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  • 1980-1984  (117)
  • 1983  (117)
  • Physical Chemistry  (117)
  • Nuclear reactions
  • 1
    Electronic Resource
    Electronic Resource
    Rate constants for the gas-phase reactions of OH radicals with a series of bi- and tricycloalkanes at 299 ± 2 K: Effects of ring strain (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 37-50 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the gas-phase reactions of OH radicals with a series of bi- and tricyclic alkanes have been determined at 299 ± 2 K, using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with cyclohexane of 7.57 × 10-12 cm3/molec·s, the rate constants obtained are (× 1012 cm3/molec·s): bicyclo[2.2.1]heptane, 5.53 ± 0.15; bicyclo[2.2.2]octane, 14.8 ± 1.0; bicyclo[3.3.0]octane, 11.1 ± 0.6; cis-bicyclo[4.3.0]nonane, 17.3 ± 1.3; trans-bicyclo[4.3.0]nonane, 17.8 ± 1.3; cis-bicyclo[4.4.0]decane, 20.1 ± 1.4; trans-bicyclo[4.4.0]decane, 20.6 ± 1.2; tricyclo[5.2.1.02,6]decane, 11.4 ± 0.4; and tricyclo[3.3.1.13,7]decane, 23.2 ± 2.1. These data show that overall ring strain energies of ≲4-5 kcal mol-1 have no significant effect on the rate constants, but that larger ring strain results in the rate constants being decreased, relative to those expected for the strain-free molecules, by ratios which increase approximately exponentially with the overall ring strain.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150105
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics of the reactions of O3 and OH radicals with furan and thiophene at 298 ± 2 K (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 51-61 
    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 O3 and OH radicals with furan and thiophene have been determined at 298 ± 2 K. The rate constants obtained for the O3 reactions were (2.42 ± 0.28) × 10-18 cm3/molec·s for furan and 〈6 ×10-20 cm3/molec·s for thiophene. The rate constants for the OH radical reactions, relative to a rate constant for the reaction of OH radicals with n-hexane of (5.70 ± 0.09) × 10-12 cm3/molec·s, were determined to be (4.01 ± 0.30) × 10-11 cm3/molec·s for furan and (9.58 ± 0.38) × 10-12 cm3/molec·s for thiophene. There are to date no reported rate constant data for the reactions of OH radicals with furan and thiophene or for the reaction of O3 with furan. The data are compared and discussed with respect to those for other alkenes, dialkenes, and heteroatom containing organics.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150106
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  • 3
    Electronic Resource
    Electronic Resource
    Mechanism and thermochemistry of oxidation of HCl and HBr at high temperatures. The heat of formation of HO2 (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 341-380 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using currently available thermochemical and kinetic data and estimation methods to analyze the thermochemistry and the kinetic parameters of the elementary reactions involved in the oxidation of HCl and HBr, reaction mechanisms are proposed which account for the previously reported reaction products, the rate law, and the kinetic data. For oxidation of HCl, two competitive pathways, the radical initiation by hydrogen abstraction and the fourcenter reaction pathway, were invoked to account for the observations. In the oxidation of HBr one must invoke a fast surface reaction of the type \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm H}_2 {\rm O}_2 + {\rm HBr}({\rm S}) \to 2{\rm H}_2 {\rm O} + {\rm Br}_2 ({\rm g}) $$\end{document} to account for the reaction.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150404
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  • 4
    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.550150501
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  • 5
    Electronic Resource
    Electronic Resource
    Investigation of the thermal isomerization of 1α,25-dihydroxycholecalciferolGeneric name is calcitriol. by nuclear magnetic resonance spectroscopy (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 381-395 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This investigation of the kinetics and thermodynamics of the thermal isomerization reaction of 1α,25-dihydroxycholecalciferol, the physiologically active metabolite of vitamin D3, is based on the simultaneous determinations of 1α,25-(OH)2D3 and its previtamin analog by nuclear magnetic resonance spectroscopy which distinguishes these compounds from possible impurities. The kinetics at different temperatures are used to obtain the activation parameters for the sigmatropic [1,7] thermal interconversion process which is shown to be compatible with a reaction that is unimolecular and concerted. The nature of the transition state of the activated complex, the reaction energetics, and the relative stabilities of 1α,25-(OH)2D3 and vitamin D3 are discussed.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150405
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  • 6
    Electronic Resource
    Electronic Resource
    Kinetics of the thermal gas-phase dimerization of hexafluoropropene (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 537-546 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reversible thermal gas-phase dimerization of hexafluoropropene to the four isomeric cyclobutanes has been studied by pressure change and by gas-liquid chromatographic analysis in the temperature range of 645-708 K with initial pressures of olefin from 802 to 4820 mm Hg. The reaction was accurately second order at low conversions of olefin to dimers, and at higher conversions it gave a very good fit to the rate equation for opposing second- and first-order reactions. The rate constants for the dimerization, calculated from initial rates of reaction, yielded the least-mean-squares Arrhenius equation (95% confidence limits): \documentclass{article}\pagestyle{empty}\begin{document}$$ \log _{10} (k_2 /{\rm dm}^3 {\rm mol}^{ - 1} s^{ - 1}) = (5.93 \pm 0.40) - (131.8 \pm 9.5)k{\rm J\,\,mol}^{{\rm - 1}}/RT\ln \,10 $$\end{document} where k2 is defined by \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{ - 1/2{\rm d}[{\rm C}_3 {\rm F}_6]}}{{dt}} = \frac{{{\rm d}[c - {\rm C}_6 {\rm F}_{12}]}}{{dt}} = k_2 [{\rm C}_3 {\rm F}_6]^2 $$\end{document} Studies carried out in a packed vessel showed no evidence of heterogeneity. The rate constants found in this work are in excellent agreement with those found at lower pressures by Atkinson and Tsiamis, and the combined results give the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \log _{10} (k_2 /{\rm dm}^{\rm 3} {\rm mol}^{{\rm - 1}} {\rm s}^{{\rm - 1}}) = (6.47 \pm 0.21) - (138.6 \pm 2.7){\rm kJ\,mol}^{{\rm - 1}} {\rm /}RT\ln 10 $$\end{document}
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150604
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  • 7
    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.550150101
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  • 8
    Electronic Resource
    Electronic Resource
    Announcement (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 107-107 
    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.550150110
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  • 9
    Electronic Resource
    Electronic Resource
    Kinetics of the gas-phase reactions of OH radicals with a series of α,β-unsaturated carbonyls at 299 ± 2 K (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 75-81 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the reaction of OH radicals with a series of α,β-unsaturated carbonyls have been determined at 299 ± 2 K, using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with propene of 2.52 × 10-11 cm3/molec·s, the rate constants obtained are (× 1011 cm3/molec·s: acrolein, 1.83 ± 0.13; crotonaldehyde, 3.50 ± 0.40; methacrolein, 2.85 ± 0.23; and methylvinylketone, 1.88 ± 0.14). These data, which are necessary input to chemical computer models of the NOx-air photooxidations of conjugated dialkenes, are discussed and compared with literature values.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150108
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetics of the reaction: 2C2H4 → C2H5 + C2H3· heat of formation of the vinyl radical (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 83-104 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The initial rates of formation of the major products in the thermal reactions of ethylene at temperatures in the neighborhood of 800 K have been measured in the presence and absence of the additives neopentane and ethane. It has been shown that in the absence of the additive the main initiation process is while in the presence of neopentane and ethane the following additional initiation processes occur: From the ratios of the rates of formation of the major products in the presence and absence of the additive the ratios kN/k1 and kE/k1 were measured over the temperature range of 750-820 K. Taking values from the literature for kN and kE, the following value was obtained for k1: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 ({\rm L}/{\rm mol} \cdot {\rm s}) = 11.27 \pm 0.6 - \frac{{64,200 \pm 2000}}{{2.3RT}} $$\end{document} Previous results using butene-1 as additive were rexamined and shown to be consistent with this measurement. From this measurement the following values were derived: ΔHf(C2H3) = 63.4 ± 2 kcal/mol and D(C2H3—H) = 103 kcal/mol.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150109
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  • 11
    Electronic Resource
    Electronic Resource
    Kinetics of dialin thermolysis (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 219-233 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The liquid-phase thermolysis of 1,2-dihydronaphthalene was studied in a batch reactor in the range of 350-400°C. The measured product distributions were in good agreement with calculations based on a free-radical scheme with rate constants estimated by thermochemical methods. The kinetic calculations were carried out by numerical integration and by the long-chain approximation (LCA), which yielded a closed-form solution.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150303
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  • 12
    Electronic Resource
    Electronic Resource
    Gas-phase elimination kinetics of 1-substituted ethyl acetates. Effect of polar substituents at the α carbon of secondary acetates (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 205-218 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase elimination of several polar substituents at the α carbon of ethyl acetates has been studied in a static system over the temperature range of 310-410°C and the pressure range of 39-313 torr. These reactions are homogeneous in both clean and seasoned vessels, follow a first-order rate law, and are unimolecular. The temperature dependence of the rate coefficients is given by the following Arrhenius equations: 2-acetoxypropionitrile, log k1 (s-1) = (12.88 ± 0.29) - (203.3 ± 2.6) kJ/mol (2.303RT)-1; for 3-acetoxy-2-butanone, log ±1(s-1) = (13.40 ± 0.20) - (202.8 ± 2.4) kJ/mol (2.303RT)-1; for 1,1,1-trichloro-2-acetoxypropane, log ℜ1 (s-1) = (12.12 ± 0.50) - (193.7 ± 6.0) kJ/mol (2.303RT)-; for methyl 2-acetoxypropionate, log ℜ1 (s-1) = (13.45 ± 0.05) - (209.5 ± 0.5) kJ/mol (2.303RT)-1; for 1-chloro-2-acetoxypropane, log ℜ1 (s-1) = (12.95 ± 0.15) - (197.5 ± 1.8) kJ/mol (2.303RT)-1; for 1-fluoro-2-acetoxypropane, log ℜ1 (s-1) = (12.83 ± 0.15)- (197.8 ± 1.8) kJ/mol (2.303RT)-1; for 1-dimethylamino-2-acetoxypropane, log ℜ1 (s-1) = (12.66 ± 0.22) -(185.9 ± 2.5) kJ/mol (2.303RT)-1; for 1-phenyl-2-acetoxypropane, log ℜ1 (s-1) = (12.53 ± 0.20) - (180.1 ± 2.3) kJ/mol (2.303RT)-1; and for 1-phenyl-3-acetoxybutane, log ℜ1 (s-1) = (12.33 ± 0.25) - (179.8 ± 2.9) kJ/mol (2.303RT)-1. The Cα—O bond polarization appears to be the rate-determining process in the transmition state of these pyrolysis reactions. Linear correlations of electron-releasing and electron-withdrawing groups along strong σ bonds have been projected and discussed. The present work may provide a general view on the effect of alkyl and polar substituents at the Cα—O bond in the gas-phase elimination of secondary acetates.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150302
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  • 13
    Electronic Resource
    Electronic Resource
