Catalysis Letters, Vol.69, No.1-2, 37-41, 2000
Transformation of propane and CO to carboxylic acid and ester by highly active CaCl2 catalyst
The functionalization reaction of propane with CO to afford carboxylic acids and an ester by CaCl2 catalyst in the presence of K2S2O8 and CF3COOH has been studied. The reaction gave isobutyric acid as the main product and n-butyric acid and isopropyl trifluoroacetate as by-products. Atmospheric pressure of propane underwent the reaction with 30 atm of CO pressure at 80 C-degrees for 24 h, giving about 95% total yield based on propane. The activation and thermodynamic parameters have been determined to be E-a = 130.3, 138.0 and 153.8 kJ/mol; A = 7.14 x 10(13), 5.83 x 10(14) and 5.80 x 10(16) l/s; Delta H double dagger = 128.0, 134.7 and 150.5 kJ/mol; Delta S double dagger = 10.3, 28.6 and 66.8 J/mol K and Delta G(253)double dagger = 124.4, 123.9 and 126.9 kJ/mol for the products of isobutyric acid, n-butyric acid and isopropyl trifluoroacetate, respectively.
Keywords:saturated hydrocarbons;propane;carbon monoxide;calcium dichloride;carboxylic acid;catalysis