Kinetics of the reactions of Cl atoms with 2-buten-1-ol, 2-methyl-2-propen-1-ol, and 3-methyl-2-buten-1-ol as a function of temperature

Abstract

The reactions of three structurally similar unsaturated alcohols, 2-buten-1-ol (crotyl alcohol), 2-methyl-2-propen-1-ol (MPO221) and 3-methyl-2-buten-1-ol (MBO321) with Cl atoms, have been investigated for the first time, using a 400 l Teflon reaction chamber coupled with gas chromatograph-coupled with flame-ionization detection (GC-FID). The experiments were performed at atmospheric pressure and at temperatures between 255 and 298 K, in air or nitrogen as the bath gas. The obtained kinetic data were used to derive the Arrhenius expressions \(k_{{\text{MPO221}}} = \left( {3.05 \pm 1.40} \right) \times 10^{ - 23} \exp {{\left( {8,760 \pm 1,279} \right)} \mathord{\left/ {\vphantom {{\left( {8,760 \pm 1,279} \right)} T}} \right. \kern-\nulldelimiterspace} T}\), \(k_{{\text{crotyl}}} = \left( {8.85 \pm 0.46} \right) \times 10^{ - 21} \exp {{\left( {7,240 \pm 1,455} \right)} \mathord{\left/ {\vphantom {{\left( {7,240 \pm 1,455} \right)} T}} \right. \kern-\nulldelimiterspace} T}\), \(k_{{\text{MBO321}}} = \left( {7.55 \pm 0.20} \right) \times 10^{ - 21} \exp {{\left( {7,361 \pm 735} \right)} \mathord{\left/ {\vphantom {{\left( {7,361 \pm 735} \right)} T}} \right. \kern-\nulldelimiterspace} T}\) (in units of cm3 molecule−1 s−1). Finally, atmospheric lifetimes of those unsaturated alcohols with respect to OH, NO3, O3 and Cl have been calculated.