Pyrovacuum Processes for Reactive and Refractory Metals

When the boiling points of metallic impurities are much lower than the boiling point of the main metal, they can simply be distilled away in most cases. The rate and the extent of the removal by distillation of these impurity elements depend upon their partial pressures over the main metal/melt. As an example, let the feasibility of distilling magnesium and magnesium chloride from titanium and calcium from the rare earths be considered. In the firstcase, at 900 °C, the pertinent vapor pressure values are P = 4 10-11 torr, PMg = 105 torr 

let the example of vanadium, which, in the as-reduced condition, may contain a variety of impurities (including aluminum, calcium, chromium, copper, iron, molybdenum, nickel, lead, titanium, and zinc) be considered. Vanadium melts at 1910 °C, and at this temperature it is considerably less volatile than many of the impurity metals present in it. The vapor pressure of pure vanadium at this temperature is 0.02 torr, whereas those of the impurity elements in their pure states are the following aluminum 22 torr calcium 1 atm, chromium 6 torr copper 23 torr iron 2 torr molybdenum 6 1CT6 torr nickel 1 torr lead 1 torr titanium 0.1 torr and zinc 1 atm. However, since most of these impurities form a dilute solution in vanadium, their actual partial pressures over vanadium are considerably lower than the values indicated. Taking this into account, the vaporization rate, mA, of an element A (the evaporating species) can be approximated by the following free evaporation equation (Langmuir equation)  

The free evaporation equation given above refers to impurity removal from a solid or a liquid solution. When the residual impurity has not formed a solution, its activity remains unity and the Langmuir equation becomes 

The free evaporation situation is obtained only in the case of vaporization in a high vacuum. 

A reaction of hydrogen, nitrogen, and oxygen with the metal can be represented by 

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