13536-85-1Relevant academic research and scientific papers
Pressure and Temperature Dependence of the Reaction F+FSO3+M->FSO2OF+M
Cobos, A. E. Croce de,Cobos, C. J.,Castellano, E.
, p. 274 - 278 (1989)
The kinetics of the reaction F+FSO3+M->FSO2OF+M (1) has been studied by using an ArF excimer laser flash photolysis/visible absorption technique to monitor the disappearance of FSO3 radicals.He, N2, and SF6 were used as bath gases in pressures ranging from 5 to 600 Torr at 298 K; CF4 was used in the same pressures between 298 and 378 K.Reaction 1 was found to be in the falloff region between second- and third-order kinetics.The following limiting high- and low-pressure recombination rate constants have been determined at 298 K: krec,=(7.6+/-1.0)*10-11 cm3 molecule-1 s-1, krec,0=(4.1+/-0.5)*10-28, (5.2+/-0.7)*10-28, (1.1+/-0.2)*10-27, and (1.3+/-0.2)*10-27 cm3 molecule-1 s-1. krec, and krec,0 showed a temperature dependence of T0.23 and T-3.1 (M=CF4), respectively.With the krec, data and the known values of the high-pressure rate constant for FSO2OF thermal decomposition, the equilibrium constant and the thermodynamical parameters of the system were obtained.An analysis of the krec,0 with respect to energy-transfer properties was performed.In terms of the canonical version of the statistical adiabatic channel model, the krec, values lead to α/β=0.49 for the ratio between the looseness and the Morse parameters.Specific rate constants derived from our experiments are also discussed.
Evidences for a new ultraviolet absorption band of the FSO3 radical
Cobos,Croce
, p. 897 - 909 (2007)
An unpublished absorption band of the fluorosulphate radical, FSO 3, based on earlier experiments of Schumacher and co-workers (Z. Phys. Chem. NF 42 (1964) 174) and detailed calculations of the whole FSO 3 spectra based on the time-dependent (TD) generalization of the density functional theory (DFT), TD-DFT, are reported. Part of this band, that increases in intensity at wavelengths below 275 nm, has been extracted from an absorption spectrum taken from equilibrated mixtures of FSO3 with the dimer FS(O2)OO(O2)SF at 403 K. A set of thirteen exchange-correlation hybrid functionals combined with the 6-311+G(3df) basis set predict an intense absorption band centred at 256±10 nm in very good agreement with the experimental observations. Another significant band peaked at 184±10 nm was also found. The calculations reproduce accurately the position of the maximum and the experimental oscillator strength of the well-known visible FSO3 band system. by Oldenbourg Wissenschaftsverlag.
Sulfur oxyfluoride derivatives. III
Ruff,Merritt
, p. 1219 - 1221 (2008/10/08)
The reaction of S2O6F2 with the anions CF3O-, SF5O-, -N(SO2F)2, and (NO2)2CCN- produced the corresponding covale
