Extractive Mettallurgy Division - Phase Diagram and Vapor Pressure in the Systems NaC1-ZrClr4, KC1-ZrCl4, and NaC1-KC1 (1: 1 molar) - ZrC14.

WORK described herein was undertaken with the aim of determining some of the physical-chemical properties of electrolytes suitable for the electrodeposition of pure zirconium metal. In this paper the phase diagram, vapor pressure, and activities in the melt are considered. In a companion paper,' the electrolytic conductivity of some of these melts is reported. The melts studied were mixtures of NaCl and/or KC1 with ZrC1,. Chloride melts were chosen for study because 1) if the electrolyte is to be useful for industrial electrodeposition of zirconium, the chlorides will be preferred to the relatively costly bromides and iodides; 2) fluoride melts were being studied in another laboratory (Horizons Inc., Cleveland); and 3) melts containing oxygen, in any form, are unsuitable for preparation of pure zirconium, because of the great affinity of this metal for oxygen. Unlike electrodeposition from aqueous solution, the fundamental behavior of fused-salt electrolysis is poorly understood. In most cases, such basic electrochemical information as the phase diagram of the melt system, activities in the melt, conductivity, the nature of the current-carrying ions, the equilibrium electrode potentials, and the overvoltage behavior of the electrodes is unknown to the researcher who would develop a new electrodeposition process employing a fused salt. This research project was designed to supply information about some of these basic physical-chemical properties so that an intelligent choice of electrolyte for electrodeposition studies could be made. Experimental The experimental difficulties-encountered in this work result from the properties of zirconium metal and ZrC1,. ZrC1, is a solid which sublimes at 334°C. It is rapidly hydrolyzed by moist air to HC1, ZrOCl,, and ZrO,. Unusual precautions were exercised in this work to prevent hydrolysis of ZrC1, and rigidly to exclude oxygen, nitrogen, hydrogen, and carbon from the melts under study. These elements are known to react with and contaminate zirconium metal. All melts were studied in vacuum systems, i.e., in the presence of ZrC1, vapor only. Transfer of ZrC1, to or from the melts was accomplished entirely by vacuum sublimation. In this way, neither the melts nor the ingredients thereof were permitted to