COMPARATIVE STUDIES OF CATALYTIC FLUORINATION OF CARBON MONOXIDE WITH ELEMENTARY FLUORINE

In spite of a lack of good understanding, the process called catalytic fluorination has been used in the past for synthesis of many volatile fluorides. The procedure involves mixing fluorine with a reactant in the presence of a mass of catalyst which may be a finely divided metal coated with a film of metal fluoride. By comparing the behavior of various “catalysts,” it has now been shown that a film of silver fluoride(s) on copper truly is a catalyst for the reaction CO + F2 = CF2O (1) and for subsequent changes producing CF3OOCF3 and CF3OF. Copper alone is much less active, and aluminum appears not to be a catalyst for reaction 1. The behavior of cesium fluoride as a catalyst for the reaction CF2O + F2 = CF3OF (2) has been confirmed and the salt has been shown not to help reaction 1. Possible mechanisms are discussed. © 1969, American Chemical Society. All rights reserved.