• Home
  • Search Results
  • Kinetics and mechanism of chlorine-atom-initiated oxidation of allyl alcohol, 3-buten-2-ol, and 2-methyl-3-buten-2-ol.

Kinetics and mechanism of chlorine-atom-initiated oxidation of allyl alcohol, 3-buten-2-ol, and 2-methyl-3-buten-2-ol.

The journal of physical chemistry. A (2010-03-10)
Kenshi Takahashi, Jia-Hua Xing, Michael D Hurley, Timothy J Wallington
ABSTRACT

The gas-phase reactions of Cl atoms with allyl alcohol (k(1)), 3-buten-2-ol (k(2)), and 2-methyl-3-buten-2-ol (k(3)) at 296 +/- 2 K have been investigated using absolute and relative rate methods in 1-700 Torr of N(2) diluent. Absolute rate studies were performed using pulsed laser photolysis/vacuum ultraviolet laser-induced fluorescence spectroscopy techniques. Relative rate studies were performed using smog chamber/Fourier transform infrared spectroscopy techniques. The absolute and relative rate studies gave consistent results. The kinetics of the reactions are dependent on pressure over the range studied. Molar yields for HCl production in 700 Torr of N(2) for reactions of chlorine atoms with allyl alcohol, 3-buten-2-ol, and 2-methyl-3-buten-2-ol were measured to be 0.26 +/- 0.03, 0.23 +/- 0.03, and 0.12 +/- 0.02, respectively. The chlorine-atom-initiated oxidation of 2-methyl-3-buten-2-ol in 700 Torr of air gave the following products (molar yields): acetone (47 +/- 4%), chloroacetaldehyde (47 +/- 5%), and HCHO (7.2 +/- 0.6%). The observation of substantial and indistinguishable yields of acetone and chloroacetaldehyde products indicates that a major fraction of the reaction proceeds via addition of chlorine atoms to the terminal carbon atom. The results are discussed with respect to the literature data.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Chloroacetaldehyde solution, ~55 wt. % in H2O
Sigma-Aldrich
2-Methyl-3-buten-2-ol, 98%
Sigma-Aldrich
Chloroacetaldehyde solution, produced by Wacker Chemie AG, Burghausen, Germany, ≥45.0% in H2O (density determination)