significant destruction of biacetyl triplets at the wall of the cell. The kinetics of the variation of Φp with [Ac2], wavelength of the absorbed light, and added gases provide new estimates of the energy relations and the rate constants for the decomposition reaction of vibrationally rich biacetyl molecules in the first excited singlet state (1Ac2
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  • 17
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    A comparative kinetic study of the N-Nitrosation of sulfanilamide by cyclohexyl nitrite and by nitrous acid (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 235-242 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A comparative study of the kinetics of the N-nitrosation of sulfanilamide by cyclohexyl nitrite and by nitrous acid has been made, using an automated technique. The results indicate that a common nitrosating species is effective in analogous reactions involving cyclohexyl nitrite or nitrous acid. The N-nitrosation reaction has been followed spectrophotometrically by coupling the diazotized product with 1-naphthol. Under certain conditions a competitive reaction takes place in which coupling occurs with unreacted sulfanilamide.
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  • 18
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    The kinetics of the addition of trichloromethyl radicals to olefins in the gas phase. Recalculation of the data (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 243-247 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550040211
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  • 19
    Electronic Resource
    Electronic Resource
    Arrhenius parameters for the reactions of trichloromethyl radicals (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 249-252 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550040212
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  • 20
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    “Kinetic Equations” by Norman Rostoker, Gordon and Breach Science Publishers, Inc., New York, 1971, 346 pp (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 253-253 
    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.550040213
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  • 21
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    Masthead (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
    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.550040301
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  • 22
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    Very low-pressure pyrolysis: VI. The decomposition of ethyl acetateThis work was supported in part by the Environmental Protection Agency Grant AP 00353-07, Air Pollution Control Administration. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 265-271 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of ethyl acetate has been studied by the very low-pressure pyrolysis (VLPP) technique. The results obtained agree well with the previously determined high-pressure Arrhenius parameters where log k∞ = 12.6 - 48.0/θ. The rate constants given by these parameters have also been shown to be consistent with the predictions of the RRK and RRKM theories and demonstrate the applicability of the technique to the study of thermal decompositions.
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  • 23
    Electronic Resource
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    The second limit of hydrogen + carbon monoxide + oxygen mixtures (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 277-292 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Previous studies by Buckler and Norrish of the second limit of CO and O2 mixtures containing small amounts (0.25-10%) of H2 have been used to obtain the velocity constant of the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm O} + {\rm CO} + {\rm M = CO}_{\rm 2} + {\rm M}$$\end{document} These estimates of k33 = 3.9 × 108 and 3.5 × 108 liter2 mole-2 sec-1 (M = H2) at 500° and 560°C, respectively, have been combined with other estimates over the range 300°-3500°K to give k33 = 3.0 × 108 exp (-3000/RT) for M = Ar; the considerable scatter in the available points does not encourage any great confidence in this expression and may be attributed at least partly to the different molecules used as M by different workers. For KCl-coated and CsCl-coated vessels at 540°C, studies of the second limit of H2 + O2 mixtures, to which CO has been added, have indicated that with both the surfaces, the effect of CO on the limit is masked by changes in the surface nature. In the case of CsCl, the results have enabled a lower limit of about 0.6 to be obtained for the efficiency of CO relative to H2 in the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm H} + {\rm O}_{\rm 2} + {\rm M = HO}_{\rm 2} + {\rm M}$$\end{document} Use of a computer treatment to interpret the second limit of CO + H2 + O2 mixtures in aged boric-acid-coated vessels at 500°C gives a value of mCO = 0.74 ± 0.04 together with an estimate of k32 (H + CO + M″ = HCO + M″)/k4 = 0.022 ± 0.003, which leads to k32 = 2.3 × 108 liter2 mole-2 sec-1 (M = H2) at 500°C.
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  • 24
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    Abstraction by hydrogen atoms from ethylene, propylene, butene-1, and cis- and trans-butene-2 (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 315-324 
    Details
    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.
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    URL: http://dx.doi.org/10.1002/kin.550040308
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  • 25
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    Vibrational excitation of deuterium fluoride and hydrogen fluoride by atomic and diatomic species (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 293-306 
    Details
    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.
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  • 26
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    The reaction of O(1D) with CH4 (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 417-432 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The room-temperature photolysis of N2O (10-100 torr) at 2139 Å to produce O(1D) has been studied in the presence of CH4 (10-891 torr). The reactions of O(1D) with CH4 were found to be \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(4)} & {{\rm O(}^{\rm 1} D{\rm)} + {\rm CH}_{\rm 4} } & \to & {{\rm HO + CH}_{\rm 3} } & {0.95 \pm 0.05} \\ {(8)} & {} & \to & {{\rm O(}^{\rm 3} P{\rm)} + {\rm CH}_{\rm 4} } & {{\rm 0}{\rm .05} \pm {\rm 0}{\rm .05}} \\ {} & {} & \to & {{\rm CH}_{\rm 2} + {\rm H}_{\rm 2} {\rm O}} & {{\rm 〈 0}{\rm .03}} \\ {} & {} & \to & {{\rm CH}_{\rm 3} {\rm OH}} & {{\rm 〈 0}{\rm .01}} \\ {} & {} & \to & {{\rm CH}_{\rm 2} {\rm O + H}_{\rm 2}} & {{\rm 〈 0}{\rm .002}} \\\end{array}$$\end{document} The method of chemical difference was used to measure the rate constant ratio k4/(k2 + k3), where reactions (2) and (3) are \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(2)} & {{\rm O(}^{\rm 1} D{\rm)} + {\rm N}_{\rm 2} {\rm O}} & { \to {\rm N}_{\rm 2} + {\rm O}_{\rm 2} } \\ {(3)} & {} & { \to 2{\rm NO}} \\\end{array}$$\end{document} The CH3 radicals produced in reaction (4) react with the O2 and NO produced in reactions (2) and (3). Thus, near the endpoint of the internal titration, φ{C2H6} gives an accurate measure of k4/(k2 + k3). For the translationally energetic O(1D) atoms produced in the photolysis, k4/(k2 + k3) = 2.28 ± 0.20. However, if He is added to remove the excess translational energy, then k4/(k2 + k3) drops to 1.35 ± 0.3.
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  • 27
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    The reaction of OH with NO2 and the deactivation of O(1D) by CO (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 529-540 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: NO2 was photolyzed with 2288 Å radiation at 300° and 423°K in the presence of H2O, CO, and in some cases excess He. The photolysis produces O(1D) atoms which react with H2O to give HO radicals \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (3)}} & {{\rm O(}^{\rm 1} D{\rm)} + {\rm H}_{\rm 2} {\rm O} \to 2{\rm HO}} \\\end{array}$$\end{document} or are deactivated by CO to O(3P) atoms \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (5)}} & {{\rm O(}^{\rm 1} D{\rm)} + {\rm CO} \to {\rm O(}^{\rm 3} P{\rm) + CO}} \\\end{array}$$\end{document} The ratio k5/k3 is temperature dependent, being 0.33 at 300°K and 0.60 at 423°K. From these two points, the Arrhenius expression is estimated to be k5/k3 = 2.6 exp(-1200/RT) where R is in cal/mole - °K. The OH radical is either removed by NO2 \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (1)}} & {{\rm OH} + {\rm NO}_{\rm 2} {\rm (+M)} \to {\rm HNO}_{\rm 3} {\rm (+M)}} \\\end{array}$$\end{document} or reacts with CO \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (2)}} & {{\rm OH} + {\rm CO} \to {\rm H} + {\rm CO}_{\rm 2} } \\\end{array}$$\end{document} The ratio k2/kα is 0.019 at 300°K and 0.027 at 423°K, and the ratio k2/k0 is 1.65 × 10-5M at 300°K and 2.84 × 10-5M at 423°K, with H2O as the chaperone gas, where kα = k1 in the high-pressure limit and k0[M] = k1 in the low-pressure limit. When combined with the value of k2 = 4.2 × 108 exp(-1100/RT) M-1sec-1, kα = 6.3 × 109 exp (-340/RT)M-1sec-1 and k0 = 4.0 × 1012M-2sec-1, independent of temperature for H2O as the chaperone gas. He is about 1/8 as efficient as H2O.
