An Elementary Study of Chemistry by William McPherson (best beach reads .txt) 📖
- Author: William McPherson
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Extraction of sulphur. Sulphur is prepared from the native substance, the separation of crude sulphur from the rock and earthy materials with which it is mixed being a very simple process. The ore from the mines is merely heated until the sulphur melts and drains away from the earthy impurities. The crude sulphur obtained in this way is distilled in a retort-shaped vessel made of iron, the exit tube of which opens into a cooling chamber of brickwork. When the sulphur vapor first enters the cooling chamber it condenses as a fine crystalline powder called flowers of sulphur. As the condensing chamber becomes warm, the sulphur collects as a liquid in it, and is drawn off into cylindrical molds, the product being called roll sulphur or brimstone.
Physical properties. Roll sulphur is a pale yellow, crystalline solid, without marked taste and with but a faint odor. It is insoluble in water, but is freely soluble in a few liquids, notably in carbon disulphide. Roll sulphur melts at 114.8°. Just above the melting point it forms a rather thin, straw-colored liquid. As the temperature is raised, this liquid turns darker in color and becomes thicker, until at about 235° it is almost black and is so thick that the vessel containing it can be inverted without danger of the liquid running out. At higher temperatures it becomes thin once more, and boils at 448°, forming a yellowish vapor. On cooling the same changes take place in reverse order.
Varieties of sulphur. Sulphur is known in two general forms, crystalline and amorphous. Each of these forms exists in definite modifications.
Crystalline sulphur. Sulphur occurs in two crystalline forms, namely, rhombic sulphur and monoclinic sulphur.
1. Rhombic sulphur. When sulphur crystallizes from its solution in carbon disulphide it separates in crystals which have the same color and melting point as roll sulphur, and are rhombic in shape. Roll sulphur is made up of minute rhombic crystals.
2. Monoclinic sulphur. When melted sulphur is allowed to cool until a part of the liquid has solidified, and the remaining liquid is then poured off, it is found that the solid sulphur remaining in the vessel has assumed the form of fine needle-shaped crystals. These differ much in appearance from the rhombic crystals obtained by crystallizing sulphur from its solution in carbon disulphide. The needle-shaped form is called monoclinic sulphur. The two varieties differ also in density and in melting point, the monoclinic sulphur melting at 120°.
Monoclinic and rhombic sulphur remain unchanged in contact with each other at 96°. Above this temperature the rhombic changes into monoclinic; at lower temperatures the monoclinic changes into rhombic. The temperature 96° is therefore called the transition point of sulphur. Heat is set free when monoclinic sulphur changes into rhombic.
Amorphous sulphur. Two varieties of amorphous sulphur can be readily obtained. These are white sulphur and plastic sulphur.
1. White sulphur. Flowers of sulphur, the preparation of which has been described, consists of a mixture of rhombic crystals and amorphous particles. When treated with carbon disulphide, the crystals dissolve, leaving the amorphous particles as a white residue.
2. Plastic sulphur. When boiling sulphur is poured into cold water it assumes a gummy, doughlike form, which is quite elastic. This can be seen in a very striking manner by distilling sulphur from a small, short-necked retort, such as is represented in Fig. 40, and allowing the liquid to run directly into water. In a few days it becomes quite brittle and passes over into ordinary rhombic sulphur.
Chemical properties of sulphur. When sulphur is heated to its kindling temperature in oxygen or in the air it burns with a pale blue flame, forming sulphur dioxide (SO2). Small quantities of sulphur trioxide (SO3) may also be formed in the combustion of sulphur. Most metals when heated with sulphur combine directly with it, forming metallic sulphides. In some cases the action is so energetic that the mass becomes incandescent, as has been seen in the case of iron uniting with sulphur. This property recalls the action of oxygen upon metals, and in general the metals which combine readily with oxygen are apt to combine quite readily with sulphur.
Uses of sulphur. Large quantities of sulphur are used as a germicide in vineyards, also in the manufacture of gunpowder, matches, vulcanized rubber, and sulphuric acid.
COMPOUNDS OF SULPHUR WITH HYDROGENHydrosulphuric acid (H2S). This substance is a gas having the composition expressed by the formula H2S and is commonly called hydrogen sulphide. It is found in the vapors issuing from volcanoes, and in solution in the so-called sulphur waters of many springs. It is formed when organic matter containing sulphur undergoes decay, just as ammonia is formed under similar circumstances from nitrogenous matter.
Preparation. Hydrosulphuric acid is prepared in the laboratory by treating a sulphide with an acid. Iron sulphide (FeS) is usually employed:
A convenient apparatus is shown in Fig. 41. A few lumps of iron sulphide are placed in the bottle A, and dilute acid is added in small quantities at a time through the funnel tube B, the gas escaping through the tube C.
