Elemental metals

The FCC structure is illustrated in figure Al.3.2. Metallic elements such as calcium, nickel, and copper fonu in the FCC structure, as well as some of the inert gases. The conventional unit cell of the FCC structure is cubic with the lengdi of the edge given by the lattice parameter, a. There are four atoms in the conventional cell. In the primitive unit cell, there is only one atom. This atom coincides with the lattice pomts. The lattice vectors for the primitive cell are given by... 

Essentially the same processes occur when chlorides (for example) of non-metallic elements dissolve in water. Thus, the enthalpy changes for hydration chloride can be represented ... 

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. 

The more metallic elements, indium and thallium, do not react in spite of the fact that In(OH)3 is amphoteric. 

In the absence of oxygen, gallium and indium are unaffected by water. Thallium, the most metallic element in Group III, reacts slowly with hot water and readily with steam to produce thallium(I) oxide, TI2O. 

The melting and boiling points of the aluminium halides, in contrast to the boron compounds, are irregular. It might reasonably be expected that aluminium, being a more metallic element than boron, would form an ionic fluoride and indeed the fact that it remains solid until 1564 K. when it sublimes, would tend to confirm this, although it should not be concluded that the fluoride is, therefore, wholly ionic. The crystal structure is such that each aluminium has a coordination number of six, being surrounded by six fluoride ions. 

In this group the outer quantum level has a full s level and two electrons in the corresponding p level. As the size of the atom increases the ionisation energy changes (see Table 8.1) and these changes are reflected in the gradual change from a typical non-metallic element, carbon, to the weakly metallic element, lead. Hence the oxides of carbon and silicon are acidic whilst those of tin and lead are amphoteric. 

Arsenic and antimony resemble phosphorus in having several allotropic modifications. Both have an unstable yellow allotrope. These allotropes can be obtained by rapid condensation of the vapours which presumably, like phosphorus vapour, contain AS4 and Sb4 molecules respectively. No such yellow allotrope is known for bismuth. The ordinary form of arsenic, stable at room temperature, is a grey metallic-looking brittle solid which has some power to conduct. Under ordinary conditions antimony and bismuth are silvery white and reddish white metallic elements respectively. 

Arsenic dissolves in concentrated nitric acid forming arsenicfV) acid, H3ASO4, but in dilute nitric acid and concentrated sulphuric acid the main product is the arsenic(III) acid, HjAsOj. The more metallic element, antimony, dissolves to form the (III) oxide Sb O, with moderately concentrated nitric acid, but the (V) oxide Sb205 (structure unknown) with the more concentrated acid. Bismuth, however, forms the salt bismulh(lll) nitrate Bi(N03)3. 5H,0. 

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. 

These elements are generally unaffected by non-oxidising acids (behaviour expected for non-metallic elements) but they do react when heated with concentrated sulphuric and nitric acids, both powerful oxidising agents. Sulphur is oxidised to sulphur dioxide by hot concentrated sulphuric acid,... 

Sulphur is less reactive than oxygen but still quite a reactive element and when heated it combines directly with the non-metallic elements, oxygen, hydrogen, the halogens (except iodine), carbon and phosphorus, and also with many metals to give sulphides. Selenium and tellurium are less reactive than sulphur but when heated combine directly with many metals and non-metals. 

Compounds in which C is united directly to a metallic element (organo-metalhc compounds). The order is according to Periodic Groups 5, 4, 3, 2, 1, 6, 7 and 8. Thus Class 23 consists of compounds in which C is attached to P, As, Sb or Bi. 

Calcium is a metallic element, fifth in abundance in the earth s crust, of which if forms more than 3%. It is an essential constituent of leaves, bones, teeth, and shells. Never found in nature uncombined, it occurs abundantly as limestone, gypsum, and fluorite. Apatite is the fluorophosphate or chlorophosphate of calcium. 

Rubidium can be liquid at room temperature. It is a soft, silvery-white metallic element of the alkali group and is the second most electropositive and alkaline element. It ignites spontaneously in air and reacts violently in water, setting fire to the liberated hydrogen. As with other alkali metals, it forms amalgams with mercury and it alloys with gold, cesium, sodium, and potassium. It colors a flame yellowish violet. Rubidium metal can be prepared by reducing rubidium chloride with calcium, and by a number of other methods. It must be kept under a dry mineral oil or in a vacuum or inert atmosphere. 

Barium is a metallic element, soft, and when pure is silvery white like lead it belongs to the alkaline earth group, resembling calcium chemically. The metal oxidizes very easily and should be kept under petroleum or other suitable oxygen-free liquids to exclude air. It is decomposed by water or alcohol. 

Key properties are its flexibility, translucency, and resistance to all known chemicals except molten alkali metals, elemental fluorine and fluorine precursors at elevated temperatures, and concentrated perchloric acid. It withstands temperatures from —270° to 250°C and may be sterilized repeatedly by all known chemical and thermal methods. 

Hafnium [7440-58-6] Hf, is in Group 4 (IVB) of the Periodic Table as are the lighter elements zirconium and titanium. Hafnium is a heavy gray-white metallic element never found free in nature. It is always found associated with the more plentiful zirconium. The two elements are almost identical in chemical behavior. This close similarity in chemical properties is related to the configuration of the valence electrons, and for zirconium and... 

Hydrogen reacts direcdy with a number of metallic elements to form hydrides (qv). The ionic or saline hydrides ate formed from the reaction of hydrogen with the alkali metals and with some of the alkaline-eartb metals. The saline hydrides ate salt-like in character and contain the hydride, ie,, ion. Saline hydrides form when pure metals and H2 react at elevated temperatures (300—700°C). Examples of these reactions ate... 

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. 

Although ceramic electrodes have received much attention (101), they have not been successful in channels operating with slag-laden flows, because of excessive electrochemical corrosion caused by the slag. Only weU-cooled metallic elements have been used successfully in slagging environments. 

Insulator Walls. Because of the unavailabiUty of electrically insulating materials which can withstand the harsh environment inside coal-fired channels, the insulator walls of the channel are typically made of metal elements which are insulated from each other to prevent any net flow of current. Like electrode walls, insulator walls are designed to operate with a slag coating. 

Production. Titanium is the seventh most common metallic element in the earth s cmst. Titanium minerals are plentiful in nature (19). The most common mineral /raw materials used for the production of titanium dioxide pigments are shown in Table 1. 

The SeBr which forms is distilled from the solution leaving the interfering elements behind. The only other metallic elements that can also distill over by this procedure are arsenic, antimony, tellurium (pardy), and germanium. 

Sihca is reduced to siUcon at 1300—1400°C by hydrogen, carbon, and a variety of metallic elements. Gaseous siUcon monoxide is also formed. At pressures of >40 MPa (400 atm), in the presence of aluminum and aluminum haUdes, siUca can be converted to silane in high yields by reaction with hydrogen (15). SiUcon itself is not hydrogenated under these conditions. The formation of siUcon by reduction of siUca with carbon is important in the technical preparation of the element and its alloys and in the preparation of siUcon carbide in the electric furnace. Reduction with lithium and sodium occurs at 200—250°C, with the formation of metal oxide and siUcate. At 800—900°C, siUca is reduced by calcium, magnesium, and aluminum. Other metals reported to reduce siUca to the element include manganese, iron, niobium, uranium, lanthanum, cerium, and neodymium (16). 

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