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  • Physical Chemistry  (175)
  • Wiley-Blackwell  (175)
  • American Association for the Advancement of Science
  • American Institute of Physics (AIP)
  • Elsevier
  • Nature Publishing Group
  • 2000-2004
  • 1995-1999  (50)
  • 1980-1984  (75)
  • 1970-1974  (50)
  • 1950-1954
Collection
Publisher
  • Wiley-Blackwell  (175)
  • American Association for the Advancement of Science
  • American Institute of Physics (AIP)
  • Elsevier
  • Nature Publishing Group
Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 8 (1995), S. 26-30 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Slight structural moiecular variations are known to affect different properties of compounds. In solution, different solute-solvent interactions are known also to alter the properties of numerous compounds. Quantitative structure-activity relationships (QSAR) are used regularly to analyze and predict the variations of different properties of compounds that are caused by structural variations and significant solute-solvent interactions. The relative basicities of n-propylamine, dipro;ylamine and tripropylamine were determined in nine different solvents from potentiometric titrations. QSAR that were developed from these experimental basicity values were used to evaluate the type and significance of the solute-solvent interactions. The important interactions that influence basicity variations for the propylamines studied are dipolarity-polarizability interaction between the solute and the solvent and hydrogen bonds from the propylammonium ions to basic solvents. The role of hydrogen bonds from the propylamines to acidic solvents is minor.
    Additional Material: 2 Tab.
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  • 2
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate parameters for the reaction of ground-state atomic sulfur, S(3P), with the olefins cis-2-butene and tetramethylethylene have been determined over a temperature range of ∽280°K. A major finding of this study was that the rate constants for both reactions showed negative temperature dependencies. When k is expressed in the form of an Arrhenius equation, this necessarily leads to negative activation energies: k1 = (4.68 ± 0.70) × 10-12 exp (+0.23 ± 0.09 kcal/mole)/RT (219°-500°K) k2 = (4.68 ± 1.70) × 10-12 exp (+1.29 ± 0.23 kcal/mole)/RT (252°-500°K) Units are cm3 molec-1s-1. When a threshold energy of 0.0 kcal/mole is assumed for reaction (2), the temperature dependence of the preexponential term has a value of T-2. Making the usual simplifying assumptions, neither collision theory nor transition state theory leads to a preexponential factor with a strong enough negative temperature dependence. A comparison of these results with those derived from studies of the reactions of atomic oxygen, O(3P), with the same olefins shows that in both studies simple bimolecular processes were being examined. Also discussed are the possible experimental and theoretical ramifications of these new results.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 6 (1974), S. 813-828 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Study of the reaction by very-low-pressure pyrolysis (VLPP) in the temperature range of 550-850°K yields for the high-pressure Arrhenius parameters \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }\,k_{\rm 1} = (15.6 \pm 0.5) - (36.0 \pm 1.0)/\theta {\rm \,(sec}^{{\rm - 1}})$$\end{document} where θ = 2.303RT in kcal/mole. These in turn yield for the high-pressure second-order recombination of tBu + NO, k-1 = (3.5 ± 1.7) × 109 1./mole·sec at 600°K. For the competing reaction l./mole·sec and E4 ≥ 4.2 kcal/mole. The bond dissociation energy DHo (tBu-NO) was determined to be (39.5 ± 1.5) kcal/mole, both from the equilibrium constant and from the activation energy of reaction (1), obtained from RRKM calculations. A ‘free-volume’ model for the transition state for dissociation is consistent with the data. A limited study of the system at 8-200 torr showed an extremely rapid inhibition by products and a very complex set of products.
    Additional Material: 3 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 345-362 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general computational method for obtaining complete solutions of time-dependent kinetic equations has been developed and applied to free radical-initiated reactions of alkanes with oxygen. The method has been applied to the low-temperature, peroxide-initiated oxidations of isobutane and isopentane. Using available independently measured and estimated values for the rate constants and activation parameters for each of the 20 proposed reaction steps for the oxidation of isobutane, the rates and products have been calculated for both the liquid phase and gas phase in the range of 100°-155°C. The calculated rates and products of oxidation agree with published experimental values. The oxidation of isopentane was examined by a 32-reaction model. The rate constants were estimated using values for the appropriate rate steps in the oxidation of n-butane and isobutane. The calculation of the oxidation rate and products agree with our experiments.
    Additional Material: 7 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 231-240 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1027-1051 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 11 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 903-917 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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-.
    Additional Material: 6 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 977-984 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 4 Tab.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 1179-1196 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The methyl-methyl reaction was studied in a shock tube using uv narrowline laser absorption to measure time-varying concentration profiles of CH3. Methyl radicals were rapidly formed initially by pyrolysis of various precursors, azomethane, ethane, or methyl iodide, dilute in argon. The contributions of the various product channels, C2H6, C2H5 + H, C2H4 + H2, and CH2 + CH4, were examined by varying reactant mixtures and temperature.The measured rate coefficients for recombination to C2H6 between 1200 and 1800 K are accurately fit using the unimolecular rate coefficients reported by Wagner and Wardlaw (1988). The rate coefficient for the C2H5 + H channel was found to be 2.4 (±0.5) × 1013 exp(-6480/T) [cm3/mol-s] between 1570 and 1780 K, and is in agreement with the value reported by Frank and Braun-Unkhoff (1988). No evidence of a contribution by the C2H4 + H2 channel was found in ethane/methane/argon mixtures, although methyl profiles in these mixtures should be particularly sensitive to this channel. An upper limit of approximately 1011 [cm3/mol-s] over the range 1700 to 2200 K was inferred for the rate coefficient of the C2H4 + H2 channel. Between 1800 and 2200 K, methyl radicals are also rapidly removed by CH3 + H ⇒ 1CH2 + H2. In this temperature range, the reverse reaction was found to have a rate coefficient of 1.3 (±0.3) × 1014 [cm3/mol-s], which is 1.8 times the room-temperature value. © 1995 John Wiley & Sons, Inc.
    Additional Material: 13 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 763-771 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Long-path FTIR spectroscopy was used to study the kinetics and mechanism of the reaction of Cl atoms with CO in air. The relative rate constants at 298 K and 760 torr for the forward direction of the reaction of Cl with 13CO and the reaction of Cl13CO with O2 were k1 = (3.4 ± 0.8) × 10-14 cm3 molecule-1 s-1 and k2 = (4.3 ± 3.2) × 10-13 cm3 molecule-1 s-1, respectively (all uncertainty limits are 2σ). The rate constant for the net loss of 13CO due to reaction with Cl in 1 atm of air at 298 K was kCl+COobs = (3.0 ± 0.6) × 10-14 cm3 molecule-1 s-1. The only observed carbon-containing product of the Cl + 12CO reaction was 12CO2, with a yield of 109 ± 18%. Our results are in good agreement with extrapolations from previous studies. The reaction mechanism and the implications for laboratory studies and tropospheric chemistry are discussed. © 1996 John Wiley & Sons, Inc.
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