  The family. The element aluminium is the most abundant member of the group of elements known as the aluminium family; indeed, the other members of the family—gallium, indium, and thallium—are of such rare occurrence that they need not be separately described. The elements of the family are ordinarily trivalent, so that the formulas for their compounds differ from those of the elements so far studied. Their hydroxides are practically insoluble in water and are very weak bases; indeed, the bases are so weak that their salts are often hydrolyzed into free base and free acid in solution. The salts formed from these bases usually contain water of crystallization, which cannot be driven off without decomposing them more or less. The trivalent metals, which in addition to aluminium include also iron and chromium, are sometimes called the earth metals. The name refers to the earthy appearance of the oxides of these metals, and to the fact that many earths, soils, and rocks are composed in part of these substances. ALUMINIUMOccurrence. Aluminium never occurs in the free state in nature, owing to its great affinity for oxygen. In combined form, as oxides, silicates, and a few other salts, it is both abundant and widely distributed, being an essential Fig. 82 Fig. 82 Preparation. Aluminium was first prepared by WÖhler, in 1827, by heating anhydrous aluminium chloride with potassium: AlCl3 + 3K = 3KCl + Al. This method was tried after it was found impossible to reduce the oxide of aluminium with carbon. The metal possessed such interesting properties and promised to be so useful that many efforts were made to devise a cheap way of preparing it. The method which has proved most successful consists in the electrolysis of the oxide dissolved in melted cryolite. Metallurgy. An iron box A (Fig. 82) about eight feet long and six feet wide is connected with a powerful generator in such a way as to serve as the cathode upon which the aluminium is deposited. Three or four rows of carbon rods B dip into the box and serve as the anodes. The box is partially filled with cryolite and the current is turned on, generating enough heat to melt the cryolite. Aluminium oxide is then added, and under the influence of the electric current it decomposes into aluminium and oxygen. The temperature is maintained above the melting point of aluminium, and the liquid metal, being heavier than cryolite, sinks to the bottom of the vessel, from which it is tapped off from time to time through the tap hole C. The oxygen in part escapes as gas, and in part combines with the carbon of the anode, the combustion being very brilliant. The process is carried on at Niagara Falls. The largest expense in the process, apart from the cost of electrical energy, is the preparation of aluminium oxide free from other oxides, for most of the oxide found in nature is too impure to serve without refining. Bauxite is the principal ore used as a source of the aluminium because it is converted into pure oxide without great difficulty. Since common clay is a silicate of aluminium and is everywhere abundant, it might be expected that this would be utilized in the preparation of aluminium. It is, however, very difficult to extract the aluminium from a silicate, and no practical method has been found which will accomplish this. Physical properties. Aluminium is a tin-white metal which melts at 640° and is very light, having a density of 2.68. It is stiff and strong, and with frequent annealing can be rolled into thin foil. It is a good conductor of heat and electricity, though not so good as copper for a given cross section of wire. Chemical properties. Aluminium is not perceptibly acted on by boiling water, and moist air merely dims its luster. Further action is prevented in each case by the formation of an extremely thin film of oxide upon the surface of the metal. It combines directly with chlorine, and when heated in oxygen burns with great energy and the liberation of much heat. It is therefore a good reducing agent. Hydrochloric acid acts upon it, forming aluminium chloride: 2Al + 6H2SO4 = Al2(SO4)3 + 6H2O + 3SO2. Alkalis readily attack the metal, liberating hydrogen, as in the case of zinc: Al + 3KOH = Al(OK)3 + 3H. Salt solutions, such as sea water, corrode the metal rapidly. It alloys readily with other metals. Uses of aluminium. These properties suggest many uses for the metal. Its lightness, strength, and permanence make it well adapted for many construction purposes. These same properties have led to its extensive use in the manufacture of cooking utensils. The fact that it is easily corroded by salt solutions is, however, a disadvantage. Owing to its small resistance to electrical currents, it is replacing copper to some extent in electrical construction, especially for trolley and power wires. Some of its alloys have very valuable properties, and a considerable part of the aluminium manufactured is used for this purpose. Aluminium bronze, consisting of about 90% copper and 10% aluminium, has a pure golden color, is strong and malleable, is easily cast, and is permanent in the air. Considerable amounts of aluminium steel are also made. Goldschmidt reduction process. Aluminium is frequently employed as a powerful reducing agent, many metallic oxides which resist reduction by carbon being readily reduced by it. The aluminium in the form of a fine powder is mixed with the metallic oxide, together with some substance such as fluorspar to act as a flux. The mixture is ignited, and the