Hydrogen Atoms As Metallurgical Reductants ? The Potential And The Difficulties

The highly negative Gibbs free energies of hydrogen atom reactions suggest that refractory oxides such as titanium dioxide should be easily reduced by hydrogen atoms. These reactions appear to be most favourable at low temperatures; oxides should be reducible even at room temperature. Since hydrogen atoms are produced in plasmas containing hydrogen a number of investigators have used hydrogen plasmas of various sorts to test these possibilities for reducing refractory oxides, in particular TiO2. None of these attempts has succeeded, a small degree of reduction being achieved in only a thin layer near the surface. A deeper consideration shows that several factors complicate the reactions expected on the basis of the negative Gibbs free energy. One factor is that the back reaction by water molecules produces molecular hydrogen, not hydrogen atoms, and the metal atoms that have been reduced may be immediately re-oxidised. In plasmas there are complications due to diffusion, thermal and charge boundary layers and charged particle reactions. Interpreting the results of hydrogen atom reactions is difficult. Hydrogen is not detectable by electron dispersive spectroscopy and amorphous products are not determinable by x-ray diffraction. Another consideration is economics. The cost of producing hydrogen atoms has a large bearing on the metals for which hydrogen atom reduction may be competitive. In this paper these factors are discussed, some necessary basic studies are highlighted and the general principles of a laboratory reactor are given, together with the results of tests using ZnFe2O4, ZnO and TiO2 as test oxides.