    Kinetics of electrophilic brominations. Mechanistic significance of the third-order term (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 249-266 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of electrophilic bromination of various donors follow complex kinetics which include both first-order and second-order dependences on bromine, especially in the less polar solvents. The second-order rate constant ks and the third-order rate constant kt are evaluated for alkene bromination in carbon tetrachloride, and they are compared to those already listed for the electrophilic brominations of substituted styrenes, arenes, and metal carbonyls in the extant literature. Despite the varying magnitudes of the second- and third-order rate constants for these diverse donors (and in different solvents), the ratio log(ks/kt) is remarkably invariant. The mechanistic implication of this unique observation is discussed in the context of charge transfer interactions which are common to the activated complexes in the electrophilic brominations of various donors.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150305
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  • 14
    Electronic Resource
    Electronic Resource
    The kinetics and mechanisms of elementary NF2 reactions with O and N atoms (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 399-415 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A combined EPR-LMR spectrometer with a fast-flow system has been used to investigate the kinetics and mechanisms of NF2 reactions with O and N atoms at 298 K. The overall rate constants of these reactions are: k0 = (2.8 ± 0.4) × 10-11 cm3/s and kN = (5.7 ± 0.8) × 10-11 cm3/s. The stoichiometry of the reactions with respect to O, N, NF2, F, and NO has been determined. The statistical theory of bimolecular reactions has been used for interpretation of the results obtained.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150502
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  • 15
    Electronic Resource
    Electronic Resource
    Complex rate law for the cerium(IV) oxidation of glycolic acid in the medium HClO4-Na2SO4-NaClO4 (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 417-432 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the cerium(IV) oxidation of glycolic acid have been studied in the medium HClO4—Na2SO4—NaClO4 at varying organic substrate (HL), hydrogen, and bisulfate ion concentrations at 25.0°C and ionic strength 2.0M. Under the experimental conditions used (0.03 ≤ [H+] ≤ 0.5M; 0.02 ≤ [HSO4-] ≤ 0.1M; 0.01 ≤ [HL] ≤ 0.1M) the observed pseudo-first-order rate constant kobs has been found to follow the complex expression where the values of the various constants have been estimated by a nonlinear least-squares method. According to this expression the oxidation process occurs significantly through three simultaneous pathways. Moreover three equilibria involving cerium(IV) and HSO4- (or SO42-) ions are important from a kinetic point of view, whereas only two equilibria involving the corresponding complexes with the organic substrate are predominant.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150503
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  • 16
    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.
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    URL: http://dx.doi.org/10.1002/kin.550150506
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  • 17
    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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  • 18
    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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  • 19
    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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  • 20
    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.
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    URL: http://dx.doi.org/10.1002/kin.550150607
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  • 21
    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.
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    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.
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  • 23
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    Electronic Resource
    Kinetics and mechanism of osmium(VIII)-catalyzed oxidation of D-proline and L(-)-methionine by hexacyanoferrate(III) (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 669-676 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The osmium(VIII)-catalyzed oxidation of D-proline and L(-)-methionine by alkaline hexacyanoferrate(III) has been studied spectrophotometrically. The reactions follow kinetics different from those of the oxidation of many amino acids investigated earlier, being first order in hexacyanoferrate(III) and osmium(VIII). The order in proline or methionine and OH- decreases from unity to zero at higher concentrations of proline or methionine and OH-, respectively. A mechanism consistent with the kinetic data is proposed and discussed.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150708
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  • 24
    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.550150801
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  • 25
    Electronic Resource
    Electronic Resource
    Sensitivity analysis and parameter estimation in dynamic modeling of chemical kinetics (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 677-696 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new approach to the dynamic modeling of chemical kinetics is presented. The technique is based on systematic planning of computer experiments, which allows an empirical model for the computed responses to be developed in the space of parameters. The empirical equations which are obtained provide complete information on the sensitivities with respect to various rate constants, disclosing their interrelationships. Utilization of these equations instead of numerical integration of the differential equations associated with the chemical reactions makes parameter estimation a trivial task. As a consequence the adequacy of the mechanism can be tested. The technique is applied to the thermal decomposition of propane.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150709
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  • 26
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    Electronic Resource
    Kinetic analysis of an extended single-path sequence of first-order reactions. The reaction of mesitonitrile in sulfuric acid (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 697-703 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The system of a sequence of five first-order reactions, A → B → C → D → E → F, has been analyzed kinetically. An actual example is proposed in the reaction of mesitonitrile in 89.8% (w/w) sulfuric acid at 98.3°C. The analysis provides estimates of concentration ratios as functions of time, and the progress of the buildup and decay of the intermediate species can be monitored. The kinetics have been measured for the hydration of mesitonitrile, the hydrolysis of mesitamide, and the sulfonation of mesitylenesulfonic acid in 89.8% sulfuric acid. The calculated values of the concentration ratios of mesitylenedisulfonic acid as a function of time were satisfactorily close to those found in experiment.
    Additional Material: 4 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550150802
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  • 27
    Electronic Resource
    Electronic Resource
    Theoretical rate constant calculations for O(3P) with saturated hydrocarbons (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 705-719 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Theoretical rate constants have been calculated for O(3P) with five saturated hydrocarbons, CH4, C2H6, C3H8, iso-C4H10, and neo-C5H12. The method of choice is bond energy-bond order (BEBO) with activated complex theory (ACT). Because the BEBO method is empirical, O(3P) + CH4 is evaluated first, and the theoretical results are compared to more rigorous calculations and to the empirical transition state method. Comparisons are also made between predictions and experimental results. All of these comparisons show that the BEBO-ACT method gives results which are consistent with experiment and other theory. Because the method is successful, the other four cases are then considered. Ambiguity arises for the higher hydrocarbons from the problem of internal rotations in the activated complexes, and three cases are evaluated. Best agreement with experiment is obtained if the primary rotor(s) in the complexes are considered to be free. Predictions of rate constants are made from 500 to 2500 K. Throughout the discussion issues of theory which are common to any ACT calculation from any method of potential energy evaluation (LEP, LEPS, or ab initio quantum mechanics) are featured.
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    URL: http://dx.doi.org/10.1002/kin.550150803
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  • 28
    Electronic Resource
    Electronic Resource
    Effects of ring strain on gas-phase rate constants. I. Ozone reactions with cycloalkenes (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 721-731 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the gas-phase reactions of O3 with a series of cycloalkenes and with cis-2-butene have been determined at 297 ± 1 K. The rate constants obtained were (in units of 10-16 cm3/molecule·s): cis-2-butene, 1.38 ± 0.16; cyclopentene, 2.75 ± 0.33; cyclohexene, 1.04 ± 0.14; cycloheptene, 3.19 ± 0.36; 1,3-cyclohexadiene, 19.7 ± 2.8; 1,4-cyclohexadiene, 0.639 ± 0.074; bicyclo[2.2.1]-2-heptene, 21.4 ± 3.5; bicyclo[2.2.1]-2,5-heptadiene, 46.8 ± 12.9; and bicyclo[2.2.2]-2-octene, 0.728 ± 0.090. These data for cis-2-butene, cyclopentene, and cyclohexene are compared with previous literature data, and the effects of ring strain on the rate constants are discussed.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150804
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  • 29
    Electronic Resource
    Electronic Resource
    Effects of diffusion on the self-termination kinetics of isopropylol radicals in solution (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 733-757 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the bimolecular self-reaction of isopropylol radicals [(CH3)2ĊOH] in various solvents are determined as functions of temperature by kinetic electron spin resonance. For hydrocarbon solvents they are well described by theoretical equations for reactions controlled by translational diffusion if diffusion coefficients of 2-propanol, a constant reaction distance, and a spin statistical factor of 1/4 are applied. Deviations from 2kt ∼ D at high diffusion constants agree with trends expected from recent theoretical models. For hydrogen-bonding solvents large negative deviations are observed. They are attributed to steric constraints and slower rotational diffusion of radical-solvent aggregates. The disproportionation-to-combination ratio of isopropylol increases with solvent viscosity. As previously for tert-butyl, this is explained by anisotropic reorientation during encounters. Further, rate data are given for the decarbonylation of the 2-hydroxy-2-methylpropanoyl radical and for several hydrogen abstraction reactions of isopropylol.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150805
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  • 30
    Electronic Resource
    Electronic Resource
    Direct conversion of synthesis gas to light hydrocarbons on heterogeneous catalysts (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 759-774 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Six catalysts consisting of mixtures of catalysts for methanol synthesis and its conversion to hydrocarbons were prepared by mechanical mixing, impregnation, and coprecipitation, followed by extrusion. Phase changes occurring during various stages of preparation and after use were followed by x-ray diffraction. The catalysts were found to be nontrivial bifunctional catalysts which selectively convert synthesis gas directly to low molecular weight hydrocarbons in the range of C1 to C4. Methanol and dimethylether were detected as intermediates. Olefins were formed, and their further hydrogenation yielded products with high paraffinic content. Carbon dioxide retards the conversion of synthesis gas to hydrocarbons, whereas steam retards the hydrogenation of olefins. On heating the commercial zinc chromite catalyst, dehydration, reduction, and solid-state reactions occur with the formation of ZnO-ZnCr2O4 solid solution. Exchanging cations within the zeolite component did not affect the space lattice, but these ions tend to occupy special sites, and during service more order was detected. Copper ions tend to diffuse in ZnO, forming a solid solution, and during service metallic copper was produced.
