Technical Papers and Notes - Institute of Metals Division - Hafnium-Zirconium Separation by Vapor Phase Dechlorination

ONE possible method for the separation of hafnium from zirconium is by the vapor phase oxidation of the purified mixed chlorides. An important factor for success depends on the difference in free energies of the following reactions: ZrCl(g) + O2 = ZrO2(s) + 2C12 [1] HfCl4(g) + O2 = HfO2(s) + 2C12. [2] Prakash and Sundaram1 have calculated these values from certain data and carried out experimental work with partial success. However, their free energy values for reaction 2 diverge rather widely from other data which are presented here. The possibility of successful separation is briefly considered in the light of these alternative values. Table I shows the free energy values (?F°) for reactions 1 and 2 derived from the recent compilation of data on oxides and chlorides by Glassner.2 The corresponding values of Prakash and Sundaram for the same temperatures are also shown. The alternative values to those of Prakash and Sundaram for reaction 2 are substantially confirmed by the data of Kubaschewski and Evans" and Cough-lin' on heats of formation, entropies, and heats of vaporization. In spite of the considerable uncertainty in the hafnium data it is reasonable to suppose that the oxide-chloride free energy difference for two such chemically similar elements would not be very far apart. These figures indicate clearly that the oxidation of hafnium chloride is appreciable at all temperatures. Nevertheless, there is a significant difference between the values for reactions 1 and 2