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  • Physical Chemistry  (139)
  • Wiley-Blackwell  (139)
  • 2015-2019
  • 1985-1989  (64)
  • 1980-1984  (75)
  • 1950-1954
  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 2 (1989), S. 117-130 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas phase ion/molecule reactions have been used to probe the structure of ions obtained by electron impact upon 1-(diphenylmethylene)cyclopropane and 2,2-diphenyl-1-methylenecyclopropane. The resulting ions of molecular composition C16H14 (m/z 206+) were reacted with charge transfer reagents (6·9 〈 IP 〈 8·8eV), giving evidence for the presence of isomeric ions with different reactivities. The less reactive ion is identified as a trimethylenemethane species (TMM+) in which one cyclopropane bond is broken; the more reactive ions are assigned as vertical ions in which the cyclopropane ring is unaffected. The vertical ions have recombination energies of 8·44 ± 0·05eV, whereas TMM+ has one of 7·41±0·05eV. The TMM+ fraction is not constant; it increases with increasing IP of the reagent. This is attributed to a reagent-catalyzed isomerization of the vertical ion to TMM+. In addition, the reagent ions are observed to undergo a unique reaction with the neutral methylenecyclopropane derivatives: electron transfer and ring opening to yield TMM+. These findings limit the application of the customary equilibrium measurements as a method to determine the substrate IP.
    Additional Material: 7 Ill.
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  • 2
    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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  • 3
    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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  • 4
    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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  • 5
    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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  • 6
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The third order rate coefficients for the addition reaction of Cl with NO2, Cl + NO2 + M → ClNO2 (ClONO) + M; k1, were measured to be k1(He) = (7.5 ± 1.1) × 10-31 cm6 molecule-2 s-1 and k1(N2) = (16.6 ± 3.0) × 10-31 cm6 molecule-2 s-1 at 298 K using the flash photolysis-resonance fluorescence method. The pressure range of the study was 15 to 500 torr He and 19 to 200 torr N2. The temperature dependence of the third order rate coefficients were also measured between 240 and 350 K. The 298 K results are compared with those from previous low pressure studies.
    Additional Material: 1 Tab.
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  • 7
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 2 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 16 (1984), S. 1139-1150 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 5 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 639-649 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Gaseous haloalkyl radicals were prepared by the photolysis of iodohaloalkanes in Pyrex vessels containing mercury (I) halides. Cleavage of the carbon-iodine bond gave mercury (II) halide and a radical which was subsequently shown to react on the ground state electronic energy surface. The usefulness of this method for chemical activation rate constant studies is illustrated by measurement of unimolecular rate constants for decomposition of CH2ClCH2Cl and CF3CH3. Possible mechanisms for photodecomposition of iodoalkanes in the presence of mercury (I) halides are discussed.
    Additional Material: 4 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 1235-1247 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechansim for the NO2-initiated oxidation of tetramethyl ethylene (TME) have been studied using the FTIR spectroscopic method in mixtures containing NO2 and TME (0.1-1.0 Torr) and N2—O2 (700 Torr) at 298 ± 2 K. While TME decayed according to -d[TME]/dt = kobs[NO2][TME], NO2 exhibited a complex kinetic behavior. Furthermore, values of kobs were dependent on [O2]. Among the products were (CH3)2CO and at least three NO2-containing compounds. These results indicate the formation of a nitro-alkylperoxy radical via reactions (1), (-1), and (2), and its subsequent reactions leading to the observed products. The [O2]-dependence of kobs yielded k1 = (1.07 ± 0.15) × 10-20 cm3 molecule-1 S-1 and k-1/k2 = (3.54 ± 0.61) × 1018 molecule cm-3.
    Additional Material: 7 Ill.
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