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    URL: http://dx.doi.org/10.1002/kin.550150806
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  • 31
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    Electronic Resource
    The kinetics and mechanisms of the gas-phase pyrolysis of ethyl 4-bromobutyrate. The ion-pair mechanism revisited (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 795-803 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase pyrolysis of ethyl 4-bromobutyrate has been investigated in a static system over the temperature range of 354.6-374.7°C and the pressure range of 51-126 torr. The elimination reaction in seasoned vessels and in the presence of at least twofold of a chain radical inhibitor is homogeneous, unimolecular, and obeys a first-order rate law. The rate coefficients are given by the Arrhenius equation log k1(s-1) = (13.31 ± 0.82) - (205.1 ± 8.6)kJ/mol/2.303RT. The partial rates for the parallel eliminations to normal dehydrobromination, lactone formation, and bromobutyric acid product have been estimated and reported. The carboethoxy substituent of the bromoester has been found to assist anchimerically the elimination process, where dihydrobromination and lactone formation arise from an intimate ion-pair mechanism.
    Additional Material: 9 Tab.
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  • 32
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    Electronic Resource
    Kinetics and mechanism of reaction of p-methoxystyrene and tetracyanoethylene. II. Effect of pressure (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 805-814 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of p-methoxystyrene and TCNE is studied in 50% CHCl3-50% CCl4 (v/v) at 25°C at high pressures up to 1000 bar by following the disappearance of the absorbance at 600 nm due to the EDA complex. By using the mixed solvent, equations required for the high-pressure kinetics are simplified. The volume of activation is -42 to -46 cm3/mol for the 1,4-cycloaddition and -55 cm3/mol for the 1,2-cycloaddition. The activation volume for the 1,4-cycloreversion is assumed to be -8 to -12 cm3/mol based on a previous study on a similar system. The rate of the cycloreversion process is affected by solvent polarity. The rate of the 1,2-cycloaddition is influenced by solvent more significantly than that of the 1,4-cycloaddition. It is concluded that the transition state is polar in both cycloadditions and that its zwitterionic character is much stronger in the 1,2-cycloaddition.
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  • 33
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    Electronic Resource
    Kinetic and mechanistic studies of oxidation of alanine and phenylalanine by sodium N-chlorobenzene sulfonamide (chloramine-B) in hydrochloric acid medium (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 775-793 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of alanine and phenylalanine by sodium N-chlorobenzene sulfonamide (CAB) has been investigated at 30°C in two ranges of acid concentrations. The reactions follow identical kinetics for both amino acids. At low acid concentration (0.03-0.10M), simultaneous catalysis by H+ and Cl- ions is noted. The rate shows a first-order dependence on [CAB], but is independent of [substrate]. A variation of the ionic strength or the dielectric constant of the medium or the presence of the added reaction product benzene sulfonamide (BSA) has no pronounced effect on the rate.At [HCl] 〉 0.2M, the rate is independent of [H+], but shows a first-order dependence on [CAB] and a fractional-order dependence on [amino acid]. The addition of BSA or Cl- ions, or a change in the ionic strength of the medium has no influence on the rate. Upon decreasing the dielectric constant of the medium, the rate increased, indicating positive ion-dipole interaction in the rate-determining step. The reaction was studied at different temperatures, and activation parameters have been computed. Rate laws in agreement with experimental results have been derived. Suitable mechanisms to account for the observed kinetics are proposed. The rate constants obtained from the derived rate laws as [H+], [Cl-], and [substrate] vary are in excellent agreement with the observed rate constants, thus justifying the proposed rate laws and hence the suggested mechanistic schemes.
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    URL: http://dx.doi.org/10.1002/kin.550150807
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    Electronic Resource
    Kinetics and equilibria in the system Br + t-BuO2H ⇆ HBr + t-BuO2. OH bond dissociation energy in t-BuO2-H (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 815-822 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and equilibria in the system Br + t-BuO2H ⇆ HBr + t-BuO2· have been measured in the range of 300-350 K using the very low pressure reactor (VLPR) technique. Using an estimated entropy change in reaction (1) ΔS1 = 3.0 ± 0.4 cal/mol·K together with the measured ΔG1, we find ΔH1 = 1.9 ± 0.2 kcal/mol and DHº (t-BuO2-H) = 89.4 ± 0.2 kcal/mol ΔHf·(tBuO2·) = 20.7 kcal/mol and DHº (t-Bu-O2) = 29.1 kcal/mol. The latter values make use of recent values of ΔHf·(t-Bu) = 8.4 ± 0.5 kcal/mol and the known thermochemistry of the other species. The activation energy E1 is found to be 3.3 ± 0.6 kcal/mol, about 1 kcal lower than the value found for Br attack on H2O2. It suggests a bond 1 kcal stronger in H2O2 than in tBuO2H.
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  • 35
    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.550150901
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    Electronic Resource
    Studies in nickel(IV) chemistry. Electron transfer kinetics of the reaction between tris(dimethylglyoximato)nickelate(IV) and hexacyanoferrate(II) in aqueous medium (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 823-833 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of electron transfer from hexacyanoferrate(II) to tris(dimethylglyoximato)-nickelate(IV), Ni(dmg)32-, to produce Fe(CN)63- and Ni(dmgH)2, follows a pseudo-first-order disappearance in the Ni(IV). The pseudo-first-order rate constants kobs are linearly dependent on [Fe(CN)64-]0 in a fiftyfold range of 2 × 10-4-1 × 10-2M, and the average values of kobs/[Fe(CN)64-]0 range from 194M-1·s-1 at pH = 5.20 to 0.2M-1·s-1 at pH = 9.07 in aqueous medium at 35°C and μ = 0.57M. Results are interpreted in terms of a probable mechanism involving rate-determining outer sphere one-electron transfer steps from the reductant and one-protonated reductant species to the unprotonated and one-protonated Ni(IV) species present in solution. The more electrophilic one-protonated reductant species apparently reacts several orders of magnitude faster than the unprotonated one.
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    URL: http://dx.doi.org/10.1002/kin.550150811
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  • 37
    Electronic Resource
    Electronic Resource
    Reaction of CF3 radicals with H2O and D2O (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 835-844 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of CF3 radicals with H2O (D2O) has been studied over the range of 533-723 K using the photolysis and the pyrolysis of CF3I as the free radical source. Arrhenius parameters for the reactions \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CF}_3 + {\rm X}_2 {\rm O\buildrel{k_x}\over{\to}CF}_3 {\rm X} + {\rm OX} $$\end{document} where X = H or D, relative to CF3 radical recombination are given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} {\rm log}k_{\rm H} /k_c^{1/2} = (5.12 \pm 0.11) - (16,804 \pm 335)/\theta \\ {\rm log}k_{\rm D} /k_c^{1/2} = (5.03 \pm 0.16) - (17,803 \pm 456)/\theta \\ \end{array} $$\end{document} where k/kc1/2 is in cm3/2/mol1/2·s1/2 and θ = 2.303RT/cal/mol. The activation energy and the primary kinetic isotope effect have been compared with those derived from the BEBO method.
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  • 38
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    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.
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  • 39
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    Electronic Resource
    Electron transfer to trans-dihydroxotetraoxoosmate(VIII). II. Kinetics of the oxidation of dimethylsulfoxide in aqueous alkaline media (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 881-890 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the oxidation of dimethylsulfoxide by oxohydroxoosmate(VIII) complex ions in alkaline media follow pseudo-first-order disappearance in Os(VIII). The values of the observed pseudo-first-order rate constant are linearly dependent on initial dimethylsulfoxide concentrations in a fortyfold range, and increase with increasing [OH-], leveling off at higher relative [OH-]. The results are interpreted in terms of outer sphere interactions involving dimethylsulfoxide and various species of the Os(VIII) complex. The more nucleophilic dihydroxotetraoxoosmate(VIII) ion reacts about 50 times faster than the trihydroxotrioxoosmate(VIII) species.
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  • 40
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    Electronic Resource
    Kinetics of the reaction F + 1,2-dibromo-1,1,2-trifluoroethane (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 891-904 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title reaction was studied in a standard flow system with F atoms produced by RF discharge in F2-He mixture. Analysis was by gas chromatography using electron capture detection. There were two major products, identified as CF2BrCF2H and CF2BrCF2Br, plus presumably HF which was not detectable. The overall rate of disappearance of reactant was found to be of mixed one and one-half order, indicating a complex reaction. A mechanism is proposed comprising six steps and involving two radical species CF2BrċFBr (R1) and CF2BrċF2. The 300 K rate constant for the initial step F + reactant → HF + R1 is evaluated to be 2.2 × 10-13 cm3/molec·s, which fits in with rates of other saturated hydrocarbon reactants containing one hydrogen atom, thus supporting the view that in this class of reactants the rates of reactions of the type F + saturated hydrocarbon depend mainly on the number of hydrogen atoms in the reactant.