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    The Reactions of H Atoms with H2S and COSThis work was supported in part by the Sulphur Research Institute and in part by the National Research Council of Canada. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 547-558 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reactions of H atoms with H2S and with COS were measured at 298deg;K in a flow system using mass-spectrometric detection. The rate constants were found to be 3.8 × 10-13 and 2.2 × 10-14 cm3 part-1 sec-1, respectively, with an estimated accuracy of 25%. At high flow rates of H2S, 0.5 molecules of H2S are consumed per H atom originally present. At all flow rates of COS, H2S is a major product, CO production equals COS consumption, and 0.5 molecules of COS are consumed per H atom. The results are consistent with the reaction HS + HS → H2S + S being the dominant process for thiyl radicals, and evidence is presented to indicate that its reaction rate is close to collisional frequency.
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    The Competitive dehydrohalogenation of 1,1,1-trifluoro-2-chloroethane in reflected shock wavesWork supported by the National Research Council of Canada. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 559-571 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of 1,1,1-trifluoro-2-chloroethane has been investigated in the single-pulse shock tube between 1120° and 1300deg;K at total reflected shock pressures from ∼2610 to 3350 torr. Under these conditions, the major reaction is the α,α-elimination of hydrogen chloride, \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CF}_{\rm 3} {\rm CH}_{\rm 2} {\rm Cl}\mathop {{\rm \rightarrow}}\limits^{k_1 } {\rm CF}_{\rm 2} {\rm CHF} + {\rm HCl}$$\end{document} with \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log(}k_1^\infty {\rm, sec}^{ - {\rm 1}} {\rm) = 13}{\rm .3} \pm {\rm 0}{\rm .4} - (65.5 \pm 2.2{\rm kcal})/2.303RT$$\end{document} The decomposition also involves the slower α,β-elimination of hydrogen fluoride, \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CF}_{\rm 3} {\rm CH}_{\rm 2} {\rm Cl}\mathop {{\rm \rightarrow}}\limits^{k_2 } {\rm CF}_{\rm 2} {\rm CHCl} + {\rm HF}$$\end{document} with the first-order rate constant given by \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log(}k_2^\infty {\rm, sec}^{ - {\rm 1}} {\rm) = 12}{\rm .7} \pm {\rm 0}{\rm .5} - (67.6 \pm 2.7{\rm kcal})/2.303RT$$\end{document} At temperatures above 1270°K, two additional minor products were observed. These were identified as CF2CFCl and CF3CHCl2 and suggest C—Cl rupture as a third reaction channel leading to complicated kinetics.
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    The rate of destruction of O2 (1Δg) by atomic hydrogen (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 255-264 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An analysis of the atmospheric observations of O2(1δg) in the dayglow and twilight confirms the crude experimental assessments of Brown [1] and the conclusions that can be made from recent work of Westenberg, Roscoe, and DeHaas [2] that the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm H} + {\rm O}_{\rm 2} (^1 \Delta g) \to {\rm OH} + {\rm O}$$\end{document} is relatively slow, much slower than was expected or can be explained easily in theoretical terms. Using a value for the concentration of atomic hydrogen at 85 km, an upper limit rate of 3×10-13 cm3 molecule-1 sec-1 would be compatible with current atmospheric models. An evaluation of the available data for the rates of several reactions involving ground state or electronically excited species, for which the values are reasonably well established, is included to better analyze the general effects of an electronically excited reactant. This further illustrates the unusual slowness of the H + O2(1Δg) reaction.
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    Reaction of H and D atoms with deuterated propylenes (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 307-314 
    Details
    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%.
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    Radical reactions of highly polar molecules. Chlorination of halopropanes (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 331-338 
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    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.
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    Computational modeling of the mechanisms of the free radical-chain reaction of alkanes with oxygen. The oxidation of isobutane, n-butane, and isopentane (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 345-362 
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    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.
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    Masthead (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
    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.550040401
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    The reaction of CH3N3 with C2H4. A homogenous, bimolecular processAbstracted from a Dissertation submitted by M. S. O'Dell, Jr. to the Graduate school of Arts and Sciences in partial fulfillment of the requirement for the Ph.D. degree of the Catholic University of America. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 363-365 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550040313
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    The reaction of C2F5 radicals with H2S (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 395-403 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of C2F5 radicals with H2S \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(2)} & {{\rm C}_{\rm 2} {\rm H}_{\rm 5} + {\rm H}_{\rm 2} {\rm S} \to {\rm C}_{\rm 2} {\rm F}_{\rm 5} {\rm H} + {\rm HS}} & {k_H } \\ \end{array}$$\end{document} was studied over the range 1°-123°C using C2F5 radicals generated by photolysis of perfluoropropionic anhydride. The rate constant kH for reaction (2) is given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_H ({\rm cm}^{\rm 3} {\rm mole}^{ - 1} \sec ^{ - 1}) = (11.70 \pm 0.19) - (4260 \pm 290)/\theta$$\end{document} where θ = 2.303RT/cal mole-1. The relevance of this result to conflicting published data on the analogous reaction between CF3 radicals and H2S is discussed. It is concluded that there is little difference in the Arrhenius parameters for reaction of CF3 and C2F5 radicals with H2S.
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  • 37
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    A flash photolysis-resonance fluorescence kinetics study of ground-state sulfur atoms: I. Absolute rate parameters for reaction of S(3P) with O2(3Σ). (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 367-382 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolysis-resonance fluorescence technique has been used to measure the reaction of ground-state sulfur atoms with molecular oxygen as a function of both temperature and total pressure. The most suitable source of S(3P) for this study was found to be COS in the presence of CO2, as a diluent gas and with the photolysis flash filtered so as to remove all radiation of wavelengths below 1650 Å. Under these conditions, it was found that over the temperature range of 252-423°K the rate data could be fit to a simple Arrhenius-type equation of the form \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = (2.24 \pm 0.27) \times 10^{ - 12} {\rm exp}\left({\frac{{{\rm - 0}{\rm .00} \pm {\rm 0}{\rm .10 kcal/mole}}}{{RT}}} \right)$$\end{document} Units are cm3 molec-1 s-1. The small A-factor for this reaction, the lack of any pressure dependence, and the direct observation of the production of O(3P) with increasing reaction time suggest that the S(3P) atom attacks the O2(3Σ) molecule end-on forming SOO which rapidly falls apart to form SO (3Σ) and O(3P).
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  • 38
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    Kinetics of the metathetical reaction between carbon tetrachloride and toluene (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 405-416 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A metathetical reaction between carbon tetrachloride and toluene to give benzyl chloride and chloroform occurs at temperatures above 200°C (k = 4.8 × 1010 e-32,900/RT cc mole-1sec-1). The reaction does not involve free radicals, as is shown by the kinetic behavior of the system, by the lack of effect of added free-radical chain inhibitors, and by the absence of the expected chain termination product, hexachloroethane. The reaction is one of a general type between carbon tetrachloride and alkanes or alkylaromatics, but at the temperatures required it is often obscured by dehydrohalogenation of the product to the highly reactive olefin. At high temperatures, benzyl chloride reacts with toluene to give bibenzyl and hydrogen chloride, apparently also by a metathetical reaction. The transition state is postulated to be four-center, in which the carbon-chlorine and carbon-hydrogen bonds are broken and reformed: The experimental preexponential factor is in good agreement with that calculated from transition-state theory.
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  • 39
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    Kinetics of the “a” and “b” band emissions of mercury excimers with added gases (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 449-461 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the “a” and “b” band emissions arising from the 1Σg+ ← 3Ou and 1Σg+ ← 3lu transitions of the diatomic mercury molecule at λmax ∼ 4850 Å and 3350 Å, respectively, have been studied at low concentrations of mercury in the presence of N2, C2H6, C3H8, and N2O. Rate constant values have been obtained for the following reactions of the excimer molecule: Hg2(3lu) + N2 → Hg2(3Ou) + N2 and Hg2(3Ou) + RH → Hg2(1Σg+) + RH, where RH = C2H6 or C3H8. From a consideration of the detailed kinetics of band emissions, it was also possible to derive rate constants for the quenching reactions of Hg(3P0) atoms. These values are in reasonable agreement with those obtained previously from monitoring atom concentrations directly by 4047 Å absorbiometry.