Explanation of the reaction. Iron sulphide is a salt of hydrosulphuric acid, and this reaction is therefore similar to the one which takes place when sulphuric acid acts upon a nitrate. In both cases a salt and an acid are brought together, and there is a tendency for the reaction to go on until a state of equilibrium is reached. This equilibrium is constantly disturbed by the escape of the gaseous acid set free, so that the reaction goes on until all of the original salt has been decomposed. The two reactions differ in that the first one is complete at ordinary temperatures, while in the case of sulphuric acid acting upon sodium nitrate, the reacting substances must be heated so as to secure a temperature at which nitric acid is a gas.
Physical properties. Hydrosulphuric acid is a colorless gas, having a weak, disagreeable taste and an exceedingly offensive odor. It is rather sparingly soluble in water at ordinary temperatures, about three volumes dissolving in one of water. In boiling water it is not soluble at all. In pure form it acts as a violent poison, and even when diluted largely with air produces headache, dizziness, and nausea. It is a little heavier than air, having a density of 1.18.
Chemical properties. The most important chemical properties of hydrosulphuric acid are the following:
1. Acid properties. Hydrosulphuric acid is a weak acid. In solution in water it turns blue litmus red and neutralizes bases, forming salts called sulphides.
2. Action on oxygen. The elements composing hydrosulphuric acid have each a strong affinity for oxygen, and are not held together very firmly. Consequently the gas burns readily in oxygen or the air, according to the equation
When there is not enough oxygen for both the sulphur and the hydrogen, the latter element combines with the oxygen and the sulphur is set free:
3. Reducing action. Owing to the ease with which hydrosulphuric acid decomposes and the strong affinity of both sulphur and hydrogen for oxygen, the substance is a strong reducing agent, taking oxygen away from many substances which contain it.
4. Action on metals. Hydrosulphuric acid acts towards metals in a way very similar to water. Thus, when it is passed over heated iron in a tube, the reaction is represented by the equation
Water in the form of steam, under similar circumstances, acts according to the equation
Salts of hydrosulphuric acid,—sulphides. The salts of hydrosulphuric acid, called sulphides, form an important class of salts. Many of them are found abundantly in nature, and some of them are important ores. They will be frequently mentioned in connection with the metals.
Most of the sulphides are insoluble in water, and some of them are insoluble in acids. Consequently, when hydrosulphuric acid is passed into a solution of a salt, it often happens that a sulphide is precipitated. With copper chloride the equation is
Because of the fact that some metals are precipitated in this way as sulphides while others are not, hydrosulphuric acid is extensively used in the separation of the metals in the laboratory.
Explanation of the reaction. When hydrosulphuric acid and copper chloride are brought together in solution, both copper and sulphur ions are present, and these will come to an equilibrium, as represented in the equation
Cu+ + S- <--> CuS.
Since copper sulphide is almost insoluble in water, as soon as a very small quantity has formed the solution becomes supersaturated, and the excess keeps precipitating until nearly all the copper or sulphur ions have been removed from the solution. With some other ions, such as iron, the sulphide formed does not saturate the solution, and no precipitate results.
OXIDES OF SULPHURSulphur forms two well-known compounds with oxygen: sulphur dioxide (SO2), sometimes called sulphurous anhydride; and sulphur trioxide (SO3), frequently called sulphuric anhydride.
Sulphur dioxide (SO2). Sulphur dioxide occurs in nature in the gases issuing from volcanoes, and in solution in the water of many springs. It is likely to be found wherever sulphur compounds are undergoing oxidation.
Preparation. Three general ways may be mentioned for the preparation of sulphur dioxide:
1. By the combustion of sulphur. Sulphur dioxide is readily formed by the combustion of sulphur in oxygen or the air:
It is also formed when substances containing sulphur are burned:
2. By the reduction of sulphuric acid. When concentrated sulphuric acid is heated with certain metals, such as copper, part of the acid is changed into copper sulphate, and part is reduced to sulphurous acid. The latter then decomposes into sulphur dioxide and water, the complete equation being
3. By the action of an acid on a sulphite. Sulphites are salts of sulphurous acid (H2SO3). When a sulphite is treated with an acid, sulphurous acid is set free, and being very unstable, decomposes into water and sulphur dioxide. These reactions are expressed in the equations
Explanation of the reaction. In this case we have two reversible reactions depending on each other. In the first reaction,
we should expect an equilibrium to result, for none of the four substances in the equation are insoluble or volatile when water is present to hold them in solution. But the quantity of the H2SO3 is constantly diminishing, owing to the fact that it decomposes, as represented in the equation
and the sulphur dioxide, being a gas, escapes. No equilibrium can therefore result, since the quantity of the sulphurous acid is constantly being diminished because of the escape of sulphur dioxide.
Physical properties. Sulphur dioxide is a colorless gas, which at ordinary temperatures is 2.2 times as heavy as air. It has a peculiar, irritating odor. The gas is very soluble in water, one volume of water dissolving eighty of the gas under standard conditions. It is easily condensed to a colorless liquid, and can be
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