Observation of a large negative temperature dependence for rate coefficients of reactions of OH with oxygenated volatile organic compounds studied at 86-112 K

Phys Chem Chem Phys. 2010 Nov 7;12(41):13511-4. doi: 10.1039/c0cp00918k. Epub 2010 Sep 22.

Abstract

The rate coefficients (k) for reactions of OH with acetone, methyl ethyl ketone (MEK) and dimethyl ether (DME) have been measured in the temperature range 86-112 K using a pulsed Laval nozzle apparatus. Large increases in k at lower temperatures were observed, with k(86K)/k(295K) = 334 for acetone, and k(93K)/k(295K) = 72 and 3, for MEK and DME respectively. A mechanism involving the formation of a hydrogen bonded complex prior to an overall barrier on the potential energy surface is proposed to explain this behaviour.