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    URL: http://dx.doi.org/10.1002/kin.550040408
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  • 40
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    The radiolysis of mixtures of carbon dioxide and hydrogenWork performed under the auspices of the U.S. Atomic Energy Commission. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 463-477 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The self-radiolysis of CO2 in excess tritium (3H2) has been studied at pressures of 0.1 to 1.0 atm, temperatures of -80° to +100°C, and in the presence of added H2O, He, or Ar. The primary products of decomposition are CO and 3H2O. Secondary products are C3H4, C23H4, and a white polymer. The rates of disappearance of CO2 and formation of products and G-;values were measured. The disappearance of CO2 initially obeys first-order kinetics, then slows down with time at a rate depending upon the initial pressure of 3H2. The initial rates are proportional to pressures of CO2 and 3H2. They are independent of temperature, decreased by addition of H2O vapor, and increased by addition of He or Ar. The proposed mechanism of decomposition of CO2 and formation of products involves ionization of CO2 followed by dissociative recombination forming CO and O. Then the O reacts with a hydrogen-containing species forming OH and H2O, and a back reaction forms CO2 from CO and OH.
    Additional Material: 6 Ill.
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  • 41
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    Masthead (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
    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.550040501
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  • 42
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    Rates of reaction of atomic oxygen with C2H3F, C2H3Cl, C2H3Br, 1,1-C2H2F2, and 1,2-C2H2F2 (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 521-527 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the reactions of atomic oxygen (O3P) with C2H3F, C2H3Cl, C2H3Br, 1,1-C2H2F2, and 1,2-C2H2F2 have been measured at 307°K using a discharge-flow system coupled to a mass spectrometer. The rate constants for these reactions are (in units of 1011 cm3 mole-1 s-1) 2.63 ± 0.38, 5.22 ± 0.24, 4.90 ± 0.34, 2.19 ± 0.18, and 2.70 ± 0.34, respectively. For some of these reactions, the product carbonyl halides were identified.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550040506
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  • 43
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    Pyrolysis of 4,4-bisperfluoromethylbutene-1,4 01 in the gas phase (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 541-545 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolysis of (CF3)2C(OH)CH2CH=CH2, the reverse of the reaction between perfluoroacetone and propene, has been studied in the gas phase between 475° and 598°K. Even at 573°K, the unimolecular reaction rate constant appears to be in its pressure-independent region at 20.0 torr pressure. In a quartz vessel, the decomposition is homogeneous. The specific unimolecular rate constant is \documentclass{article}\pagestyle{empty}\begin{document}$$k = T^{1/2} 10[^{(10.3 \pm 0.10) - (\frac{{40300 \pm 300}}{{4.575T}})}]\sec ^{ - 1}$$\end{document} where the limits are for one standard deviation. Combining these results with the previously reported results on the reverse reaction, the equilibrium constant for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm C}_{\rm 3} {\rm H}_{\rm 6} + {\rm CF}_{\rm 3} {\rm COCF}_{\rm 3} {\rm \rightleftharpoons(CF}_{\rm 3} {\rm)}_{\rm 2} {\rm C(OH)CH}_{\rm 2} {\rm CH = CH}_{\rm 2}$$\end{document} is \documentclass{article}\pagestyle{empty}\begin{document}$$k_p = 10[^{(1/4.575)(-34.0 \pm 1.0) + (\frac{{18700 \pm 400}}{T})}]atm^{ - 1}$$\end{document} It is noteworthy that in the temperature range of the study of the forward reaction (448° to 573°K), the percentage of back reaction in the times of the experiments varies from less than 0.1 to 1.5. Using group additivities and the above ΔH0, ΔHf0 of (CF3)2CO is calculated to be -325.2 kcal/mole at 600°K and the average C—C bond is 42.0 kcal/mole.
    Additional Material: 1 Tab.
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    Electronic Resource
    Masthead (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
    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.550040601
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    Table of the Kassel integralThis work was supported by the U.S. Air Force under Contract F04701-71-C-0172. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 591-637 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An e×tensive table is given of the Kassel integral \documentclass{article}\pagestyle{empty}\begin{document}$$I(S,B,D) = \Gamma \mathop {(S)}\limits^1 \int_0^\infty {\frac{{x^{S - 1} e^{ - x} dx}}{{1 + 10^D \left({\frac{x}{{B + x}}} \right)^{S - 1} }}}$$\end{document} that occurs in the Rice-Ramsperger-Kassel theory of unimolecular gas reactions.
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    URL: http://dx.doi.org/10.1002/kin.550040603
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  • 46
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    Decay kinetics of the triplet and anthrasemiquinone radicals in aqueous organic media (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 639-644 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electron transfer involving triplet molecules of anthraquinone sulfonates has been studied by flash photolysis. It was revealed that semiquinone radicals were formed in one-electron oxidation of carbonate anions. Absorption spectra and the kinetics of decay transients in aqueous and aqueous-alcoholic solutions have been studied.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550040604
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  • 47
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    The mechanism of thermal dehydrochlorination. Pyrolysis of 1-Chloro-1-fluoroethane and 1-chloro-1, 1-difluoroethane (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 645-655 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decompositions of 1-chloro-1-fluoroethane and 1-chloro-1,1-difluorethane at atmospheric pressure have been studied in the temperature range 500-600°C in a flow system. The dehydrochlorinations are homogenous in a carbonaceous reactor and unimolecular. The rate constants are given by \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm I} = 10^{13.94 \pm 0.05} \exp (- 57,015 \pm 200/RT)^{\sec - 1}$$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm II}} = 10^{14.35 \pm 0.12} \exp (- 60,200 \pm 500/RT)^{\sec - 1}$$\end{document} The criteria for molecular or chain processes in thermal dehydrochlorinations are discussed.
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    URL: http://dx.doi.org/10.1002/kin.550040605
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  • 48
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    The rate of dissociation of allyl iodide in shock wavesWork supported in part by the Army Research Office, Durham, N. C. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 87-102 
    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 allyl iodide has been measured from 742plusmn;K to 1068±K and from 169 to 1429 torr using a shock tube method in which the disappearance of allyl iodide and the appearance of iodine are followed simultaneously. The kinetics are first order in allyl iodide and probably are slightly dependent upon total pressure. Mathematical modeling shows that they are compatible with a mechanism consisting of three reactions: The experiments yield the rate constant k1, the high-pressure limiting value of which is found to be \documentclass{article}\pagestyle{empty}\begin{document}$$\log _{10} k_\infty (\sec ^{ - 1}) = (14.45 \pm 0.4) - (42.8 \pm 2.4{\rm kcal})/2.3RT$$\end{document} in reasonable agreement with that predicted using the methods of Benson and O'Neal [1].
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    URL: http://dx.doi.org/10.1002/kin.550040108
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  • 49
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    Bromination of dichloromethane, chlorofluoromethane, and dichlorofluoromethaneThis paper is part XXIV of the series “Free Radical Substitution in Aliphatic Compounds.” For part XXIII, see ref [1]. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 69-77 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dichloromethane, chlorofluoromethane, and dichlorofluoromethane have been brominated competitively with each other and with chloroform and methyl chloride. Using the literature values for the rates of bromination of these latter two compounds, the rate constants for the three former compounds have been determined: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} k_2 ({\rm CH}_{\rm 2} {\rm Cl}_{\rm 2} {\rm)} = (9.77 \pm 1.44) \times 10^9 \exp (- 10,860 \pm 480{\rm cal}/RT) \\ k_2 ({\rm CH}_{\rm 2} {\rm F Cl)} = (7.76 \pm 1.59) \times 10^{10} \exp (- 14,800 \pm 800{\rm cal}/RT) \\ k_2 ({\rm CHF Cl}_{\rm 2} {\rm)} = (1.05 \pm 1.48) \times 10^{10} \exp (- 13,300 \pm 570{\rm cal}/RT) \\ \end{array}$$\end{document} where R is taken to be 1.987 cal deg-1 mol-1 (1 cal = 4.186 J).
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  • 50
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    The reactions of C2F5 radicals with benzene in the vapor phase (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 79-86 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C2F5 radicals were generated in the presence of benzene vapor by the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$({\rm C}_{\rm 2} {\rm F}_{\rm 5} {\rm CO})_2 {\rm O} + hv \to {\rm CO} + {\rm CO}_2 + 2{\rm C}_{\rm 2} {\rm F}_5 $$\end{document} The radicals react with the benzene by addition and pseudo H abstraction The rate constant kadd for the addition reaction (7) is given by \documentclass{article}\pagestyle{empty}\begin{document}$$\log k_{add} /k_{c^{1/2} } {\rm cm}^{{\rm 3/2}} {\rm mole}^{ - 1/2} \sec ^{ - 1/2} = (4.49 \pm 0.10) - (4210 \pm 150)/\theta $$\end{document} where θ = 2.303RT cal/mole and kc is the rate constant for combination of C2F5 radicals. The addition becomes reversible above 110°C. The reactions of CF3 and C2F5 radicals with benzene vapor are compared.
