An Elementary Study of Chemistry, William McPherson [icecream ebook reader txt] 📗
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Oxides of iron. Iron forms several oxides. Ferrous oxide (FeO) is not found in nature, but can be prepared artificially in the form of a black powder which easily takes up oxygen, forming ferric oxide:
Ferric oxide is the most abundant ore of iron and occurs in great deposits, especially in the Lake Superior region. It is found in many mineral varieties which vary in density and color, the most abundant being hematite, which ranges in color from red to nearly black. When prepared by chemical processes it forms a red powder which is used as a paint pigment (Venetian red) and as a polishing powder (rouge).
Magnetite has the formula Fe3O4 and is a combination of FeO and Fe2O3. It is a very valuable ore, but is less abundant than hematite. It is sometimes called magnetic oxide of iron, or lodestone, since it is a natural magnet.
Ferrous salts. These salts are obtained by dissolving iron in the appropriate acid, or, when insoluble, by precipitation. They are usually light green in color and crystallize well. In chemical reactions they are quite similar to the salts of magnesium and zinc, but differ from them in one important respect, namely, that they are easily changed into compounds in which the metal is trivalent. Thus ferrous chloride treated with chlorine or aqua regia is changed into ferric chloride:
Ferrous hydroxide exposed to moist air is rapidly changed into ferric hydroxide:
Ferrous sulphate (copperas, green vitriol) (FeSO4·7H2O). Ferrous sulphate is the most familiar ferrous compound. It is prepared commercially as a by-product in the steel-plate mills. Steel plates are cleaned by the action of dilute sulphuric acid upon them, and in the process some of the iron dissolves. The liquors are concentrated and the green vitriol separates from them.
Ferrous sulphide (FeS). Ferrous sulphide is sometimes found in nature as a golden-yellow crystalline mineral. It is formed as a black precipitate when a soluble sulphide and an iron salt are brought together in solution:
It can also be made as a heavy dark-brown solid by fusing together the requisite quantities of sulphur and iron. It is obtained as a by-product in the metallurgy of lead:
It is used in the laboratory in the preparation of hydrosulphuric acid:
Iron disulphide (pyrites) (FeS2). This substance bears the same relation to ferrous sulphide that hydrogen dioxide does to water. It occurs abundantly in nature in the form of brass-yellow cubical crystals and in compact masses. Sometimes the name "fool's gold" is applied to it from its superficial resemblance to the precious metal. It is used in very large quantities as a source of sulphur dioxide in the manufacture of sulphuric acid, since it burns readily in the air, forming ferric oxide and sulphur dioxide:
Ferrous carbonate (FeCO3). This compound occurs in nature as siderite, and is a valuable ore. It will dissolve to some extent in water containing carbon dioxide, just as will calcium carbonate, and waters containing it are called chalybeate waters. These chalybeate waters are supposed to possess certain medicinal virtues and form an important class of mineral waters.
Ferric salts. Ferric salts are usually obtained by treating an acidified solution of a ferrous salt with an oxidizing agent:
They are usually yellow or violet in color, are quite soluble, and as a rule do not crystallize well. Heated with water in the absence of free acid, they hydrolyze even more readily than the salts of aluminium. The most familiar ferric salts are the chloride and the sulphate.
Ferric chloride (FeCl3). This salt can be obtained most conveniently by dissolving iron in hydrochloric acid and then passing chlorine into the solution:
When the pure salt is heated with water it is partly hydrolyzed:
This is a reversible reaction, however, and hydrolysis can therefore be prevented by first adding a considerable amount of the soluble product of the reaction, namely, hydrochloric acid.
Ferric sulphate (Fe2(SO4)3). This compound can be made by treating an acid solution of green vitriol with an oxidizing agent. It is difficult to crystallize and hard to obtain in pure condition. When an alkali sulphate in proper quantity is added to ferric sulphate in solution an iron alum is formed, and is easily obtained in large crystals. The best known iron alums have the formulas KFe(SO4)2·12H2O and NH4Fe(SO4)2·12H2O. They are commonly used when a pure ferric salt is required.
Ferric hydroxide (Fe(OH)3). When solutions of ferric salts are treated with ammonium hydroxide, ferric hydroxide is formed as a rusty-red precipitate, insoluble in water.
Iron cyanides. A large number of complex cyanides containing iron are known, the most important being potassium ferrocyanide, or yellow prussiate of potash (K4FeC6N6), and potassium ferricyanide, or red prussiate of potash (K3FeC6N6). These compounds are the potassium salts of the complex acids of the formulas H4FeC6N6 and H3FeC6N6.
