Metals volatilising

The first mechanism proposes that metal volatilisation causes rupture of molten droplets (as with magnesium), whereas the second considers the production of a volatile oxide such as CO inside materials such as steels that contain an excess of 0.1% carbon. The third mechanism involves the formation of oxy-nitride compounds which decompose at high temperatures, liberating nitrogen (as with titanium). 

The precautions stated are to avoid uptake of oxygen, nitrogen and other impurities which render the metal brittle the excess magnesium and magnesium chloride can be removed by volatilisation above 1300 K. 

Treatment of impure gold is largely via the Miller process (30) in which chlorine is bubbled through the molten metal and converts the base metals to chlorides, which volatilise. Silver is converted to the chloride, which is molten and can be poured. The remaining gold is less pure (99.6%) than that produced by the WohlwiU process and may require additional treatment such as electrolysis. If platinum-group metals (qv) are present, the chlorine process is unsuitable. 

L oss of Catalyst by Vapor Transport. The direct volatilisation of catalytic metals is generally not a factor in catalytic processes, but catalytic metal can be lost through formation of metal carbonyl oxides, sulfides, and hahdes in environments containing CO, NO, O2 and H2S, and halogens (24). 

Section 1.9 showed that as long as an oxide layer remains adherent and continuous it can be expected to increase in thickness in conformity with one of a number of possible rate laws. This qualification of continuity is most important the direct access of oxidant to the metal by way of pores and cracks inevitably means an increase in oxidation rate, and often in a manner in which the lower rate is not regained. In common with other phase change reactions the volume of the solid phase alters during the course of oxidation it is the manner in which this change is accommodated which frequently determines whether the oxide will develop discontinuities. It is found, for example, that oxidation behaviour depends not only on time and temperature but also on specimen geometry, oxide strength and plasticity or even on specific environmental interactions such as volatilisation or dissolution. 

Much of the difficulty in demonstrating the mechanism of breakaway in a particular case arises from the thinness of the reaction zone and its location at the metal-oxide interface. Workers must consider (a) whether the oxide is cracked or merely recrystallised (b) whether the oxide now results from direct molecular reaction, or whether a barrier layer remains (c) whether the inception of a side reaction (e.g. 2CO - COj + C)" caused failure or (d) whether a new transport process, chemical transport or volatilisation, has become possible. In developing these mechanisms both arguments and experimental technique require considerable sophistication. As a few examples one may cite the use of density and specific surface-area measurements as routine of porosimetry by a variety of methods of optical microscopy, electron microscopy and X-ray diffraction at reaction temperature of tracer, electric field and stress measurements. Excellent metallographic sectioning is taken for granted in this field of research. 

The more important cases of oxide volatilisation occur in the platinum metals " and with the refractory metals at high temperatures. In these systems, unlike the aforementioned, it is the higher valence oxide which is the more volatile so that at sufficiently high temperature the metal may be oxide free. Gulbransen has shown that the rate of oxidation is then con-... 

Rhodium-platinum alloys containing up to 40% Rh are used in the form of wire or ribbon in electrical resistance windings for furnaces to operate continuously at temperatures up to 1 750°C. Such windings are usually completely embedded in a layer of high-grade alumina cement or flame-sprayed alumina to prevent volatilisation losses from the metal due to the free circulation of air over its surface. Furnaces of this type are widely employed for steel analysis, ash fusions and other high-temperature analytical procedures. 

Insensitive to impact, it decomposes, sometimes explosively, above its m.p. [1], particularly if heated rapidly [2], Although used in aqueous solutions as a preservative in pharmaceutical preparations, application of freeze-drying techniques to such solutions has led to problems arising from volatilisation of traces of hydrazoic acid from non-neutral solutions, condensation in metal lines, traps or filters, and formation of heavy metal azides in contact with lead, copper or zinc components in the drying plant [3,4],... 

Atoms of a metal are volatilised in a flame and their absorption of a narrow band of radiation produced by a hollow cathode lamp, coated with the particular metal being determined, is measured. 

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