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  • 51
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    The kinetics of the reactions of O(3P) atoms with dimethyl ether and methanol (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 103-116 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction of O + CH3OCH3 were investigated using fast-flow apparatus equipped with ESR and mass-spectrometric detection. The concentration of O(3P) atoms to CH3OCH3 was varied over an unusually large range. The rate constant for reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm O} + {\rm CH}_{\rm 3} {\rm OCH}_3 \to {\rm OH} + {\rm CH}_{\rm 2} {\rm OCH}_{\rm 3} $$\end{document} was found to be k = (5.0 ± 1.0) × 1012 exp [(-2850 ± 200/RT)] cm3 mole-1 sec-1. The reaction O + CH3OH was studied using ESR detection. Based on an assumed stoichiometry of two oxygen atoms consumed per molecule of CH3OH which reacts, we obtain a value of k = (1.70 ± 0.66) × 1012 exp [(-2,280 ± 200/RT)] cm3 mole-1 sec-1 for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm O} + {\rm CH}_{\rm 3} {\rm OH} \to {\rm OH} + {\rm CH}_{\rm 2} {\rm OH}$$\end{document} The results obtained in this study are compared with the results from other workers on these reactions. The observation of essentially equal activation energies in these two reactions is indicative of approximately equal C—H bond strengths in CH3OCH3 and CH3OH. This is in agreement with recent measurements of these bond energies.
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    Masthead (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972) 
    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.550040201
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  • 53
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    Kinetics of the thermal reaction of 1,1,2-trimethylcyclopropane (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 117-126 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction kinetics of 1,1,2-trimethylcyclopropane have been studied in the temperature range of 700-755°K. First-order unimolecular rate constants for over-all reactant disappearance fit the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log }k_0 {\rm (sec}^{ - {\rm 1}} {\rm)} = {\rm 14}{\rm .47} - \frac{{61.08 \pm 0.51}}{\theta }$$\end{document} Reaction products and the relative rates of their formation are found to be reasonably consistent with the biradical mechanism.
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    Rate constants for alkyl radical recombination. II. The isopropyl radical This work has been supported in part by Grant No. AP 00353-06 of the Environmental Protection Agency, Air Pollution Control Administration, and in part by an A.C.S.-P.R.F., Type D, grant. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 151-157 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Products of radical combination from the free-radical buffer system \documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}$${{\rm R}^{\rm .} + {\rm R}^{\rm '} {\rm I}\mathop {\leftrightharpoons}\limits^{{\rm K}_{{\rm RR}}}{\rm RI} + {\rm R}^{'}}$$\end{document}. have been analyzed for the two cases, R = Me, R′ = iPr and R = Et, R′ = iPr. Results are consistent with the previously examined system where R = Me, R′ = Et, and give a value of kP for iPr· combination of 108.6±1.1 M-1 sec-1.
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    URL: http://dx.doi.org/10.1002/kin.550040203
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    A quantitative study of alkyl radical reactions by kinetic spectroscopy. II. Combination of the methyl radical with the oxygen molecule (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 129-149 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}_{\rm 3} + {\rm O}_{\rm 2} (+ {\rm M}) \to {\rm CH}_{\rm 3} {\rm O}_{\rm 2} {\rm (+ M)}$$\end{document} have been studied, using the technique of flash photolysis and kinetic spectroscopy to follow the methyl radical concentration. The order of the reaction lies between 2 and 3 throughout the range of pressure from 25 to 380 torr at 22°C, and the results are consistent with a single reaction sequence: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} {\rm CH}_{\rm 3} + {\rm O}_{\rm 2} \mathop {{\rm \rightleftharpoons}}\limits_{\rm b}^{\rm a} {\rm CH}_{\rm 3} {\rm O}_{\rm 2} ^* \\ {\rm CH}_{\rm 3} {\rm O}_{\rm 2} ^* {\rm } + {\rm M}\mathop {{\rm \rightarrow}}\limits^{\rm c} {\rm CH}_{\rm 3} {\rm O}_{\rm 2} {\rm + M} \\ \\\end{array}$$\end{document} The limiting values of the third-order rate coefficients at low pressures are (3.6±0.3) × 1011 1.2 mole-2 sec-1 when M is neopentane, and (0.94 ± 0.03) × 1011 1.2 mole-2 sec-1 when M is nitrogen. The limiting value of the second-order rate coefficient at high pressures is (3.1 ± 0.3) × 108 1. mole-1 sec-1. The rate constant for the independent second-order reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}_{\rm 3} + {\rm O}_{\rm 2} \to {\rm CH}_{\rm 2} {\rm O} \to {\rm OH}$$\end{document} is shown to be not much greater than 2 × 105 1. mole-1 sec-1, so that this reaction does not complete significantly with the combination reaction.This new interpretation is contrary to currently accepted views.
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    The Gas-phase thermal unimolecular isomerization of n-propylidenecyclopropylamine to 5-ethyl-1-pyrroline (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 169-174 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase thermal isomerization of N-propylidenecyclopropylamine has been studied in the temerature range of 573° to 635°K. The reaction is homogeneous and kinetically first order and yields 5-ethyl-1-pyrroline as the sole product. The rate constants are independent of pressure in the range of 2.5 to 55 torr and fit the Arrhenius relationship log k(sec-1) = (14.05 ± 0.06) - (47.77 ± 0.16)/θ where θ = 2.303 RT in units of kcal/mole, or log k(sec-1) = (14.05 ± 0.06) - (199.9 ± 0.7)/θ, where θ = 2.303RT in kJ/mole. From considerations of a biradical pathway it is concluded that the resonance stabilization energy of the substituted 2-aza-allyl radical is very similar to that of the methallyl radical.
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  • 57
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    Secondary hydrogen isotope effect for the transition from olefin to free radical (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 325-330 
    Details
    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.
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  • 58
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    Carbon-nitrogen bond dissociation energy values in C-nitrosocompounds (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 339-343 
    Details
    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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    URL: http://dx.doi.org/10.1002/kin.550040311
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  • 59
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    Very low-pressure pyrolysis. VII. The decomposition of methylhydrazine, 1,1-dimethylhydrazine, 1,2-dimethylhydrazine, and tetramethylhydrazine. Concerted deamination and dehydrogenation of methylhydrazineThis work was supported in part by Air Force Rocket Propulsion Laboratory, Contract No. FO-4611-69-C-0096, and in part by the National Aeronautics and Space Administration Contract No. NAS7-472. (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 433-448 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants (kuni) for the first-order disappearance of the title molecules have been determined under VLPP conditions. The kuni are not the rate constants of ultimate interest since they reflect the fact that energy transfer competes with the chemical decomposition. Use of the Rice-Ramsperger-Kassel-(Marcus) [RRK(M)] theory allows the determination of the high-pressure rate constants (kα), if the mode of decomposition is known. The heats of formation of the radicals NH2, CH3NH, and (CH3)2N are known. These values should be usable for prediction of the activation energy for N—N bond homolysis in the hydrazines. Measured rate constants for UDMH and TMH bear this out, but the rate constant for MMH does not. This and other evidence lead to the conclusion that MMH decomposes via molecular concerted elimination of NH3 and H2 not and by N—N bond scission. The following values are preferred from this work (θ = 2.303RT in kcal/mole). Mode of decomposition is N - N bond scission unless noted otherwise in parenthesis: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{ll} \underline{{{{\rm Molecule}}}}& \underline{{{{\rm log }k_\infty /\sec ^{ - 1} (298^\circ {\rm K})}}}\\ {{{{\rm MMH}}}}&{{{13.2{\rm - }54/\theta (- {\rm NH}_{\rm 3});}}}\\ {} & {13.5{\rm - }57/\theta (- {\rm H}_{\rm 2})} \\ {{\rm UDMH}} & {17.0{\rm - }63/\theta } \\ {{\rm SDMH}} & {{\rm 13}{\rm .5 - 57/}\theta {\rm (} - {\rm H}_{\rm 2} {\rm)}} \\ {{\rm TMH}} & {{\rm 17}{\rm .4 - 54/}\theta } \\\end{array}$$\end{document}.
