Compare the abundance of Al with that of Fe.
260. Compounds of Al.--Al occurs only in combination with other elements. Feldspar, mica, slate, and clay are silicates of it. It occurs in all rocks except CaCO3 and SiO2, and in nearly 200 minerals. Though found in all soils, its compounds are not taken up by plants, except by a few cryptogams. Corundum, Al2O3, is the richest of its ores. Compute its percent of Al. Compounds of Al are very infusible and difficult of reduction.
261. Reduction.--Like most other metals not easily reducible by C or H, it was originally obtained by electrolysis, but more recently from its chloride, by the reducing action of strongly heated K or Na. Al2Cl6 + 6 Na = 6 NaCl + 2 Al.
What is the chief use of Na? As it takes three pounds of Na to make one pound of Al, the cost of the latter has been fifteen dollars or more per pound. Its use has thus been restricted to light apparatus and aluminium bronze, an alloy of Cu 90, Al 10, which is not unlike gold in appearance.
Al2O3 has lately been reduced by C. Higher temperatures than have heretofore been known are obtained by means of the electric arc and large dynamo machines. Afurnace made of graphite, because fire-clay melts like wax at such a high temperature, is filled with Al2O3--corundum, --C, and Cu. In the midst of this are embedded large carbon terminals, connected with dynamos. The reduction takes several hours.
The following reaction takes place: Al2O3 + 3 C = 2 Al + 3 CO. Cu is also added, and an alloy of Al and Cu is thus formed. This alloy is not easily separable into its elements. Explain the action of the C. CO escapes through perforations in the top of the furnace, burning there to CO2. Only alloys of Al have yet been obtained by this process. This method has not been employed before, simply because the highest temperatures of combustion, 2000 degrees or 2500 degrees, would not effect a reduction. In the same way Si, B, K, Na, Ca, Mg, Cr, have recently been reduced from their oxides; but a process has yet to be found for separating them easily from their alloys.
262. Properties and Uses.--Al is a silvery white metal, lighter than gla.s.s, and only one-third the weight of iron. It does not readily rust or oxidize, it fuses at 1000 degrees (compare with Fe), is unaffected by acids, except by HCl and, slightly, by H2SO4, is a good conductor of electricity, can be cast and hammered, and alloys with most metals, forming thus many valuable compounds. Every clay-bank is a mine of this metal, which has so many of the useful properties of metals and has so few defects that, if it could be obtained in sufficient quant.i.ties, it might, for many purposes, take the place of iron, steel, tin, and other metals. From its properties state any advantages which it would have over iron in ocean vessels, railroads, and bridges. Why is it better than Sn or Cu for culinary utensils? An alloy of Al, Cu, and Si is used for telephone wires in Europe, and the Bennett-Mackay cable is of the same material. Washington monument, the tallest shaft in the world, is capped with a pyramid of Al,ten inches high.
For the uses of alumina, Al2O3, and its silicates, see page 133.
ZINC AND ITS COMPOUNDS.
Examine zincite, sphalerite, Smithsonite, sheet zinc, galvanized iron, granulated zinc, zinc dust.
263. Compounds.--The compounds of zinc are abundant. Its chief ores are zincite, ZnO, sphalerite or blende, ZnS, Smithsonite, ZnCO3. For their reduction these ores are first roasted, i.e.
heated in presence of air. With ZnS this reaction takes place: ZnS + 3 O = Zn0 + S02. The oxide is reduced with C, and then Zn is distilled. State the reaction. Zinc is sublimed-in the form of zinc dust-like flowers of S. Granulated Zn is made by pouring a stream of the molten metal into water.
Experiment 121.--Burn a strip of Zn foil, and note the color of the flame and of the product. State the reaction. The red color of zincite is supposed to be imparted by Mn present in the compound.
264. Uses.--Name any use of Zn in the chemical laboratory. It is employed for coating wire and sheet iron --galvanized iron. This is done by plunging the wire or the sheets of iron into melted Zn. Describe the use of Zn as an alloy. See page 136.
ZnO forms the basis of a white paint called zinc white. White vitriol, ZnSO4 + 7 H2O, is employed in medicine. Name two other vitriols.
CHAPTER XLVIII.
IRON AND ITS COMPOUNDS.
Examine magnet.i.te, hemat.i.te, limonite, siderite, pig-iron, wrought-iron, steel.
