Alkali and Alkaline Earth Metal

The s and f block elements present a particular challenge in the molecular mechanics field because the metal-ligand interactions in both cases are principally electrostatic. Thus, the most appropriate way to model the M-L bonds is with a combination of electrostatic and van der Waals nonbonded interactions. Indeed, most reported studies of modeling alkali metal, alkaline earth metal and rare earth complexes have used such an approach. 

The types of alkali and alkaline earth metal complexes subjected to molecular mechanics modeling fall into four categories crown ethers1255-2 ], cryptands1262 263 , spherands[264 2651, and other biologically important ligands such as ionophores and cyclic antibiotics1266-2691. 

The aims of studies on the first three groups have been broadly similar - principally elucidation of the origins of metal ion selectivity and investigation of the conformational variability. All of the studies were reasonably successful in reproducing observed structures or in rationalizing the differences predicted on the basis of gas phase calculations and those determined in the solid state or solution. 

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Forms water-soluble alkali and alkaline earth metal salts. Heating with KCN gives benzonitrile and phenol is formed by fusion with NaOH or KOH. Further sulphonation at 250°C gives benzene-1,3-disulphonic acid. 

For the most part it is true to say that the chemistry of the alkali and alkaline earth metal compounds is not that of the metal ion but rather that of the anion with which the ion is associated. Where appropriate, therefore, the chemistry of these compounds will be discussed in other sections, for example nitrates with Group V compounds, sulphates with Group VI compounds, and only a few compounds will be discussed here. 

All the azides are potentially dangerous, and liable to detonate on heating, but those of the alkali and alkaline earth metals can be heated with caution if pure they then evolve pure nitrogen. 

The sulphates of the alkali and alkaline earth metals and man-ganese(II) are stable to heat those of heavier metals decompose on heating, evolving sulphur trioxide and leaving the oxide or the metal ... 

Precipitated (hydrated) siUca reacts vigorously with fluorosulfuric acid to give siUcon tetrafluoride [7783-61-1] (21), but glass (qv) is not attacked in the absence of moisture (20). Alkali and alkaline-earth metal chlorides are readily converted to fluorosulfates by treatment with fluorosulfuric acid (7,13,22,23). 

Alkali and alkaline earth metals, e.g. sodium, potassium lithium, magnesium, calcium, powdered aluminium Anhydrous ammonia Ammonium nitrate... 

Explosive reactions can occur between oxygen and a wide range of chemicals including organic compounds (such as acetone, acetylene, secondary alcohols, hydrocarbons), alkali and alkaline earth metals, ammonia, biological specimens previously anaesthetized with ether, hydrogen and foam rubber. 

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 ... 

The authors report that the six-armed host is a remarkably powerful complex ligand for cations . These compounds apparently can strongly bind alkali and alkaline earth metals including Li", Na", K", Rb", Cs", Mg ", Ca ", and Sr ". These ligands were relatively unsuccessful in binding several heavy metals which were tested. 

Alkali and alkaline earth metallates are obtained by heating the appropriate oxides, in the pres-enee of oxygen where neeessary. For instanee, the reaetion... 

Tabushi, I. Yamamura, K. Water Soluble Cyclophanes as Hosts and Catalysts, 113,145-182 (1983). Takagi, M., and Ueno, K. Crown Compounds as Alkali and Alkaline Earth Metal Ion Selective Chromogenic Reagents. 121, 39-65 (1984). 

Section 20.1 deals with the processes by which these metals are obtained from their principal ores. Section 20.2 describes the reactions of the alkali and alkaline earth metals, particularly those with hydrogen, oxygen, and water. Section 20.3 considers the redox chemistry of the transition metals, their cations (e.g., Fe2+, Fe3+), and their oxoanions (e.g., Cr042-). ... 

Metals and the periodic table. The periodic table groups discussed in this chapter are Groups 1 and 2, the alkali and alkaline earth metals (shaded in blue), and the transition metals (shaded in yellow). Symbols are shown for the more common metals. 

I Table 20.1 Reactions of the Alkali and Alkaline Earth Metals ... 

The compounds formed by the reaction of hydrogen with the alkali and alkaline earth metals contain H- ions for example, sodium hydride consists of Na+ and H- ions. These white crystalline solids are often referred to as saline hydrides because of their physical resemblance to NaCL Chemically, they behave quite differently from sodium chloride for example, they react with water to produce hydrogen gas. Typical reactions are... 