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  • 41
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    Electronic Resource
    Couloamperometry. A fast kinetic technique for halogenations. I. Bromination rate constants of highly reactive enol ethers (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 855-866 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new couloamperometric apparatus has been designed to extend the range of this kinetic technique to the measurement of very high rate constants, 108M-1s-1, by using TFCR-EXSEL conditions (TFCR - very low reactant concentration; EXSEL - salt excess), which give half-lives of a few seconds for very fast second-order reactions. Very low faradaic currents, in the nanoampere range for halogens, corresponding to very low reactant concentrations of 10-8-10-9M, are measured selectively by compensating the eddy currents, principally the residual and the induced currents. When the electroactive species is bromine, the concentration is demonstrated to be linearly related to the limiting reduction current in the very low concentration range. The upper limit of this technique for bromination is at present 3 × 108M-1s-1. The method is applied to the kinetic study of highly reactive enol ethers EtO-C(R) = CH-R′, where R and R′ are H or Me. A value of 2.2 × 108M-1s-1 is obtained for kBr2, the rate constant for free bromine addition to EtO-CH = CH2, by extrapolating the kinetic bromide ion effects to [Br-] = 0. An α-methyl effect (kα-Me/kH)EtO of 15 is found; this is a small decrease in the methyl effect compared to the marked increase in the double bond reactivity. For the enol acetate MeCOO-CH = CH2, whose rate constant is 6 × 102M-1s-1, (kα-Me/kH)OCOMe is 21. The dependence of substituent effects on reactivity is discussed in terms of the Hammond effect on the transition state position and of charge delocalization by group G of olefins G-CH = CH2.
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    URL: http://dx.doi.org/10.1002/kin.550150902
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    Studies in nickel(IV) Chemistry. Kinetics of the aquacopper(II)-catalyzed oxidation of phenylhydrazine by tris(dimethylglyoximato)-nickelate(IV) in aqueous medium (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 867-880 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of electron transfer in the redox system containing phenylhydrazine (S) and tris(dimethylglyoximato)nickelate(IV), in the presence of catalytic amounts of added Cu(II)aq, have been studied in aqueous medium at an ionic strength of 0.25M in the pH range of 6.01-9.06. The kinetics exhibit pseudo-zero-order disappearance of Ni(IV) when an excess of [S]0 and small amounts of Cu(II) are present. While the pseudo-zero-order rate constants are almost linearly dependent on [S]0 at constant [Cu(II)] and pH tending to become non-linearly dependent on higher relative [S]0, they are linearly dependent on [Cu(II)] in a 20-fold range. The pH-rate profiles with low [S]0 and [Cu(II)] show a monotonic decrease in rates with increasing pH, the rates tending to attain limiting values at higher relative pH. Results are interpreted in terms of a probable mechanism involving the formation of precursor complexes of phenylhydrazine and Cu(II) species in the medium, followed by the rate-determining breakdown of the precursors with concomitant electron transfer. The hydrolyzed species of Cu(II) reacts more slowly than does the aquacopper(II). Ni(IV) does not appear to have any kinetic role in the redox system and is involved only in rapid product formation steps. The oxidation product of phenylhydrazine is 4-hydroxyazobenzene.
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    Erratum (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 941-941 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550150909
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    Electronic Resource
    High-temperature determination of the rate coefficient for the reaction H2 + CN → H + HCN (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 915-923 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate coefficient of the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$(2){\rm H}_2 {\rm CN} \to {\rm H} + {\rm HCN}$$\end{document} has been determined in the temperature range of 2700-3500 K using a shock tube technique. C2N2—H2—Ar mixtures were heated behind incident shock waves and the early-time CN history was monitored using broad-band absorption spectroscopy. The rate coefficient providing the best fit to the data was \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm k = (7}{\rm .5}_{ - 2.0}^{{\rm + 2}{\rm .5}} {\rm)} \times {\rm 10}^{{\rm 13}} {\rm cm}^3 /{\rm mol} \cdot {\rm s} $$\end{document} in good agreement with extrapolations of previously published low-temperature results.
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    URL: http://dx.doi.org/10.1002/kin.550150907
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  • 45
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    Electronic Resource
    The reaction of cyclopentyl radicals with carbon tetrachloride (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 905-913 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis of azocyclopentane in the presence of cyclopentane-carbon tetrachloride mixtures has been investigated in the gas phase. Product analysis data have been used to determine the Arrhenius parameters for the reactions \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(4)_C - {\rm C}_5 {\rm H}_{9.} + {\rm CCl}_4 \to _C - {\rm C}_5 {\rm H}_9 + {\rm CCl}_{3.} } \hfill & {k_4 = 10^{9.0 \pm 0.6} {\rm exp}[- (10.3 \pm 1.0){\rm kcal}/{\rm mol}/{\rm RT}]} \hfill \\ {(6){\rm CCl}_{3.} + _C - {\rm C}_5 {\rm H}_{10} \to {\rm CCl}_3 {\rm H} + _C - {\rm C}_5 {\rm H}_{9.} } \hfill & {k_6 = 10^{8.4 \pm 0.4} {\rm exp}[- (10.0 \pm 0.7){\rm kcal}/{\rm mol}/{\rm RT}]} \hfill \\ \end{array}$$\end{document} The rate data for chlorine atom abstraction from CCl4 by the cyclopentyl radical were compared with available data for other alkyl radicals in both the gas and the solution phases. The results indicate that the rate constant for chlorine atom abstraction in the gas phase is fairly insensitive to the nature of the attacking alkyl radical and that the activation energy for a secondary radical is about 4 kcal/mol higher than the corresponding reaction in the solution phase.
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    URL: http://dx.doi.org/10.1002/kin.550150906
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  • 46
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    Electronic Resource
    Kinetics and mechanism of the cerium (IV) oxidation of α-Hydroxycycloalkanecarboxylic acids and cyclic alcohols in acidic perchlorate media (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 925-940 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Ce(IV) oxidation of the five-, six-, and seven-membered ring α-hydroxycycloalkanecarboxylic (C5, C6, and C7) acids to the corresponding cyclic ketones has been studied in acidic perchlorate media. The data may be interpreted in terms of a mechanism which involves fast preequilibrium complexation steps between Ce(IV) and the hydroxy acids, yielding two complexes which differ only by a proton. Complexation is followed by rate-determining decarboxylation to an intermediate (free radical?), which reacts quickly with another Ce(IV) to give products. Of the two proposed complexes, the protonated one is virtually unreactive. The C7 ring acid is oxidized more rapidly than the C6 acid, which, in turn, is oxidized faster than the C5 acid.For comparison, the oxidation of the five-, six-, and seven-membered ring cyclic alcohols to the corresponding cyclic ketones by Ce(IV) in acidic perchlorate was also studied. The order of reactivity is cyclopentanol 〉 cycloheptanol 〉 cyclohexanol. The differences in observed reactivities between the hydroxy acids and the cyclic alcohols are explained in terms of differences in transition state structure.The stepwise hydrolysis constants of Ce(IV) leading to Ce(OH)3Plus; and Ce(OH)22+ were determined. In the case of the hydroxy acids, evidence is in favor of Ce(OH)3+ as the reactive ceric species in aqueous acidic perchlorate media.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150908
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    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.550151001
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  • 48
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    Electronic Resource
    Kinetic and mechanistic studies on the oxidation of nitrite by peroxomonophosphoric acid (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 989-995 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of nitrite to nitrate by peroxomonophosphoric acid in aqueous acid medium have been studied. The observed monotonic fall in rate with increasing pH of the medium has been rationalized on the basis of proton-dissociation equilibria of the substrate as well as the oxidant species. It is found that only HNO2 reacts with the different PMPA species.
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  • 49
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    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.
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  • 50
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    Electronic Resource
    Studies in nickel(IV) chemistry. Kinetics of electron transfer from dimethyl sulfoxide to oxohydroxonickel(IV) in aqueous acid medium (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 945-958 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of decomposition of “oxohydroxonickel(IV)” [Ni(IV)] with concomitant intramolecular electron transfer to produce hexaaquanickel(II) and dioxygen in aqueous acid solutions show pseudo-first-order dissappearance of the Ni(IV). The pseudo-first-order rate constants for the acid decomposition (kad) satisfy \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm ad}} = k_{\rm d} {\rm K}_{{\rm MH}} [{\rm H}^ +]/(1 + {\rm K}_{{\rm MH}} [{\rm H}^ +])$$\end{document} where KMH and kd refer to the equilibrium protonation constant and the decomposition constant of the protonated species of the Ni(IV) respectively. The values of KMH and kd in aqueous medium at 45°C and μ = 2.0M are 25.5 ± 1M-1 and (1.7 ± 0.1) × 10-5 s-1, respectively.The kinetics of the intermolecular electron transfer from dimethyl sulfoxide (DMSO) to the Ni(IV), producing Ni(H2O)62+ and dimethyl sulfone as products, have been investigated by monitoring the formation of Ni(H2O)62+. The pseudo-first-order rate constants for the electron transfer kobs are linearly dependent on [DMSO]0 or [H+], attaining limiting values at higher relative [DMSO]0 or [H+], in accordance with \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm obs}} = \frac{{[{\rm DMSO}]_0 }}{{1 + K_{{\rm MH}} [{\rm H}^ +]}}\left({\frac{{k_{1{\rm x}} K_{1{\rm c}} }}{{1 + K_{1{\rm c}} [{\rm DMSO}]_0 }} + \frac{{k_{2{\rm x}} K_{2{\rm c}} }}{{1 + K_{2{\rm c}} [{\rm DMSO}]_0 }}} \right)$$\end{document} where K1c and K2c represent the formation constants of the precursors involving DMSO and the unprotonated and one-protonated Ni(IV) species, respectively, and k1x and k2x are the corresponding decomposition rate constants of the precursors. The values of K2c and k2x are (2.3 ± 0.1) × 104M-1 and 19 ± 1 s-1, respectively, at 45°C and μ = 1.0M. Results are interpreted in terms of probable mechanisms involving (1) a rate-determining decomposition of the protonated Ni(IV) followed by rapid product formation steps, and (2) precursor complex formation between DMSO and the unprotonated or the protonated species of the Ni(IV) followed by rate-determining decomposition with electron transfer.
