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  • Physical Chemistry  (16)
  • Wiley-Blackwell  (16)
  • National Academy of Sciences
  • American Geophysical Union (AGU)
  • 1
    Electronic Resource
    Electronic Resource
    A kinetic study of the reaction of chlorine and fluorine atoms with CF3CHO at 295 ± 2 K (1993)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 819-824 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a relative rate technique the reactions of chlorine and fluorine atoms with CF3CHO have been determined to proceed with rate constants of (1.8 ± 0.4) × 10-12 and (2.7 ± 0.1)×10-11 cm3 molecule-1 s-1, respectively. Experiments were performed at 295 ± 2 K and 700 torr total pressure of nitrogen. The results are discussed with respect to the design and interpretation of laboratory studies of the atmospheric chemistry of CFC replacements. © 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550251003
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  • 2
    Electronic Resource
    Electronic Resource
    Atmospheric chemistry of CF3COOH: Kinetics of fluorine and chlorine atom reaction at 295 ± 2 K (1995)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 27 (1995), S. 189-194 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a relative rate technique the reactions of fluorine and chlorine atoms with CF3COOH have been determined to proceed with rate constants of (5.6 ± 0.7) × 10-11 and 〈1 × 10-17 cm3 molecule-1 s-1, respectively. Quoted errors for the F atom rate constant reflect statistical uncertainty (two standard deviations). Systematic errors could add an additional 20% uncertainty. Experiments were performed at 295 ± 2 K and 700 torr total pressure of nitrogen diluent. The reactions of Cl and F atoms with CF3COOH are of no atmospheric importance. Rainout is believed to be the dominant mechanism by which CF3COOH is removed from the atmosphere. The results from this study are discussed with respect to the design and interpretation of laboratory studies of the atmospheric chemistry of CFC replacements. © 1995 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550270209
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  • 3
    Electronic Resource
    Electronic Resource
    Comment: A kinetic study of chlorine radical reactions with ketones by laser-photolysis technique by Olsson et al. (1998)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 309-310 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Reduction of hexachloroiridate (IV) by benzene-1,2-diol in aqueous perchloric acid (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1081-1088 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction between benzene-1,2-diol(catechol) and hexachloroiridate (IV) have been measured in aqueous acidic perchlorate solutions by the stopped-flow method. The reaction is second order overall, and first order in each reactant. A reverse reaction also occurs, but it is much slower than the forward process. Observed rate constants are dependent on acidity, but the variation can be attributed to activity rather than mechanistic effects. The reaction appears to proceed predominantly by an outer sphere electron transfer mechanism, yielding o-benzoquinone and hexachloroiridate (III), although monoaquopentachloroiridate (III) is formed also at the higher [catechol]/[IrCl62-]ratios.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111006
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  • 5
    Electronic Resource
    Electronic Resource
    The atmospheric chemistry of Oxygenated fuel additives: t-Butyl alcohol, dimethyl ether, and methylt-butyl ether (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 1257-1269 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550221205
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  • 6
    Electronic Resource
    Electronic Resource
    Kinetics and mechanisms of the reactions of chlorine atoms with ethane, propane, and n-butane (1997)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 29 (1997), S. 43-55 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute (flash photolysis) and relative (FTIR-smog chamber and GC) rate techniques were used to study the gas-phase reactions of Cl atoms with C2H6 (k1), C3H8 (k3), and n-C4H10 (k2). At 297 ± 1 K the results from the two relative rate techniques can be combined to give k2/k1 = (3.76 ± 0.20) and k3/k1 = (2.42 ± 0.10). Experiments performed at 298-540 K give k2/k1 = (2.0 ± 0.1)exp((183 ± 20)/T). At 296 K the reaction of Cl atoms with C3H8 produces yields of 43 ± 3% 1-propyl and 57 ± 3% 2-propyl radicals, while the reaction of Cl atoms with n-C4H10 produces 29 ± 2% 1-butyl and 71 ± 2% 2-butyl radicals. At 298 K and 10-700 torr of N2 diluent, 1- and 2-butyl radicals were found to react with Cl2 with rate coefficients which are 3.1 ± 0.2 and 2.8 ± 0.1 times