Alkali binary

Metallic Antimonides. Numerous binary compounds of antimony with metallic elements are known. The most important of these are indium antimonide [1312-41 -0] InSb, gallium antimonide [12064-03-8] GaSb, and aluminum antimonide [25152-52-7] AlSb, which find extensive use as semiconductors. The alkali metal antimonides, such as lithium antimonide [12057-30-6] and sodium antimonide [12058-86-5] do not consist of simple ions. Rather, there is appreciable covalent bonding between the alkali metal and the Sb as well as between pairs of Na atoms. These compounds are useful for the preparation of organoantimony compounds, such as trimethylstibine [594-10-5] (CH2)2Sb, by reaction with an organohalogen compound. 

Phosphides are binary compounds containing anionic phosphorus (P ). Heavy metal, alkali, and alkaline earth metal phosphides exist but few of them are commercially important. Phosphides hydrolyze to the flammable and toxic gas phosphine (PH3). The hydrolysis reaction of aluminum phosphide is given below ... 

Many binary and pseudo-binary compounds of the alkali metals are more conveniently treated within the context of the chemistry of the other element and for this reason discussion Is deferred to later chapters, e.g. borides (p. 145),... 

Carbon forms binary compounds with most elements those with metals are considered in this section whilst those with H, the halogens, O, and the chalcogens are discussed in subsequent sections. Alkali metal fullerides and encapsulated (endohedral) metallafullerenes have already been considered (pp. 285, 288 respectively) and met-allacarbohedrenes (metcars) will be dealt with later in this section (p. 300). Silicon carbide is discussed on p. 334. General methods of preparation of metal carbides are ... 

No binary hydrides have been characterized, but reactions of the metal powders with alkali metal hydrides in a hydrogen atmosphere lead to Li3RhH4 (planar RhH4 ) and M3MH6 (M = Li, Na M = Rh, Ir) with octahedral MHj [34],... 

Of course, the chemistry of zirconium cluster phases has been well described and reviewed in the literature [1-4]. Apart from a very few examples, mostly in the binary halides, almost all reduced zirconium halides contain octahedra of zirconium atoms centred on an interstitial atom Z. Several possible and experimentally realized Z include H, Be-N, K, Al-P, and the transition metals Mn-Ni. All these compounds have the general formula Ax"[(Zr6Z)Xi2X[J], with a " = alkali or alkaline earth metal cation, X=C1 Br or I, X =inner edge-bridging halide [5], X =outer exo-bonded halide, and 0[Pg.61]

A remarkable variety of compounds in the Ca-(B,C,N) system has opened a window for research in related fields. With the elements boron, carbon and nitrogen, substance classes such as borocarbides, boronitrides, and carbonitrides can be considered to contain anionic derivatives of binary compounds B4C, BN, and C3N4. Until now, most compounds in these substance classes have been considered to contain alkali, alkaline-earth, or lanthanide elements. Lanthanide borocarbides are known from the work of Bauer [1]. Lanthanide boronitrides represent a younger family of compounds, also assigned as nitridoborates [2] following the nomenclature of oxoborates. 

Low-temperature solvents are not readily available for many refractory compounds and semiconductors of interest. Molten salt electrolysis is utilized in many instances, as for the synthesis and deposition of elemental materials such as Al, Si, and also a wide variety of binary and ternary compounds such as borides, carbides, silicides, phosphides, arsenides, and sulfides, and the semiconductors SiC, GaAs, and GaP and InP [16], A few available reports regarding the metal chalcogenides examined in this chapter will be addressed in the respective sections. Let us note here that halide fluxes provide a good reaction medium for the crystal growth of refractory compounds. A wide spectrum of alkali and alkaline earth halides provides... 

Binary alkali nitrates have been systematically studied the isotherms are shown in Fig. 6. The Chemla effect occurs in all systems except for (Li, Na)N03. Figure 6 shows that with an increase in temperature the crossing point shifts toward higher concentrations of the smaller cation. 

Figure 6. Isotherms of the internal mobilities in 10 binary alkali nitrates. C Chemla erossing point marked only for the unelear eases. (Reprinted from M. Chemla and I. Okada, lonie Mobilities of Monovalent Cations in Molten Salt Mixtures, Electrochim. Acta 35 1761-1776, Fig. 5. Copyright 1990 with permission from Elsevier Seienee.)...

In such systems as (M, Mj (i/2))X (M, monovalent cation Mj, divalent cation X, common anion), the much stronger interaction of M2 with X leads to restricted internal mobility of Mi. This is called the tranquilization effect by M2 on the internal mobility of Mi. This effect is clear when Mj is a divalent or trivalent cation. However, it also occurs in binary alkali systems such as (Na, K)OH. The isotherms belong to type II (Fig. 2) % decreases with increasing concentration of Na. Since the ionic radius of OH-is as small as F", the Coulombic attraction of Na-OH is considerably stronger than that of K-OH. 

Sato et al. " measured the viscosities of some binary and ternary alkali carbonates. Since melt creep must be prevented, a highly sintered alumina crucible was used instead of a gold-plated nickel crucible. Homogeneity of a mixture sample was achieved by gas bubbling. A laser beam is combined with a computer-assisted time counter to obtain the logarithmic decrement. Roscoe s equationi3i has been used for calculation of the viscosity, while it has been claimed by Abe et al. that the viscosities calculated from Roscoe s equation are 0.6-1.5% lower than those from more rigorous equations. 

The binary alloy is pyrophoric and may ignite in contact with water, as do other alkali metal germanides. 

Figure 7.5 Enthalpy of formation of binary compounds of the alkali metals.

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