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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Energy & fuels 3 (1989), S. 284-287 
    ISSN: 1520-5029
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Environmental science & technology 24 (1990), S. 108-111 
    ISSN: 1520-5851
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 98 (1994), S. 5906-5912 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
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  • 4
    ISSN: 1573-0662
    Keywords: Elemental mercury ; dimethyl mercury ; fast-flow discharge technique ; gas phase FT-IR ; product study ; atmospheric chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Tropospheric mercury is dominated by gas phase species. In this paper, the gas phase reactions between the nitrate radical and volatile biogenic mercury species have been investigated. An upper limit for the gas phase rate coefficient for reaction between elemental mercury and NO3-radicals was determined to 4 × 10−15 cm3 molecule−1 s−1 by using the fast flow-discharge technique. The reaction between dimethyl mercury and NO3, previously shown to be rapid, has also been studied in the laboratory with respect to product distribution using FT-IR. The result from the product study is consistent with a transformation of dimethyl mercury into inorganic, divalent mercury. All carbon delivered as dimethyl mercury was transformed into formaldehyde, methanol and methyl peroxynitrate. Hg was observed as a minor (≈2%) product. By exclusion, HgO is proposed as the mercury-containing product. Thus, the reaction between dimethyl mercury and the nitrate radical is excluded as a source of monomethyl mercury species in the atmosphere.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Water, air & soil pollution 81 (1995), S. 121-134 
    ISSN: 1573-2932
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The importance of nitrogen dioxide for oxidation of gaseous mercury in the atmosphere and in combustion flue gases was investigated. The reaction rate was studied by a stopped flow technique in a temperature interval from 20 °C to 900 °C and at surface-to-volume ratios of 1.8 and 4 cm−1. The reaction exhibits a first-order dependence with respect to mercury and a second-order dependence with respect to NO2 in the temperature range from 20 °C to 200 °C. From 250 °C to 500 °C, the NO2 dependence is lost and a partly heterogeneous reaction is proposed. Above 500 °C, no reaction was detectable. The Hg-NO2 reaction appears to have little significance for the atmospheric chemistry of mercury nor for the transformation of mercury in combustion processes, It might, however, have some importance on the oxidation of elemental mercury in aging combustion plumes.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 26 (1994), S. 367-380 
    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.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 195-201 
    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.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 857-866 
    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.
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  • 9
    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.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 467-474 
    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.
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