    Additional Material: 4 Ill.
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    Rate constants for radical recombination. III. The trifluoromethyl radicalThis work has been supported in part by Contract No. F44620-71-C-0103 of the Air Force Office of Scientific Research and in part by an A.C.S.-P.R.F., Type D, Grant (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 479-486 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Products of the radical reactions arising from t-Bu2O2, CF3I, and CH3I at 146°C in the vapor phase have been measured over a 33-fold range of CH3I/CH3I ratios and shown to be governed by the rapidly established equilibrium \documentclass{article}\pagestyle{empty}\begin{document}$${\rm Me} \cdot + {\rm CF}_{\rm 3} {\rm I}\mathop {{\rm \rightleftharpoons}}\limits^K {\rm MeI} + {\rm CF}_{\rm 3} \cdot$$\end{document} Together with K estimated by thermochemical methods, the results yield, for the rate of recombination for CF3· radicals, kr = 109.7 ± 0.5 M-1 sec-1.
    Additional Material: 4 Tab.
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    The kinetics of chemically induced dynamic nuclear polarization (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 513-520 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550040505
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  • 62
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    The thermal isomerization of cyclobutenes. XVI. 1,2-bis(trimethylsiloxy)cyclobutene (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 85-88 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase thermal isomerization of 1,2-bis(trimethylsiloxy)cyclobutene has been studied in the temperature range 172°-204°C. The reaction is homogeneous, kinetically first order, and yields 2,3-bis(trimethylsiloxy)buta-1,3-diene as the only product. The rate constants fit the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {k = 10^{13.509 \pm 0.120} \exp \left( {{{ - 148,920 \pm 1060\,{\rm J}\,{\rm mole}^{ - 1} } \mathord{\left/ {\vphantom {{ - 148,920 \pm 1060\,{\rm J}\,{\rm mole}^{ - 1} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right)\sec ^{ - 1} } \hfill \\ {\left[ {k = 10^{13.509 \pm 0.120} \exp \left( {{{ - 35,590 \pm 250\,{\rm cal mole}^{ - 1} } \mathord{\left/ {\vphantom {{ - 35,590 \pm 250\,{\rm cal mole}^{ - 1} } {RT}}} \right. \kern-\nulldelimiterspace} {RT}}} \right)\sec ^{ - 1} } \right]} \hfill \\ \end{array}$$\end{document} These results, taken with those obtained previously, demonstrate the insensitivity of the kinetics of the reaction to the nature of the groups substituted on the 1- and/or 2-positions of the cyclobutene ring.
    Additional Material: 1 Tab.
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    Computer simulation of cage processes and some difficulties with present models (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 97-104 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple model involving random displacements of particles in a cubic lattice is used to evaluate the importance of primary and secondary recombination in cage processes and leads to estimates of the lifetime of cage pehnomena. However, it is pointed out that all such models, and treatments which attempt to relate processes at the molecular level with bulk viscosity or diffusion constants, are inherently qualitative since they ignore the important correlation between motions of neighboring molecules.
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  • 64
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    Some aspects of theory and experiment in the ethane-methyl radical systemThis work was supported by the National Science Foundation. Abstracted in part from the Ph.D. Thesis of E.V.W. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 105-125 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A critical examination has been made of some aspects of the thermal decomposition of ethane and the reverse recombination reaction. The experimental Arrhenius A-factors for ethane are, in general, smaller than those which are calculated from thermodynamic quantities together with the observed rate constants for methyl recombination. Theoretical calculations also illustrate a discrepancy between the experimental work on recombination and decomposition. The experimental shapes of k/kα falloff curves and the pressure region of falloff are compared with the predictions of RRKM theory for various models.
    Additional Material: 2 Ill.
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  • 65
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    Rotating sector study of the gas phase photolysis of the 1,1,1-trichloro-2,2,2-trifluoroethane-cyclohexane systemWork based on the Ph.D. thesis by F. B. Wampler. Submitted to the University of Missouri, Columbia, Missouri, 1970. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 137-144 
    Details
    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).
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    Rotating sector study of the gas phase photolysis of the carbon tetrachloride-cyclohexane systemWork based on the Ph.D. thesis by M. L. White, submitted to the University of Missouri, Columbia, Missouri, 1969. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 127-136 
    Details
    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 trichloromethyl radicals in the gas phase has been measured by applying the rotating sector technique to the gas phase carbon tetrachloride-cyclohexane photochemical system. A temperature-independent rate constant, k5, of 3.9 ± 1.0 × 1012 cc mole-1 sec-1 was found. Arrhenius parameters for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CCl}_{\rm 3} + c - {\rm C}_{\rm 6} {\rm H}_{{\rm 12}} \mathop {\hbox to 30pt{\rightarrowfill}}\limits^{k_4 } {\rm CHCl}_{\rm 3} + c - {\rm C}_{\rm 6} {\rm H}_{{\rm 11}} $$\end{document} were found to be given by the expression log k4 = 11.79 - (10,700/2.3 RT).
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  • 67
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    The reaction of the hydroxyl radical with acetylene (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 145-153 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of OH with acetylene was studied in a discharge flow system at room temperature. OH was generated by the reaction of atomic hydrogen with NO2 and was monitored throughout the reaction using ESR spectroscopy. Mass-spectrometric analysis of the reaction products yielded the following results: (1) less than 3 molecules of OH were consumed, and less than 2 molecules of H2O were formed for every molecule of acetylene that reacted; (2) CO was identified as the major carbon-containing product; (3) NO, formed in the generation of OH, reacted with a reaction intermediate to give among other products N2O. These observations placed severe limitations on the choice of a reaction mechanism. A mechanism containing the reaction OH + C2H2 → HC2O + H2 better accounted for the experimental results than one involving the abstraction reaction OH + C2H2 → C2H + H2O. The rate constant for the initial reaction was measured as 1.9 ± 0.6 × 10-13 cm3 molecule-1 sec-1.
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  • 68
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    The addition of methyl radicals to hexafluoropropylene (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 155-160 
    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 hexafluoropropylene has been studied over the temperature range 81°-203°C using a mass-balance technique involving the photolysis of biacetyl in the presence of hexafluoropropylene-isobutane mixtures. For the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CH}_{\rm 3} + {\rm C}_3 {\rm F}_6 \to {\rm CH}_3 {\rm C}_{\rm 3} {\rm F}_6$$\end{document} the rate constant is given by the equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}k{\rm (in mole}^{- {\rm 1}} {\rm cm}^{\rm 3} {\rm sec}^{- {\rm 1}} {\rm) = (12}{\rm .04} \pm {\rm 0}{\rm .06)} - \frac{{6200 \pm 110}}{{2.303RT}}$$\end{document} The result suggests that methyl radicals are very unselective in their behavior reacting with tetrafluoroethylene and hexafluoropropylene at similar rates. This is in marked contrast to the behavior of oxygen atoms with these olefins.
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    Abstraction of hydrogen by methyleneThis work was partially supported by the U.S. Atomic Energy Commission and the National Aeronautics and Space Administration. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 293-305 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of CD2CO at 313 nm in the presence of neopentane was carried out over the temperature range 576-706 K. Analysis of the products and isotopic analysis of the methanes demonstrate abstraction of H from neopentane and D from CD2CO by methylene. The relative kinetics of abstraction of H and D have been measured over the temperature range, and the absolute value for the collision yield of the abstraction of H from neopentane by CD2 at 653 K has been been estimated to be about 1.5 × 1011 mole-1 cm3 sec-1, a value 103 times larger than the corresponding reaction of CH3.