265. Ores and Irons.--As Fe occurs native only in meteorites and in small quant.i.ties of terrestrial origin, it is obtained from its ores. There are four of these ores--magnet.i.te (Fe3O4), hemat.i.te (Fe2O3), limonite (2 Fe2O3 + 3 H2O), and siderite (FeCO3). Which is richest in Fe? Compute the proportion. FeCO3 occurs mostly in Europe. The reduction of these ores, as well as of other metallic oxides, consists in removing O by C at a high tempera- ture. As ordinarily cla.s.sified there are three kinds of iron,--pig- or cast-iron, steel, and wrought-iron.
Study this table, noting the purity, the fusing-point, and the per cent of C in each case.
Per Cent Fe Fusibility. Per Cent (general). C.
Pig.........90 1200 degrees 2-6 Steel........99 1400 degrees 0.5-2 Wrought.......99.7 1500 degrees Fraction.
Pure iron melts at about 1800 degrees. Pig-iron is obtained from the ore by smelting, and from this are made steel and wrought- iron.
266. Pig-Iron.--The ore is reduced in a blast furnace (Fig. 47), in some cases eighty or one hundred feet high, and having a capacity of about 12,000 cubic feet. The reducing agent is either charcoal, anthracite coal, or c.o.ke,bituminous coal being too impure. Charcoal is the best agent, and is used in preparing Swedish iron; but it is too expensive for general use.
Fig. 47. Blast furnace. F, entrance of tuyeres, or blast-pipes.
E, F, hottest part. C, conductor for gases, which are subsequently used to heat the air going into the tuyeres. G, upper portion, slag, lower portion, melted iron.
Were ores absolutely pure, only C would be needed to reduce them.
Complete: Fe3O4 + 4 C =? Fe3O4 + 2C=?
Much earthy material--gangue--containing silica and silicates is always found with iron ores. These are infusible, and something must be added to render them fusible. CaO forms with SiO2 just the flux needed. See page 132. Ca0 + Si02 = ? Which of these is the basic, and which the acidic compound? CaO results from heating CaCO3; hence the latter is employed instead of the former. In what case would Si02 be used as the flux?
Into the blast furnace are put, in alternate layers, the fuel, the flux, and the ore. The fire, once kindled, is kept burning for months or years. Hot air is driven in through the tuyeres (tweers). O unites with C of the fuel, forming CO2 and CO. The C also reduces the ore. Fe2O3 + 3 C = ? CO accomplishes the same thing. 3 CO + Fe2O3 = ? The intense heat fuses CaO and SiO2 to a silicate which, with other impurities, forms a slag; this, rising to the surface of the molten ma.s.s, is drawn off. The iron is melted, falls in drops to the bottom, and is drawn off into sand molds. See Figure 47. This is pig-iron. It contains as impurities, C, Si, S, P, Mn, etc. If too much S or P is present in an ore, it is worthless. This is why the abundant mineral FeS2 cannot be used as a source of iron. From the top of the furnace N, CO, CO2, H2O, etc., escape. These gases are used to heat the air which is forced through the tuyeres, and to make steam in boilers.
267. Steel.--The manufacture of steel and wrought-iron consists in removing most of the impurities from pig-iron. It will be seen that the most common compounds of C, S, Si, and P, are their oxides, and these are for the most part gases. Hence these elements are removed by oxidation.
Bessemer steel is prepared by melting pig-iron and blowing hot air through it. A converter (Fig. 48) lined with siliceous sand, and holding several tons, is partially filled with the molten metal; blasts of hot air are driven into it, and the C and other impurities, together with a little of the Fe, are oxidized. The exact moment when the process has gone far enough, and most of the impurities have been removed, is indicated by the appearance of the escaping flame. It usually takes from five to ten minutes.
The blast is then stopped, and the metal has about the composition of wrought-iron; it contains some uncombined O. A white pig-iron (spiegeleisen), which contains a known quant.i.ty of C and of Mn, is at once added. Mn removes part of the extra O, and, though it remains, does not injure the metal. The C is "dissolved" by the Fe, which is then run into molds (ingots).
This process, the Bessemer, invented in 1856, has revolutionized steel manufacture. No less than ten tons of iron have been converted into steel, in five minutes, in a single converter.
