The thermal unimolecular decomposition of HCO: effects of state specific rate constants on the thermal rate constant

摘要: An experimental study on the thermal decomposition of formyl radicals (HCO) under high pressure conditions is presented for first time. The covered in this range from 1 to 140 bar helium and temperatures between 590 800 K. Furthermore, reaction was studied at 700 K pressures 14 nitrogen obtain information kinetics combustion conditions. analysis dependence rate constants shows that standard treatments like a Lindemann–Hinshelwood model or master equation formalism are not able describe experimentally observed adequately. isolated resonance model, however, which based calculated lifetimes H.-M. Keller, H. Floetmann, A. J. Dobbyn, R. Schinke, H.-J. Werner, C. Bauer P. Rosmus (J. Chem. Phys., 1996, 102, 4983) allows description T- p-dependence. Based our data obtained as well results by S. Timonen, E. Ratajczak, D. Gutman F. Wagner Phys. Chem., 1987, 91, 5325) we give simple expression constant 500 1000 0.01 100 bar: k(T,[M]) = 3.3 × 109 × {[N2]/(1019 cm−3)}0.865 × exp{−(70.15 kJ mol−1)/RT} s−1. uncertainty estimated be 30%.