Relative rate measurements of reactions of unsaturated alcohols with atomic chlorine as a function of temperature

Abstract

The kinetics of two structurally similar unsaturated alcohols, 3-butene-2-ol and 2-methyl-3-butene-2-ol (MBO232), with Cl atoms have been investigated for the first time, as a function of temperature using a relative method. As far as we know, the present work also provides the first value for 3-buten-2-ol. The coefficient at room temperature was also obtained for 2-propene-1-ol (allyl alcohol). The reactions were investigated using a 400 L Teflon reaction chamber coupled with gas chromatograph-coupled with flame-ionization detection (GC-FID) detection. The experiments were performed at atmospheric pressure and at temperatures between 256 and 298 K in air or nitrogen as the bath gas. The obtained kinetic data were used to derive the Arrhenius expressions, k MBO232=(2.83±2.50)×10 −14 exp (2670±249)/ T, k 3-buten-2-ol=(0.65±1.60)×10 −15 exp (3656±695)/ T (in units of cm 3 molecule −1 s −1). Finally, results and atmospheric implications are discussed and compared with the reactivity with OH and NO 3 radicals.