Oxide phases

The electrophilic character of boron is again evident when we consider the oxida tion of organoboranes In the oxidation phase of the hydroboration-oxidation sequence as presented m Figure 6 11 the conjugate base of hydrogen peroxide attacks boron Hydroperoxide ion is formed m an acid-base reaction m step 1 and attacks boron m step 2 The empty 2p orbital of boron makes it electrophilic and permits nucleophilic reagents such as HOO to add to it... 

FIGURE 6 11 The oxidation phase in the hydroboration-oxidation of 1 methylcydo pentene... 

Niobium Oxides. The solubihty of oxygen in niobium obeys Henry s law to the solubiHty limit of the first oxide phase of 850—1300°C (123). The amount of oxygen in solution in niobium is 1.3 at. % at 850°C and nearly 2 at. % at 1000°C (124). Only three clearly defined anhydrous oxides of niobium have been obtained in bulk, ie, NbO, Nb02, and Nb20. Niobium monoxide, NbO, is obtained by hydrogen reduction of the pentoxide at... 

Examination of the metallic product (regulus) of such aluminothermically produced vanadium metal reveals the presence of oxide phases in the metal matrix. This suggests that there is a decreasing solubiHty for aluminum and oxygen below the melting point. To date, no purification processes have been developed that take advantage of the purification potential of this phenomenon. 

The nickel oxide modification obtained electrochemicaHy in KOH electrolyte contained potassium ion and its nickel oxidation level are higher than that of NiO 5. Conclusions regarding the transitions between the reduced and oxidized products within the two series are that the redox process was not reversible and although the oxidized phases of the P- and the y-nickel hydroxides differ in energy contents, differences in analyses and x-ray patterns are not significant. 

Fig. 1. Calcium carbide—calcium oxide phase diagram using A, pure CaC2, and B, technical-grade...

After preparing a homogeneous solution of the precursors, powder precipitation is accompHshed through the addition of at least one complexing ion. For PLZT, frequently OH in the form of ammonium hydroxide is added as the complexing anion, which results in the formation of an amorphous, insoluble PLZT-hydroxide. Other complexing species that are commonly used are carbonate and oxalate anions. CO2 gas is used to form carbonates. Irrespective of the complexing anion, the precipitated powders are eventually converted to the desired crystalline oxide phase by low temperature heat treatment. 

In all of these oxide phases it is possible that departures from the simple stoichiometric composition occur dirough variation of the charges of some of the cationic species. Furthermore, if a cation is raised to a higher oxidation state, by the addition of oxygen to tire lattice, a conesponding number of vacant cation sites must be formed to compensate tire structure. Thus in nickel oxide NiO, which at stoichiomen ic composition has only Ni + cations, oxidation leads to Ni + ion formation to counterbalance the addition of extra oxide ions. At the same time vacant sites must be added to the cation lattice to retain dre NaCl sUmcture. This balanced process can be described by a normal chemical equation thus... 

The difference in stability between FeO and NiO is not as large as that between iron and copper oxides, and so the preferential oxidation of iron is not so marked in pentlandite. Furthermore, the nickel and iron monoxides form a continuous series of solid solutions, and so a small amount of nickel is always removed into die oxide phase (Table 9.2). 

Another example of the use of neutron diffraction to understand the role of atomic vacancies in producing a superconducting metal oxide phase is work that has been performed on Bao Kq 4fii03. This work demonstrates that at the synthesis temperature (700° C), under the proper conditions, oxygen vacancies are created to allow the formation of the parent phase with bismuth largely in the +3 oxidation state. The presence of the vacancies allows the incorporation of potassium in the... 

Boulesteix, C. (editor) (1998) Oxides Phase Transitions, Non-Stoichiometry, Superconductors in Key Engineering Materials, vol. 155-156. 

This section considers a number of extremely important structure types in which A1 combines with one or more other metals to form a mixed oxide phase. The most significant of these from both a theoretical and an industrial viewpoint are spinel (MgAl204) and related compounds, Na- -alumina (NaAlnOi ) and related phases, and tricalcium aluminate (Ca3Al20g) which is a major constituent of Portland cement. Each of these compounds raises points of fundamental importance in solid-state chemistry and each possesses properties of crucial significance to... 

Nonstoichiometric oxide phases are of great importance in semiconductor devices, in heterogeneous catalysis and in understanding photoelectric, thermoelectric, magnetic and diffusional properties of solids. They have been used in thermistors, photoelectric cells, rectifiers, transistors, phosphors, luminescent materials and computer components (ferrites, etc.). They are cmcially implicated in reactions at electrode surfaces, the performance of batteries, the tarnishing and corrosion of metals, and many other reactions of significance in catalysis. ... 

Finally, oxygen is soluble in metallic titanium up to a composition of TiOo.s with the oxygen atoms occupying octahedral sites in the hep metal lattice distinct phases that have been crystallographically characterized are TieO, TisO and Ti20. It seems likely that in all these reduced oxide phases there is extensive metal-metal bonding. 

Niobium and tantalum also form various oxide phases but they are not so extensive or well characterized as those of vanadium. Their pentoxides are relatively much more stable and difficult to reduce. As they are attacked by cone HF and will dissolve in fused alkali, they may perhaps... 

The dioxides of molybdenum (violet) and tungsten (brown) are the final oxide phases produced by reduction of the trioxides with hydrogen they have rutile structures sufficiently distorted to allow the formation of M-M bonds and concomitant metallic conductivity and diamagnetism. Strong heating causes disproportionation ... 

No other oxide phases below MO2 have been established but a yellow hydroxide , precipitated by alkali from aqueous solutions of chromium(II), spontaneously evolves H2 and forms a chromium(III) species of uncertain composition. The sulfides, selenides and tellurides of this triad are considered on p. 1017. 

BaAn" 03 (An = Th Am) all have the perovskite strueture and are obtained from the aetinide dioxide. In aeeord with normal redox behaviour, the Pa and U eompounds are only obtainable if O2 is rigorously exeluded, and the Am eompound if O2 is present. Aetinide dioxides also yield an extensive series of nonstoiehiometrie, mixed oxide phases in whieh a seeond oxide is ineorporated into the fluorite lattiee of the An02. The UO2/PUO2 system, for example, is of great importanee in the fuel of fast-breeder reaetors. 

It is generally agreed that the four known oxide phases in the Pu-0 system are PU2O3 (hexagonal, La203 type), PuOi.52 (bcc), PuOl.61 Cfee, tentative), and Pu02 (fee, fluorite type). Above... 

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