aluminium unites with the An enormous quantity of heat is liberated in this reaction, and a temperature as high as 3500° can be reached. The heat of the reaction is turned to practical account in welding car rails, steel castings, and in similar operations where an intense local heat is required. A mixture of aluminium with various metallic oxides, ready prepared for such purposes, is sold under the name of thermite. Fig. 83 Fig. 83 Preparation of chromium by the Goldschmidt method. A mixture of chromium oxide and aluminium powder is placed in a Hessian crucible (A, Fig. 83), and on top of it is placed a small heap B of a mixture of sodium peroxide and aluminium, into which is stuck a piece of magnesium ribbon C. Powdered fluorspar D is placed around the sodium peroxide, after which the crucible is set on a pan of sand and the magnesium ribbon ignited. When the flame reaches the sodium peroxide mixture combustion of the aluminium begins with almost explosive violence, so that great care must be taken in the experiment. The heat of this combustion starts the reaction in the chromium oxide mixture, and the oxide is reduced to metallic chromium. When the crucible has cooled a button of chromium will be found in the bottom. Aluminium oxide (Al2O3). This substance occurs in several forms in nature. The relatively pure crystals are called corundum, while emery is a variety colored dark gray or black, usually with iron compounds. In transparent crystals, tinted different colors by traces of impurities, it forms such precious stones as the sapphire, oriental ruby, topaz, and amethyst. All these varieties are very 2Al(OH)3 = Al2O3 + 3H2O. The natural varieties, corundum and emery, are used for cutting and grinding purposes; the purest forms, together with the artificially prepared oxide, are largely used in the preparation of aluminium. Aluminium hydroxide (Al(OH)3). The hydroxide occurs in nature as the mineral hydrargyllite, and in a partially dehydrated form called bauxite. It can be prepared by adding ammonium hydroxide to any soluble aluminium salt, forming a semi-transparent precipitate which is insoluble in water but very hard to filter. It dissolves in most acids to form soluble salts, and in the strong bases to form aluminates, as indicated in the equations Al(OH)3 + 3HCl = AlCl3 + 3H2O, Al(OH)3 + 3NaOH = Al(ONa)3 + 3H2O. It may act, therefore, either as a weak base or as a weak acid, its action depending upon the character of the substances with which it is in contact. When heated gently the hydroxide loses part of its hydrogen and oxygen according to the equation Al(OH)3 = AlO·OH + H2O. This substance, the formula of which is frequently written HAlO2, is a more pronounced acid than is the hydroxide, and its salts are frequently formed when aluminium compounds are fused with alkalis. The magnesium salt Mg(AlO2)2 is called spinel, and many other of its salts, called aluminates, are found in nature. When heated strongly the hydroxide is changed into oxide, which will not again take up water on being moistened. Mordants and dyeing. Aluminium hydroxide has the peculiar property of combining with many soluble coloring materials and forming insoluble products with them. On this account it is often used as a filter to remove objectionable colors from water. This property also leads to its wide use in the dye industry. Many dyes will not adhere to natural fibers such as cotton and wool, that is, will not "dye fast." If, however, the cloth to be dyed is soaked in a solution of aluminium compounds and then treated with ammonia, the aluminium salts which have soaked into the fiber will be converted into the hydroxide, which, being insoluble, remains in the body of it. If the fiber is now dipped into a solution of the dye, the aluminium hydroxide combines with the color material and fastens, or "fixes," it upon the fiber. A substance which serves this purpose is called a mordant, and aluminium salts, particularly the acetate, are used in this way. Aluminium chloride (AlCl3·6 H2O). This substance is prepared by dissolving the hydroxide in hydrochloric acid and evaporating to crystallization. When heated it is converted into the oxide, resembling magnesium in this respect: 2(AlCl3·6 H2O) = Al2O3 + 6HCl + 9H2O. The anhydrous chloride, which has some important uses, is made by heating aluminium turnings in a current of chlorine. Alums. Aluminium sulphate can be prepared by the action of sulphuric acid upon aluminium hydroxide. It has the property of combining with the sulphates of the alkali metals to form compounds called alums. Thus, with potassium sulphate the reaction is expressed by the equation K2SO4 + Al2(SO4)3 + 24H2O = 2(KAl(SO4)2·12H2O). Under similar conditions ammonium sulphate yields ammonium alum: (NH4)2SO4 + Al2(SO4)3 + 24H2O = 2(NH4Al(SO4)2·12H2O). Other trivalent sulphates besides aluminium sulphate can form similar compounds with the alkali sulphates, and these compounds are also called alums, though they contain no aluminium. They all crystallize in octahedra and contain twelve molecules of water of crystallization. The alums most frequently prepared are the following:
