Reactions of Chlorine Fluorides and Oxyfluorides with the Nitrate Anion and Alkali-Metal Fluoride Catalyzed Decomposition of ClF5

摘要

The binary chlorine fluorides ClF5, ClF3, and ClF, when used in an excess, all undergo facile fluorine-oxygen exchange reactions with the nitrate anion, forming FClO2, unstable FClO, and ClONO2, respectively, as the primary products. Whereas FClO3 does not react with LiNO3 at temperatures as high as 75 C, FClO2 readily reacts with either LiNO3 or N2O5 to give ClONO2 and O2 in high yield, probably via the formation of an unstable O2ClONO2 intermediate. With an excess of ClF, chlorine nitrate undergoes a slow reaction to give FNO2 and Cl2O as the primary products, followed by Cl2O reacting with ClF to give Cl2, ClF, and FClO2. The alkali-metal fluorides CsF, RbF, and KF catalyze the decomposition of ClF5 to ClF3 and F2, which can result in the generation of substantial F2 pressures at temperatures as low as 25 C. Keywords: Chlorine penta fluoride, Chlorine trifluoride, Monochloro fluoride, Fluorochlorite, Chloronitrate, Fluorochlorate, Fluoronitrite, Lithium nitrate, Nitrogen pentoxide. Reprints. (AW)