Theoretical Prediction of the Thermochemistry and Kinetics of Reactions of CF2O with Hydrogen Atom and Water

M. R. Zachariah, W. Tsang, P. R. Westmoreland, D. R. F. Burgess
1995 The Journal of Physical Chemistry  
A theoretical investigation of transition states and reaction products for reaction of carbonyl difluoride (CF20) with H atoms and water has been conducted. Bond-additivity-corrected (BAC) MP4 calculations have been used to obtain the thermochemistry of equilibrium and transition state structures. R R W m a s t e r equation as well as bimolecular-QRRK analysis of the H atom reaction manifold has been compared with available experimental rate constants and shows excellent agreement. The major
more » ... ction pathway is through attack on the oxygen, followed by chemically activated 1,2-elimination of HF. Analysis of carbonyl difluoride reaction with water indicates that the primary reaction is through a concerted reaction to form fluoroformic acid (FCO(0H)) and HF. Calculated rate constants for CF20 with water are considerably slower than reaction with H atoms, and even in hydrocarbon flames, where the water concentration is high, the H atom reaction should dominate. Reaction with OH was found not to be competitive with the other two processes and proceeds to FC02 + HF.
doi:10.1021/j100033a023 fatcat:qxd2sp62indr7mtu7oq54bynbi