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  • 1
    ISSN: 1573-0662
    Keywords: Monoterpenes ; OH radical reactions ; O3 reactions ; carbonyl products
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract The formation yields of nine carbonyl products are reported from the gas-phase OH radical-initiated reactions (in the presence of NO x ) and the O3 reactions with seven monoterpenes. The products were identified using GC/MS and GC-FTIR and quantified by GC-FID analyses of samples collected on Tenax solid adsorbent cartridges. The identities of products from camphene, limonene and β-pinene were confirmed by comparison with authentic standards. Sufficient quantities of products from the 3-carene, limonene, α-pinene, sabinene and terpinolene reactions were isolated to allow structural confirmation by proton NMR spectroscopy. The measured total carbonyl formation yields ranged from non-detectable for the OH radical reaction with camphene and the O3 reactions with 3-carene and limonene to ∼0.5 for the OH radical reaction with limonene and the O3 reaction with sabinene.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 839-847 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the reaction of OH radicals with a series of ketones have been determined at 299 ± 2 K, using methyl nitrite photolysis in air as a source of hydroxyl radicals. Using a rate constant for the reaction of OH radicals with cyclohexane of 7.57 × 10-12 cm3 molecule-1 s-1, the rate constants obtained are (× 1012 cm3 molecule-1 s-1): 2-pentanone, 4.74 ± 0.14; 3-pentanone, 1.85 ± 0.34; 2-hexanone, 9.16 ± 0.61; 3-hexanone, 6.96 ± 0.29; 2,4-dimethyl-3-pentanone, 5.43 ± 0.41; 4-methyl-2-pentanone, 14.5 ± 0.7; and 2,6-dimethyl-4-heptanone, 27.7 ± 1.5. These rate constants indicate that while the carbonyl group decreases the reactivity of C—H bonds in the α position toward reaction with the OH radical, it enhances the reactivity in the β position.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 919-926 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the gas-phase reactions of OH radicals with a series of alkyl nitrates have been determined at 299 ± 2 K, using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with cyclohexane of 7.57 × 10-12 cm3/molec·s, the rate constants obtained are (× 1012 cm3/molec·s): 2-propyl nitrate, 0.18 ± 0.05; 1-butyl nitrate, 1.42 ± 0.11; 2-butyl nitrate, 0.69 ± 0.10; 2-pentyl nitrate, 1.87 ± 0.12; 3-pentyl nitrate, 1.13 ± 0.20; 2-hexyl nitrate, 3.19 ± 0.16; 3-hexyl nitrate, 2.72 ± 0.22; 3-heptyl nitrate, 3.72 ± 0.43; and 3-octyl nitrate, 3.91 ± 0.80. These rate constants, which are the first reported for the alkyl nitrates, are significantly lower than those for the parent alkanes, and a formula, based on the numbers of the various types of C—H bonds in the alkyl nitrates, is derived for rate constant estimation purposes.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 957-966 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the gas-phase reactions of NO3 radicals with a series of cycloalkenes have been determined at 298 ± 2 K, using a relative rate technique. Using an equilibrium constant for the NO2 + NO3 ⇄ N2O5 reactions of 3.4 × 10-11 cm3 molecule-1, the following rate constants (in units of 10-13 cm3 molecule-1 s-1) were obtained: cyclopentene, 4.52 ± 0.52; cycloheptene, 4.71 ± 0.56; bicyclo[2.2.1]-2-heptene, 2.41 ± 0.28; bicyclo[2.2.2]-2-octene, 1.41 ± 0.17; bicyclo[2.2.1]-2,5-heptadiene, 9.92 ± 1.13; and 1,3,5-cycloheptatriene, 12.6 ± 2.9. When combined with previous literature rate constants for cyclohexene and 1,4-cyclohexadiene, these data show that the rate constants for the nonconjugated cycloalkenes studied depend to a first approximation on the number of double bonds and the degree and configuration of substitution per double bond. No obvious effects of ring strain energy on these NO3 radical addition rate constants were observed. Our previous a priori predictive techniques for the alkenes and cycloalkenes can now be extended to strained cycloalkenes.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 15 (1983), S. 75-81 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relative rate constants for the reaction of OH radicals with a series of α,β-unsaturated carbonyls have been determined at 299 ± 2 K, using methyl nitrite photolysis in air as a source of OH radicals. Using a rate constant for the reaction of OH radicals with propene of 2.52 × 10-11 cm3/molec·s, the rate constants obtained are (× 1011 cm3/molec·s: acrolein, 1.83 ± 0.13; crotonaldehyde, 3.50 ± 0.40; methacrolein, 2.85 ± 0.23; and methylvinylketone, 1.88 ± 0.14). These data, which are necessary input to chemical computer models of the NOx-air photooxidations of conjugated dialkenes, are discussed and compared with literature values.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 837-846 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas phase reaction of OH radicals with dimethyl sulfide (CH3SCH3) have been studied at various temperatures and total pressures using two relative rate methods and a flash photolysis technique. For the relative rate methods, rate constants were measured at 296 ± 2 K as a function of the O2 pressure at a total pressure of ca. 740 torr. Data from these three experimental techniques were not in agreement. It is concluded that the relative rate techniques are subject to secondary reactions, possibly involving CH3S radicals. A rate constant of (2.5-0.6+0.9) × 10-12 e(130 = 102)/T cm3 molecule-1 s-1 obtained using the flash photolysis-resonance fluorescence data in the absence of O2, and which is in agreement with the lower range of values previously reported in the literature, is recommended.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 3-Methylfuran has been identified as a product of the gas-phase reaction of the OH radical with isoprene, and under simulated atmospheric conditions a formation yield of 0.044 ± 0.006 was determined. In an analogous manner, the OH radical reaction with 1,3-butadiene formed furan with a yield of 0.039 ± 0.011. Using a relative rate method, a rate constant for the reaction of the OH radical with 3-methylfuran of 9.35 × 10-11 cm3 molecule-1 s-1 (with an estimated overall uncertainty of ±20%) at 296 ± 2 K was also determined. These data show that 3-methylfuran is a reactive compound which will be present in the troposphere at concentrations ≤5% of those of its isoprene precursor.
