Basic oxides from metals

Basic oxides of metals such as Co, Mn, Fe, and Cu catalyze the decomposition of chlorate by lowering the decomposition temperature. Consequendy, less fuel is needed and the reaction continues at a lower temperature. Cobalt metal, which forms the basic oxide in situ, lowers the decomposition of pure sodium chlorate from 478 to 280°C while serving as fuel (6,7). Composition of a cobalt-fueled system, compared with an iron-fueled system, is 90 wt % NaClO, 4 wt % Co, and 6 wt % glass fiber vs 86% NaClO, 4% Fe, 6% glass fiber, and 4% BaO. Initiation of the former is at 270°C, compared to 370°C for the iron-fueled candle. Cobalt hydroxide produces a more pronounced lowering of the decomposition temperature than the metal alone, although the water produced by decomposition of the hydroxide to form the oxide is thought to increase chlorine contaminate levels. Alkaline earths and transition-metal ferrates also have catalytic activity and improve chlorine retention (8). 

AI2O3, Si02 (impurities), and other acidic or amphoteric oxides are the main structural promoters of iron-based catalyst. In the total surface area of catalyst after reduction, in addition to the surface area of basic oxides and metal iron, it should also include the surface occupied by acidic or amphoteric oxides. Subtracting the surface area of metal iron and basic oxides from the total surface area of catalyst results in the surface area of acidic and amphoteric oxides, also known as acid surface area (/Sa), that is,... 

Nitrogen is unusual in forming so many oxides. The acidity of the Group V oxides falls from phosphorus, whose oxides are acidic, through arsenic and antimony whose oxides are amphoteric, to the basic oxide ofbismuth. This change is in accordance with the change from the non-metallic element, phosphorus, to the essentially metallic element, bismuth. The +5 oxides are found, in each case, to be more acidic than the corresponding + 3 oxides. 

All elements in the s block are reactive metals that form basic oxides. The p-block elements tend to gain electrons to complete dosed shells they range from metals through metalloids to nonmetals. 

Metals typically form basic oxides and nonmetals typically form acidic oxides, but what about the elements that lie on the diagonal frontier between the metals and nonmetals Along this frontier from beryllium to polonium, metallic character blends into nonmetallic character, and the oxides of these elements have both acidic and basic character (Fig. 10.7). Substances that react with both acids and bases are classified as amphoteric, from the Greek word for both. For example, aluminum oxide, A1203, is amphoteric. It reacts with acids ... 

Metals form basic oxides, nonmetals form acidic oxides the elements on a diagonal line from beryllium to polonium and several d-block metals form amphoteric oxides. 

The valence electron configuration of the atoms of the Group 2 elements is ns1. The second ionization energy is low enough to be recovered from the lattice enthalpy (Fig. 14.18). Flence, the Group 2 elements occur with an oxidation number of +2, as the cation M2+, in all their compounds. Apart from a tendency toward nonmetallic character in beryllium, the elements have all the chemical characteristics of metals, such as forming basic oxides and hydroxides. 

A second separation technique is leaching, which uses solubility properties to separate the components of an ore. For example, modem gold production depends on the extraction of tiny particles of gold from gold-bearing rock deposits. After the rock is crushed, it is treated with an aerated aqueous basic solution of sodium cyanide. Molecular oxygen oxidizes the metal, which forms a soluble coordination complex with the cyanide anion ... 

The phosphate bonded cements described in this chapter are the products of the simple acid-base reaction between an aqueous solution of orthophosphoric acid and a basic oxide or silicate. Such reactions take place at room temperature. Excluded from this chapter are the cementitious substances that are formed by the heat treatment of aqueous solutions of acid metal phosphates. 

Those ions which take no part in the reaction are known as spectator ions , and from these considerations, the following definitions can be derived. A basic oxide (or hydroxide) is a metallic oxide (or hydroxide) which contains the 02 (or OFT) ion it will react with an acid to form a salt and water only. It is necessary to realize the importance of the word only in this definition, as were it to be omitted, then certain compounds which are quite different from basic metallic oxides and hydroxides would be covered by this definition. Thus, Pb(IV) oxide reacts with hydrochloric acid to produce Pb(II) chloride (a salt) and water, but does not belong to the class of bases because chlorine gas is also produced ... 

The relative stabilities of the dioxides, sesquioxides and monoxides for first period transition metals are given in Figure 7.11(c). The stability of the higher oxidation state oxides decreases across the period. As we will discuss later, higher oxidation states can be stabilized in a ternary oxide if the second metal is a basic oxide like an alkaline earth metal. The lines in Figure 7.11(c) can in such cases be used to estimate enthalpies of formation for unstable oxidation states in order to determine the enthalpy stabilization in the acid-base reactions see below. Finally, it should be noted that the relative stability of the oxides in the higher oxidation states increases from the 3d via 4d to the 5d elements, as illustrated for the Cr, Mo and W oxides in Figure 7.11(d). 

Figure 7.15 (a) Enthalpy of formation of ternary oxides and nitrides from their binary constituent compounds as a function of the ratio of ionic potential [16]. Reprinted with permission from [16] Copyright (1997) American Chemical Society, (b) Gibbs energy of the oxide-sulfide equilibrium for group 1 and 2 metals at 1773 K as a function of the optical basicity of the metal. 

Many promoters have been used to improve the performance of Ni/Al203 catalysts. The effect of the basic oxides of Na, K, Mg, and Ca on Ni/Al203 was examined by a number of authors (178,203,211 -213). They found that these added oxides markedly decrease the carbon deposition. The kinetics results showed that the added metal oxides changed the reaction order in CH4 from negative to positive and that in C02 from positive to negative. This observation implies that the surface of a nickel catalyst incorporating basic metal oxides is abundant in adsorbed C02, whereas the surfaces devoid of these oxides are abundant in adsorbed CH4 (178). The coverage of nickel with C02 is most likely unfavorable to CH4 decomposition... 

In this chapter, we have discussed the application of metal oxides as catalysts. Metal oxides display a wide range of properties, from metallic to semiconductor to insulator. Because of the compositional variability and more localized electronic structures than metals, the presence of defects (such as comers, kinks, steps, and coordinatively unsaturated sites) play a very important role in oxide surface chemistry and hence in catalysis. As described, the catalytic reactions also depend on the surface crystallographic structure. The catalytic properties of the oxide surfaces can be explained in terms of Lewis acidity and basicity. The electronegative oxygen atoms accumulate electrons and act as Lewis bases while the metal cations act as Lewis acids. The important applications of metal oxides as catalysts are in processes such as selective oxidation, hydrogenation, oxidative dehydrogenation, and dehydrochlorination and destructive adsorption of chlorocarbons. 

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