Ammonolysis of perchloryl fluoride

Abstract

Perchloryl fluoride (ClO 3F) reacts with aqueous or liquid anhydrous NH 3 to form a mixture of NH 4F and NH 4NHClO 3. Ammonolysis of ClO 3F in liquid NH 3 is greatly accelerated by traces of NaNH 2 (base catalysis). From an aqueous solution of NH 4F + NH 4NHClO 3, concentrated aqueous or alcoholic solutions of caesium or potassium hydroxides precipitate salts of the types K 2NClO 3 and KNHClO 3. The former are isomorphous with the corresponding metal sulphates. The latter are nearly isomorphous with the corresponding perchlorates. These salts are highly explosive, and when dry are very sensitive to flame, shock and friction. Potentiometric titration of K 2NClO 3 with strong acid gives a curve corresponding to the ionization of the amide ClO 3NH 2: HaNClO3⇌H ++HNClO3 −(pH=3.7HNClO3 −⇌H ++NClO3 2−(pH=8.6) The identity of the ions NHClO 3 − and NClO 3 2− was further established by ion exchange analysis.