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    A Mass-spectrometric study of propionaldehyde oxidation in the negative temperature coefficient region (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 997-1012 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of propionaldehyde has been investigated in a 1-L Pyrex reactor at total pressures of 50-120 torr and temperatures 553-713 K. Detection of reactants and products was principally by molecular beam mass spectrometry, although certain species could only be measured by gas-chromatographic analysis. At 553 K the yield of water was ∼83% of the propionaldehyde consumed, leading to the conclusion that OH is the principal chain carrier near the beginning of the negative temperature coefficient region. Many oxygenated organics (CH2O, CH3CHO, C2H5OH, C2H5O2H, CH3O2H) and C2H4 are formed during the oxidation process. These oxidation products are consistent with the important role of O2 addition to C2H5 radicals at 553 K followed by subsequent reactions of the C2H5O2 radical. As the temperature is increased, the product concentrations smoothly change to a much simpler distribution in which C2H4, H2O2, and CO are the dominant products.
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  • 52
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    Electronic Resource
    Kinetics of the reaction between methane and iodine from 830 to 1150 K in the presence and absence of oxygen (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1031-1043 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The formation of methyl iodide was determined by radiochemical methods and by massspectroscopic analyses in mixtures of Ar-CH4-I2 and Ar—CH4—I2—O2, heated by a reflected shock wave to temperatures of 830-1150 K. The rate of formation of CH3I was consistent with the chain mechanism \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} {\rm I} + {\rm CH}_4 \to {\rm CH}_3 + {\rm HI} \\ {\rm CH}_3 + {\rm I}_2 \to {\rm CH}_3 {\rm I} + {\rm I} \\ \end{array}$$\end{document} where the indicated rate constant for reaction between I and CH4 is given by k2(cm3/mol · s) = 1014.17 exp(-32.9 ± 0.8 kcal/mol/RT). No effect on the reaction rate by the presence of O2 was detected. However, in one experiment at 1097 K with 3.86 mol % O2 the formation of CH2O was indicated by the mass-spectroscopic analysis, presumably from the reaction of O2 with CH3.
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  • 53
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    Electronic Resource
    Formation of nitrous acid and nitric oxide in the heterogeneous dark reaction of nitrogen dioxide and water vapor in a smog chamber (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1013-1029 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dark reaction of NOx and H2O vapor in 1 atm of air was studied for the purpose of elucidating the recently discussed unknown radical source in smog chambers. Nitrous acid and nitric oxide were found to be formed by the reaction of NO2 and H2O in an evacuable and bakable smog chamber. No nitric acid was observed in the gas phase. The reaction is not stoichiometric and is thought to be a heterogeneous wall reaction. The reaction rate is first order with respect to NO2 and H2O, and the concentrations of HONO and NO initially increase linearly with time. The same reaction proceeds with a different rate constant in a quartz cell, and the reaction of NO2 and H218O gave H18ONO exclusively. Taking into consideration the heterogeneous reaction of NO2 and H2O, the upper limit of the rate constant of the third-order reaction NO + NO2 + H2O → 2HONO was deduced to be (3.0 ± 1.4) × 10-10 ppm-2-min-1, which is one order of magnitude smaller than the previously reported value. Nitrous acid formed by the heterogeneous dark reaction of NO2 and H2O should contribute significantly to both an initially present HONO and a continuous supply of OH radicals by photolysis in smog chamber experiments.
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    URL: http://dx.doi.org/10.1002/kin.550151006
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  • 54
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    Electronic Resource
    Kinetics and mechanism of the reactions of the superoxide ion in solutions. I. Absorption spectra and interaction with solvents and cations (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1045-1056 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absorption spectra of the superoxide ion have been studied in dimethylformamide (DMF) and acetonitrile (AN). It was found that the superoxide ion existed in equilibrium with an ion pair in AN (Keq = 20M-1, Bu4N+ is the cation) and as “free” (solvated) ion in DMF. The addition of DMF caused the destruction of an ion pair in AN. The addition of the proton donors HX (water or ethanol) to the \documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document} solutions in DMF and AN caused the formation of new ion pairs (Bu4N+\documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document})2HX. The equilibrium constants of these ion pairs were determined in DMF and AN.
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  • 55
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    Kinetics and mechanism of the reactions of the superoxide ion in solutions. II. The kinetics of protonation of the superoxide ion by water and ethanol (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1057-1062 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constants for the protonation of “free” (that is, solvated) superoxide ions by water and ethanol are equal to 0.5-3.5 ×10-3M-1·s-1 in DMF and AN at 20º. It has been found that the protonation rates for the ion pairs of \documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document} with the Bu4N+ cation are much slower than those for “free” \documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document}. It is suggested that the effects of aprotic solvents on the protonation rates of \documentclass{article}\pagestyle{empty}\begin{document}${\rm O}_{\rm 2}^{\overline {\rm .} }$\end{document} are mainly due to the fact that the proton donors form solvated complexes of different stability in these solvents.
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    URL: http://dx.doi.org/10.1002/kin.550151009
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  • 56
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    Electronic Resource
    Kinetics and mechanism of the reactions of the superoxide ion in solutions. III. Kinetics and mechanism of the reaction of the superoxide ion with ethyl acetate in dimethylformamide, acetonitrile, and their mixtures (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1063-1068 
    Details
    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 the superoxide ion with ethyl acetate have been studied in DMF, AN, and their mixtures. It was shown that the rate constants depend on the ethyl acetate concentration, which indicates the formation of an intermediate in this process. Equilibrium constants for the process of the intermediate formation and the rate constants for its decay have been determined. It is concluded that aprotic solvents affect mainly the stage of the intermediate decay in this reaction.
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    URL: http://dx.doi.org/10.1002/kin.550151010
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  • 57
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    Method for the measurement of diffusion coefficients of labile gas-phase species: The diffusion coefficient of O(3P) in He at 294 K (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1081-1097 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dispersion of a pulse of O(3P) atoms in flowing helium has been analyzed by a modification of Taylor's method in order to determine the diffusion coefficient. Atoms of O(3P) were produced in a flowing stream of helium by a pulsed microwave discharge of molecular oxygen. After traversing a known length of the flow tube, the arrival time distribution of the O(3P) atoms was obtained using a mass spectrometer. The value obtained for D0 at 294 K, where D0 = D[He], is (2.40 ± 0.06) × 1019 cm-1 ·s-1, which corresponds to a diffusion coefficient of (731 ± 18) cm2/s at 1 torr. In addition to D0, analysis of the arrival time distributions gives an estimate of the mean flow velocity for O atoms in helium. There was no significant difference between the value of the velocity found this way and that obtained from the mean bulk gas flow measurement. Thus for this system there is no evidence for a chromatographic effect for O(3P) atoms on the walls of the flow tube.