An alum may therefore be regarded as a compound derived from two molecules of sulphuric acid, in which one hydrogen atom has been displaced by the univalent alkali atom, and the other three hydrogen atoms by an atom of one of the trivalent metals, such as aluminium, iron, or chromium. Very large, well-formed crystals of an alum can be prepared by suspending a small crystal by a thread in a saturated solution of the alum, as shown in Fig. 84. The small crystal slowly grows and assumes a very perfect form. Fig. 84 Fig. 84 Other salts of aluminium. While aluminium hydroxide forms fairly stable salts with strong acids, it is such a weak base that its salts with weak acids are readily hydrolyzed. Thus, when an aluminium salt and a soluble carbonate are 3Na2CO3 + 2AlCl3 = Al2(CO3)3 + 6NaCl. But if it is formed at all, it instantly begins to hydrolyze, the products of the hydrolysis being aluminium hydroxide and carbonic acid, Al2(CO3)3 + 6H2O = 2Al(OH)3 + 3H2CO3. Similarly a soluble sulphide, instead of precipitating aluminium sulphide (Al2S3), precipitates aluminium hydroxide; for hydrogen sulphide is such a weak acid that the aluminium sulphide at first formed hydrolyzes at once, forming aluminium hydroxide and hydrogen sulphide: 3Na2S + 2AlCl3 + 6H2O = 2Al(OH)3 + 6NaCl + 3H2S. Alum baking powders. It is because of the hydrolysis of aluminium carbonate that alum is used as a constituent of some baking powders. The alum baking powders consist of a mixture of alum and sodium hydrogen carbonate. When water is added the two compounds react together, forming aluminium carbonate, which hydrolyzes into aluminium hydroxide and carbonic acid. The carbon dioxide from the latter escapes through the dough and in so doing raises it into a porous condition, which is the end sought in the use of a baking powder. Aluminium silicates. One of the most common constituents of rocks is feldspar (KAlSi3O8), a mixed salt of potassium and aluminium with the polysilicic acid (H4Si3O8). Under the influence of moisture, carbon dioxide, and changes of temperature this substance is constantly being broken down into soluble potassium compounds and hydrated aluminium silicate. This compound has the formula Al2Si2O7·2H2O. In relatively pure condition it is called kaolin; in the impure state, mixed with sand and other Ceramic industries. Many articles of greatest practical importance, ranging from the roughest brick and tile to the finest porcelain and chinaware, are made from some form of kaolin, or clay. No very precise classification of such ware can be made, as the products vary greatly in properties, depending upon the materials used and the treatment during manufacture. Porcelain is made from the purest kaolin, to which must be added some less pure, plastic kaolin, since the pure substance is not sufficiently plastic. There is also added some more fusible substance, such as feldspar, gypsum, or lime, together with some pure quartz. The constituents must be ground very fine, and when thoroughly mixed and moistened must make a plastic mass which can be molded into any desired form. The article molded from such materials is then burned. In this process the article is slowly heated to a point at which it begins to soften and almost fuse, and then it is allowed to cool slowly. At this stage, a very thin vessel will be translucent and have an almost glassy fracture; if, however, it is somewhat thicker, or has not been heated quite so high, it will still be porous, and partly on this account and partly to improve its appearance it is usually glazed. Glazing is accomplished by spreading upon the object a thin layer of a more fusible mixture of the same materials as compose the body of the object itself, and again heating until the glaze melts to a transparent glassy coating upon the surface of the vessel. In some cases fusible mixtures of quite different composition from that used in fashioning the vessel may be used as a glaze. Oxides of lead, zinc, and barium are often used in this way. When less carefully selected materials are used, or quite thick vessels are made, various grades of stoneware are produced. The inferior grades are glazed by throwing a quantity of common salt into the kiln towards the end of the first firing. In the form of vapor Vitrified bricks, made from clay or ground shale, are burned until the materials begin to fuse superficially, forming their own glaze. Other forms of brick and tile are not glazed at all, but are left porous. The red color of ordinary brick and earthenware is due to an oxide of iron formed in the burning process. The decorations upon china are sometimes painted upon the baked ware and then glazed over, and sometimes painted upon the glaze and burned in by a third firing. Care must be taken to use such pigments as are not affected by a high heat and do not react chemically with the constituents of the baked ware or the glaze. EXERCISES1. What metals and compounds studied are prepared by electrolysis? 2. Write the equation for the reaction between aluminium and hydrochloric acid; between aluminium and sulphuric acid (in two steps). 3. What hydroxides other than aluminium hydroxide have both acid and basic properties? 4. Write equations showing the methods used for preparing aluminium hydroxide and sulphate. 5. Write the general formula of an alum, representing an atom of an alkali metal by X and an atom of a trivalent metal by Y. 6. What is meant by the term polysilicic acid, as used in the discussion of aluminium silicates? 7. Compare the properties of the hydroxides of the different groups of metals so far studied. 8. In what respects does aluminium oxide differ from calcium oxide in properties? 9. Supposing bauxite to be 90% aluminium hydroxide, what weight of it is necessary for the preparation of 100 kg. of aluminium? |
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