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  • 1980-1984  (117)
  • 1900-1904
  • 1890-1899
  • 1983  (117)
  • 1902
  • Physical Chemistry  (117)
  • 101
    Electronic Resource
    Electronic Resource
    Pyrolysis studies of main group metal-alkyl bond dissociation energies: VLPP of GeMe4, SbEt3, PbEt4, and PEt3 (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 167-185 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bond dissociation energies of tetramethyl germane, triethyl stibine, tetraethyl lead, and triethylphosphine were determined using the technique of very-low-pressure pyrolysis. Arguments are presented for log A ≥ 17.0. The respective dissociation energies ΔH298 are 83, 57, 54, and 68 (±2) kcal/mol. A consistent set of methyl bond energies to main group metals is determined from these and previous results, and is examined for trends. Bond energies for various radicals to tin are also derived.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150207
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  • 102
    Electronic Resource
    Electronic Resource
    Relative rate constants for removal of vibrationally excited OH(X2πi)v=9 by some small molecules at room temperature (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 151-165 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vibrationally excited OH in v = 9 [designated OH†(9)] was generated by the reaction of hydrogen atoms with ozone in a fast-flow discharge system at 300 ± 3 K and a total pressure of 1.1 ± 0.1 torr, with argon as the carrier gas. The addition of a species X, which can deactivate the OH†(9) or react with it, led to a decrease in the Meinel band chemiluminescent emission intensities at both 626 nm (9 → 3 band) and 519 nm (9 → 2 band), which were monitored as a function of the concentration of X. Application of the kinetic scheme developed previously for this chemical system gave the relative rate constant for the removal of OH†(9) by X. The relative rate constants determined in this study, taking O2 as the reference deactivator (kO2 = 1.0), are as follows: He ≤ 0.02; H2 ≤ 0.05; SF6 0.09 ± 0.01; CF4 0.19 ± 0.01; N2O 3.5 ± 0.4; NO 17.7 ± 1.5; H2O 74.3 ± 2.9; D2O 57.6 ± 2.0; NH3 61.3 ± 1.9; ND3 58.7 ± 1.6; SO2 7.1 ± 1.4; COS 8.4 ± 1.7; H2S 33.7 ± 8.4; CH4 1.56 ± 0.03; CD4 1.06 ± 0.06. Application of these relative rate constants to conditions in the upper atmosphere (60-100 km) suggests that OH†(9) is removed primarily by deactivation by O2, and at altitudes ≳90 km, possibly by O(3P). However, since O2 is unusually efficient for a homonuclear diatomic in deactivating OH†(9), it may not be the primary deactivator for the lower (v ≤ 8) vibrational levels. These results are compared to earlier studies of OH†(9), and possible mechanisms of interaction of OH†(9) with these molecules are discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150206
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  • 103
    Electronic Resource
    Electronic Resource
    Reaction of pentafluoroethyl radicals with hydrogen cyanide (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 187-196 
    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 HCN has been studied over the range of 533-673 K using the pyrolysis of pentafluoroethyl iodide as the free-radical source. Arrhenius parameters for the reaction relative to C4F10 recombination are given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_{\rm H} /k_{c^{1/2} } = (5.36 \pm 0.15) - (57.3 \pm 1.8)/\theta $$\end{document} where θ = 2.303RT kJ/mol and kH/kc1/2 is in cm3/2/mol1/2·s1/2.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150208
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  • 104
    Electronic Resource
    Electronic Resource
    Intramolecular hydrogen isotope effect in the pyrolysis of diethyl carbonate-1,1,1,2,2-d5 (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 461-468 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal unimolecular decomposition of diethyl carbonate-1,1,1,2,2-d5 has been examined in the high-pressure-limiting region. The observed chemistry is consistent with a simple, competitive two-channel model: The intramolecular isotope effect kH/kD has been determined, and the relative Arrhenius parameters for the two channels are given by \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{\rm H} /k_D = (0.80 \pm 0.18)\,\exp [(1140 \pm 260){\rm cal/mol/RT}] $$\end{document} over the temperature range of 540-620 K. These Arrhenius parameters predict an isotope effect kH/kD = 5.4 at 300 K.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150506
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  • 105
    Electronic Resource
    Electronic Resource
    The use of transition-state theory to extrapolate rate coefficients for reactions of OH with alkanes (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 503-504 
