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Pulsed laser photolysis vacuum UV laser-induced fluorescence kinetic study of the gas-phase reactions of Cl(2P3/2) atoms with C3-C6 ketones


, : Pulsed laser photolysis vacuum UV laser-induced fluorescence kinetic study of the gas-phase reactions of Cl(2P3/2) atoms with C3-C6 ketones. Journal of Physical Chemistry. A 111(7): 1271-1276

The gas-phase reactions of Cl atoms with acetone, butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, and cyclopentanone at 295 +/- 2 K were studied using pulsed laser photolysis vacuum UV laser-induced fluorescence (PLP-LIF) techniques. Cl(2P(3/2)) atoms were produced by photolysis of Cl2 at 351 nm and monitored by LIF spectroscopy at 134.72 nm (3p(5) 2P(3/2)-3p(4)4s 2P(3/2) transition). Rate coefficients for reactions of Cl atoms with acetone, butanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, and cyclopentanone are (2.30 +/- 0.12) x 10(-12), (4.08 +/- 0.21) x 10(-11), (1.23 +/- 0.13) x 10(-10), (8.87 +/- 0.92) x 10(-11), (2.08 +/- 0.32) x 10(-10), (1.43 +/- 0.19) x 10(-10) and (1.16 +/- 0.12) x 10(-10) cm3 molecule(-1) s(-1), respectively. The results for acetone and butanone are consistent with previous studies. The results for 2-pentanone, 3-pentanone, 2-hexanone, and 3-hexanone are approximately a factor of 2-3 higher than those from previous absolute rate studies. Likely explanations for these discrepancies are discussed. Tropospheric lifetimes of ketones with respect to reaction with Cl atoms are estimated and discussed.

US$19.90

PMID: 17266289

DOI: 10.1021/jp066410c


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