| Summary: | The reactions of five structurally similar unsaturated alcohols, i.e., (<i>Z</i>)-2-penten-1-ol, (<i>E</i>)-2-hexen-1-ol, (<i>E</i>)-3-hexen-1-ol, (<i>Z</i>)-3-hexen-1-ol, and 1-octen-3-ol, with Cl atoms in the gas phase, were investigated at 296 ± 2 K and 1 atm by the relative-rate kinetic technique using a 600-L Teflon reaction chamber. Selected ion flow tube mass spectrometry (SIFT-MS) was used simultaneously to monitor the decay of the alcohols of interest and selected reference compounds. Tetrahydrofuran (THF), propan-1-ol, and octane were used as reference compounds. Chlorine atoms were produced by the photolysis of molecular chlorine (Cl<sub>2</sub>) using broadband actinic lamps near 365 nm. The estimated rate constant values (in 10<sup>−10</sup> cm<sup>3</sup>∙molecule<sup>−1</sup>∙s<sup>−1</sup>) followed the order 2.99 ± 0.53 ((<i>Z</i>)-2-penten-1-ol) < 3.05 ± 0.59 ((<i>E</i>)-3-hexen-1-ol) < 3.15 ± 0.58 ((<i>Z</i>)-3-hexen-1-ol) < 3.41 ± 0.65 ((<i>E</i>)-2-hexen-1-ol) < 4.03 ± 0.77 (1-octen-3-ol). The present work provides the first value of the rate constant for the reaction of 1-octen-3-ol with Cl atoms. The results are discussed and interpreted in relation to other studies where literature data are available. The structure−activity relationship and the atmospheric implications are discussed as well.
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