Oxidation of ferrous salts. It has just been seen that when a ferrous salt is treated with an oxidizing agent in the presence of a free acid a ferric salt is formed:
In this reaction oxygen is used up, and the valence of the iron is changed from 2 to 3. The same equation may be written
Hydrogen ions have been oxidized to water, while the charge of each iron ion has been increased from 2 to 3.
In a similar way the conversion of ferrous chloride into ferric chloride may be written
Here again the valence of the iron and the charge on the iron ion has been increased from 2 to 3, though no oxygen has entered into the reaction. As a rule, however, changes of this kind are brought about by the use of an oxidizing agent, and are called oxidations.
The term "oxidation" is applied to all reactions in which the valence of the metal of a compound is increased, or, in other words, to all reactions in which the charge of a cation is increased.
Reduction of ferric salts. The changes which take place when a ferric salt is converted into a ferrous salt are the reverse of the ones just described. This is seen in the equation
In this reaction the valence of the iron has been changed from 3 to 2. The same equation may be written
It will be seen that the charge of the iron ions has been diminished from 3 to 2. Since these changes are the reverse of the oxidation changes just considered, they are called reduction reactions. The term "reduction" is applied to all processes in which the valence of the metal of a compound is diminished, or, in other words, to all processes in which the charge on the cations is diminished.
NICKEL AND COBALTThese elements occur sparingly in nature, usually combined with arsenic or with arsenic and sulphur. Both elements have been found in the free state in meteorites. Like iron they form two series of compounds, but the salts corresponding to the ferrous salts are the most common, the ones corresponding to the ferric salts being difficult to obtain. Thus we have the chlorides NiCl2·6H2O and CoCl2·6H2O; the sulphates NiSO4·7H2O and CoSO4·7H2O; the nitrates Ni(NO3)2·6H2O and Co(NO3)2·6H2O.
Nickel is largely used as an alloy with other metals. Alloyed with copper it forms coin metal from which five-cent pieces are made, with copper and zinc it forms German silver, and when added to steel in small quantities nickel steel is formed which is much superior to common steel for certain purposes. When deposited by electrolysis upon the surface of other metals such as iron, it forms a covering which will take a high polish and protects the metal from rust, nickel not being acted upon by moist air. Salts of nickel are usually green.
Compounds of cobalt fused with glass give it an intensely blue color. In powdered form such glass is sometimes used as a pigment called smalt. Cobalt salts, which contain water of crystallization, are usually cherry red in color; when dehydrated they become blue.
EXERCISES1. In the manufacture of cast iron, why is the air heated before being forced into the furnace?
2. Write the equations showing how each of the following compounds of iron could be obtained from the metal itself: ferrous chloride, ferrous hydroxide, ferrous sulphate, ferrous sulphide, ferrous carbonate, ferric chloride, ferric sulphate, ferric hydroxide.
3. Account for the fact that a solution of sodium carbonate, when added to a solution of a ferric salt, precipitates an hydroxide and not a carbonate.
4. Calculate the percentage of iron in each of the common iron ores.
5. One ton of steel prepared by the Bessemer process is found by analysis to contain 0.2% carbon. What is the minimum weight of carbon which must be added in order that the steel may be made to take a temper?
CHAPTER XXVIII COPPER, MERCURY, AND SILVERThe family. By referring to the periodic arrangement of the elements (page 168), it will be seen that mercury is not included in the same family with copper and silver. Since the metallurgy of the three elements is so similar, however, and since they resemble each other so closely in chemical properties, it is convenient to class them together for study.
1. Occurrence. The three elements occur in nature to some extent in the free state, but are usually found as sulphides. Their ores are easy to reduce.
2. Properties. They are heavy metals of high luster and are especially good conductors of heat and electricity. They are not very active chemically. Neither hydrochloric nor dilute sulphuric acid has any appreciable action upon them. Concentrated sulphuric acid attacks all three, forming metallic sulphates and evolving sulphur dioxide, while nitric acid, both dilute and concentrated, converts them into nitrates with the evolution of oxides of nitrogen.
3. Two series of salts. Copper and mercury form oxides of the types M2O and MO, as well as two series of salts. In one series the metals are univalent and the salts have formulas like those of the sodium salts. They are called cuprous and mercurous salts. In the other series the metals are divalent and resemble magnesium salts in formulas. These are called cupric and mercuric salts. Silver forms only one series of salts, being always a univalent metal.
COPPEROccurrence. The element copper has been used for various purposes since the earliest days of history. It is often found in the metallic state in nature, large masses of it occurring pure in the Lake Superior region and in other places to a smaller extent. The most valuable ores are the following:
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