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    URL: http://dx.doi.org/10.1002/kin.550151012
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  • 58
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    Kinetic and equilibrium study of gas-phase interconversions of 1,3,6-cyclooctatriene, 1,3,5-cyclooctatriene and bicyclo[4.2.0]octa-2,4-diene (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1069-1080 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase equilibrium and rate constants for the isomerizations of 1,3,6-cyclooctatriene (136COT) to 1,3,5-cyclooctatriene (135COT) [reaction (1)] and bicyclo[4.2.0]octa-2,4-diene (BCO) to 135COT [reaction (-2)] have been measured between 390 and 490 K and between 330 and 475 K, respectively. The rate constant of reaction (1) obeys the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$k_{\rm 1} = 10^{10.93 \pm 0.08} {\rm exp}[- (115.9 \pm 0.7{\rm kJ}/{\rm mol})/RT]{\rm s}^{ - 1}$$\end{document} The corresponding equilibrium constant is given by the van′t Hoff equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm In K}_{\rm 1}^{\rm 0} = (0.24 \pm 0.04) + (13.78 \pm 0.15{\rm kJ}/{\rm mol})/RT$$\end{document} The strain energy of the 136COT ring is calculated to be 31.7 kJ/mol, based on the known value of 37.2 kJ/mol for 135COT, and ΔHf0(298 K) for gaseous 136COT is 196.3 kJ/mol. The rate constant of reaction (-2) obeys the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$k_{{\rm - 2}} = 10^{12.38 \pm 0.23} {\rm exp}[(- 106.9 \pm 1.5{\rm kJ}/{\rm mol})/RT]{\rm s}^{ - 1}$$\end{document} The equilibrium constant for 135COT ⇆ BCO fits the van′t Hoff equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm In K}_{\rm 2}^{\rm 0} = (- 1.20 \pm 0.02) - (0.40 \pm 0.07{\rm kJ}/{\rm mol})/RT$$\end{document} The strain energy of the BCO skeleton is calculated to be 108.3 kJ/mol, and ΔHf0(298 K) for gaseous BCO is 183.3 kJ/mol.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151011
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    Nonlinear structure-reactivity correlations. The hydrolysis of 2,4,6-trinitrophenyl acetate catalyzed by general bases (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1099-1110 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hydrolysis of 2,4,6-trinitrophenyl acetate was studied in the presence of several carboxylic bases and tertiary amines. Carboxylic bases pyridine and imidazole react as nucleophilic catalysts, while 2,4-dimethyl and 2,4,6-trimethyl pyridine react as general-base catalysts. The nonlinear structure-reactivity correlations (log kcat versus log kOH and log kcat versus pK of the leaving group) for the series of aryl acetates are discussed, and it is suggested that there is a change in transition-state structure along the series.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151013
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  • 60
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    Electronic Resource
    Kinetic study of the reactions of the hydroxyl radical with ethane and propane (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1111-1118 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate coefficients for the reactions of the hydroxyl radical with ethane (k1, 297-300 K) and propane (k2, 297-690 K) were measured using the flash photolysis-resonance fluorescence technique. The rate coefficient data were fit by the following temperature-dependent expressions, in units of cm3/molecule·s: k1(T) = 1.43 × 10-14T1.05 exp (-911/T) and k2(T) = 1.59 × 10-15T1.40 exp (-428/T). Semiquantitative separation of OH-propane reactivity into primary and secondary H-atom abstraction channels was obtained.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151014
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  • 61
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    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.550151101
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  • 62
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    Electronic Resource
    Continuous-wave CO2 laser-induced dehydrochlorination of 1,1,1-trichloroethane. A hot-tube radical-chain reaction with a molecular mechanism (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1119-1123 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No ABSTRACT.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151015
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  • 63
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    Electronic Resource
    Methyl thiirane: Kinetic gas-phase titration of sulfur atoms in SX OY systems (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1127-1132 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction SO + SO →l S + SO2(2) was studied in the gas phase by using methyl thiirane as a titrant for sulfur atoms. By monitoring the C3H6 produced in the reaction \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm S} + {\rm CH}_3\hbox{---} \overline {{\rm CH\hbox{---}CH}_2\hbox{---} {\rm S}} \to {\rm S}_2 + {\rm C}_3 {\rm H}_6 (7) $\end{document}, we determined that k2 ≃ 3.5 × 10-15 cm3/s at 298 K.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151102
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  • 64
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    Electronic Resource
    The azoethane-initiated thermal reaction of isobutene. Heat of formation of the 2-methyl-2-pentyl radical (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1133-1145 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The azoethane-sensitized thermal reaction of isobutene has been studied at 526-565 K. The initial concentrations of azoethane and isobutene were in the ranges of 1.40-10.5 × 10-4 and 6.78-26.6 × 10-4 mol/dm3, respectively. From the initial rates of formation of ethane and 2-methylpentane the heat of formation of the 2-methyl-2-pentyl radical was determined. The result obtained is ±Hf0(2-methyl-2-pentyl) = 0.8 ± 2.0 kcal/mol. The entropy of the radical, obtained from statistical mechanical calculations and experimentally, is S0(2-methyl-2 pentyl) = 92.8 ± 1.5 cal/mol°K. The results support the high heat of formation of the t-butyl radical suggested by different authors.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550151103
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  • 65
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    Stopped-flow determination of carbon dioxide-diethanolamine reaction mechanism: Kinetics of carbamate formation (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1147-1160 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction mechanism of carbon dioxide with diethanolamine (DEA) is investigated using the stopped-flow method with optical detection in the ranges of concentration [DEA] = 0.111-8.4 × 10-2M and [CO2] = 2.94-5.6 × 10-3M. The comparison of the fast time-dependent light transmission change of a pH indicator with theoretical simulations of integrated rate equations requires a kinetic model in which a simple carbamate formation takes place simultaneously with hydration reactions, whose contributions are far from being negligible. A first-order reaction relative to DEA is thus found with a rate constant for carbamate formation smaller than usually predicted (110 ± 15M-1s-1 at 25°C). The equilibrium constant for the same reaction is also determined giving pKR = 5.3 at 25°C, in satisfactory agreement with values assumed so far.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151104
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  • 66
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    Electronic Resource
    Effects of ring strain on gas-phase rate constants. 2. OH radical reactions with cycloalkenes (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1161-1177 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the gas-phase reactions of OH radicals with a series of cycloalkenes have been determined at 298 ± 2 K using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with isoprene of 9.60 × 10-11 cm3 molecule-1 s-1, the rate constants obtained were (X 1011 cm3 molecule-1 s-1): cyclopentene 6.39 ± 0.23, cyclohexene 6.43 ± 0.17, cycloheptene 7.08 ± 0.22, 1,3-cyclohexadiene 15.6 ± 0.5, 1,4 cyclohexadiene 9.48 ± 0.39, bicyclo[2.2.1]-2-heptene 4.68 ± 0.39, bicyclo[2.2.1] 2,5 heptadiene 11.4 ± 1.0, and bicyclo[2.2.2] 2 octene 3.88 ± 0.19. These data show that the rate constants for the nonconjugated cycloalkenes studied depend on the number of double bonds and the degree of substitution per double bond, and indicate that there are no obvious effects of ring strain energy on these OH radical addition rate constants. A predictive technique for the estimation of OH radical rate constants for alkenes and cycloalkenes is presented and discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151105
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  • 67
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    Gas-phase thermal isomerization of hexachlorocyclopropane (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1179-1187 
    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 hexachlorocyclopropane to hexachloropropene at 208-283°C is first order and unaffected by changes in the surface-to-volume ratio or by the addition of iodine, tetrachloroethylene, and oxygen. The first-order rate constants fit the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log}k({\rm s}^{ - 1}) = (15.74 \pm .022) - (45,660 \pm 526)/4.576T$$\end{document} The reaction was interpreted as an unimolecular process taking place with chlorine atom migration. A comparison of the reactivities of several chlorocyclopropanes is made.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550151106
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  • 68
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    Electronic Resource
    Third-order rate constants of atmospheric importance (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1189-1227 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Input data and results are presented for the calculation of a number of third-order rate constants of atmospheric interest using Troe′s approximate method. A comparison with experimental data indicates that this approach provides a reliable method for predicting unknown rate constants and estimating temperature dependences. These calculations form the basis of the recommendations of the NASA review panel for third-order rate constants to be used in atmospheric modeling.
    Additional Material: 27 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151107
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  • 69
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    Electronic Resource
    Recombination rates of chlorine atoms in flash photolysis of chlorine molecules (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1235-1236 
    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.550151109
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  • 70
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    Energy of activation and temperature for the hydrolysis of sucroseTaken in part from the M.S. thesis of M. S. Owens, Furman University, 1983. (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1229-1234 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have reinvestigated temperature effects on the rates of hydrolysis of 0.0585M sucrose in 0.57M HCl solutions over the range of 10-40°C using polarimetry as a physical method to follow the reaction while simultaneously analyzing the solutions by HPLC for the disappearance of sucrose and by GLC for the appearance of glucose. When the polarimetric data are corrected for the mutarotation lag, the energy of activation values are the same by all three analytical methods and are temperature-independent.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151108
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  • 71
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    Electronic Resource
    Shock-tube determination of the rate coefficient for the reaction CN + HCN → C2N2 + H (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1237-1241 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151110
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  • 72
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    Announcement (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1244-1244 
    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.550151112
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  • 73
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    Chemical dynamics via molecular beam and laser techniques, by R. B. Bernstein. No publisher supplied (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1243-1243 
    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.550151111
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  • 74
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    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.550151201
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  • 75
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    Electronic Resource
    Catalytic isomerization of 1-hexene on hy zeolite (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1249-1274 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The isomerization of 1-hexene on 70/80 mesh HY zeolite was studied at 200°C. The observed reaction products are formed via a variety of processes including double bond shift, cis-trans isomerization, skeletal rearrangement, cracking, hydrogen transfer, polymerization, cyclization, and coke formation. By applying the time-on-stream theory, the products have been classified as primary, secondary, or both, according to their OPE curves on product selectivity plots. 2-Ethyl-1-butene, which is present as an impurity in the feed, is found to react about 30 times faster than 1-hexene. Both 2-hexenes and 3 hexenes are formed primarily from 1-hexene, while 3 methyl 2 pentenes and 3-methyl-1-pentene formed from 2-ethyl-1-butene. The ratio of the initial rate of deprotonation to that of hydrogen shift in these reactions is ∼15 and ∼100, respectively. All products of skeletal rearrangement are observed to be secondary. Cracking products are produced mainly from precoke, which is also the source of hydrogen in the formation of paraffins. A detailed reaction network along with its associated mechanisms are presented and discussed.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151202
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  • 76
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    Pyrolysis of 5-chloropentan-2-one and 4-chloro-1-phenylbutan-1-one. Participation of the carbonyl group (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1275-1282 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rates of elimination of 5-chloropentan-2-one and 4-chloro-1-phenylbutan-1-one in the gas phase have been determined in a static system, seasoned with allyl bromide, and in the presence of the chain inhibitor propene. The reactions are unimolecular and follow a first-order rate law. The working temperature and pressure ranges were 339.4-401.1°C and 46-117 torr, respectively. The rate coefficients for the homogeneous reactions are given by the following Arrhenius equations: for 5-chloropentan-2-one, log k1(s-1) = (13.12 ± 0.88) - (207.8 ± 11.0)kJ/mol/2.303RT; and for 4-chloro-1-phenylbutan-1-one, log k1(s-1) = (12.28 ± 1.09) - (185.2 ± 12.0)kJ/mol/2.303RT. The carbonyl group at the γ position of the C—Cl bond of haloketones apparently participates in the rate of pyrolysis. The five-membered conformation appears to be a favorable structure for anchimeric assistance of the C=O group in the gas-phase elimination of chloroketones.