Heating with the following solids, their fusions, or vapours (a) oxides, peroxides, hydroxides, nitrates, nitrites, sulphides, cyanides, hexacyano-ferrate(III), and hexacyanoferrate(II) of the alkali and alkaline-earth metals (except oxides and hydroxides of calcium and strontium) (b) molten lead, silver, copper, zinc, bismuth, tin, or gold, or mixtures which form these metals upon reduction (c) phosphorus, arsenic, antimony, or silicon, or mixtures which form these elements upon reduction, particularly phosphates, arsenates,... 

A mercury cathode finds widespread application for separations by constant current electrolysis. The most important use is the separation of the alkali and alkaline-earth metals, Al, Be, Mg, Ta, V, Zr, W, U, and the lanthanides from such elements as Fe, Cr, Ni, Co, Zn, Mo, Cd, Cu, Sn, Bi, Ag, Ge, Pd, Pt, Au, Rh, Ir, and Tl, which can, under suitable conditions, be deposited on a mercury cathode. The method is therefore of particular value for the determination of Al, etc., in steels and alloys it is also applied in the separation of iron from such elements as titanium, vanadium, and uranium. In an uncontrolled constant-current electrolysis in an acid medium the cathode potential is limited by the potential at which hydrogen ion is reduced the overpotential of hydrogen on mercury is high (about 0.8 volt), and consequently more metals are deposited from an acid solution at a mercury cathode than with a platinum cathode.10... 

Alkali and alkaline-earth metals have the most negative standard reduction potentials these potentials are (at least in ammonia, amines, and ethers) more negative than that of the solvated-electron electrode. As a result, alkali metals (M) dissolve in these highly purified solvents [9, 12] following reactions (1) and (2) to give the well-known blue solutions of solvated electrons. 

Although the ion pairs of a-substituted benzyl anions and the corresponding cations are chiral species, which, in addition, often bear a pyramidal and hence stereogenic carbon atom, in most cases rapid racemization of the alkali and alkaline earth metal derivatives occurs in solution... 

Coordination compounds of alkali and alkaline earth metals with covalent molecules. P. N. Kapoor and R. C. Mehrotra, Coord. Chem. Rev., 1974, 14,1-27 (120). 

Crown compounds as alkali and alkaline earth metal ion selective chromogenic reagents. M. Takagi and K. Ueno, Top. Curr. Chem., 1984,121, 39-65 (37),... 

Alkali and alkaline earth metal cryptates. D. Parker, Adv. Inorg. Chem. Radiochem., 1983, 27, 1-26 (150). 

Another marked physical difference between sulphides and sulphoxides (or sulphones) is that sulphoxides (and lower alkyl sulphones) are hygroscopic and dissolve quite readily in water or protic solvents such as alcohols, and even more so lower alkyl or alkyl aryl sulphoxides are almost freely miscible with water. This can be accounted for by the formation of the strong hydrogen bond between the S—O bond in the sulphoxides and water molecules. Moreover, lower alkyl sulphoxides and sulphones such as dimethyl sulphoxide (DMSO) or sulpholene can dissolve a number of metallic salts, especially those of alkali and alkaline earth metals, and hence these compounds have been widely utilized as versatile and convenient solvents in modern organic chemistry26 (Table 3). 

A note on good practice The oxides and hydroxides of the alkali and alkaline earth metals are not Bronsted bases the oxide and hydroxide ions they contain are the bases (the cations are spectator ions). However, for convenience, chemists often refer to the compounds themselves as bases. 

Foreign cations can increasingly lower the yield in the order Fe, Co " < Ca " < Mn < Pb " [22]. This is possibly due to the formation of oxide layers at the anode [42], Alkali and alkaline earth metal ions, alkylammonium ions and also zinc or nickel cations do not effect the Kolbe reaction [40] and are therefore the counterions of choice in preparative applications. Methanol is the best suited solvent for Kolbe electrolysis [7, 43]. Its oxidation is extensively inhibited by the formation of the carboxylate layer. The following electrolytes with methanol as solvent have been used MeOH-sodium carboxylate [44], MeOH—MeONa [45, 46], MeOH—NaOH [47], MeOH—EtsN-pyridine [48]. The yield of the Kolbe dimer decreases in media that contain more than 4% water. 

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