The Metallic Elements

The metals found in group IA of the periodic table are known as the alkali metals, and those in group IIA are the alkaline earths. Metals found in the groups between IIA and IIIA (the so-called d-block metals) are the transition metals. The series of elements following lanthanum (Z = 57, the/-block metals) 355 

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This is an exothermic process, due largely to the large hydration enthalpy of the proton. However, unlike the metallic elements, non-metallic elements do not usually form hydrated cations when their compounds dissolve in water the process of hydrolysis occurs instead. The reason is probably to be found in the difference in ionisation energies. Compare boron and aluminium in Group III ... 

Strong oxidising acids, for example hot concentrated sulphuric acid and nitric acid, attack finely divided boron to give boric acid H3CO3. The metallic elements behave much as expected, the metal being oxidised whilst the acid is reduced. Bulk aluminium, however, is rendered passive by both dilute and concentrated nitric acid and no action occurs the passivity is due to the formation of an impervious oxide layer. Finely divided aluminium does dissolve slowly when heated in concentrated nitric acid. 

Two methods are used to measure pH electrometric and chemical indicator (1 7). The most common is electrometric and uses the commercial pH meter with a glass electrode. This procedure is based on the measurement of the difference between the pH of an unknown or test solution and that of a standard solution. The instmment measures the emf developed between the glass electrode and a reference electrode of constant potential. The difference in emf when the electrodes are removed from the standard solution and placed in the test solution is converted to a difference in pH. Electrodes based on metal—metal oxides, eg, antimony—antimony oxide (see Antimony AND ANTIMONY ALLOYS Antimony COMPOUNDS), have also found use as pH sensors (8), especially for industrial appHcations where superior mechanical stabiUty is needed (see Sensors). However, because of the presence of the metallic element, these electrodes suffer from interferences by oxidation—reduction systems in the test solution. 

K. M. Mackay, Hydrogen Compounds of the Metallic Elements, E. and F. N. Spon, London, 1966, 168 pp. Hydrides, Comprehensive Inorganic Chemistry, Vol. 1, Chap. 2, Pergamon Press, Oxford, 1973. 

The general group trends, and a comparison with the chemistry of the metallic elements of Group 13 (Al, Ga, In and Tl), will be deferred until the next chapter. 

Many of the most important naturally occurring minerals and ores of the metallic elements are sulfides (p. 648), and the recovery of metals from these ores is of major importance. Other metal sulfides, though they do not occur in nature, can be synthesized by a variety of preparative methods, and many have important physical or chemical properties which have led to their industrial production. Again, the solubility relations of metal sulfides in aqueous solution form the basis of the most widely used scheme of elementary qualitative analysis. These various more general considerations will be briefly discussed before the systematic structural chemistry of metal sulfides is summarized. 

Two types of chemical bonds, ionic and covalent, are found in chemical compounds. An ionic bond results from the transfer of valence electrons from the atom of an electropositive element (M) to the atom(s) of an electronegative element (X). It is due to coulombic (electrostatic) attraction between the oppositely charged ions, M (cation) and X (anion). Such ionic bonds are typical of the stable salts formed by combination of the metallic elements (Na, K, Li, Mg, etc.) with the nonmetallic elements (F, Cl, Br, etc.). As an example, the formation of the magnesium chloride molecule from its elemental atoms is shown by the following sequence ... 

The metallic element titanium (11) is relatively abundant in nature it accounts for 0.56% of the earth s crust. This number may not seem very impressive until you realize that it exceeds the combined abundances of ten familiar elements H, N, C, P, S, Cl, Cr, Ni, Cu, and Zn. The most important ore of titanium is ilmenite. a mineral commonly found as a deposit of black sand along beaches in the United States, Canada, Australia, and Norway. In ilmenite. titanium is chemically combined with iron and oxygen. The presence of iron makes the ore magnetic. 

The location of the metals in the periodic table is shown in Figure 17-4. We see that the metals are located on the left side of the table, while the nonmetals are exclusively in the upper right corner. Furthermore, the elements on the left side of the table have relatively low ionization energies. We shall see that the low ionization energies of the metallic elements aid in explaining many of the features of metallic behavior. 

Transition-metal oxides are particularly effective decomposition and burning-rate catalysts. The metal elements can demonstrate variable valence or oxidation states. 

The metallic elements may also be roughly located on the map, though the significance and usefulness of their map positions is not so great as for the non-metals. 

The transition elements comprise groups 3 to 12 and are found in the central region of the standard periodic table, an example of which is reproduced on the endpaper. This group is further subdivided into those of the first row (the elements scandium to zinc), the second row (the elements yttrium to cadmium) and the third row (the elements lanthanum to mercury). The term transition arises from the elements supposed transitional positions between the metallic elements of groups 1 and 2 and the predominantly non-metallic elements of groups 13 to 18. Nevertheless, the transition elements are also, and interchangeably, known as the transition metals in view of their typical metallic properties. 

The most important undesired metallic impurities are nickel and vanadium, present in porphyrinic structures that originate from plants and are predominantly found in the heavy residues. In addition, iron may be present due to corrosion in storage tanks. These metals deposit on catalysts and give rise to enhanced carbon deposition (nickel in particular). Vanadium has a deleterious effect on the lattice structure of zeolites used in fluid catalytic cracking. A host of other elements may also be present. Hydrodemetallization is strictly speaking not a catalytic process, because the metallic elements remain in the form of sulfides on the catalyst. Decomposition of the porphyrinic structures is a relatively rapid reaction and as a result it occurs mainly in the front end of the catalyst bed, and at the outside of the catalyst particles. 

Ternary and quaternary metal telluride materials have been prepared from the metallic elements in telluride fluxes, as the compounds CsAgsTe-j, 1 K0.33Ba0.67AgTe2,1052... 

Hydrogen Compounds of the Metallic Elements, Mackay, K. M., London, Spon, 1966... 

Copper is a metallic element brass is an alloy or mixture of the metallic elements copper and zinc. The surfaces of copper and brass items tarnish with prolonged exposure to air, particularly in moist environments with high carbon dioxide (CO2) or sulfur dioxide (SO2) concentrations (see color Fig. 5.2.1). The compounds that form on the surface, ranging in color from black to blue to dark green, dissolve readily in acidic solutions. Vinegar contains acetic acid, ketchup contains tomatoes rich in ascorbic acid (Vitamin C), and onions contain malic acid and citric acid. All of these foods provide variable amounts of acid to dissolve the tarnish on copper surfaces. 

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