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Reactions of Methyl Perfluoroalkyl Ethers with Isopropyl Alcohol: Experimental and Theoretical Studies
Industrial & Engineering Chemistry Research
  • Howard Knachel, University of Dayton
  • Vladimir Benin, University of Dayton
  • Chadwick Barklay, University of Dayton
  • Janine C. Birkbeck, B&W Pantex
  • Billy D. Faubion, B&W Pantex
  • William E. Moddeman, B&W Pantex
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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 1H and 19F 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 ∼1 ppm per year at a laboratory temperature of 20 °C. Measurements over the temperature range of 6° to 100 °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 (ΔH⧧) and entropy (ΔS⧧) of activation were determined based on several different kinetic measurements. The ΔH⧧ values are in the range of 20–25 kcal/mol and the corresponding ΔS⧧ values range from −32 to −15 cal/(mol K). These are in good agreement with the theoretical values. While the range of ΔH⧧ values does not change appreciatively, the ΔS⧧ 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 ΔS⧧ value.

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American Chemical Society
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Citation Information
Howard Knachel, Vladimir Benin, Chadwick Barklay, Janine C. Birkbeck, et al.. "Reactions of Methyl Perfluoroalkyl Ethers with Isopropyl Alcohol: Experimental and Theoretical Studies" Industrial & Engineering Chemistry Research Vol. 51 Iss. 32 (2012)
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