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Further studies of the temperature dependence of the rate coefficients for the reactions of OH with a series of ethers under simulated atmospheric conditions (1993)

Semadeni, Marco ; Stocker, David W. ; Kerr, J. Alistair

Springer

Journal of atmospheric chemistry 16 (1993), S. 79-93

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ISSN: 1573-0662

Keywords: Atmospheric photo-oxidation ; hydroxyl radicals ; diethyl ether ; methyln-butyl ether ; ethyln-butyl ether ; di-n-butyl ether ; di-n-pentyl ether ; relative rate coefficients ; smog chamber kinetic studies

Source: Springer Online Journal Archives 1860-2000

Topics: Chemistry and Pharmacology , Geosciences

Notes: Abstract The following temperature-dependent rate coefficients (k/cm3 molecule−1 s−1) of the reactions of hydroxyl radicals with aliphatic ethers have been determined over the temperature range 247–373 K by a competitive flow technique: diethyl ether,k OH=5.2×10−12 exp[(262±150)/T]; methyln-butyl ether,k OH=5.4×10−12 exp[(309±150)/T]; ethyln-butyl ether,k OH=7.3×10−12 exp[(335±150)/T]; di-n-butyl ether,k OH=5.5×10−12 exp[(502±150)/T] and di-n-pentyl ether,k OH=8.5×10−12 exp[(417±150)/T]. The data have been measured relative to the rate coefficientk(OH + 2,3-dimethylbutane)=6.2×10−12 cm3 molecule−1 s−1 independent of temperature. Previous discrepancies in the room-temperature rate coefficients for the OH reactions with ethyln-butyl ether and di-n-butyl ether, obtained in the flow and static experiments of Bennett and Kerr (J. Atmos. Chem. 8, 87–94, 1989;10, 29–38, 1990) compared with those of Wallingtonet al. (Int. J. Chem. Kinet. 20, 541–547, 1988;21, 993–1001, 1989) and of Nelsonet al. (Int. J. Chem. Kinet. 22, 1111–1126, 1990) have been resolved. The results are considered in relation to the available literature data and evaluated rate expressions are deduced where possible. The data are also discussed in terms of structure-activity relationships.

Type of Medium: Electronic Resource

URL: http://dx.doi.org/10.1007/BF00696626

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The temperature dependence of the OH radical reactions with some aromatic compounds under simulated tropospheric conditions (1995)

Semadeni, Marco ; Stocker, David W. ; Kerr, J. Alistair

New York, NY : Wiley-Blackwell

International Journal of Chemical Kinetics 27 (1995), S. 287-304

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ISSN: 0538-8066

Keywords: Chemistry ; Physical Chemistry

Source: Wiley InterScience Backfile Collection 1832-2000

Topics: Chemistry and Pharmacology

Notes: The temperature dependence of the rate coefficients for the OH radical reactions with toluene, benzene, o-cresol, m-cresol, p-cresol, phenol, and benzaldehyde were measured by the competitive technique under simulated atmospheric conditions over the temperature range 258-373 K. The relative rate coefficients obtained were placed on an absolute basis using evaluated rate coefficients for the corresponding reference compounds. Based on the rate coefficient k(OH + 2,3-dimethylbutane) = 6.2 × 10-12 cm3 molecule-1s-1, independent of temperature, the rate coefficient for toluene kOH = 0.79 × 10-12 exp[(614 ± 114)/T] cm3 molecule-1 s-1 over the temperature range 284-363 K was determined. The following rate coefficients in units of cm3 molecule-1 s-1 were determined relative to the rate coefficient k(OH + 1,3-butadiene) = 1.48 × 10-11 exp(448/T) cm3 molecule-1 s-1: o-cresol; kOH = 9.8 × 10-13 exp[(1166 ± 248)/T]; 301-373 K; p-cresol; kOH = 2.21 × 10-12 exp[(943 ± 449)/T]; 301-373 K; and phenol, kOH = 3.7 × 10-13 exp[(1267 ± 233)/T]; 301-373 K. The rate coefficient for benzaldehyde kOH = 5.32 × 10-12 exp[(243 ± 85)/T], 294-343 K was determined relative to the rate coefficient k(OH + diethyl ether) = 7.3 × 10-12 exp(158/T) cm3 molecule-1 s-1. The data have been compared to the available literature data and where possible evaluated rate coefficients have been deduced or updated. Using the evaluated rate coefficient k(OH + toluene) = 1.59 × 10-12 exp[(396 ± 105)/T] cm3 molecule-1 s-1, 213-363 K, the following rate coefficient for benzene has been determined kOH = 2.58 × 10-12 exp[(-231 ± 84)/T] cm3 molecule-1 s-1 over the temperature range 274-363 K and the rate coefficent for m-cresol, kOH = 5.17 × 10-12 exp[(686 ± 231)/T] cm3 molecule-1 s-1, 299-373 K was determined relative to the evaluated rate coefficient k(OH + o-cresol) = 2.1 × 10-12 exp[(881 ± 356)/T] cm3 molecule-1 s-1. The tropospheric lifetimes of the aromatic compounds studied were calculated relative to that for 1,1,1-triclorethane = 6.3 years at 277 K. The lifetimes range from 6 h for m-cresol to 15.5 days for benzene. © 1995 John Wiley & Sons, Inc.

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