Production and use

Rock salt deposits are usually mined; occasionally water is pumped down, and brine, containing about 25 percent sodium chloride, is brought to the surface. When the brine is evaporated, impurities separate first and can be removed. In warm climates salt is obtained by evaporation of shallow seawater by the Sun, producing bay salt.

Chlorine is produced on a large scale by any of a number of different methods:

1. By electrolysis of a concentrated solution of sodium chloride in water. Hydrogen is generated at the cathode and chlorine at the anode. At the same time, sodium hydroxide is produced in the electrolyte; hence, this process is often referred to as chlorine-alkali electrolysis.

   The chemical reactions that take place at each electrode and the overall cell process are given in the following equations:

   

   in which the symbol e⁻ represents a single electron. In the reaction vessel, free chlorine and hydroxide ions must not come in contact with each other, because chlorine would be consumed according to the reaction

   

   To accomplish the separation of chlorine gas and the hydroxide ion, a porous wall is inserted between the electrodes (diaphragm process), or the iron cathode is replaced by a cathode consisting of liquid mercury (mercury cathode process), which avoids the production of hydroxide ions at the electrode. Instead, free sodium is discharged at the cathode, and this metal is readily dissolved in the mercury, forming an amalgam, as follows:

   

   The amalgam is allowed to react with water outside the cell:

   

   The overall process is equivalent to the cell process given above.

2. By electrolysis of fused sodium chloride, which also produces metallic sodium; chlorine is again evolved at the anode.

3. By electrolysis of fused magnesium chloride, in which chlorine is formed as a by-product in the manufacture of metallic magnesium.

4. By oxidation of hydrogen chloride, in which gaseous hydrogen chloride mixed with air or oxygen is passed over pumice in contact with cupric chloride as a catalyst, as shown in the following equation:

   

   The equilibrium constant for this reaction decreases with increase of temperature; i.e., the reaction proceeds less extensively at higher temperatures. In practice, however, a temperature of 400 °C (750 °F) is required to achieve a reasonable rate of conversion.

5. Of historical interest is the process in which a mixture of almost any solid chloride and manganese dioxide (MnO₂) yields chlorine when heated with concentrated sulfuric acid (H₂SO₄). The reaction occurs, as follows:

   

In the laboratory chlorine is frequently prepared by the oxidation of concentrated hydrochloric acid with permanganate or dichromate salts:

Most of the chlorine produced is used for chemical processes involving the introduction of chlorine into organic compounds, yielding carbon tetrachloride (used as a solvent, a fire extinguisher, and a dry-cleaning agent), glycols (used as antifreeze), and other organic compounds for the manufacture of plastics (polyvinyl chloride), dyes, and synthetic rubber. Sulfur chloride, made by the action of chlorine on carbon disulfide or by combining sulfur and chlorine, is used in the vulcanization of rubber and as a chlorinating agent in organic synthesis. Sulfur dioxide combines with chlorine to give sulfuryl dioxide. Chlorine and carbon monoxide form carbonyl chloride (COCl₂), or phosgene, which was employed as a chemical weapon in World War I and is used mainly in the preparation of isocyanates and polyurethanes and in metallurgy to transform certain oxides into chlorides. The reactions that form phosgene and sulfuryl dioxide (SO₂Cl₂) are

Much chlorine is used to sterilize water and wastes, and the substance is employed either directly or indirectly as a bleaching agent for paper or textiles and as “bleaching powder” (Ca[OCl]₂∙CaCl₂∙Ca[OH]₂∙2H₂O). Chlorine is applied in the manufacturing of high-purity hydrochloric acid, the extraction of titanium with the formation of titanium tetrachloride (TiCl₄), and the removal of tin from old tinplate. Anhydrous aluminum chloride (AlCl₃) is made by the reaction of chlorine with scrap aluminum or with aluminum oxide and carbon. Chlorine is also used to prepare silicon tetrachloride (SiCl₄) and methyl chloride (CH₃Cl), which are employed in the synthesis of silicon materials. Chlorine enters directly, or indirectly as an intermediate, into many organic syntheses of industrial importance.

Analysis

Free chlorine may be recognized by its smell, its colour, and its characteristic reaction with mercury to produce white mercury dichloride (HgCl₂). Tests for chloride ions are:

1. The formation of a white precipitate of silver chloride (AgCl) on addition of silver nitrate (AgNO₃) in dilute nitric acid (HNO₃). (This precipitate is soluble in the presence of ammonia.)

2. The formation of chromyl chloride (CrO₂Cl₂), a red gas, by heating a solid sample with potassium dichromate (K₂Cr₂O₇) and concentrated sulfuric acid. When chromyl chloride is passed into water, a yellow chromate solution forms (bromides and iodides do not form analogous compounds).

3. The evolution of free chlorine by heating the sample with manganese dioxide (MnO₂) and concentrated sulfuric acid.

The following methods are available for the quantitative determination of free chlorine:

1. The chlorine-containing gas is shaken with an aqueous solution of potassium iodide (KI), and the resulting iodine is determined by titration.

2. Chlorine is reduced in alkaline solution by an alkali arsenite (e.g., NaAsO₂). Back-titration of excess arsenite is carried out with potassium bromate (KBrO₃).

3. In the presence of an alkali hydroxide (e.g., NaOH), chlorine is reduced to the chloride ion by hydrogen peroxide (H₂O₂), and the excess alkali hydroxide is back-titrated with acid.

4. With sulfur dioxide (SO₂) or sodium thiosulfate (Na₂S₂O₃), chlorine is reduced to chloride, and the latter is analyzed as silver chloride (see below).

5. Colorimetric measurements are carried out in the presence of o-toluidine in hydrochloric acid.

For the determination of chloride ions, one of the following methods may be recommended:

1. Gravimetric analysis (analysis by weight of a given product) as silver chloride.

2. Titration of a neutral chloride solution with silver nitrate in the presence of potassium chromate.

3. Potentiometric titration (measurement of voltage changes) with silver nitrate, a process that can be carried out in the presence of bromide and iodide ions.

Most insoluble chlorides can be melted with soda (Na₂CO₃), and the resulting melt is then usually soluble in water. Organic compounds containing chlorine are heated with alkali peroxide, and the product is dissolved in water.