Extractive Metallurgy Division - Observations on the Preparation of Iodide Titanium - Discussion

J. M. Blocher, Jr. and I. E. Campbell (Battelle Memorial Institute, Columbus, Ohio)—Since the de Boer-Van Arkel process for making titanium metal involves a number of steps in a fairly compact unit, it is difficult to determine simply which of the steps is rate controlling. In any statement as to which step constitutes the rate-controlling process, qualifications appear to be in order. It is possible to design a reaction bulb in which any one of a number of steps is made to be controlling. I—With the filament removed some distance from the crude, as in the case of the authors' experiments, the interdiffusion of iodine and iodide may be controlling. 2—If, as is usually done, the crude metal is placed in a perforated cylindrical basket, or as a briquetted mass, in close proximity to the filament, the rate of deposition is increased (we obtained rates of deposition 5 to 10 times those cited in the authors' paper), and another rate-limiting factor, such as the reactivity of the crude, may take over. In this regard, we have noticed radically different rates of deposition with different crudes, and with crudes in various stages of exhaustion. 3—With a very reactive crude metal and with optimum practical geometry, still another process may be controlling. It is felt that this is a diffusion process in the immediate vicinity of the filament involving the fundamentally adverse situation of a net flow of particles away from the filament. The separate experiments on the reactivity of iodine with titanium are interesting but somewhat inconclusive. Data is still needed on the partial pressure of iodine in an operating decomposition bulb. A knowledge of the gradient of iodine partial pressure from the crude to the filament would be particularly enlightening. Optical absorption may be a useful technique here. Accurate measurements of the total pressure within a decomposition bulb under various conditions would be quite revealing. Preliminary measurements have been made at Battelle in following this line of attack. It is interesting to note that the authors' data on the temperature dependence of deposition rate indicate that the overall rate is not controlled by the kinetics of the decomposition reaction at the filament: TiI1 ? Ti + 4I Any reasonable estimate of the activation energy of this reaction would, if its kinetics were controlling, dictate a much greater temperature dependence than is observed here. The authors apparently attribute the drop in deposition rate (eventually to zero) with increased TiI4 pressure solely to a decrease in diffusion rate. However, there is an equilibrium factor involved here that must not be overlooked. As the partial pressure of TiI4 is increased, a point is reached where, due to the competing reaction of the tetraiodide with titanium to form lower iodides, the equilibrium partial pressure of titanium is reduced to the point that it equals the vapor pressure of titanium at the filament temperature and the deposition rate falls to zero. This effect would