    Additional Material: 6 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550151203
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  • 77
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    Laser-induced kinetics: Arrhenius parameters for t-C4H9 + XI → i-C4H9X + I (X = H,D) and the Heat of Formation of the t-butyl radical (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1283-1300 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metathesis reaction of DI with t-C4H9 generated by 351-nm photolysis of 2,2′-azoisopropane was studied in a low-pressure reactor (VLPφ Knudsen cell) in the temperature range of 302-411 K. The data obeyed the following Arrhenius relation when combined with recent data by Rossi and Golden gathered by the same technique (t-C4H9 by thermal decomposition of 2,2′-azoisobutane): log k2D(M-1s-1) = 9.60 - 1.90/θ, where θ = 2.303RT kcal/mol for 302 K 〈 T 〉 722 K. The metathesis reaction of HI with t-C4H9 was studied at 301 K and resulted in k2H(M-1·s-1) = (3.20 ± 0.62) × 108. An analogous Arrhenius relation was calculated for the protiated system if the small primary isotope effect k2H/k2D was assumed to be √2 at 700 K. It was of the following form: log k2H(M-1·s-1) = 9.73 - 1.68/θ.Preliminary data of Bracey and Walsh indicate that earlier Arrhenius parameters determined for the reverse reaction are somewhat in error. Their value of log k1(M-1·s-1) = 11.5 - 23.8/θ yields 7delta;Hf,3000(t-butyl) = 9.2 kcal/mol and S3000(t-butyl) = 74.2 cal/mol7°K when taken in conjuction with this study.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550151204
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  • 78
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    Kinetics and mechanism of photochemical reactions of peroxomonosulfate in the presence and absence of 2-propanol (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1301-1310 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photochemical decomposition of peroxomonosulfate (PMS) in the presence and absence of 2-propanol at 25°C was found to obey an overall first-order rate - d[PMS]/dt = kφ[PMS]. In the absence of 2-propanol, the quantum yield ≤ for the decomposition of PMS was found to depend upon the concentration of PMS at [PMS] 〉 2 × 10-M, and is independent of concentration at [PMS] 〉 2 × 10-2M. The quantum yield in the presence of 2-propanol was found to be 3.03 at [PMS] = 1 × 10-2M and 4.45 at higher concentrations of PMS. In the pH range of 2-9.0 the quantum yield was found to be independent of pH, and the overall rate constant kφ was found to be 6.49 × 10-3 s-1 and 1.68 × 10-3 s-1, respectively, in the presence and absence of isopropanol. A suitable chain mechanism is proposed and explained.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550151205
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  • 79
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    Involvement of formic acid in the Belousov-Zhabotinskii oscillator (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1335-1336 
    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.550151209
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  • 80
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    Kinetics and mechanism of the decomposition of N-brominated alanine in aqueous solution (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1321-1328 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aqueous bromine reacts with alkyl-sidechain amino acids through a series of steps resulting in the formation of the corresponding alkyl aldelydes and nitriles. The kinetics and the mechanism of the interaction of bromine with alanine are examined. The products and the rates of this reaction are dependent in a complex way on the initial reactant concentration and pH. Acetaldeyde production is favored at low bromine-to-alanine ratios, low bromine concentrations, and pH values above 6. The first-order rate constant for the formation of acetaldelyde from alanine under these conditions is k4 = 1.98 × 1015 e-22,500/RT min-1. At higher concentration the nitrile is formed through a bromoimine intermediate. Under most conditions the nitrile appears to form from a catalyzed decomposition of the bromoimine which is too fast to be followed by the methods used in this study. However, residual amounts of the bromoimine decay by a slower first-order mechanism. The rate constant for this slower reaction in the case of alanine at pH 6.8-6.9 and alanine concentrations of 1 × 10-4M is k6 = 1.75 × 105 e-10,400/RT min-1.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550151207
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  • 81
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    Kinetic study of the reactions of CL and BR with H2O2 (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1311-1319 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of Cl and Br atoms with H2O2 have been studied in the range of 300-350 K using the very-low-pressure-reactor technique. It was found that metathesis to produce HX and HO2 is the only significant process (≤99%). For the reaction of Br \documentclass{article}\pagestyle{empty}\begin{document}$${\rm Br}+{\rm H}_2{\rm O}_2\buildrel{2}\over{\rightarrow}{\rm Hbr} + {\rm HO}_2$$\end{document} k2 (300 K) = 1.3 ± 0.45 × 10-14 and k2 (350 K) = 3.75 ± 1.1 × 10-14 cm3/molecules·s, with an activation energy of 4.6 ± 0.7 kcal/mol. Using an estimated A factor for A2, we find \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} k_2 ({\rm benttransitionstate}) = 1.6 \times 10^{ - 11 - 4.3/\theta } \\ k_2 ({\rm lineartransitionstate}) = 4 \times 10^{ - 12 - 3.5/\theta } \\ \end{array}$$\end{document} suggesting that a best choice is E2 = 3.9 ± 0.4 kcal/mol. The relation of these values to ΔHf0 (HO2) is discussed.
    Additional Material: 5 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550151206
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    The kinetics of the reactions of i-C3F7 radicals with BR2 and HBr (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1329-1334 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{l} (2)i - {\rm C}_3 {\rm H}_7 + {\rm Br}_2 \to i - {\rm C}_3 {\rm F}_7 {\rm Br} + {\rm Br} \\ (3)i - {\rm C}_3 {\rm H}_7 + {\rm HBr}_2 \to i - {\rm C}_3 {\rm F}_7 {\rm H} + {\rm Br} \\ \end{array}$$\end{document} have been studied competitively in the vapor phase over the range of 52-204°C. The i-C3F7 radicals were generated by means of the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm Br} + i - {\rm C}_3 {\rm F}_7 {\rm I} \to {\rm IBr} + i - {\rm C}_3 {\rm F}_7 $$\end{document} It was found that \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log} k({\rm s}^{ - 1}) = (15.74 \pm .022) - (45,660 \pm 526)/4.576T $$\end{document} where θ = 2.303RT J/mol. Absolute Arrhenius parameters are derived for the reactions \documentclass{article}\pagestyle{empty}\begin{document}$${\rm R} + {\rm HBr} \to {\rm RH} + {\rm Br}$$\end{document} where R = CF3, C2F5, and i-C3F7.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550151208
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  • 83
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    Mechanism of acetylene-chlorine mixture explosion initiated by small additions of oxygen (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 1-4 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An improved radical-chain scheme of acetylene-chlorine mixture explosion initiated by small additions of oxygen is proposed. It includes among others the three-body formation of chemically activated state (2) and describes the inhibiting effect of oxygen below the explosion limit.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150102
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  • 84
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    Acid-catalyzed hydrolysis of some diazoacetophenones in aqueous dioxan (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 25-35 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants and activation parameters for the acid-catalyzed hydrolysis of eight ring-substituted diazoacetophenones have been measured in three dioxan-water mixtures. An isokinetic relationship applies to the results obtained using a 50% dioxan-water mixture as solvent. Solvent and substituent effects are discussed together with some mechanistic aspects. Substituent constants are reported for the —COCHN2 group.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150104
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  • 85
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    Thermal reaction of hydrogen-butene-2-cis mixtures at 500°C: Hydrogenation, hydrogenolysis, and thermal reaction of the olefin (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 5-23 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reaction of hydrogen-butene-2-cis mixtures has been studied in a static system at low extent of reaction around 500°C. Hydrogen does not affect the thermal reaction itself of the olefin, but gives rise to new stoichiometries of hydrogenolysis and hydrogenation, which are specified: \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} {\rm H}_2 + cis - 2 - {\rm C}_4 {\rm H}_8 = {\rm CH}_4 + {\rm C}_3 {\rm H}_6 \\ {\rm H}_2 + cis - 2 - {\rm C}_4 {\rm H}_8 = {\rm H}_2 + 1 - {\rm C}_4 {\rm H}_8 \\{\rm H}_2 + cis - 2 - {\rm C}_4 {\rm H}_8 = n - {\rm C}_4 {\rm H}_{10} \\ \end{array} $$\end{document} The reaction is described in terms of a molecular and free-radical mechanism. It is shown that the key process for the hydrogenolysis-hydrogenation reaction is and that the rate constant of this process can be determined from either propylene, or methane, or butene-1 formations: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm k}_{{\rm 7'}} \simeq {\rm 10}^{{\rm 13}{\rm .1 - 24}{\rm .2/}\theta } \,{\rm cm}^{\rm 3} {\rm /mol} \cdot {\rm s} $$\end{document} with θ = 4.57 × 10-3 T kcal/mol. Other rate constants are estimated and agree with literature data.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150103
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  • 86
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    Induced heterogeneity, a novel technique for the study of gas-phase reactions. Part I. Determination of the arrhenius parameters for C—C bond scission in propane (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 63-73 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that, by deliberate activation of the reaction vessel, heterogeneous reaction at the wall can be made to dominate chain termination in a complex gas-phase reaction. For a homogeneous process, characterized, as is often the case, by multiple terminations, this has the effect of simplifying the mechanism and allowing explicit solution of the relevant steady-state equations so that the rate constants of some individual steps can be evaluated without assumption as to the values of those of others.The pyrolysis of propane, in the vicinity of 500°C, has been used as an example of this approach. Enhancement of the wall activity leads to the reaction providing, almost exclusively, chain termination. As a result, rate constants for the initiation step can be directly determined. The results of this study provide the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 (s^{ - 1}) = 16.71 \pm 0.54 - 83400 \pm 1950{\rm cal}/{\rm mol}/2.303RT $$\end{document} In combination with current thermochemical values this result gives k-1 = 1013.40 cm3/mol·s which, in turn, implies, via the geometric mean rule, kEt-Et = 1012.9 cm3/mol·s for ethyl-ethyl recombination, in good accord with the most recent determinations and compatible with the newly proposed value of the enthalpy of formation of ethyl.The first-order wall constant k8 has been evaluated as k8〈104.2 s-1. This appears to be the first occasion on which a wall constant has been evaluated from data for a high-temperature complex gas reaction.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150107
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  • 87
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    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.550150201
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  • 88
