Mixed oxides, phase equilibria metal-oxygen

Figure 2.33. Ni-Co-O phase diagram (isothermal section at 1600 K). log p02 (oxygen partial pressure) is plotted against the molar fraction in the metallic alloy. The metallic alloy, (Ni, Co) solid solution is stable in (1) and the mixed oxide (Ni, Co)0 solid solution in (3). In the intermediate region (2) we have coexistence of alloy and oxide. For the value of the partial oxygen pressure corresponding to y, within the two-phase field, we will have the alloy of composition xt in equilibrium with an oxide containing the two metals in the ratio x2-...

Catalysts considered in the present discussion cover a wide spectrum of solids reducible multivalent metal oxides as well as non reducible basic compounds Reducible metal oxides possess some inherent problems whereas these problems are less for the alkali ions promoted alkaline earth oxides. Alkaline earth oxides seem to be more suitable for working at low partial pressure of oxygen. By doping alkaline earth oxides with alkali metal compounds it is conceivable that O species can be stabilized for dissociative absorption of methane. Reducible metal oxides will tend to transform into lower valent oxides or even upto metallic state partly under applied reaction conditions specially at low partial pressure of O2. Both activity and selectivity will be deteriorated. But for the non reducible basic oxides structural changes will be quite different. They will tend to reach an equilibrium state in the surface level amongst the oxide, hydroxide and carbonate phases on reacting with evolved H2O and CO. Both the lattice distortion and the formation of O species can occur in the alkali earth oxides in doping with alkali ions as they can not build a mixed oxide lattice. 

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