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  • 70
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    The reactions of CF3 and CD3 radicals with boron trimethyl (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 307-317 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hydrogen abstraction from boron trimethyl has been studied using the abstracting radicals CF3 and CD3, from the photolysis of the corresponding ketones over the temperature range of 150° to 300°C. The following Arrhenius parameters were obtained: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} {\rm (CD}_{\rm 3} {\rm + BME}_{\rm 3} {\rm); log }A{\rm = 11}{\rm .8, }E{\rm = 9}{\rm .98 kcal/mole} \\ {\rm (CF}_{\rm 3} {\rm + BMe}_{\rm 3} {\rm); log }A{\rm = 11}{\rm .6, }E{\rm = 6}{\rm .59 kcal/mole} \\ \end{array}$$\end{document} The difference ECD3 - ECF3 in the case of BMe3 is considered due, in part, to polar effects. An exchange reaction is proposed for both CF3 and CD3 in collisions with BMe3: \documentclass{article}\pagestyle{empty}\begin{document}$${\rm R} + {\rm B}({\rm Me})_3 \to {\rm Me} + {\rm RBMe}_2$$\end{document} Radical combination of CF3 and CH2BMe2 leads to a hot molecule which undergoes a β-fluoro rearrangement elimination process, or a stabilized molecule which can thermally decompose:
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    The mercury-sensitized oxidation of carbon monoxide (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 319-341 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mercury-photosensitized oxidation of CO was studied at 275°C over a wide range of [O2]/[CO] ratios in the absence and presence of the oxygen atom scavenger 2-trifluoromethylpropene (TMP) and at 25°C at low [O2]/[CO] ratios in the presence of TMP. By following the quantum yield of CO2 production, Φ {CO2}, as a function of the [O2]/[CO] ratio, the reactions of vibrationally excited CO (v υ 9) and electronically excited O2, probably in the c1Σ-u state, were studied. At low [O2]/[CO] ratios the predominant reactions are of vibrationally excited CO (v υ 9). Relative rate constants for chemical reaction versus deactivation of CO (v υ 9) were obtained. At higher [O2]/[CO] ratios, the principal reactions are of electronically excited O2. Relative rate constants for chemical reactions and deactivation of this electronically excited O2 with CO, O2, and TMP were obtained. From the effect of total pressure on Φ {CO2}, it is proposed that an intermediate CO3 is formed in the reaction of electronically excited O2 with CO.
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    The free-radical reaction of tri-n-butyltin hydride with peroxidesIssued as NRCC Number 12000. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 343-357 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the tri-n-butyltin radical (Sn ·) induced decomposition of a number of peroxides have been measured in benzene at 10°C. The values range from ∼100 M-1 sec-1 for di-t-butyl peroxide to 2.6 × 107 M-1 sec-1 for di-t-butyl diperoxyisophthalate. The majority of the peroxides, including diethyl peroxide, diacetyl peroxide, and t-butyl peracetate, have rate constants of ∼105 M-1 sec-1. It is shown that di-n-alkyl disulfides are ten times as reactive toward Sn · as di-n-alkyl peroxides, although the exothermicities of these reactions are ∼15 and ∼39 kcal/mole, respectively. The enhanced reactivity of the disulfides is attributed to the easier formation of an intermediate or transition state with 9 electrons around sulfur, compared with an analogous species with 9 electrons around oxygen.The following bond strengths (kcal/mole) have been estimated: D[Sn—OR] = 77; D[Sn—H] = 82; D[Sn—SR] = 83; and D[Sn—OC(O)R] = 86, where R = alkyl. Rate constants for reaction of Sn · with some benzyl esters have also been measured. It has been found that t-butoxy radicals can add to benzene and abstract hydrogen from benzene at ambient temperatures.
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    Report on the international colloquium on chemically induced dynamic nuclear polarization and its impact on the study of reaction mechanisms, Brussels, Belgium, March 18-19, 1971 (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 375-376 
    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.550030407
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    Orientation of addition of hydrogen atoms to propylene, butene-1, and isobutene (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 395-410 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The orientation of addition of H atoms to the asymmetric olefins propylene, butene-1, and isobutene has been determined as a function of atom concentration, olefin concentration, hydrogen pressure, total pressure, and olefin conversion. Conditions have been determined for which complicating secondary processes are believed to be unimportant. The percentage of nonterminal addition is 5.7, 5.7, and 0.48 for propylene, butene-1, and isobutene, respectively. From these data activation energy differences between nonterminal and terminal addition of 1.7 and 3.2 kcal/mole for the linear olefins and isobutene, respectively, may be calculated. For D atom addition to propylene, a small isotope effect was observed, nonterminal addition being 5.4%. These observations are consistent with a predominantly free radical or electroneutral character for H atoms.
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    Reactions of radicals. XXVI. On the use of activation parameters as a test for concerted decomposition of initiatorsAbstracted in part from the Ph.D. Dissertation of Kennedy Smith, Louisiana State University, Baton Rouge, August 1969. This work was partially supported by Grant GM 11908 from the National Institutes of Health, U.S. Public Health Service. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 387-394 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In 1958, Bartlett and Hiatt [1] suggested that the number of bonds which are rotationally “frozen” at the transition state for decomposition of peresters can be determined from the magnitude of the values of ΔH
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  • 76
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    Kinetics of the thermal gas phase reactions of 1,2-epoxy-2-methylpropane (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 443-452 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase decomposition of 1,2-epoxy-2-methylpropane has been studied over the temperature range 377°-436°C at pressures between 5.3 and 61.6 torr. Isomerization reactions to give isobutyraldehyde, isopropenyl methyl ether, and 2-methyl-prop-2-en-l-ol account for over 95% of the epoxide decomposition. These isomerizations are homogeneous first-order, nonradical processes: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} k({\rm isobutyraldehyde)} = {\rm 10}^{{\rm 13}{\rm .32} \pm {\rm 0}{\rm .18}} \exp (- 52720 \pm 570/1.987T)\sec ^{- 1} \\ {\rm}k({\rm isopropenyl methyl ether)} = {\rm 10}^{{\rm 13}{\rm .55} \pm {\rm 0}{\rm .47}} \exp (- 56140 \pm 1460/1.987T)\sec ^{- 1} \\ {\rm}k({\rm 2 - methyl - prop - 2 - en - l - ol)} = {\rm 10}^{{\rm 11}{\rm .53} \pm {\rm 0}{\rm .67}} \exp (- 49680 \pm 2080/1.987T)\sec ^{- 1} \\ \end{array}$$\end{document}
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  • 77
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    Masthead (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971) 
    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.550030601
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  • 78
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    Masthead (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/kin.550030501
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  • 79
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    A preliminary study of the reaction between nitrous oxide and nitrogen dioxide (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 381-383 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 80
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    The reactions of O(3P) with ozone and carbonyl sulfide (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 467-482 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The competitive reactions between 2-trifluoromethylpropene (TMP) and OCS for O(3P) atoms were studied between 300° and 523°K, using the mercury-senstitized photolysis of N2O as a source of O(3P). From the known value for the rate constant of the O(3P) + TMP reaction, k3 was found to be 1.6 × 10-11 exp (-4500/RT) cm3/particle-sec, where reaction (3) is \documentclass{article}\pagestyle{empty}\begin{document}$${\rm (3) O(}^{\rm 3} {\rm P)} + {\rm OCS} \to {\rm CO} + {\rm SO}$$\end{document}Mixtures of O3 and OCS were photolyzed at 197°, 228°, 273°, and 299°K with radiation above 4300 Å to produce O(3P) from the photolysis of O3, and thus study the competition between reaction (3) and \documentclass{article}\pagestyle{empty}\begin{document}$${\rm (1)O(}^{\rm 3} {\rm P)} + {\rm O}_{\rm 3} \to 2{\rm O}_{\rm 2}$$\end{document} From the above value of k3, k1 could be computed. When combined with all the previous data, the best espression for k1 is k1 = 1.2 × 10-11 exp (-4300/RT) cm3/particle-sec.
    Additional Material: 6 Ill.
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    Chemically activated 3-methyl-l-butene and 2-methyl-l-butene from photolysis of diazomethane-isobutene-neopentane-oxygen mixturesThe National Science Foundation is gratefully acknowledged for financial support. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 453-465 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An experimental study of the decomposition kinetics of chemically activated 2-methyl-l-butene and 3-methyl-l-butene produced from photolysis of diazomethane-isobutene-neopentane-oxygen mixtures is reported. The experimental rate constants for 3-methyl-l-butene decomposition were 1.74 ± 0.44 × 108 sec-1 and 1.01 ± 0.25 × 108 sec-1 at 3660 and 4358 Å, respectively. 2-Methyl-l-butene experimental decomposition rate constants were found to be 5.94 ± 0.59 × 107 sec-1 at 3660 Å and 3.42 ± 0.34 × 107 sec-1 at 4358 Å. Activated complex structures giving Arrhenius A-factors calculated from absolute rate theory of 1016.6 ± 0.5 sec-1 for 3-methyl-l-butene and 1016.2 ± 0.4 sec-1 for 2-methyl-l-butene, both calculated at 1000°K, were required to fit RRKM theory calculated rate constants to the experimental rate constants at reasonable E0 and E* values. Corrected calculations (adjusted E0 values) on previous results for 2-pentene decomposition gave an Arrhenius A-factor of 1016.45 ± 0.35 sec-1 at 1000°K. The predicted A-factors for these three alkene decompositions giving resonance-stabilized methylully radicals are in good internal agreement. The fact that these A-factors are only slightly less than those for related alkane decompositions indicates that methylallylic resonance in the decomposition products leads to only a small amount of tightening in the corresponding activated complexes. This tightening is a significantly smaller factor than the large reduction in the critical energy due to resonance stabilization.