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    Kinetics of benzene photochlorination (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 119-128 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An empirical approach to the kinetic investigations of photo-initiated liquid-phase chlorination of benzene is presented. Reaction order and the reaction constants for chlorine consumption and for the production of hexachlorocyclohexane isomers were evaluated from experimental data.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150203
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  • 89
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    Kinetics and thermochemistry of electron attachment to SF6 (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 109-117 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Thermochemical analysis of the electron capture process of SF6 leads to a rate constant for the reverse process \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm SF}_6^ - \mathop \to \limits^2 {\rm SF}_6 + e^ -,k_2 = 1.5 \times 10^{13 - 31.4/\theta } {\rm s}^{{\rm - 1}} $\end{document}, where θ = 2.303RT, in kcal/mol. The electron affinity of 32±3 kcal/mol is deduced from the observed bimolecularity of the capture process down to 0.1 torr Ar bath gas and estimated entropies of SF6 and SF6-. The capture process is discussed from the view point of the formation of a metastable SF6- electron (SF6·eL-) Langevin complex which appears to have a lifetime of about 2 × 10-13 s. Curve crossing from the SF6·eL- complex to vibrationally excited (SF6-)* appears to have a normal rate and A factor. This is interpreted to indicate near-resonant coupling between the orbiting electron and the vibronic motions of SF6, together with similarity in structure of SF6 and SF6-. It is shown that the apparent slowness of thermal electron ejection from SF6- is a result of an unfavorable equilibrium constant rather than a slow rate.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150202
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  • 90
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    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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  • 91
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    Kinetics of oxidative coupling of phenols: Oxidation of naphthols by alkaline hexacyanoferrate (III) (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 197-203 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of naphthols by alkaline hexacyanoferrate(III), at constant ionic strength, gave coupled products. The rate of the reaction was dependent on the first powers of the concentrations of substrate, oxidant, and alkali. The activation energies were 31.8 and 34.5 kJ/mol for α naphthol and β naphthol, respectively. The reaction pathway was via the formation of a radical intermediate, which was detected by electron spin resonance spectroscopy.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550150209
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  • 92
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    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.550150301
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  • 93
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    Recommendations for measuring second-order rate constants and kinetic solvent isotope effects on acid-catalyzed reactions (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 235-248 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic solvent isotope effects (KSIE) were measured for the hydrolyses of acetals of benzaldehydes in aqueous solutions covering the pH (pD) range of 1-6. For p-methoxybenzaldehyde diethyl acetal, kD+/kH+ = 1.8-3.1, depending on the procedure used to calculate the KSIE and on the pH (pD) range used as the basis for kH+(kD+). It is shown that this variation is an experimental artifact, and is a characteristic of KSIE measurements in general. It is recommended that kL+ be calculated from a least-squares fit of data to the equation kobs = kL+[L+], and that the KSIE be reported as kD+/kH+. The limitation remains, however, that the KSIE measured for a variety of substances over quite different pH (pD) ranges may not be comparable to more than ℜ20%. The source of these observations is discussed in terms of small changes in the activity coefficient ratios (a specific salt effect), including the solvent isotope effect on the activity coefficient ratio [eq. (3)].
    Additional Material: 7 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550150304
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  • 94
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    Rate constants for the bimolecular self-reaction of cyano-substituted alkyl radicals in solution (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 267-279 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cyano-substituted methyl radicals (cyanomethyl-hand 2-cyano-2-propyl radicals) and syn-and anti-1-cyano-allyl radicals were generated, and their recombination kinetics in solution were investigated between -50 and +50°C by time-resolved electron-spin-resonance spectroscopy. The comparison of the activation energies for recombination with the activation energies of the solution viscosities proves that the dimerizations of the radicals are diffusion controlled with rate constants on the order of 108-109M-1·s-1. In the case of cyanomethyl radicals an additional pseudo-first-order process, hydrogen abstraction, was detected and analyzed kinetically. Product analyses support the kinetic measurements.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150306
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  • 95
    Electronic Resource
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    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.550150401
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  • 96
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    The kinetics of the addition of alkyl radicals to carbonyl groups. Part I. The addition of methyl radicals to hexafluoroacetone in the gas phase. The formation of the hexafluoro-t-butoxy radical (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 281-291 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By pyrolyzing di-t-butyl peroxide over the temperature range of 405-450 K in the presence of hexafluoroacetone the kinetics of the addition reaction (1), CH3 + (CF3)2CO→; (CF3)2C(Ȯ)CH3, have been studied. Detailed analyses have shown that the principal product of the adduct radical, (CF3)2C(Ȯ)CH3, is CF3COCH3 from reaction (2), (CF3)2C(Ȯ)CH3 → CF3COCH3 + CF3. The rate constant of the addition reaction was determined to be k1(dm3/mol·s) = (1.1 ± 4.0) + 109 exp(-(3680 ± 480)/T) over the temperature range 405-450 K, based on the value k3 = 2.2 × 1010 dm3/mol·s for reaction (3), 2CH3 → C2H6. The results are discussed in relation to existing data for radical additions to carbonyl groups.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550150307
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  • 97
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    The kinetics of the gas phase decomposition reactions of the hexafluoro-t-butoxy radical (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 293-303 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hexafluoro-t-butoxy radicals have been generated by reacting fluorine with hexafluoro-2-methyl isopropanol: Over the temperature range of 406-600 K the hexafluoro-t-butoxy radical decomposes exclusively by loss of a CF3 radical [reaction (-2)] rather than by loss of a CH3 radical [reaction (-1)]: The limits of detectability of the product CF3COCF3, by gas-chromatographic analysis, place a lower limit on the ratio k-2/k-1 of ∼80. The implications of this finding in relation to the reverse radical addition reactions to the carbonyl group are briefly discussed.A thermochemical kinetic calculation reveals a discrepancy in the kinetics and thermodynamics of the decomposition and formation reactions of the related t-butoxy radical:
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    URL: http://dx.doi.org/10.1002/kin.550150308
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  • 98
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    A novel kinetic and mechanistic study of the oxidation of pinacol by acid bromate - homogeneous catalysis of maganous ions (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 307-321 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed kinetic study of the Mn(II)-catalyzed and -uncatalyzed oxidation of pinacol by bromate has been carried out in aqueous acetic acid media containing Hg(II) ions. The uncatalyzed reaction exhibits 1.5 order that is, 0.5 order in [pinacol] and 1.0 in [bromate]. A decrease in k1 by increasing [bromate] has been accounted for due to the formation of Br2O5, which is inactive toward reduction. Mn(II)-catalyzed oxidation follows first order in [oxidant], 0.5 order in [manganous ion], and variable order with respect to [pinacol]. At lower [pinacol] (0.005-0.025M) the order is 0.5, but at higher concentration (0.03-0.15M) it becomes negative (-1.0). These observations can be accounted for qualitatively by the formation of 1:1 and 1:2 Mn(II)-pinacol complexes of which only 1:1 is active toward bromate oxidation. At higher [pinacol] the ratio of 1:2 and 1:1 complexes reached 98.2. All reactions were accelerated with acidity, and the rate constant follows the h0 function. Participation of H2O in the rate-limiting step and a free-radical mechanism were proposed for the manganous-ion-catalyzed reaction, whereas for the uncatalyzed reaction this was not true. The effects of NaClO4, Na4P2O7, and the dielectric constant of the media are also in accordance with the proposed mechanism.
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    URL: http://dx.doi.org/10.1002/kin.550150402
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  • 99
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    The oxidation of HI at low temperatures and the heat of formation of HO2 (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 323-339 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the oxidation of hydrogen iodide (HI + O2) at low temperature (414-499 K) in the gas phase by the method of iodination kinetics is complicated by a heterogeneous reaction between hydrogen iodide and oxygen. Present work leads to an upper limit for the bimolecular rate constant k1 for the first and rate-determining step These data are combined with an estimated A factor A1 = 109.3±0.2 L/mol·s (assuming a tight linear I···H···O -  transition state), to calculate the lower limit of the activation energy for the forward reaction E1. This leads to a minimum value for the heat of formation of the HO2 radical, ΔHf298°(HO2) 〈 3.0 kcal/mol.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550150403
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  • 100
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    Thermochemistry and kinetics of the reaction of methyl mercaptan with iodine (1983)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 433-453 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gas-phase reaction CH3SH + I2 has been studied spectrophotometrically over the temperature range of 476-604 K. It was found that the reaction undergoes H abstraction by I at ≤575 K, leading to the formation of MeSI and followed by a secondary reaction which leads to the formation of MeSSMe: Taking into consideration the effect of reaction (2), the equilibrium constant K1 (554 K) has been evaluated to be 0.025 ± 0.004. This value was combined with the estimated values S2980 (CH3SI, g) = 73.7 ± 1.0 eu and 〈ΔCp1,5540〉 = 0.87 ± 0.3 eu to obtain ΔH1,2980 = 4.03 ± 0.73 kcal/mol. This yields ΔHf2980 (CH3SI, g) = 7.16 ± 0.73 kcal/mol when combined with known thermochemical values for CH3SH, HI, and I2. A kinetic study was vitiated by the concurrent heterogeneous reaction of MeSH and I2 at lower temperatures and the rather complicated chemistry occurring at elevated temperatures. However, attempts at measuring rate constants at 554 K lead to a lower limit of ΔHf2980 (CH3S·, g) ≥ 29.5 ± 2 kcal/mol when an estimated value of A = 1010.8 ± 0.2 L/mol·s for the reactionc is used. DH2980 (CH3S-I) is estimated to be 49.3 ± 1.7 kcal/mol. The bond strengths of some divalent sulfurs and the reaction mechanisms are discussed. A crude estimate of DH0(H-CH2SH) = 96 ± 1 kcal has been obtained from the kinetic data.
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    URL: http://dx.doi.org/10.1002/kin.550150504
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