Experimental and theoretical study of the homogeneous, unimolecular gas-phase elimination kinetics of 2-furoic acid

The kinetics of the gas-phase elimination kinetics of CO2 from furoic acid was determined in a static system over the temperature range 415-455 degrees C and pressure range 20-50 Torr. The products are furan and carbon dioxide. The reaction, which is carried out in vessels seasoned with allyl bromide and in the presence of the free-radical suppressor toluene and/or propene, is homogeneous, unimolecular, and follows a first-order rate law. The observed rate coefficient is expressed by the following Arrhenius equation: log k(1) (s(-1)) = (13.28 +/- 0.16) - (220.5 +/- 2.1) kJ mol(-1) (2.303 RT)(-1). Theoretical studies carried out at the B3LYP/6-31++G** computational level suggest two possible mechanisms according to the kinetics and thermodynamic parameters calculated compared with experimental values. (c) 2007 Wiley Periodicals, Inc.