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  • Physical Chemistry  (9)
  • Wiley-Blackwell  (9)
  • Annual Reviews
  • Oxford University Press
  • Springer
  • 1980-1984
  • 1975-1979  (9)
  • 1950-1954
  • 1978  (9)
Collection
Keywords
Publisher
  • Wiley-Blackwell  (9)
  • Annual Reviews
  • Oxford University Press
  • Springer
Years
  • 1980-1984
  • 1975-1979  (9)
  • 1950-1954
Year
  • 1
    Electronic Resource
    Electronic Resource
    A kinetics study of the reactions of OH with several aromatic and olefinic compounds (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 783-804 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of hydroxyl radicals with eight substituted aromatic hydrocarbons and four olefins were studied utilizing the flash photolysis-resonance fluorescence technique. The rate constants were measured at 298°K using either Ar or He as the diluent gas. The values of the rate constants (k × 1012) in the units of cm3/molec. sec are (a) OH + o-xylene → products: (12.9±3.8), 20 torr He; (13.0±0.3), 20 torr Ar; (12.4±0.1), 200 torr He;(b) OH + m-xylene → products: (15.6±1.4), 3 torr Ar; (19.4±0.8), 20 torr Ar; (21.4±0.2), 20 torr He; (20.3±1.9), 200 torr Ar; (20.6±1.3), 200 Torr He;(c) OH + p-xylene → products: (8.8±1.2), 3 torr Ar; (10.1±1.0), 20 torr He; (10.5±0.6), 200 torr He;(d) OH + ethyl benzene → products: (7.50±0.38), 3 torr He; (7.06±0.26), 20 torr He; (7.95±0.28), 200 torr He;(e) OH + n-propylbenzene → products: (6.40±0.36), 20 torr He; (5.86±0.16), 200 torr He;(f) OH + isopropylbenzene → products: (7.79±0.40), 200 torr He;(g) OH + hexafluorobenzene → products: (0.221±0.020), 20 torr He; (0.219±0.016) 200 torr He;(h) OH + n-propyl pentafluorobenzene → products: (2.52±0.54), 3 torr He; (3.01±0.76), 20 torr He; (3.06±0.24), 200 torr He;(i) OH + propylene → products: (25.6±1.2), 20 torr He; (26.3±1.2), 200 torr He;(j) OH + 1-butene → products: (29.6±1.9), 3 torr He; (29.4±1.4), 20 torr He;(k) OH + cis-2-butene → products: (43.2±4.1), 3 torr He; (42.6±2.5), 20 torr He;(l) OH + tetramethylethylene → products: (56.9±1.3), 20 torr He.
    Additional Material: 15 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100802
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetics of the thermal decomposition of trans-1,2-dicyanocyclobutane (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 453-459 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermal decomposition of trans-1,2-dicyanocyclobutane, which yields only vinyl cyanide, have been studied in the temperature range of 570°-660°K using a stirred-flow reactor. The reaction was found to be first order and homogeneous with rate constants represented by the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}k{\rm (sec}^{- 1} {\rm) =}{{{\rm (16}{\rm .0} \pm {\rm 0}{\rm .3)} - {\rm (52}{\rm .9} \pm {\rm 0}{\rm .8)}} \mathord{\left/ {\vphantom {{{\rm (16}{\rm .0} \pm {\rm 0}{\rm .3)} - {\rm (52}{\rm .9} \pm {\rm 0}{\rm .8)}} \theta}} \right. \kern-\nulldelimiterspace} \theta} $$\end{document} where θ = 2.303 RT kcal/mol. The Arrhenius parameters are considerably higher than previously reported. On the assumption of a biradical mechanism the results are consistent with a cyano stabilization energy of ∼5 kcal/mol, in good agreement with the results of recent studies of related systems.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100504
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  • 3
    Electronic Resource
    Electronic Resource
    The thermal reaction of 2-pentene around 500°C at low extent of reaction (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 529-544 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reaction of 2-pentene (cis or trans) has been performed in a static system over the temperature range of 470°-535°C at low extent of reaction and for initial pressures of 20-100 torr. The main products of decomposition are methane and 1,3-butadiene. Other minor primary products have been monitored: trans-2-pentene, trans- and cis-2-butenes, ethane, 1,3-pentadienes, 3-methyl-1-butene, propylene, 1-butene, hydrogen, ethylene, and 1-pentene. The initial orders of formation, 0.8-1.1 for most of the products and 1.5-1.8 for 1-pentene, increase with temperature. The formation of the products and the influence of temperature on their orders can be essentially explained by a free radical chain mechanism. But cis-trans or trans-cis isomerization and hydrogen elimination from cis-2-pentene certainly involve both molecular and free radical processes. The formation of 1-pentene mainly occurs from the abstraction of the hydrogen atom of 2-pentene by resonance stabilized free radicals (C5H9.).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100602
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  • 4
    Electronic Resource
    Electronic Resource
    Very low-pressure pyrolysis (VLPP) of cyclopentene (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 117-123 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The unimolecularity of the thermal dehydrogenation of cyclopentene has been confirmed using the technique of very low-pressure pyrolysis (VLPP). Application of RRKM theory shows that the experimental unimolecular rate constants obtained over the temperature range of 942°-1152°K are consistent with the high-pressure Arrhenius parameters given by\documentclass{article}\pagestyle{empty}\begin{document}$$ \log (k/\sec ^{-1}) = 13.35 - 61/\theta $$\end{document} where θ = 2.303 RT kcal/mol. These parameters are in good agreement with static and shock tube studies. No firm evidence could be found for any side reactions or reversibility under the experimental conditions used.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100110
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  • 5
    Electronic Resource
    Electronic Resource
