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  • 1990-1994  (2)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 665-671 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative rate technique has been used to measure rate constants for the reaction of chlorine atoms with nitro methane, nitro ethane, nitro propane, nitro butane, nitro pentane, ethyl nitrate, isopropyl nitrate, n-propyl nitrate, 2-pentyl nitrate, and 2-heptyl nitrate. Decay rates of these organic species were measured relative to one or more of the following reference compounds; n-butane, ethane, chloroethane, and methane. Using rate constants of 2.25 × 10-10 5.7 × 10-11, 8.04 × 10-12, and 1.0 × 10-13 cm3 molecule-1 s-1 for the reaction of Cl atoms with n-butane, ethane, chloroethane, and methane, respectively, the following rate constants were derived, in units of cm3 molecule-1 s-1: nitro methane, 〈7 × 10-15; nitro ethane, (2.05 ± 0.14) × 10-13; nitro propane, (1.13 ± 0.05) × 10-11; nitro butane, (5.13 ± 0.68) × 10-11; nitro pentane, (1.40 ± 0.14) × 10-10; ethyl nitrate, (3.70 ± 0.24) × 10-12; n-propyl nitrate, (2.15 ± 0.13) × 10-11; i-propyl nitrate, (3.94 ± 0.48) × 10-12; 2-pentyl nitrate, (1.00 ± 0.06) × 10-10; and 2-heptyl nitrate, (2.84 ± 0.50) × 10-10. Quoted errors represent 2σ and do not include possible systematic errors due to errors in the reference rate constants. Experiments were performed at 295 ± 2 K and atmospheric pressure (≃740 torr) of synthetic air. The results are discussed with respect to the previous literature data and to the modeling of these compounds in the atmosphere.
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 1257-1269 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanisms for the Cl-initiated and OH-initiated atmospheric oxidation of t-butyl alcohol (TBA), methyl t-butyl ether (MTBE), and dimethyl ether (DME) have been determined. For TBA the only products observed are equimolar amounts of H2CO and acetone, and its atmospheric oxidation can be represented by (7), The mechanism for the atmospheric oxidation of DME is also straight forward, with the only observable product being methyl formate, The mechanism for the atmospheric oxidation of MTBE is more complex, with observable products being t-butyl formate (TBF) and H2CO. Evidence is presented also for the formation of 2-methoxy-2-methyl propanal (MMP), which is highly reactive and presumably oxidized to products. The atmospheric oxidation of MTBE can be represented by (9) and (10), In terms of atmospheric reactivity, DME, TBA, and MTBE all compare favorably with methanol. In terms of rate of reaction in the atmosphere, DME, MTBE, and TBA are 1.4, 0.40, and 0.28 times as reactive as CH3OH towards OH on a per carbon basis. With regard tochemistry, atmospheric oxidation of CH3OH yields highly reactive H2CO as the sole carbon-containing product. In contrast, only 25% of the carbon in TBA is converted to H2CO, with the balance yielding unreactive acetone. For DME, all the carbon is converted to methyl formate which is unreactive. Finally, for MTBE, 60% is converted to unreactive TBF while the remaining 40% produces highly reactive MMP.Final assessment of the impact of these materials on the atmospheric reactivity of vehicle emissions requires the determination of their emissions rates under realistic operating conditions.
    Additional Material: 9 Ill.
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