268. Wrought-Iron.--The chemical principle involved in making wrought-iron is the same as that in making steel, but the process is different. Impurities are burned out from pig-iron in an open reverberatory furnace, by constantly stirring the metal in contact with air. This is called puddling. A reverberatory furnace is one in which the fuel is in one compartment, and the heat is reflected downward into another, that holds the substance to be acted upon (Fig. 49).
Steel may also be made by carburizing wrought-iron. Iron and charcoal are packed together and heated for days, without melting, when it is found that, in some unknown way, solid C has penetrated solid Fe. The finer kinds of steel are made in this way, but they are very expensive.
Wrought-iron may also be made directly from the ore in an open hearth furnace, with charcoal. This was the original mode.
269. Properties.--The varying properties of pig-iron, steel, and wrought-iron are due in part to the proportion of C and of other elements present, either as mixtures or as compounds, and in part to other causes not well understood. Wrought-iron is fibrous, as though composed of fine wires, and hence is ductile, malleable, tough, and soft, and cannot be hardened or tempered, but it is easily welded. Pig-iron is crystalline, and so is not ductile or malleable; it is hard and brittle, and cannot be welded. On account of its low melting-point it is generally employed for castings. Steel is crystalline in structure, and when suddenly cooled from red heat by plunging into cold water, becomes hard and brittle. The tempering can be varied by afterwards heating to any required degree, indicated by the color of the oxide formed on the exterior. The higher temperatures give the softer steel.
270. Salts of Iron.--Examine FeSO4, FeS, FeS2.
Fe has a valence of 2 or 4. This gives rise to two kinds of salts, ferrous and ferric, as in FeCl2 and Fe2Cl6 The valence of Fe in ferric salts is 4. Ferrous sulphate is FeSO4; ferric sulphate, Fe2(SO4)3. Write the symbols for ferrous and ferric hydrate; for the oxides; for the nitrates. Write the graphic symbols for each.
271. Colors.--The characteristic color of ferrous salts is green, as in FeSO4. These salts give the green color to the chlorophyll in leaves and gra.s.s, and bottle gla.s.s owes its green color to ferrous silicate. Ferric salts are a brownish red, as shown in hemat.i.te and limonite, and in some bottles. Red sandstone, and most soils and earths, are ill.u.s.trations of this coloring action.
The blood of vertebrates owes its color to ferric salts. Bricks are made from a greenish blue clay in which iron exists in the ferrous state. On being heated, ferrous salts are oxidized to ferric, and their color is changed to red. Iron rust is hydrated ferric oxide, Fe2O3 and Fe2(OH)6.
272. Change of Valence.
Experiment 122.--Dissolve 2 g. of iron filings in diluted HCl.
Filter or pour off the clear liquid, divide it into two parts, and add NH4OH to one part till a ppt. occurs. Notice the greenish color of Fe(OH)2. Oxidize the other part by adding a few drops of HNO3 and boiling a minute. Now add NH4OH, and observe the reddish color of the ppt., Fe2(OH)6.
Solutions of ferrous salts will gradually change to ferric, if allowed to stand, thus showing the greater stability of the latter. In changing from FeCl2 to Fe2Cl6 oxidation does not consist in adding O, but in increasing the negative element or radical. This is possible only by changing the valence of Fe from 2 to 4. Hence oxidation, in its larger sense, means increasing the valence of the positive element. To oxidize FeSO4 is to make it Fe2(SO4)3, changing the valence of Fe as before. Reduction or deoxidation diminishes the valence of the positive element.
Ill.u.s.trate this by the same iron salts. Ill.u.s.trate it by PbO and Pb02; AuCl and AuCl3; Sb2S3 and Sb2S5. In this sense define an oxidizing agent. A reducing agent.
273. Ferrous Sulphate.
Experiment 123.--Dissolve a few iron filings in dilute H2SO4, and slowly evaporate for a few minutes. Write the equation.
Ferrous sulphate, green vitriol, or copperas, FeSO4 + 7 H2O, is the source of what acid? See page 66. It is also one of the ingredients in many writing inks. On being heated, or exposed to the air, it loses its water of crystallization and becomes a white powder. It is prepared as above, or by oxidizing moistened FeS2 by exposure to the air.
Ferrous sulphide, protosulphide of iron, FeS, is how prepared?
See Experiment 6. State its use. See Experiment 108. It also occurs native.
Ferric sulphide, pyrite, FeS2, occurs native in large quant.i.ties.
What is its use? See page 65.
CHAPTER XLIX.