    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.550150509
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  • 106
    Electronic Resource
    Electronic Resource
    Masthead (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983) 
    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.550150601
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  • 107
    Electronic Resource
    Electronic Resource
    Rate of formation of toluene from ethylbenzene (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 469-474 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of formation of toluene from ethylbenzene was studied at atmospheric pressure in the temperature range of 600-725°C in conventional flow equipment. Residence times were 0.55-1.7 s, and initial partial pressures of ethylbenzene (H2O diluent) were 0.05-0.17 atm. The rate of appearance of toluene measures [1] the rate of the reaction C6H5C2H5 → C6H5CH3· + CH3·, with log k = 15.70 - 74.49 ± 3.2/θ. From the activation energy, E0 for the decomposition is estimated to be 72.2 ± 3.2 kcal/mol. The results are compatible with those of Esteban et al. [2], for which regression analysis gives log k1 = 14.79 - 70.76/θ. A composite, log k = 15.10 - 72.0/θ, fits both sets of data and is experimentally indistinguishable from Robaugh and Steina's [3] recent estimate by the VLPP technique or other estimates in the literature [4-6]. In light of the high overall conversion of ethylbenzene studied (2-80%), the industrial-type flow equipment, and the widely differing methods of characterization and analysis, the excellent agreement with the results of [2,3,5] is worthy of note. The data are compatible with current estimates of the heat of formation of benzyl radicals [6,7].
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150507
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  • 108
    Electronic Resource
    Electronic Resource
    The thermal decomposition of n-hexane (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 475-502 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the pyrolysis of n-hexane was studied in a conventional static reactor over a temperature range of 650-840 K. The overall reaction is essentially first order with the kinetic parameters A = 1013.92 s-1 and EA = 260.3 kJ/mol. The distributions of the main products were analyzed by gas chromatography. A reaction model involving 240 elementary reactions was developed to describe the experimental rate data. The agreement of the model with experimental data was surprisingly good over a wide range of temperatures and pressures and up to medium extents of conversion. Methods for sensitivity studies based upon the quasi-stationary-state assumption (QSSA) were developed, and for a number of more detailed effects, such as self-inhibition, explanations could be given. It was also shown that the hexyl isomerization reactions influence strongly the product distribution. The outstanding capability of kinetic modeling with computer simulations in handling complex kinetic systems is demonstrated.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150508
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  • 109
    Electronic Resource
    Electronic Resource
    Kinetics of gas-phase decomposition of oxetan and oxetan-2,2-d2 (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 505-519 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pressure dependence of the first-order rate coefficient of oxetan and oxetan-2,2-d2 decomposition has been studied in the pressure range from about 7 kPa down to 0.01 kPa at various temperatures between 673 and 758 K. Experimental data were analyzed using RRKM theory. Interpretation of the fall-off curves lends support to the high-pressure Arrhenius parameters A = 1015.42s-1 and EA = 259.5 kJ/mol derived from measurements made in the pressure-independent range. Decomposition of oxetan is found to occur via biradical intermediates. Data for the kinetic isotope effect were used to derive kinetic parameters for the ring-opening elementary steps in oxetan and oxetan-d2 decomposition.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150602
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  • 110
    Electronic Resource
    Electronic Resource
    The kinetics of secondary reactions in the iodination of monogermane. The effect of iodine substitution on the Ge—H bond dissociation energy (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 561-568 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A study has been made both of secondary reactions occurring during the reaction of I2 with GeH4, and of the direct reaction between I2 and GeH3I. Both these studies show that the abstraction reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm I}^ \cdot + {\rm GeH}_{\rm 3} {\rm I} \to {\rm \dot GeH}_{\rm 2} {\rm I + HI} $$\end{document} occurs about 30 times faster than the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm I}^ \cdot + {\rm GeH}_{\rm 4} \to {\rm \dot GeH}_{\rm 3} {\rm + HI} $$\end{document} in the temperature range of 425-446 K. This information is used to show that iodine substitution weakens Ge-H bonds by 14.4 ± 2.5 kJ/mol and that D(H2IGe—H) = 332 ± 10 kJ/mol (79.3 kcal/mol). Possible reasons for the effects of halogen substituents on Ge—H and Si—H bond strengths are discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150606