    The heat of formation of the acetonyl radical VLPP studies of acetonyl bromide, isopropenylmethylether, and hexanedione-2,5 in a search for acetonyl stabilization energy (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 295-306 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of acetonyl bromide, isopropenylmethylether, and hexanedione-2,5 was studied using the very-low-pressure pyrolysis (VLPP) technique. The acetonyl radical is a product of each reaction. Arrhenius parameters determined are or acetonyl bromide ← acetonyl + Br: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k\left({\sec ^{- 1}} \right) = 16.0 - 62.5/\theta\,{\rm at}\,300^{\rm o} {\rm K} $$\end{document} and for isopropenylmethylether ← acetonyl + CH3: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k\left({\sec ^{- 1}} \right) = 15.8 - 66.3/\theta\,{\rm at}\,300^{\rm o} {\rm K} $$\end{document} These lead to values of acetonyl stabilization energy (SE) of 0.8 and -4.0 kcal/mol, respectively. Comparison of the pyrolyses of hexanedione-2,5 and 2,5-dimethylhexane indicate a value of SE ∼ 2 kcal/mol. The total of these results is taken, along with previous work, to indicate that 0 ≲ SE ≲ 2 kcal/mol.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100306
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  • 6
    Electronic Resource
    Electronic Resource
    Absolute rate constants for the reactions of O(3P) atoms with DCl and DBr (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1-14 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Earlier work on the reactions of O(3P) atoms with HCl and HBr has been extended by measuring rate constants for A flow-tube method was used with chemiluminescent monitoring of the removal of atomic oxygen. Rate constants were measured at temperatures between 340 and 489 K for (2a) and 295 and 419 K for (2b); they can be matched by the Arrhenius expressions: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{2a} = 3.7(\pm 0.9) \times 10^{- 12} \exp \left({\frac{{- (7.0 \pm 0.5kcal/mole)}}{{RT}}} \right) $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{2b} = 5.8(\pm 0.5) \times 10^{- 12} \exp \left({\frac{{- (3.5 \pm 0.2kcal/mole)}}{{RT}}} \right) $$\end{document} where the units are cm3 molecule-1 sec-1 and the errors correspond to a single standard deviation. The results of a quasiclassical trajectory study of collisions of O(3P) with HCl (v = 0,1, and 2) and DCl (v= 0,1, and 2) are also reported. These strengthen the conclusion that, although the rates of reactions (1a) and (2a) are selectively enhanced by vibrationally exciting HCl or DCl, molecules with 0 〈 v ≤ 2 are mainly removed in collisions with O(3P) atoms by nonreactive relaxation.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100102
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  • 7
    Electronic Resource
    Electronic Resource
    Application of RRKM theory to the reactions OH + NO2 + N2 → HONO2 + N2 (1) and ClO + NO2 + N2 → ClONO2 + N2 (2); a modified gorin model transition state (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 489-501 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants as a function of both temperature and pressure were calculated for the title reactions using RRKM theory in conjunction with a modified Gorin transition state. The modification introduces a hindrance parameter which accounts for repulsive interactions between the rotating fragments. At the highest stratospheric pressures (∼50 torr) and at stratospheric temperature (∼220°K), the extent of “falloff” from first-order [N2] dependence is ∼70% for reaction (1) and ∼35% for reaction (2).
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100507
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  • 8
    Electronic Resource
    Electronic Resource
    Very low-pressure pyrolysis (VLPP) of but-1-yne the heat of formation and stabilization energy of the propargyl radicalPresented in part at the Fifth International Symposium on Gas Kinetics, Manchester, U.K., July 1977 (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 545-555 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The unimolecular decomposition of but-1-yne has been investigated over the temperature range of 1052° - 1152°K using the technique of very low-pressure pyrolysis (VLPP). The primary process is C—C bond fission yielding methyl and propargyl radicals. Application of RRKM theory shows that the experimental rate constants are consistent with the highpressure Arrhenius parameters given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{- 1}) = (1.55 \pm 0.3) - (74.2 \pm 2.0)/\theta $$\end{document} where θ = 2.303 RT kcal/mol. The parameters are in good agreement with estimates based on shock-tube studies. The activation energy, combined with thermochemical data, leads to DH°[HCCCH2—CH3] = 76.0, ΔHf°(HCCĊCH2,g) = 81.4, and DH° [HCCCH2—H] = 89.2, all in kcal/mol at 300°K. The stabilization energy of the propargyl radical SE° (HCCĊCH2) has been found to be 8.8 kcal/mol. Recent result for the shock-tube pyrolysis of some alkynes have been analyzed and shown to yield values for the heat of formation and stabilization energy of the propargyl radical in excellent agreement with the present work. From a consideration of all results it is recommended that ΔHf,300°(HCCĊCH2,g) = 81.5±1.0, DH300°[HCCCH2—H] = 89.3 ± 1.0, and SE° (HCCĊCH2) = 8.7±1.0 kcal/mol.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550100603
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  • 9
    Electronic Resource
    Electronic Resource
    The kinetics of ClO formation in the flash photolysis of chlorine-oxygen mixtures (1978)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1233-1244 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The production of ClOO and ClO radicals following the flash photolysis of chlorine + oxygen mixtures has been studied. For the mechanism the following kinetic parameters were measured: k3K = 1.3 × 1010 l2/mol2·sec; k2/k3 = 17; and k3/∊(ClOO; 250 nm) = 9.7 × 105 cm/sec. Then k3 = 5.9 × 109 l/mol·sec, k2 = 1.0 × 1011 l/mol·sec, and ∊(ClOO; 250 nm) = 6.1 × 103 l/mol·cm. From limits established for the equilibrium constant K, ΔH°f (ClOO) = 94 ± 2 kJ/mol.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550101206
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