The gas phase reactivity of aliphatic polyethers towards OH radicals: Measurements and predictions

✍ Scribed by Philippe Dagaut; Renzhang Liu; Timothy J. Wallington; Michael J. Kurylo

• Publisher: John Wiley and Sons
• Year: 1989
• Tongue: English
• Weight: 383 KB
• Volume: 21
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550211210

✦ Synopsis

Using the flash photolysis resonance fluorescence technique, absolute rate constants were determined for the gas phase reactions of hydroxyl radicals with a series of aliphatic polyethers. At 298 K, the measured rate constants (in units of lo-'' cm3 molecule-' sK1) were: 2,2-dimethoxypropane, (3.9 ? 0.2); 2,2-diethoxypropane, (11.7 2 1.3); 1,2-dimethoxypropane, (14.3 ? 1.5); 2-methoxyethylether, (17.5 t 1.1); 2-ethoxyethlyether, (26.8 ? 2.4); 1,l-dimethoxyethane, (8.9 2 1.0); and 1,1,3-trimethoxypropane, (16.7 f 1.0).

The temperature dependencies of the rate constants for 2,2-dimethoxypropane and 2,2-diethoxypropane, reactions (1) and ( 2), were studied over the temperature range 240-440 K and are expressed by the Arrhenius equations: k, = (3.55 ? 0.39) x lo-'* exp[(30 ? 35)/T] cm3 molecule-' s-' k z = (1.06 t 0.25) x lo-'' exp[(l5 ? 75)/T] em3 molecule-' 5-l Implications of the results are discussed in terms of reaction mechanisms and the prediction of gas phase OH radical reaction rates for aliphatic polyethers.