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  • 111
    Electronic Resource
    Electronic Resource
    Masthead (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983) 
    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.550150701
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  • 112
    Electronic Resource
    Electronic Resource
    Rate constants for the gas-phase reactions of OH radicals with β-dimethylstyrene and acetone. Mechanism of ββdimethylstyrene NOx - air photooxidation (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 579-586 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants of gas-phase reactions of the hydroxyl radical with β-dimethylstyrene and acetone have been determined by a relative method at 298 K. The values obtained are β-dimethylstyrene (3.3 ± 0.5) × 10-11 cm3/molecule·s and acetone (6.6 ± 0.9) × 10-13 cm3/molecule·s. A simplified kinetic treatment of the experimental data shows that β-dimethylstyrene is stoichiometrically converted to benzaldehyde and acetone. In the photooxidation study of benzaldehyde, carbon dioxide was the only detected product. The ratio between carbon dioxide produced and benzaldehyde reacted was ≥1.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150608
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  • 113
    Electronic Resource
    Electronic Resource
    Kinetics of the gas-phase reaction CH3F + I2 ⇆ CH2FI + HI: The C—H bond dissociation energy in methyl and methylene fluorides (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 569-577 
    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 reaction of CH3F with I2 have been studied spectrophotometrically from 629 to 710 K, and were determined to be consistent with the following mechanism: A least-squares analysis of the kinetic data taken in the initial stages of reaction resulted in \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_4 (M^{ - 1} \cdot s^{ - 1}) = (11.3 \pm 0.1) - (30.8 \pm 0.2)/\theta $$\end{document} where θ = 4.575T/1000 kcal/mol. The errors represent one standard deviation. The experimental activation energy E4 = 30.8 ± 0.2 kcal/mol was combined with the assumption E3 = 1 ± 1 kcal/mol and estimated heat capacities to obtain \documentclass{article}\pagestyle{empty}\begin{document}$$ \Delta H_r^\circ (4,g,298K) = 30.0 \pm 1{\rm kcal}/{\rm mol} $$\end{document} The enthalpy change at 298 K was combined with selected thermochemical data to derive \documentclass{article}\pagestyle{empty}\begin{document}$$ DH^\circ ({\rm CH}_{\rm 2} {\rm F} - {\rm H}) = 101.2 \pm 1{\rm kcal/mol} $$\end{document} The kinetic studies of ĊHF2 and CH2F2 have been reevaluated to yield \documentclass{article}\pagestyle{empty}\begin{document}$$ DH^ \circ \left( {{\rm CHF}_{\rm 2} - {\rm H}} \right) = 103.2 \pm 1\,{{{\rm kcal}} \mathord{\left/ {\vphantom {{{\rm kcal}} {{\rm mol}}}} \right. \kern-\nulldelimiterspace} {{\rm mol}}} $$\end{document} These results are combined with literature data to yield the C—H, C—F, and C—Cl bond dissociation energies in their respective fluoromethanes, and the effect of α-fluorine substitution is discussed.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150607
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  • 114
    Electronic Resource
    Electronic Resource
    TI(III) oxidation of alkenes and alkynes and Ru(III) catalysis in the oxidation of alkenes: A kinetic and mechanistic study (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 587-602 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of trans-stilbene, phenylacetylene, and diphenylacetylene by Tl(OAc)3 in aqueous acetic acid medium in the presence of HClO4 follows the rate law \documentclass{article}\pagestyle{empty}\begin{document}$$ -\frac{{d[{\rm TI(OAc})_3]}}{{dt}} = k_2 [{\rm substrate}][{\rm TI(OAc}_3)]H_0 $$\end{document} in [H+] of 0.1-1.0M, the [H+] dependence below 0.1M being marginal. The reactions are strongly dielectric dependent. The order of reactivity among the substrates is styrene 〉 phenylacetylene and trans-stilbene 〉 diphenylacetylene. A mechanism involving the oxythallation adduct by the Tl+(OAc)2 species has been discussed. The use of Ru(III) as a homogeneous catalyst brings a change in the kinetic orders for trans-stilbene, the rate law being \documentclass{article}\pagestyle{empty}\begin{document}$$ -\frac{{d[{\rm TI(OAc})_3]}}{{dt}} = \frac{{kK[{\rm substrate}][{\rm Ru(III})][{\rm TI(OAc})_3]^\circ }}{{1 + K[{\rm substrate}]}} $$\end{document} The formation constants K for the Ru(III)-alkene π complex at 40, 50, and 60°C are 90.14M-1, 105.2M-1, and 127.7M-1, respectively. Interestingly the oxidation of phenylacetylene and diphenylacetylene does not undergo catalysis by Ru(III). The mechanism involving the metal-arene π complex is discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150609
