Relative and absolute kinetic studies of 2-butanol and related alcohols with tropospheric Cl atoms

Physical Chemistry Chemical Physics Pub Date: 2007-01-18 DOI: 10.1039/B614531K

Abstract

A newly constructed chamber/Fourier transform infrared system was used to determine the relative rate coefficient, ki, for the gas-phase reaction of Cl atoms with 2-butanol (k1), 2-methyl-2-butanol (k2), 3-methyl-2-butanol (k3), 2,3-dimethyl-2-butanol (k4) and 2-pentanol (k5). Experiments were performed at (298 ± 2) K, in 740 Torr total pressure of synthetic air, and the measured rate coefficients were, in cm3 molecule?1 s?1 units (±2σ): k1 = (1.32 ± 0.14) × 10?10, k2 = (7.0 ± 2.2) × 10?11, k3 = (1.17 ± 0.14) × 10?10, k4 = (1.03 ± 0.17) × 10?10 and k5 = (2.18 ± 0.36) × 10?10, respectively. Also, all the above rate coefficients (except for 2-pentanol) were investigated as a function of temperature (267–384 K) by pulsed laser photolysis–resonance fluorescence (PLP-RF). The obtained kinetic data were used to derive the Arrhenius expressions: k1(T) = (6.16 ± 0.58) × 10?11exp[(174 ± 58)/T], k2(T) = (2.48 ± 0.17) × 10?11exp[(328 ± 42)/T], k3(T) = (6.29 ± 0.57) × 10?11exp[(192 ± 56)/T], and k4(T) = (4.80 ± 0.43) × 10?11exp[(221 ± 56)/T] (in units of cm3 molecule?1 s?1 and ±σ). Results and mechanism are discussed and compared with the reported reactivity with OH radicals. Some atmospheric implications derived from this study are also reported.

Graphical abstract: Relative and absolute kinetic studies of 2-butanol and related alcohols with tropospheric Cl atoms
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