Stable oxides

The tendency of elements of higher atomic number to retain the s electrons as an inert pair is also encountered in Group IV, and in this case it is found that for lead the most stable oxidation state is + 2, achieved by loss of two p electrons. 

The oxidation state -1-4 is predominantly covalent and the stability of compounds with this oxidation state generally decreases with increasing atomic size (Figure 8.1). It is the most stable oxidation state for silicon, germanium and tin, but for lead the oxidation state +4 is found to be less stable than oxidation state +2 and hence lead(IV) compounds have oxidising properties (for example, see p. 194). 

All Group IV elements form both a monoxide, MO, and a dioxide, MO2. The stability of the monoxide increases with atomic weight of the Group IV elements from silicon to lead, and lead(II) oxide, PbO, is the most stable oxide of lead. The monoxide becomes more basic as the atomic mass of the Group IV elements increases, but no oxide in this Group is truly basic and even lead(II) oxide is amphoteric. Carbon monoxide has unusual properties and emphasises the different properties of the group head element and its compounds. 

The many possible oxidation states of the actinides up to americium make the chemistry of their compounds rather extensive and complicated. Taking plutonium as an example, it exhibits oxidation states of -E 3, -E 4, +5 and -E 6, four being the most stable oxidation state. These states are all known in solution, for example Pu" as Pu ", and Pu as PuOj. PuOl" is analogous to UO , which is the stable uranium ion in solution. Each oxidation state is characterised by a different colour, for example PuOj is pink, but change of oxidation state and disproportionation can occur very readily between the various states. The chemistry in solution is also complicated by the ease of complex formation. However, plutonium can also form compounds such as oxides, carbides, nitrides and anhydrous halides which do not involve reactions in solution. Hence for example, it forms a violet fluoride, PuFj. and a brown fluoride. Pup4 a monoxide, PuO (probably an interstitial compound), and a stable dioxide, PUO2. The dioxide was the first compound of an artificial element to be separated in a weighable amount and the first to be identified by X-ray diffraction methods. 

The oxidation of most modem alloys is dependent on the formation of a compact protective film of a slow growing chemically stable oxide such as chromium (ITT) oxide [1308-38-9], alumina [1344-28-1], AI2O2, or siUca [7631-86-9], Si02. These oxides grow much more slowly than do the oxides... 

Thermal Reduction. Magnesium metal can also be formed by the thermal reduction of magnesium oxide with a reactive metal, such as siUcon [7440-21-3] which forms a stable oxide. 

The abihty of iron to exist in two stable oxidation states, ie, the ferrous, Fe ", and ferric, Fe ", states in aqueous solutions, is important to the role of iron as a biocatalyst (79) (see Iron compounds). Although the cytochromes of the electron-transport chain contain porphyrins like hemoglobin and myoglobin, the iron ions therein are involved in oxidation—reduction reactions (78). Catalase is a tetramer containing four atoms of iron peroxidase is a monomer having one atom of iron. The iron in these enzymes also undergoes oxidation and reduction (80). 

The most common oxidation states and the corresponding electronic configurations of osmium ate +2 and + (t5 ), which ate usually octahedral. Stable oxidation states that have various coordination geometries include —2 and 0 to +8 (P] The single most important appHcation is OsO oxidation of olefins to diols. Enantioselective oxidations have also been demonstrated. 

Zirconium [7440-67-7] is classified ia subgroup IVB of the periodic table with its sister metallic elements titanium and hafnium. Zirconium forms a very stable oxide. The principal valence state of zirconium is +4, its only stable valence in aqueous solutions. The naturally occurring isotopes are given in Table 1. Zirconium compounds commonly exhibit coordinations of 6, 7, and 8. The aqueous chemistry of zirconium is characterized by the high degree of hydrolysis, the formation of polymeric species, and the multitude of complex ions that can be formed. 

Cerium Oxide. The most stable oxide of cerium is cerium dioxide [1306-38-3] Ce02, also called ceria or ceric oxide. When cerium salts are calcined in air or if oxygen is present, this tetravalent Ce(IV) oxide is formed, cerium sesquioxide [1345-13-7] can be prepared in strongly reducing... 

Effect of Thermal History. Many of the impurities present in commercial copper are in concentrations above the soHd solubihty at low (eg, 300°C) temperatures. Other impurities oxidize in oxygen-bearing copper to form stable oxides at lower temperatures. Hence, because the recrystallization kinetics are influenced primarily by solute atoms in the crystal lattice, the recrystallization temperature is extremely dependent on the thermal treatment prior to cold deformation. 

Zinc is attacked at high pH. However, in weakly alkaline solutions near room temperature, corrosion is actually very slight, being less than 1 mil/y (0.0254 mm/y) at a pH of 12. The corrosion rate increases rapidly at higher pH, approaching 70 mil/y (1.8 mm/y) at a pH near 14. Just as in aluminum corrosion, protection is due primarily to a stable oxide film that forms spontaneously on exposure to water. High alkalinity dissolves the oxide film, leading to rapid attack. 

Experimental values for tire sputtering efficiency tend to show lower values of a for elements, such as aluminium and mngsten which form stable oxides, compared with the metals such as gold and platinum which do not under normal experimental conditions. This is probably due to the presence of a surface oxide, since industrial sources of argon, which are used as a source of ions for example, usually contain at least 1 ppm of oxygen, which is more than enough to oxidize aluminium and tungsten. 

There is a significant difference between rhodium and the odier metals in that rhodium forms a relatively stable oxide, RI12O3. The Gibbs energy of formation of this oxide is given by the equation... 

The composition of turbine blades is a complex mixture of alloying elements in solid solution in nickel. A typical alloy would contain Al, Cr, Mo, Co or Ta in amounts up to 10 atom per cent of the particular elements which are chosen. Of drese all except cobalt form substantially more stable oxides than... 

Stable oxides, such as those of clrromium, vanadium and titanium cannot be reduced to the metal by carbon and tire production of these metals, which have melting points above 2000 K, would lead to a refractoty solid containing carbon. The co-reduction of the oxides widr iron oxide leads to the formation of lower melting products, the feno-alloys, and tlris process is successfully used in industrial production. Since these metals form such stable oxides and carbides, tire process based on carbon reduction in a blast furnace would appear to be unsatisfactory, unless a product samrated with carbon is acceptable. This could not be decarburized by oxygen blowing without significairt re-oxidation of the refractory metal. 

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