Alkali-metal Oxides

The Oxidative Transformation of Methane over the Nickel-based Catalysts Modified by Alkali Metal Oxide and Rare Earth Metal Oxide... 

We expected to control the direction of OTM reaction over NiO by sur ce modification, namely making use of the interaction between NiO and other conq>onents to beget a synergistic effect. In this paper, two completely different behaviors of the oxidative transformation of methane were performed over the nickel-based catalysts because of the different modifications by alkali metal oxide and rare earth metal oxide and the different interactions between nickel and supports. Furthermore, the two completely different reactions were related with the acid-base properties of catalysts and the states of nickel present. 

Addition of an alkali metal oxide as a "network modifier to the "network former causes pH sensitivity, i.e., small amounts of alkali metal induce superficial gel layer formation as a merely local chemical attack and so with limited alkali error larger amounts will result in more pronounced dissolving properties of the glass up to complete dissolution, e.g., water-glass with large amounts of sodium oxide. Simultaneous addition of an alkaline earth metal oxide, however, diminishes the dissolution rate. Substitution of lithium for sodium in pH-sensitive glass markedly reduces the alkali error. 

When the positions of cations and anions are interchanged, the same structure types result for the CsCl, NaCl and zinc blende type. In the case of the fluorite type the interchange also involves an interchange of the coordination numbers, i.e. the anions obtain coordination number 8 and the cations 4. This structure type sometimes is called anti-fluorite type it is known for the alkali metal oxides (Li20,..., Rb20). 

Rowley, A. T. et al., Inorg. Chem. Acta, 1993, 211(1), 77 Preparation of metal oxides by fusing metal halides with lithium oxide in a sealed tube leads to explosions if halide hydrates are employed, particularly lanthanide trihalide hydrates. The preparation succeeds with anhydrous halides. This will be purely a question of vapour pressure above an exothermic reaction the question is whether the vapour is water, or metal halide, and the reaction oxide formation, or hydration of lithium oxide. Like other alkali metal oxides, hydration is extremely energetic. 

Palladium and platinum. These are resistant to chemical attack (Pt more than Pd). Both metals dissolve in fused alkali metal oxides and peroxides. Pt is attacked, at high temperature, by molten alkali and alkaline earth halogenides and by several compounds of B, Si, Pb, P, As, Sb, Bi. Pd dissolves slowly in oxidizing acids Pt is dissolved by aqua regia. 

Another method at the molecular level is the inhibition of oxidation catalysis by alkali and transition metal impurities. In particular, alkali metal oxides in traces serve as effective catalyst with almost ubiquitous presence in technological environments. The mechanism of operation is well described in the literature [64,72-77] despite its complex and multi-pathway behavior. 

The basicity of the molten carbonate is defined as equal to -log (activity of O ) or -log aM20, where a is the activity of the alkali metal oxide M2O. Based on this definition, acidic oxides are associated with carbonates (e g., K2CO3) that do not dissociate to M2O, and basic oxides are formed with highly dissociated carbonate salts (e.g., U2CO3). The solubility of NiO in binary carbonate melts shows a clear dependence on the acidity/basicity of the melt (18,19). In relatively acidic melts, NiO dissolution can be expressed by... 

Alkali metal ion-exchanged zeolites and occluded alkali metal oxide zeolites have been investigated extensively and applied as basic catalysts for a variety of organic transformations (1,41,221,222). Zeolites modified with alkaline earth compounds have been applied much less frequently as base catalysts for organic reactions. 

Remark of the translator More recent experience does not agree with this explanation of the promoting action of alkali metal oxides. On the one hand the sulfur retention by alkalinized iron is only weak on the other hand, the promoter action by alkali oxides is also observed in the sulfur free system. 

Osmium This metal had already been found by Haber to be an excellent ammonia catalyst. Its activity is further increased by alkali metal oxides, especially by potassium hydroxide. As the pure metal 2% ammonia, promoted, 4%. 

Scheme 1. Structural changes in boron centers with increasing levels of Na20 (or other alkali metal oxide) modifier...

The transformations are aided by or may require the presence of impurities or added mineralizers such as alkali metal oxides. Indeed, it has been suggested that tridymite cannot be formed at all in the absence of impurities, and some texts assert that pure Si02 occurs in only two forms quartz and cristobalite... 

Tridymite. Tridymite is reported to be the silica form stable from 870—1470°C at atmospheric pressure (44). Owing to the sluggishness of the reconstructive tridymite—quartz conversion, which requires mineralizers such as sodium tungstate, alkali metal oxide, or the action of water under pressure, tridymite may persist as a metastable phase below 870°C. It occurs in volcanic rocks and stony meteorites. 

The devitrification rate is extremely sensitive to both surface and bulk impurities, especially alkali. Increased alkali levels tend to increase the devitrification rate and lower the temperature at which the maximum rate occurs. For example, a bulk level of 0.32 wt % soda increases the maximum devitrification rate 20—30 times and lowers the temperature of maximum devitrification to approximately 1400°C (101). The impurity effect is present even at trace levels (<50 ppm) and can be enhanced with the addition of alumina. The devitrification rate varies inversely with the ratio of alumina-to-alkali metal oxide. The effect is a consequence of the fact that these impurities lower glass viscosity (102). 

The symmetry between cations and anions in the bond valence model can best be seen in the compounds of the alkali metals and alkaline earths where the cation valences are similar to those of the anions. Binary compounds such as NaCl (18189), CsCl (22173), and ZnO (67454) are invariant under the interchange of the cations and anions since both kinds of ions occupy equivalent sites. For compounds such as CaF2 (29008) which crystallizes with the fluorite structure, changing the signs of ions gives the antifluorite structure adopted by the alkali metal oxides such as Na20 (60435). Although the antifluorite... 

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