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 775-799 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nitroarene products of the gas-phase reactions of acenaphthylene, acenaphthene, phenanthrene, and anthracene-d10 with N2O5 and the OH radical (in the presence of NOx) are reported. The calculated atmospheric lifetimes of these polycyclic aromatic hydrocarbons (PAH), as well as those of naphthalene, 1- and 2-methylnaphthalene, biphenyl, fluoranthene, pyrene, and acephenanthrylene, show that reaction with the OH radical is the dominant loss process for these PAH, with the exception of acenaphthylene, acenaphthene, and acephenanthrylene which contain an external cyclopenta-fused ring. For these latter PAH, reaction with the NO3 radical, and for acenaphthylene and acephenanthrylene reaction with O3, are also expected to be important atmospheric loss processes.The nitroarenes observed as products of the atmospherically-important gas-phase reactions of the PAH in environmental chamber studies are compared with the nitroarenes measured in ambient air samples collected in California. It is concluded that although nitroarenes are formed in low yields (≲5%) from the OH radical-initiated reactions of the PAH, atmospheric formation of nitroarenes may contribute significantly to ambient nitroarene concentrations.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 273-281 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase reactions of the OH radical with (C2H5O)3PO and (CH3O)2P(S)Cl and of the reactions of NO3 radicals and O3 with (CH3O)2P(S)Cl have been studied at room temperature. Using a relative rate technique, the rate constants determined for the reactions of the OH radical with (C2H5O)3PO and (CH3O)2P(S)Cl at 296 ± 2 K and 740 torr total pressure of air were (5.53 ± 0.35) × 10-11 and (5.96 ± 0.38) × 10-11 cm3 molecule-1 s-1, respectively. Upper limits to the rate constants for the NO3 radical and O3 reactions with (CH3O)2P(S)Cl of 〈3 × 10-14 cm3 molecule-1 s-1 and 〈2 × 10-19 cm3 molecule-1 s-1, respectively, were obtained. These data are compared and discussed with previous literature data for organophosphorus compounds.
    Additional Material: 2 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 20 (1988), S. 513-539 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the atmospherically important gas-phase reactions of acenaphthene and acenaphthylene with OH and NO3 radicals, O3 and N2O5 have been investigated at 296 ± 2 K. In addition, rate constants have been determined for the reactions of OH and NO3 radicals with tetralin and styrene, and for the reactions of NO3 radicals and/or N2O5 with naphthalene, 1- and 2-methylnaphthalene, 2,3-dimethylnaphthalene, toluene, toluene-α,α,α-d3 and toluene-d8. The rate constants obtained (in cm3 molecule-1 s-1 units) at 296 ± 2 K were: for the reactions of O3; acenaphthene, 〈5 × 10-19 and acenaphthylene, ca. 5.5 × 10-16; for the OH radical reactions (determined using a relative rate method); acenaphthene, (1.03 ± 0.13) × 10-10; acenaphthylene, (1.10 ± 0.11) × 10-10; tetralin, (3.43 ± 0.06) × 10-11 and styrene, (5.87 ± 0.15) × 10-11; for the reactions of NO3 (also determined using a relative rate method); acenaphthene, (4.6 ± 2.6) × 10-13; acenaphthylene, (5.4 ± 0.8) × 10-12; tetralin, (8.6 ± 1.3) × 10-15; styrene, (1.51 ± 0.20) × 10-13; toluene, (7.8 ± 1.5) × 10-17; toluene-α,α,α-d3, (3.8 ± 0.9) × 10-17 and toluene-d8, (3.4 ± 1.9) × 10-17. The aromatic compounds which were observed to react with N2O5 and the rate constants derived were (in cm3 molecule-1 s-1 units): acenaphthene, 5.5 × 10-17; naphthalene, 1.1 × 10-17; 1-methylnaphthalene, 2.3 × 10-17; 2-methylnaphthalene, 3.6 × 10-17 and 2,3-dimethylnaphthalene, 5.3 × 10-17. These data for naphthylene and the alkylnaphthalenes are in good agreement with our previous absolute and relative N2O5 reaction rate constants, and show that the NO3 radical reactions with aromatic compounds proceed by overall H-atom abstraction from substituent-XH bonds (where X = C or O), or by NO3 radical addition to unsaturated substituent groups while the N2O5 reactions only occur for aromatic compounds containing two or more fused six-membered aromatic rings.
    Additional Material: 12 Ill.
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