SALTPETRE (from the Lat. sal, salt, petra, a rock), the commercial name given to three naturally occurring nitrates, distinguished as (i) ordinary saltpetre, nitre, or potassium nitrate, (2) Chile saltpetre, cubic nitre, or sodium nitrate, (3) wall-saltpetre or calcium nitrate. These nitrates generally occur as efflorescences caused by the oxidation of nitrogenous matter in the presence of the alkalies and alkaline earths.
i. Ordinary Saltpetre or Potassium Nitrate, KNOs, occurs, mingled with other nitrates, on the surface and in the superficial layers of the soil in many countries, especially in certain parts of India, Persia, Arabia and Spain. The deposits in the great limestone caves of Kentucky, Virginia and Indiana have been probably derived from the overlying soil and accumulated by percolating water; they are of no commercial value. The actual formation of this salt is not quite clear; but it is certainly conditioned by the simultaneous contact of decaying nitrogenous matter, alkalies, air and moisture. The demand for saltpetre as an ingredient of gunpowder led to the formation of saltpetre plantations or nitriaries, which at one time were common in France, Germany, and other countries; the natural conditions were simulated by exposing heaps of decaying organic matter mixed with alkalies (lime, etc.) to atmospheric action. The salt is obtained from the soil in which it occurs naturally, or from the heaps in which it is formed artificially, by extracting with water, and adding to the solution wood-ashes or potassium carbonate. The liquid is filtered and then crystallized. Since potassium nitrate is generally more serviceable than the sodium salt, whose deliquescent properties inhibit its use for gunpowder manufacture, the latter salt, of which immense natural deposits occur (see below (2) Chile saltpetre), is converted into ordinary saltpetre in immense quantities. This is generally effected by adding the calculated amount of potassium chloride (of which immense quantities are obtained as a by-product in the Stassfurt salt industry) dissolved in hot water to a saturated boiling solution of sodium nitrate; the common salt, which separates on boiling down the solution, is removed from the hot solution, and on cooling* the potassium nitrate crystallizes out and is separated and dried.
As found in nature, saltpetre generally forms aggregates of delicate acicular crystals, and sometimes silky tufts; distinctly developed crystals are not found in nature. When crystallized from water, crystals belonging to the orthorhombic system, and having a prism angle of 61 10', are obtained; they are often twinned on the prism planes, giving rise to pseudo-hexagonal groups resembling aragonite. There are perfect cleavages parallel to the dome (on). The hardness is 2, and the specific gravity 2-1. It is fairly soluble in water; 100 parts at o dissolving 13-3 parts of the salt, and about 30 parts at 20; the most saturated solution contains 327-4 parts of the salt in 100 of water; this solution boils at 114-1. It fuses at 339 to a colourless liquid, which solidifies on cooling to a white fibrous mass, known in pharmacy as sal prunella. It is an energetic oxidizing agent, and on this property its most important applications depend. At a red heat it evolves oxygen with the formation of potassium nitrite, which, in turn, decomposes at a higher temperature. Heated with many metals it converts them into oxides, and with combustible substances, such as charcoal, sulphur, etc., a most intense conflagration occurs. Its chief uses are in glass-making to promote fluidity, in metallurgy to oxidize impurities, as a constituent of gunpowder and in pyrotechny; it is also used in the manufacture of nitric acid.
Potassium nitrate was used at one time in many different diseased conditions, but it is now never administered internally, as its extremely depressant action upon the heart is not compensated for by any useful properties which are not possessed by many other drugs. One most valuable use it has, however, in the treatment of asthma. All nitrites (e.g. sodium nitrite, ethyl nitrite, amyl nitrite) cause relaxation of involuntary muscular fibre and therefore relieve the asthmatic attacks, which depend upon spasm of the involuntary muscles in the bronchial tubes. Saltpetre may be made to act as a nitrite by dissolving it in water in the strength of about fifty grains to the ounce, soaking blotting-paper in the solution and letting the paper dry. Pieces about 2 in. square are then successively put into a jar and lighted. The patient inhales the fumes, which contain a considerable proportion of nitrogen oxides. This treatment is frequently very successful indeed in relaxing the bronchial spasm upon which the most obvious features of an attack depend.
2. Chile saltpetre, cubic nitre or sodium nitrate, NaNOj, occurs under the same conditions as ordinary saltpetre in deposits covering immense areas in South America, which are known locally as caliche or terra salitrosa, and abound especially in the provinces of Tarapaca and Antofagasta in Chile. The nitrate fields are confined to a narrow strip of country, averaging 2j m. in width, situated on the eastern slopes of the coast ranges and extending from north to south for 260 geographical miles, between the latitudes 25 45' and 19 12' S. The nitrate forms beds, varying in thickness from 6 in. to 12 ft., under a covering of conglomerate locally known as lostra, which is itself overlain by a loose sandy soil. The conglomerate consists of rock fragments, sodium chloride and various sulphates, cemented together by gypsum to form a hard compact mass 6 to 10 ft. in thickness. The caliche has often a granular structure, and is yellowishwhite, bright lemon-yellow, brownish or violet in colour. It contains from 48 to 75% of sodium nitrate and from 20 to 40% of common salt, which are associated with various minor saline components, including sodium iodate and more or less insoluble mineral, and also some organic matter, e.g. guano, which suggests the idea that the nitrate was formed by the nitrification of this kind of excremental matter. The caliche is worked up in loco for crude nitrate by extracting the salts with hot water, allowing the suspended earth to settle, and then transferring the clarified liquor, first to a cistern where it deposits part of its sodium chloride at a high temperature, and then to _another where, on cooling, it yields a crop of crystals of purified nitrate. The nitre thus refined is exported chiefly from Valparaiso, whence the name of " Chile saltpetre." The mother liquors used to be thrown away, but are now utilized for the extraction of their iodine (q.v.).
Chemically pure sodium nitrate can be obtained by repeated recrystallization of Chile saltpetre or by synthesis. It forms colourless, transparent rhombohedra, like those of Iceland spar; the angles are nearly equal to right angles, being 73 30', so that the crystals look like cubes: hence the name of cubic saltpetre." There are perfect cleavages parallel to the rhombohedral faces, and the crystals exhibit a strong negative double refraction, like calcite. One hundred parts of water at o and at 100 dissolve 72-9 and 180 parts of the salt; at 120" the boiling-point of the saturated solution, 216 parts. The salt fuses at 316"; at higher temperatures it loses oxygen (more readily than the corresponding potassium salt) with the formation of nitrite which, at very high temperatures, is reduced ultimately to a mixture of peroxide, Na,Oj, and oxide, NasO. The chief applications of Chile saltpetre are in the nitric acid industry, and in the manufacture of ordinary saltpetre for making gunpowder, ordinary Chile saltpetre being unsuitable by reason of its deliquescent nature, a property, however, not exhibited by the perfectly pure salt. It is also employed as a manure. For references to memoirs descriptive of the Chilian nitrate deposits, see G. P. Merrill, The Non-Metallic Minerals (New York, 1904).
3. Wall-saltpetre or lime saltpetre, calcium nitrate, Ca(NOj) 2 , is found as an efflorescence on the walls of stables; it is now manufactured in large quantities by fixing atmospheric nitrogen, i.e. by passing a powerful electric arc discharge through moist air and absorbing the nitric acid formed by lime. Its chief applications are as a manure and in the nitric acid industry.
Note - this article incorporates content from Encyclopaedia Britannica, Eleventh Edition, (1910-1911)