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  • 115
    Electronic Resource
    Electronic Resource
    A reexamination of the pyrolysis of bis trifluoromethyl peroxide. Addendum: Concerning D(CF3O2-CF3) and D(CF3-O2) (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 605-607 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Earlier arguments concerning D(CF3O2-CF3) and D(CF3-O2) are shown to be probably wrong. New values of 86 and 49 kcal/mol, respectively, are derived. C-O bond strengths are compared between CF3- and CH3-containing compounds.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150702
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  • 116
    Electronic Resource
    Electronic Resource
    Induced heterogeneity, a novel technique for the study of gas-phase reactions. 2. Direct study of C—C bond scission in ethane (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 845-853 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Deliberate activation of the reaction vessel surface leads to the domination of chain termination in ethane pyrolysis by the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ (5) {\rm H} \to \frac{1}{2}{\rm H}_2 $$\end{document}As a result, chains are dramatically reduced in length, methane yields are entirely primary and larger in proportion to other products, and values of k1 \documentclass{article}\pagestyle{empty}\begin{document}$$ (1){\rm C}_2 {\rm H}_6 \to 2{\rm CH}_3 $$\end{document} can be directly determined from methane yield data without ambiguity. Experiments carried out in the temperature range of 841-913K at initial ethane pressures of 1-20 torr, without and with added nitrogen, yield the infinite pressure Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}k_{\rm 1} ({\rm s}^{ - 1}) = 16.52 \pm 0.44 - 87900 \pm 1760{\rm cal}/{\rm mol}/2.303RT $$\end{document}It is shown that most previously published data can be combined with those of this study to yield \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}k_{\rm 1} ({\rm s}^{ - 1}) = 16.63 \pm 0.18 - 88400 \pm 720{\rm cal}/{\rm mol}/2.303RT $$\end{document}Fall-off curves for k1 as a function of pressure are in good agreement with those from other laboratories. From these the relevant data for k-1 can be extracted for use in other kinetic studies.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150813
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  • 117
    Electronic Resource
    Electronic Resource
    Sensitivity analysis in chemical kinetics by the method of polynomial approximations (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 959-987 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new approach, the method of polynomial approximations (PAM), to the sensitivity analysis in chemical kinetics is presented. The method is based on first dividing the time domain of interest into subintervals, and then, within each subinterval, using low-degree interpolation polynomials to mimic the system temporal behavior. This procedure forces all parametric dependences of the system to reside in the expansion coefficients and transforms the differential sensitivity equations into a set of algebraic ones. The major computational effort of PAM is proportional to the number of components in the system, not to the number of parameters. In addition, higher order sensitivity coefficients in PAM can be generated quite readily once first-order ones are known. The information required to divide the time domain comes from a preliminary simulation study of the system temporal behavior, which is always available in any kind of modeling studies. Typically, for an interpolation polynomial of degree 3-4, only 10-20 subintervals are needed to attain satisfactory accuracy. The application of PAM is well suited to large-scale kinetic models, especially when an inexpensive scanning of the system sensitivity behavior is desired. The extremely high computational speed of PAM in securing sensitivity informations was demonstrated by two illustrative kinetic examples. Furthermore the problem of utilizing sensitivity information to unravel the functional dependence of a species concentration upon rate coefficients, to simplify a complex reaction model, and to elucidate mechanistic details of a reaction process was examined in detail.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151003
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