Experimental and modeling study of the reaction C2F4 (+M) = CF2 + CF2 (+M).

C. J. COBOS; A. E. CROCE; K. LUTHER; L. SÖLTER; E. TELLBACH; J. TROE

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

Lugar: Washington; Año: 2013 vol. 117 p. 11420 - 11429

1089-5639

The thermal dissociation reaction C2F4 = 2 CF2 was studied in shock waves monitoring CF2 radicals by their UV absorption. The absorption coefficients as functions of wavelength and temperature were redetermined and are represented in analytical form. Dissociation rate constants as functions of bath gas concentration [M] and temperature, from previous and the present work, are presented analytically employing falloff expressions from unimolecular rate theory. Equilibrium constants are determined between 1200 and 1500 K. The data are shown to be consistent with a C-C bond energy of 67.5 (+/- 0.5) kcal mol-1. High pressure limiting rate constants for dissociation and recombination are found to be unusually small. This phenomenon can be attributed to an unusually pronounced anisotropy of the potential energy surface such as demonstrated by quantum-chemical calculations of the potential energy surface.