Kinetics of methylchlorosilane formation on Zn-promoted Cu3Si

The kinetics of the direct synthesis reaction (Si + 2CH₃Cl → (CH₃)₂SiCl₂) were measured on a Cu₃Si alloy containing 1.2 atom % Zn. Reaction was carried out in a differential reactor (520–595 K, 1 atm) attached to an ultrahigh vacuum (UHV) system. Auger spectroscopy was used to characterize the surface before and after reaction. Zinc does not significantly change the overall rate of reaction, but it changes selectivity to dimethyldichlorosilane (the desired product), surface composition, activation energies, and induction times. The rate of silicon diffusion to the surface is not limiting in the presence of zinc. Zinc is found to be a promoter for improved selectivity only in low concentrations, and only a fraction of the surface appears to be active for reaction. The kinetics appear relatively insensitive to the surface composition or the form of surface carbon. A Cu₃Si surface with Zn is shown to be a good model catalyst for the direct synthesis reaction.     

Gas-phase structures and mass spectra of binary pentafluorides

Most known non-radioactive pentafluorides have been examined by molecular-beam mass spectrometry and by the deflection of molecular beams in inhomogeneous electric fields. Extensive association of the vapors occurs for all but the lighter pentafluorides and the interhalogens. The interhalogen pentafluorides are strongly polar, consistent with the accepted C_4v symmetry. The transition-metal and Group V pentafluorides are all non-polar, except VF₅ and CrF₅ for which temperature-dependent polarity is observed. However, uncertainty exists as to whether these observations are applicable to monomeric pentafluorides in all cases. Mass-spectral cracking patterns are presented for all species.     

Raman study of the O2F2 + VF5 reaction: Isolation and identification of an unstable reaction intermediate

The reaction of O₂F₂ with polymeric VF₅ in the temperature range -119 to -78°C leads first to the reaction intermediates

. On increasing the temperature of this intermediate, a new compound O⁺₂V₂F^-₁₁ is formed which in turn decomposes rapidly at room temperature. Raman studies of these species as well as of O₂F₂(solid), VF₅, KVF₆, KV₂F₁₁, CsVF₆ and CsV₂F₁₁ are reported and discussed.     

The multifractal spectrum of statistically self-similar measures

We calculate the multifractal spectrum of a random measure constructed using a statistically self-similar process. We show that with probability one there is a multifractal decomposition analogous to that in the deterministic self-similar case, with the exponents given by the solution of an expectation equation.