1495-28-9Relevant articles and documents
Kinetics of the Association Reactions of NO with the Series of Chlorofluoromethyl Radicals CFxCl3-x
Ley, L.,Masanet, J.,Caralp, F.,Lesclaux, R.
, p. 1953 - 1960 (1995)
The kinetics of the reactions CF2Cl+NO+M->CF2ClNO+M and CFCl2+NO+M->CFCl2NO+M have been investigated using pulsed laser photolysis/time-resolved mass spectrometry in the pressure range 1-12 Torr and the temperatures of 233, 298, 333 K, using N2 as the buffer gas.The results, along with those obtained in preceding works for the homologous reactions CF3+NO+M->CF3NO+M and CCl3+NO+M->CCl3NO+H (refs 5 and 7), were analyzed by a variational RRKM method.This analysis shows that all kinetic, structural, and thermochemical data of this series of species and of their corresponding reactions are internally consistent within the framework of the variational RRKM model used.By fitting the usual Troe's expression to the RRKM calculated rate constants values, themselves based on the experimental data, the broadening factor Fcca.0.6 was obtained.Setting Fc=0.6 for all reactions, the following rate expressions have been obtained (units of cm6 molecule-2 s-1 for k0 and cm3 molecule-1 s-1 for k: k0(CF3)=(2.0+/-0.4) x 1E-29(T/298)-3.2; k(CF3)=(1.9+/-0.4) x 1E-11(T/298)-1.0; k0(CF2Cl)=(1.8+/-)0.35) x 1E-29(T/298)-4.4; k(CF2Cl)=(1.9+1.0-0.5) x 1E-11(T/298)-1.5; k0(CFCl2)= (1.0+/-0.25) x 1E-29(T/298)-4.8; k(CFCl2)=(1.9+1.0-0.5) x 1E-11(T/298)-1.5; k0(CCl3)=(0.85+/-0.2) x 1E-29(T/298)-5.5; k(CCl3)=(0.55+/-0.12) x 1E-11(T/298)-1.6.It appears that in the low-pressure part of the falloff, the RRKM theory may be used in a predictive way for association reactions forming nitroso compounds: from the experimental determination of k0, a reliable evaluation of the enthalpy of reaction can be obtained (within +/-8 kJ mol-1), using βcca.0.2 and vice versa.The values of k have been found equal within uncertainties for those species containing fluorine.This is to be compared to the almo st equal enthalpies of their corresponding reactions.In the case of CCl3, both k and the reaction enthalpy have lower values than those obtained for the other species of the series.In contrast, k0 decreases regulary in the series, from CF3 to CCl3, and this trend is well accounted for by the calculations.