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  • Physical Chemistry  (75)
  • Wiley-Blackwell  (75)
  • American Association for the Advancement of Science
  • American Meteorological Society
  • Annual Reviews
  • 1980-1984  (75)
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Verlag/Herausgeber
  • Wiley-Blackwell  (75)
  • American Association for the Advancement of Science
  • American Meteorological Society
  • Annual Reviews
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  • 1
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 231-240 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Atmospheric photodissociation rate coefficients and photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate were calculated as a function of altitude from their measured visible and near ultraviolet photoabsorption cross sections at 298 K. The lifetime of methyl nitrite is nearly independent of altitude and is approximately 2 min. From 0 to 50 km the lifetime of nitromethane varies from 10 to 0.5 hr, while that of methyl nitrate changes from 5.3 to 0.09 days, respectively.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1027-1051 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Kinetics of the basic hydrolysis of glyceryl trinitrate (TNG) were investigated in CO2-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature controlled reactor vessel with provision for continuous N2 sparging of the reaction mixture. TNG hydrolyzed via second-order reaction at 25°C, 18°C, and 10°C. The activation energy of the hydrolysis reaction of TNG was calculated from the kinetic data and found to be equal to 27.53 kcal/mol. The major products of the hydrolysis of TNG in solution of calcium hydroxide were calcium nitrate and calcium nitrite, accounting for approximately 50% of the degradation products. The minor identified products such as calcium oxalate and nitrate esters amounted to approximatey 6% of the products. The remaining 30% of the isolated products was a mixture of calcium formate, a nitrate ester, and unidentified volatiles, polymerlike substances, and other organic residue.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 903-917 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Kinetics of the basic hydrolysis of 1-glyceryl mononitrate (1-MNG) and 2-glyceryl mononitrate (2-MNG) were investigated in CO2-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature-controlled reactor vessel with provision for continuous N2 sparging of the reaction mixture. Both glyceryl nitrate esters hydrolyzed via second-order reaction at 25°C. 2-MNG in calcium hydroxide solution isomerized to 1-MNG, which subsequently hydrolyzed to form NO3-. In strongly basic aqueous solutions of NaOH (30%), 2-MNG is converted to glycidol and NO3-.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 977-984 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Pyridiniumchlorochromate (PCC) oxidizes aniline and substituted anilines except nitro anilines smoothly in chlorobenzene-nitrobenzene mixtures in the presence of dichloroacetic acid. The reaction has unit dependence on each of the aniline, PCC, and dichloroacetic acid concentrations. Electron-releasing substituents accelerate the reaction, whereas electronwithdrawing groups retard the reaction, and the rate data obey Hammett's relationship. The reaction constant ρ is -3.75. Azobenzene and p-benzoquinone have been obtained as products. The observed experimental data have been rationalized in terms of the formation of an intermediate complex involving PCC-amine undergoing a rapid decomposition to products.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 641-646 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An iterative method has been devised for the simulation of chemiluminescence data during the oxidative decomposition of αα′ azobisisobutyronitrile in the presence of ethylbenzene. From this simulation the cross termination rate constant of the two types of peroxy radicals present has been estimated.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1139-1150 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The unimolecular decomposition of methyl nitrite in the temperature range 680-955 K and pressure range 0.64 to 2.0 atm has been studied in shock-tube experiments employing real-time absorption of CW CO laser radiation by the NO product. Computer kinetic modeling using a set of 23 reactions shows that NO product is relatively unreactive. Its initial rate of production can be used to yield directly the unimolecular rate constant, which in the fall-off region, can be represented by the second-order rate coefficient in the Arrhenius form: \documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = 10^{17.90 \pm 0.21} \exp (- 17200 \pm 400/T){\rm cm}^{\rm 3} {\rm mol}^{ - 1} {\rm s}^{ - 1}$$\end{document} A RRKM model calculation, assuming a loose CH3ONO≠ complex with two degrees of free internal rotation, gives good agreement with the experimental rate constants.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 7
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 605-621 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The previously reported extensive mechanism for the pyrolysis of propane and n-butane around 800 K is reexamined in the light of a recent reevaluation of the rate constant data base, and the sensitivity of model simulations to variations in the rate parameters is studied. The pyrolysis rates of butane and the product distribution of propane remain in good agreement with the available experiments, while the rate of propane and the product distribution of butane now show significant differences. The linear sensitivity analysis of the reaction matrix demonstrates an intimate coupling between initiation, hydrogen abstraction, radical decomposition, and recombination reactions as primarily responsible for the overall behavior of the mechanism. The role of unsaturated radicals in the self-inhibition of the pyrolysis process is quantitatively established. The study of the sensitivity coefficients for butane product formation has permitted pinpointing those specific reaction steps in the mechanism which are most likely responsible for the remaining discrepancies between model and experiment. This particular example demonstrates the usefulness of sensitivity calculations for the isolation of reactions for which improvements in rate parameter values are needed.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 8
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 755-770 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The thermal decomposition of cyclopentyl cyanide has been investigated in the temperature range of 905-1143 K using both conventional stirred-flow reactor and very low-pressure pyrolysis (VLPP) techniques. The results from both techniques are consistent. The main primary processes are HCN elimination to form cyclopentene: and ring fragmentation to form vinyl cyanide plus propylene and ethylene plus cyanopropenes: Under the experimental conditions cyclopentene undergoes further decomposition to cyclopentadiene plus hydrogen. There is evidence for conversion of some of the reactant to a solid residue, presumably polymer. From the stirred-flow reactor results the following Arrhenius expressions were obtained: log k1(s-1) = (12.8 ± 0.3) - (65.6 ± 1.3)/θ and log k2(s-1) = (16.0 ± 0.3) - (80.0 ± 1.1)/θ, where θ = 2.303RT kcal/mol. Application of RRKM theory shows that the VLPP experimental rate constants are consistent with high-pressure Arrhenius parameters given by log k1(s-1) = (12.8 ± 0.3) - (67.8 ± 2.5)/θ for HCN elimination, and log k4(s-1) = (16.3 ± 0.3) - (80.1 ± 2.0)/θ for the sum of the ring fragmentation pathways. The rate parameters for HCN elimination are in good agreement with previous VLPP studies of alkyl cyanides and with theoretical predictions. The difference in activation energies for the ring opening of cyclopentane and cyclopentyl cyanide is reasonably close to the established value for the cyano stabilization energy. This supports the assumption of a biradical mechanism.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 9
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 13 (1981), S. 85-96 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of oxidation of dimethyl, dipropyl, and diphenyl sulfides by pyridinium chloro chromate in chlorobenzene-nitrobenzene mixtures are reported. The rate data show Michaelis-Menten behavior. The oxidation process is catalyzed by the organic acids like dichloro and trichloro acetic acids. The rate-determining step appears to be a unimolecular decomposition of a complex of the reactants.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 10
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1009-1026 
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Kinetics of the basic hydrolysis of 1,2-glyceryl dinitrate (1,2-DNG) and 1,3-glyceryl dinitrate (1,3-DNG) esters were investigated in CO2-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature controlled reactor vessel with provision for continuous N2 sparging of the reaction mixture. Both glyceryl dinitrate esters hydrolyzed via second-order reaction at 25°C. 1,2-DNG in basic solutions isomerized to 1,3-DNG which subsequently hydrolyzed to yield products. The main hydrolysis product of 1,3-DNG was identified as glycidyl nitrate. Other products formed during the basic hydrolysis of DNGs were nitrites and nitrates.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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