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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 substances, it forms common clay. Mica is another very abundant mineral, having varying composition, but being essentially of the formula KAlSiO4. Serpentine, talc, asbestos, and meerschaum are important complex silicates of aluminium and magnesium, and granite is a mechanical mixture of quartz, feldspar, and mica.

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 the salt attacks the surface of the baked ware and forms an easily fusible sodium silicate upon it, which constitutes a glaze.

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.

EXERCISES

1. 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?

CHAPTER XXVII THE IRON FAMILY
SYMBOL ATOMIC WEIGHT DENSITY APPROXIMATE MELTING POINT OXIDES Iron Fe 55.9 7.93 1800° FeO, Fe2O3 Cobalt Co 59.0 8.55 1800° CoO, Co2O3 Nickel Ni 58.7 8.9 1600° NiO, Ni2O3

The family. The elements iron, cobalt, and nickel form a group in the eighth column of the periodic table. The atomic weights of the three are very close together, and there is not the same gradual gradation in the properties of the three elements that is noticed in the families in which the atomic weights differ considerably in magnitude. The elements are very similar in properties, the similarity being so great in the case of nickel and cobalt that it is difficult to separate them by chemical analysis.

The elements occur in nature chiefly as oxides and sulphides, though they have been found in very small quantities in the native state, usually in meteorites. Their sulphides, carbonates, and phosphates are insoluble in water, the other common salts being soluble. Their salts are usually highly colored, those of iron being yellow or light green as a rule, those of nickel darker green, while cobalt salts are usually rose colored. The metals are obtained by reducing the oxides with carbon.

IRON

Occurrence. The element iron has long been known, since its ores are very abundant and it is not difficult to prepare the metal from them in fairly pure condition. It occurs in nature in many forms of combination,—in large deposits as oxides, sulphides, and carbonates, and in smaller quantities in a great variety of minerals. Indeed, very few rocks or soils are free from small amounts of iron, and it is assimilated by plants and animals playing an important part in life processes.

Metallurgy. It will be convenient to treat of the metallurgy of iron under two heads,—Materials Used and Process.

Materials used. Four distinct materials are used in the metallurgy of iron:

1. Iron ore. The ores most frequently used in the metallurgy of iron are the following:

Hematite Fe2O3. Magnetite Fe3O4. Siderite FeCO3. Limonite 2Fe2O2·3H2O.

These ores always contain impurities, such as silica, sulphides, and earthy materials. All ores, with the exception of the oxides, are first roasted to expel any water and carbon dioxide present and to convert any sulphide into oxide.

2. Carbon. Carbon in some form is necessary both as a fuel and as a reducing agent. In former times wood charcoal was used to supply the carbon, but now anthracite coal or coke is almost universally used.

3. Hot air. To maintain the high temperature required for the reduction of iron a very active combustion of fuel is necessary. This is secured by forcing a strong blast of hot air into the lower part of the furnace during the reduction process.

4. Flux. (a) Purpose of the flux. All the materials which enter the furnace must leave it again either in the form of gases or as liquids. The iron is drawn off as the liquid metal after its reduction. To secure the removal of the earthy matter charged into the furnace along with the ore, materials are added to the charge which will, at the high temperature of the furnace, combine with the impurities in the ore, forming a liquid. The material added for this purpose is called the flux; the liquid produced from the flux and the ore is called slag.

(b) Function of the slag. While the main purpose of adding flux to the charge is to remove from the furnace in the form of liquid slag the impurities originally present in the ore, the slag thus produced serves several other functions. It keeps the contents of the furnace in a state of fusion, thus preventing clogging, and makes it possible for the small globules of iron to run together with greater ease into one large liquid mass.

(c) Character of the slag. The slag is really a kind of readily fusible glass, being essentially a calcium-aluminium silicate. The ore usually contains silica and some aluminium compounds, so that limestone (which also contains some silica and aluminium) is added to furnish the calcium required for the slag. If the ore and the limestone do not contain a sufficient amount of silica and aluminium for the formation of the slag, these ingredients are added in the form of sand and feldspar. In the formation of slag from these materials the ore is freed from the silica and aluminium which it contained.

Fig. 85 Fig. 85

Process. The reduction of iron is carried out in large towers called blast furnaces. The blast furnace (Fig. 85) is usually about 80 ft. high and 20 ft. in internal diameter at its widest part, narrowing somewhat both toward the top and toward the bottom. The walls are built of steel and lined with fire-brick. The base is provided with a number of pipes T, called tuyers, through which hot air can be forced into the furnace. The tuyers are supplied from a large pipe S, which circles the furnace as a girdle. The base has also an opening M, through which the liquid metal can be drawn off from time to time, and a second opening P, somewhat above the first, through which the excess of slag overflows. The top is closed by a movable trap C and C', called the cone, and through this the materials to be used are introduced. The gases produced by the combustion of the fuel and the reduction of the ore, together with the nitrogen of the air forced in through the tuyers, escape through pipes D, called downcomer pipes, which leave the furnace near the top. These gases are very hot and contain combustible substances, principally carbon monoxide; they are therefore utilized as fuel for the engines and also to heat the blast admitted through the tuyers. The lower part of the furnace is often furnished with a water jacket. This consists of a series of pipes W built into the walls, through which water can be circulated to reduce their temperature.

Charges consisting of coke (or anthracite coal), ore, and flux in proper proportions are introduced into the furnace at intervals through the trap top. The coke burns fiercely in the hot-air blast, giving an intense heat and forming carbon monoxide. The ore, working down in the furnace as the coke burns, becomes very hot, and by the combined reducing action of the carbon and carbon monoxide is finally reduced to metal and collects as a liquid in the bottom of the furnace, the slag floating on the molten iron. After a considerable amount of the iron has collected the slag is drawn off through the opening P. The molten iron is then drawn off into large ladles and taken to the converters for the manufacture of steel, or it is run out into sand molds, forming the bars or ingots called "pigs." The process is a continuous one, and when once started it is kept in operation for months or even years without interruption.

It seems probable that the first product of combustion of the carbon, at the point where the tuyers enter the furnace, is carbon dioxide. This is at

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