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  • Physical Chemistry  (5)
  • 1
    Electronic Resource
    Electronic Resource
    Rates of reaction between the nitrate radical and some aliphatic ethers (1994)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 367-380 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate coefficients for the reaction of NO3 with dimethyl ether, diethyl ether, di-n-propyl ether, and methyl t-butyl ether (MTBE) have been determined. Absolute rates were measured at temperatures between 258 and 373 K using the fast flow-discharge technique. Relative rate experiments were also made at 295 K in a reactor equipped with White optics and using FTIR spectroscopy to follow the reactions. The measured rate coefficients (in units of 10-15 cm3 molecule-1 s-1) at 295 K are: 0.26 ± 0.11, 2.80 ± 0.23, 6.49 ± 0.65, and 0.64 ± 0.06 for dimethyl ether, diethyl ether, di-n-propyl ether, and methyl t-butyl ether, respectively. The corresponding activation energies are 21.0 ± 5.0, 17.2 ± 4.0, 15.5 ± 2.1, and 20.1 ± 1.7 kJ mole-1. The error limits correspond to the 95%-confidence interval. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550260307
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  • 2
    Electronic Resource
    Electronic Resource
    A kinetic study of chlorine radical reactions with ketones by laser photolysis technique (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 195-201 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate coefficients for reactions between Cl radicals and four ketones were determined at 294 ± 1 K with a relative rate method using a laser photolysis technique. The experiments were conducted in synthetic air in a flow system at atmospheric pressure. A mixture of Cl2/ClONO2 was photolyzed and the formation of NO3 through the reaction Cl + ClONO2 → Cl2 + NO3 was measured with and without ketones in the reaction mixture. The NO3 radical concentration was measured by optical absorption using a diode laser as the light source. The rate coefficients for the Cl-ketone reactions could then be evaluated. The following rate coefficients were obtained (in units of cm3 molecule-1 s-1): cyclohexanone (7.00 ± 1.15) × 10-11; cyclopentanone (4.76 ± 0.33) × 10-11; acetone (1.69 ± 0.32) × 10-12; and 2,3-butanedione (7.62 ± 1.66) × 10-13. The accuracy of the method employed was tested by using the well-studied reaction between Cl and methane and a rate coefficient of (9.37 ± 1.04) × 10-14 cm3 molecule-1 s-1 was obtained, which is in good agreement with previous work. The errors are at the 95% confidence level. The results in this work indicate that a carbonyl group in a ketone lowers the reactivity towards α-hydrogen abstraction by Cl radicals, compared to the corresponding Cl-alkane reactions. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 195-201, 1997.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    A kinetic study of the decomposition of HNO3 and its reaction with NO (1988)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 857-866 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate of reaction between NO and HNO3 and the rate of thermal decomposition of HNO3 have been measured by FTIR spectroscopy. The measurements were made in a teflon lined batch reactor having a surface to volume ratio of 14 m-1. During the experiments, with initial HNO3 concentrations between 2 and 12 ppm and NO concentrations between 2 and 30 ppm, a reactant stoichiometry of unity and a first order NO and HNO3 dependence were confirmed. The observed rate constant for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$${\rm HNO}_{\rm 3} + {\rm NO} \longrightarrow {\rm HNO}_{\rm 2} + {\rm NO}_2$$\end{document} at 22°C and atmospheric pressure was determined to 1.1 (±0.3) 10-5 ppm-1 min-1. At atmospheric pressure, HNO3 decomposes into NO2 and other products with a first order HNO3 dependence and with a rate constant of 2.0 (±0.2) 10-3 min-1. The apparent activation energy for the decomposition is 13 (±4) kJ mol-1.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550201104
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  • 4
    Electronic Resource
    Electronic Resource
    Atmospheric chemistry of di-tert-butyl ether: Rates and products of the reactions with chlorine atoms, hydroxyl radicals, and nitrate radicals (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 299-306 
    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 gas-phase reactions of di-tert-butyl ether (DTBE) with chlorine atoms, hydroxyl radicals, and nitrate radicals have been determined in relative rate experiments using FTIR spectroscopy. Values of k(DTBE+CI) = (1.4 ± 0.2) × 10-10,k(DTBE+OH) = (3.7 ± 0.7) × 10-12, and k(DTBE+N03) = (2.8 ± 0.9) × 10-16 cm3 molecule-1 s-1 were obtained. Tert-butyl acetate was identified as the major product of both Cl atom and OH radical initiated oxidation of DTBE in air in the presence of NOx. The molar tert-butyl acetate yield was 0.85 ± 0.11 in the Cl atom experiments and 0.84 ± 0.11 in OH radical experiments. As part of this work the rate constant for reaction of Cl atoms with tert-butyl acetate at 295 K was determined to be (1.6 ± 0.3) &times 10-11 cm3 molecule-1 s-1. The stated errors are two standard deviations (2σ). © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.8
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  • 5
    Electronic Resource
    Electronic Resource
    Rates of reaction between the nitrate radical and some unsaturated alcohols (1996)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 467-474 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate coefficients for nitrate radical gas-phase reactions with prop-2-en-l-ol (allyl alcohol), but-1-en-3-ol, and 2-methylbut-3-en-2-ol have been determined. Both absolute (fast flow discharge with diode laser detection of NO3) and relative (batch reactor and FTIR spectroscopy) rate techniques were used to measure the rate coefficients. The rate coefficients at 294 K are: (1.3 ± 0.2) × 10-14, (1.2 ± 0.3) × 10 -14, and (2.1 ± 0.3) × 10-14 cm3 molecule-1 s-1 for prop-2-en-1-ol, but-1-en-3-ol, and 2-methylbut-3-en-2-ol, respectively. The activation energy for reaction of NO3 with prop-2-en-1-ol was determined to 2.8 ± 2.5 kJ mol-1 in the temperature range between 273 and 363 K. The atmospheric importance of unsaturated alcohols and structure-reactivity considerations are also discussed. © 1996 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.9
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