화학공학소재연구정보센터
Industrial & Engineering Chemistry Research, Vol.51, No.32, 10525-10534, 2012
Reactions of Methyl Perfluoroalkyl Ethers with Isopropyl Alcohol: Experimental and Theoretical Studies
The reaction of an isomeric mixture of the methyl perfluoroalkyl ether, C4F9OCH3 (Novec-7100), in the presence of isopropyl alcohol (IPA) and/or water has been studied by measuring the rate of product formation using an ion-selective electrode (ISE) for fluoride ion, Karl Fisher coulometric titrations for water, and H-1 and F-19 NMR spectroscopy for product identification and rate studies. The results showed the methyl perfluoroalkyl ether to be very stable with products forming at the rate of similar to 1 ppm per year at a laboratory temperature of 20 degrees C. Measurements over the temperature range of 6 degrees to 100 degrees C were made on samples aged for periods up to 1.8 years. Density functional theory calculations (DFT, B3LYP/6-31+G(d)) were employed to investigate different reaction pathways and formulate the probable reaction mechanism. The experimental enthalpy (Delta H double dagger) and entropy (Delta S double dagger) of activation were determined based on several different kinetic measurements. The Delta H double dagger values are in the range of 20-25 kcal/mol and the corresponding Delta S double dagger values range from -32 to -15 cal/(mol K). These are in good agreement with the theoretical values. While the range of Delta H double dagger values does not change appreciatively, the Delta S double dagger values are dependent on the proportion of vapor to liquid involved in the reaction of C4F9OCH3 with IPA so that the more vapor the more negative the Delta S double dagger Value.