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  • 82
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    Multistage reactions, equilibrium, and detailed balancing: A linear algebra approach (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 491-499 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methods of linear algebra are applied to (a) the problem of determining whether detailed balancing for some or all stages of a chemical process is implicit from the existence of steady state for some or all of the chemical species involved, and (b) the formulation of general concentration-type equilibrium relationships solely from kinetic considerations and the assumption of full detailed balancing.
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  • 83
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    The reactions of O(1D) with ozone and nitrous oxide (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 501-508 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ozone was photolyzed at room temperature in the presence of N2O at 2537 Å and 2288 Å to produce O(1D) atoms. These atoms can react with either O3 or N2O via From the quantum yield of N2, the relative rate constants k6a/k6 and k2/k6 could be obtained, where k6 + k6a + k6b. The former rate constant ratio was found to be 0.37 ± 0.03 at 2537 Å and 0.33 ± 0.03 at 2288 Å, in good agreement with an earlier report from our laboratory. The ratio k2/k6 was found to be 2.6 at 2537 Å, but 4.1 at 2288 Å. The difference in the two numbers, if real, may reflect differences in reactivity due to different amounts of excess translational energy in the O(1D) atom at the two wavelengths.
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    Second international symposium on gas kinetics, July 5-9, 1971, University College of Swansea, United Kingdom (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 553-554 
    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.550030608
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  • 85
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    Disproportionation-combination ratios of small alkyl radicals formed by the mercury-photosensitized hydrogenation of olefins in the gas phase (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 523-534 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Disproportionation-combination ratios have been obtained for small alkyl radicals produced in the mercury-photosensitized hydrogenation of ethylene, propylene, butene-1, butene-2, and isobutene. For conditions favoring thermalized radicals, kd/kc (ethyl, ethyl) = 0.14, kd/kc (isopropyl, isopropyl) = 0.69, kd/kc (isopropyl, n-propyl) = 0.41, kd/kc (2-butyl, 2-butyl) = 0.77, kd/kc (2-butyl, n-butyl) = 0.45, and kd/kc (t-butyl, t-butyl) = 3.1. The results are consistent with kd/kc (n-propyl, n-propyl) = 0.15 and kd/kc (n-butyl, n-butyl) = 0.14. The general agreement between these disproportionation-combination ratios and those obtained where photolytic radical sources have been used indicates that under appropriate conditions, H atom addition to olefins is a suitable source for the study of thermalized alkyl radicals and may be especially useful for larger alkyl radicals for which clean photolytic precursors are not available.
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    Disproportionation-combination ratios of large branched alkyl radicalsThis work was supported by the Office of Naval Research. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 535-551 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The disproportionation-combination reactions of radicals 4,4-dimethylpentyl-2 and 2,4-dimethylpentyl-2, produced by collisional stabilization of the respective chemically activated species, have been studied at 298°K, with and without getter radicals. Use of getters t-C4H9 and C2H5 with 4,4-dimethylpentyl-2, and of iso-C3H7 with 2,4-dimethylpentyl-2 yielded disproportionation-combination ratios ω for parent-getter and t-C4H9-C2H5 cross reactions, and for the mutual reaction of t-C4H9 radicals. The unstabilized hot radicals decompose, and these experiments also yielded values for the high-pressure rate constant ka∞ of 1.70 × 108sec-1 and 2.11 × 107sec-1 for 4,4-dimethylpentyl-2 and 2,4-dimethylpentyl-2, respectively. The results, compared to those for other large alkyl radical systems obtained earlier, suggest that steric effects influence the accessibility of H atoms for transfer.
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    Kinetics of the gas phase reaction of methyl benzoate with bromine and iodine: The methoxyl C—H bond strength of methyl estersThis work supported in part by Grant No. 00353-06 from the Environmental Protection Agency, Air Pollution Control Administration. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 509-522 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas phase reactions of PhCOOCH3 with I2 and Br2 were studied spectrophotometrically in a static system over the temperature ranges 344-359° and 246-303°, respectively. For each system the initial rate was first order in PhCOOCH3 and half order in halogen as the concentration of PhCOOCH3 was varied from 1.4 to 15.2 torr, that of I2 from 6.2 to 26.4 torr, and that of Br2 from 3.0 to 13.6 torr. The rate-determining step is the extraction of a methoxyl hydrogen atom: Empirical assignment of A-factors for k1 lead to \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(k}_{\rm 1} {\rm /M}^{- {\rm 1}} {\rm sec}^{- {\rm 1}} {\rm) = (11}{\rm .5} \pm {\rm 0}{\rm .3)} - (29.9 \pm 0.8)/\theta $$\end{document} for the I2 system, and to \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(k}_{\rm 1} {\rm /M}^{- {\rm 1}} {\rm sec}^{- {\rm 1}} {\rm)} = {\rm (11}{\rm .3} \pm {\rm 0}{\rm .3)} - (14.6 \pm 0.8)/\theta $$\end{document}for the Br2 system, where φ = 2.303RT in kcal/mole. Combined with the assumption that E-1 = 1 ± 1 kcal/mole and 2 ± 1 kcal/mole for HI and HBr, respectively, DH2980 (PhCOOCH2—H) calculated from the two systems shows excellent agreement at 100.2 ± 1.3 kcal/mole and 100.1 ± 1.3 kcal/mole. Using a value of δHf,2980 (PhCOOMe) = -65.6 ± 1.5 kcal/mole obtained from group additivity estimates, δHf,2980 (PhCOOCH2) is calculated to be -16.7 ± 2.0 kcal/mole. Unimolecular decomposition of the Ph(CO)O°CH2 radical was also observed: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Ph}\left( {{\rm CO}} \right){\rm O\dot CH}_{\rm 2} \mathop {\hbox to 20pt{\rightarrowfill}}\limits^3 {\rm Ph\dot CO} + {\rm H}_{\rm 2} {\rm CO} $$\end{document} with a rate constant equal to \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log(}k_{\rm 3} {\rm /sec}^{- {\rm 1}} {\rm)} = {\rm (15} \pm {\rm 0}{\rm .5)} - (26 \pm 3)/\theta $$\end{document} The abnormally high methoxyl C—H bond strength is discussed in relation to the bonding in ethers, alkanes, and esters.
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    Masthead (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971) 
    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.550030101
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  • 89
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    Some particular aspects of the low-temperature oxidation of methane initiated by nitric acid (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 15-23 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: During methane oxidation initiated by nitric acid or nitrogen dioxide, it is possible to observe, under certain conditions of temperature, initiator content, and flow rates, the formation of an adiabatic “temperature peak.” Because the maximum temperature of the peak does not exceed the initial temperature of the reactor by more than 220°C, the recorded temperature-increase curves were used for a kinetic interpretation. The obtained kinetic parameters (overall n and E) agree with the values reported in the literature for isothermal methane oxidation and suggest that the overall mechanism does not change in the conditions of “temperature peak.”
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  • 90
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    Chemically activated 1,1-dimethylcyclopropane from photolysis of isobutene-neopentane-diazomethane-oxygen mixtures (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 25-37 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study of the structural isomerization rate of chemically activated 1,1-dimethylcyclopropane from singlet methylene addition to the double bond of isobutene is reported. Singlet methylenes were produced from the 4358- and 3660-Å photolysis of diazomethane in the presence of added oxygen. Theoretical rates calculated via RRKM theory are in excellent agreement with experiment for calculations utilizing activated complex structures and critical energies consistent with known thermal Arrhenius parameters, and excitation energies consistent with previous determinations of ΔHf00(CH2) + E*(CH2) = 116.1 and 112.6 kcal/mole for diazomethane photolyses at 3660 and 4358 Å, respectively.