greater than the corresponding reactions with O2. A flash-photolysis technique was used to measure k1 = (5.75 ± 0.45) × 10-11 and k2 = (2.15 ± 0.15) × 10-10 cm3 molecule-1 s-1 at 298 K, giving a rate coefficient ratio k2/k1 = 3.74 ± 0.40, in excellent agreement with the relative rate studies. The present results are used to put other, relative rate measurements of the reactions of chlorine atoms with alkanes on an absolute basis. It is found that the rate of hydrogen abstraction from a methyl group is not influenced by neighboring groups. The results are used to refine empirical approaches to predicting the reactivity of Cl atoms towards hydrocarbons. Finally, relative rate methods were used to measure rate coefficients at 298 K for the reaction of Cl atoms with 1- and 2-chloropropane and 1- and 2-chlorobutane of (4.8 ± 0.3) × 10-11, (2.0 ± 0.1) × 10-10, (1.1 ± 0.2) &times 10-10, and (7.0 ± 0.8) × 10-11 cm3 molecule-1 s-1, respectively. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 43-55, 1997.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Kinetics of the reaction of cyclopentane with trichloroethylene (1969)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 1 (1969), S. 325-337 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the thermally and radiation initiated chain reaction between trichloroethylene and cyclopentane to produce 1,1-dichlorovinylcyclopentane and hydrogen chloride have been investigated in the temperature range 250-360°C at high pressure in the gas phase. The rate governing step in the chain is (k3 = 3.3 × 109 exp -(4800/RT) cc mole-1 sec -1). The rate of the unimolecular decomposition of trichloroethylene is 1.4 × 1014 exp -(61,200/RT) sec-1.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550010305
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  • 8
    Electronic Resource
    Electronic Resource
    Kinetics of the metathetical reaction between carbon tetrachloride and toluene (1972)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 4 (1972), S. 405-416 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A metathetical reaction between carbon tetrachloride and toluene to give benzyl chloride and chloroform occurs at temperatures above 200°C (k = 4.8 × 1010 e-32,900/RT cc mole-1sec-1). The reaction does not involve free radicals, as is shown by the kinetic behavior of the system, by the lack of effect of added free-radical chain inhibitors, and by the absence of the expected chain termination product, hexachloroethane. The reaction is one of a general type between carbon tetrachloride and alkanes or alkylaromatics, but at the temperatures required it is often obscured by dehydrohalogenation of the product to the highly reactive olefin. At high temperatures, benzyl chloride reacts with toluene to give bibenzyl and hydrogen chloride, apparently also by a metathetical reaction. The transition state is postulated to be four-center, in which the carbon-chlorine and carbon-hydrogen bonds are broken and reformed: The experimental preexponential factor is in good agreement with that calculated from transition-state theory.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550040405
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  • 9
    Electronic Resource
    Electronic Resource
    A relative rate study of the reaction of Cl atoms with a series of alkyl nitrates and nitro alkanes in air at 295 ± 2 K (1990)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 22 (1990), S. 665-671 
    Details
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550220702
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetics of the reaction of OH radicals with t-amyl methyl ether revisited (1993)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 265-272 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the reaction of OH radicals with t-amyl methyl ether (TAME) have been reinvestigated using both absolute (flash photolysis resonance fluorescence) and relative rate techniques. Relative rate experiments were conducted at 295 K in 99 kPa (740 torr) of synthetic air using ethyl t-butyl ether, cyclohexane, and di-isopropyl ether as reference compounds. Absolute rate experiments were performed over the temperature range 240-400 K at a total pressure of 4.7 kPa (35 torr) of argon. Rate constant determinations from both techniques are in good agreement and can be represented by k1=(6.32 ± 0.72) × 10-12 exp[(-40 ± 70)/T] cm3 molecule-1 s-1. Quoted errors represent 2σ from the least squares analysis and do not include any estimate of systematic errors. We show that results from the previous kinetic study of reaction (1) are in error due to the presence of a reactive impurity. Results are discussed in terms of the atmospheric chemistry of TAME. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550250406
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