Under favorable conditions the half-lives at 298 K for the dissociation of F 3SSF and CF 3SF 2SCF 3 are found to be ca. The rates for dissociation and decomposition are strongly surface-dependent and the kinetics of the two processes have been studied separately. In both systems (1) and (2) the achievement of the equilibrium is comparatively slow at −30 to 30 ☌. The equilibrium between F 3SSF and SF 2 is disturbed by a decomposition reaction of these compounds yielding SF 4 and SSF 2. The equilibrium constants and dissociatíon enthalpies have been determined by i.r. These equilibria are unusual because they involve two different bonds (SF and SS). Thus we have found that SF 2 and CF 3SF exist in chemical equilibria with their dimers. In order to understand more about the instability of sulfur difluoride, we have investigated the chemical interrelations between each of the monomers SF 2 and CF 3SF and the corresponding dimers F 3SSF and CF 3SF 2SCF 3.
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