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  • 91
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    Hydrogen abstraction reactions from organosilicon compounds. The reactions of fluoromethyl radicals with trichlorosilane. The photolyses of di- and tetrafluoroacetone (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 1-14 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolyses of 1,3-difluoro- and 1,1,3,3-tetrafluoroacetone have been reinvestigated as sources of fluoromethyl radicals, and the following rate constant ratios were determined θ= 2.303 RT in kcal/mole. The results are in substantial agreement with the original investigations. The photolyses of the fluoroacetones were used as sources of CH2F and CHF2 radicals, and the following Arrhenius parameters were obtained for the hydrogen abstraction reactions R + SiHCl3 → RH + SiCl3: TextRT(°K)E (kcal/mole)log A (mole-1 cc sec-1)log k (400°K) (mole-1 cc sec-1)CH2F335-4436.06 ± 0.1510.79 ± 0.087.48 CHF2CHF2334-4426.82 ± 0.0911.32 ± 0.057.59The rates of reactions of CH2F and CHF2 radicals toward hydrogen abstraction from SiHCl3 are an order of magnitude lower than the corresponding rates for the CH3, C2H5, and CF3 radicals as a result of increased activation energies for the CH2F and CHF2 reactions. The interpretation of the results is hindered by a lack of accurate thermochemical data on the radicals. The activation energies, as they stand, can be rationalized in terms of a polar repulsion between SiHCl3 and the radicals, increasing regularly and leading to a progressive increase in activation energy with increasing fluorine substitution in the radical. This interpretation is consistent with the estimates D(CH2F—H) ∝ D(CHF2—H) ∝ 97 kcal/mole. On the other hand, there is some indication, from the spread of A-factors in the series of fluoromethyl radicals reacting with SiHCl3, that internal compensation of Arrhenius parameters is occurring in some of the reactions; and when this is taken into account, the interpretation of activation energies is more difficult.
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    A critical review of the kinetics of the dissociation-recombination reactions of fluorine and chlorineThis work was supported by the Office of Standard Reference Data, N.B.S., and the Naval Ordnance Systems Command ORD 3311 as part of a program to foster production of tables of chemical kinetics. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 39-68 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A critical evaluation of the rates of the dissociation and recombination reactions of fluorine and chlorine is given. Data are presented graphically and in tabular form. The effect of various third bodies is discussed. Rate expressions for specified temperature ranges are recommended, while comparison with theoretical values obtained from the Benson and Fueno theory is made where applicable.
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    Hydrogen abstraction from organosilicon compounds. The reactions of fluoromethyl radicals with tetramethylsilane. Polar effects in gas phase reactions (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 69-84 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of 1,1,3,3-tetrafluoroacetone has been reinvestigated as a source of CHF2 radicals at temperatures up to 578°K, and the following rate constant ratio was determined for the reactions θ= 2.303 RT in kcal/mole. 1,1-Difluoro- and 1,1,3,3-tetrafluoroacetone were photolyzed in the presence of tetramethylsilane, and Arrhenius parameters were measured for the hydrogen abstraction reactions: R + Me4Si → RH + Me3SiCH2 TextRT(°K)E (kcal/mole)log A (mole-1cc sec-1)log k (500°K) (mole-1cc sec-1)CH2F473-58612.00 ± 0.3011.68 ± 0.126.44CHF2416-52610.18 ± 0.3311.65 ± 0.157.21By comparing with previous data on the CH3 and CF3 reactions, the activation energies were interpreted in terms of the enthalpy changes for the reactions and a polar effect operative between the attacking fluoromethyl radicals and the substrate which tends to reduce the activation energy progressively as the fluorine content of the radical increases. This polar effect, which decreases the activation energy for hydrogen abstraction from SiMe4 along the series CH3, CH2F, CHF2, and CF3, is in marked contrast to the polar repulsion between the fluorinated radicals and SiHCl3 which was tentatively proposed to explain the increase in activation energy observed in the same series of reactions with SiHCl3.
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    Chlorine-photosensitized oxidations of chloroethanes and chloroethylenes in the gas phase (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 89-96 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Long-chain chlorine-photosensitized oxidation has been observed in the gas phase at about 355°K for 1,1,2,2- and 1,1,1,2-C2H2Cl4, C2HCl5, and C2Cl4 but not for C2H6, 1,2-C2H4Cl2, 1,1,1-C2H3Cl3, C2H4, and 1,2-C2H2Cl2. This is shown to depend on the exothermicity of the dissociation of the chloroethoxy radicals which must be involved in each reaction system.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030108
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  • 95
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    Masthead (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971) 
    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.550030201
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  • 96
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    The arrhenius factors for some six-center unimolecular reactionsContribution No. 486 from the Research Council of Alberta, Edmonton, Canada (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 187-193 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Pyrolysis of ethyl formate has been carried out in the temperature range 557°-630° and the rate expression k = 1012.34 e-48,100±500/RT sec-1 was obtained, in agreement with the prediction of O'Neal and Benson [1]. Calculated Arrhenius A-factors and experimental rate constants have been used to obtain the activation energies for the decomposition of the following compounds by the six-center molecular mechanism (in kcal/mole): 2-pentanone 59; methoxyacetone, 58; 2,4-pentanedione, 51; methyl butyrate, ≥ 70; 1-heptene, 54, and 4-methyl-1-hexene, 54-55.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030210
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  • 97
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    Quenching cross sections for the deactivation of metastable mercury 6 (3P0) (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 175-186 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By monitoring the relative concentrations of mercury 3P0 atoms using absorption photometry, absolute rate constants have been measured for the excimer-forming reaction Hg (3P0) + Hg + N2 → Hg2* + N2 and for the quenching of Hg (3P0) atoms by ethane, propane, deuterated propanes, and nitrous oxide.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030209
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  • 98
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    Rates and mechanism of alkyne ozonationThis paper presents the results of one phase of research carried out at the Jet Propulsion Laboratory, California Institute of Technology, under Contract No. NAS 7-100, sponsored by the National Aeronautics and Space Administration. (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 161-173 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates and products of the reactions of ozone with acetylene, methylacetylene, dimethylacetylene, and ethylacetylene have been studied in a long-path infrared cell at 21 ± 1°C. The gas phase reaction gives products formed by cleavage of the carbon-carbon triple bond. A mechanism is proposed that involves formation of a short-lived acid anhydride intermediate, which is energized by virtue of the reaction exothermicity and undergoes unimolecular decomposition. Formation of an α-dicarbonyl was observed in every case, but there is evidence that a side reaction on the walls accounted for that product. The general relationship between alkyne and alkene ozonation is discussed. The rate measurements showed that, unlike the alkenes, the rate of alkyne ozonation is not greatly affected by substitution with simple alkyl groups. The rate constant for C2H2 agrees with earlier work and thus provides additional support for the previously derived high A-factor for acetylene ozonation relative to alkenes.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030208
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  • 99
    Electronic Resource
    Electronic Resource
    Masthead (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971) 
    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.550030301
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  • 100
    Electronic Resource
    Electronic Resource
    The pyrolysis of neopentane at small extents of reaction (1971)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 3 (1971), S. 197-213 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of neopentane, at small extents of reaction, was studied by gas chromatography, in Pyrex reaction vessels between 450° and 530°C and in the initial pressure range 25-200 mm Hg. At initial time, this thermal decomposition can be essentially represented by a homogeneous long-chain radical mechanism. The rate constant of the unimolecular initiation process is approximately given by the expression \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 0} \simeq 10^{13} {\rm exp}\left({\frac{{50,000}}{{RT}}} \right){\rm mole}^{- {\rm 1/2}} {\rm .ml}^{- {\rm 1/2}} {\rm .s}^{- {\rm 1}}$$\end{document} The initial rate constant of the global reaction (order 3/2) is nearly equal to \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 1} + 10^{16.8} {\rm exp}\left({\frac{{82,000}}{{RT}}} \right){\rm s}^{- {\rm 1}}$$\end{document} This reaction is strongly inhibited by propene or isobutene and self-inhibited by the isobutene formed; an interpretation of all these inhibition phenomena of the neopentane pyrolysis is proposed. Our observations and conclusions, which have been summarized in communications during 1968 and 1969, are compared to those of other authors, particularly to the recent ones of Purnell and colleagues [13] and of Taylor and colleagues [14], [15].
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550030302
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