Page:EB1911 - Volume 02.djvu/693

From Wikisource
Jump to navigation Jump to search
This page has been proofread, but needs to be validated.
651
ARSENIC

engineer store, magazines, raw material store, timber yard, breaking-up store, unserviceable store. Under B—Gun factory, carriage factory, laboratory, small-arms factory, harness and tent factory, powder factory, &c. In a second-class arsenal there would be workshops instead of these factories. C—Under the head of administration would be classed the chief director of the arsenal, officials military and civil, non-commissioned officers and military artificers, civilian foremen, workmen and labourers, with the clerks and writers necessary for the office work of the establishments. In the manufacturing branches are required skill, and efficient and economical work, both executive and administrative; in the storekeeping part, good arrangement, great care, thorough knowledge of all warlike stores, both in their active and passive state, and scrupulous exactness in the custody, issue and receipt of stores. For fuller details the reader is referred to papers by Sir E. Collen, R. A., in vol. viii., and Lieut. C. E. Grover, R. E., in vol. vi. Proceedings of R. Artillery Institution. In England the Royal Arsenal, Woolwich, manufactures and stores the requirements of the army and navy (see Woolwich).

ARSENIC (symbol As, atomic weight 75.0), a chemical element, known to the ancients in the form of its sulphides. Aristotle gave them the name σανδαράκη, and Theophrastus mentions them under the name ἀρσενικόν. The oxide known as white arsenic is mentioned by the Greek alchemist Olympiodorus, who obtained it by roasting arsenic sulphide. These substances were all known to the later alchemists, who used minerals containing arsenic in order to give a white colour to copper. Albertus Magnus was the first to state that arsenic contained a metal-like substance, although later writers considered it to be a bastard or semi-metal, and frequently called it arsenicum rex. In 1733 G. Brandt showed that white arsenic was the calx of this element, and after the downfall of the phlogiston theory the views concerning the composition of white arsenic were identical with those which are now held, namely that it is an oxide of the element.

Arsenic is found in the uncombined condition in various localities, but more generally in combination with other metals and sulphur, in the form of more or less complex sulphides. Native arsenic is usually found as granular or curvilaminar masses, with a reniform or botryoidal surface. These masses are of a dull grey colour, owing to surface tarnish; only on fresh fractures is the colour tin-white with metallic lustre. The hardness is 3.5 and the specific gravity 5.63–5.73. Crystals of arsenic belong to the rhombohedral system, and have a perfect cleavage parallel to the basal plane; natural crystals are, however, of rare occurrence, and are usually acicular in habit. Native arsenic occurs usually in metalliferous veins in association with ores of antimony, silver, &c.; the silver mines of Freiberg in Saxony, St Andreasberg in the Harz, and Chañarcillo in Chile being well-known localities. Attractive globular aggregates of well-developed radiating crystals have been found at Akatani, a village in the province Echizen, in Japan.

Arsenic is a constituent of the minerals arsenical iron, arsenical pyrites or mispickel, tin-white cobalt or smaltite, arsenical nickel, realgar, orpiment, pharmacolite and cobalt bloom, whilst it is also met with in small quantities in nearly all specimens of iron pyrites. The ordinary commercial arsenic is either the naturally occurring form, which is, however, more or less contaminated with other metals, or is the product obtained by heating arsenical pyrites, out of contact with air, in earthenware retorts which are fitted with a roll of sheet iron at the mouth, and an earthenware receiver. By this method of distillation the arsenic sublimes into the receiver, leaving a residue of iron sulphide in the retort. For further purification, it may be sublimed, after having been previously mixed with a little powdered charcoal, or it may be mixed with a small quantity of iodine and heated. It can also be obtained by the reduction of white arsenic (arsenious oxide) with carbon. An electro-metallurgical process for the extraction of arsenic from its sulphides has also been proposed (German Patent. 67,973). These compounds are brought into solution by means of polysulphides of the alkali metals and the resultant liquor run into the cathode compartment of a bath, which is divided by diaphragms into a series of anode and cathode chambers; the anode divisions being closed and gas-tight, and containing carbon or platinum electrodes. The arsenic solution is decomposed at the cathode, and the element precipitated there.

Arsenic possesses a steel-grey colour, and a decided metallic lustre; it crystallizes on sublimation and slow condensation in rhombohedra, isomorphous with those of antimony and tellurium. It is very brittle. Its specific gravity is given variously from 5.395 to 5.959; its specific heat is 0.083, and its coefficient of linear expansion 0.00000559 (at 40° C.). It is volatile at temperatures above 100° C. and rapidly vaporizes at a dull red heat. It liquefies when heated under pressure, and its melting point lies between 446° C. and 457° C. The vapour of arsenic is of a golden yellow colour, and has a garlic odour. The vapour density is 10.6 (air = 1) at 564° C., corresponding to a tetratomic molecule As4; at a white heat the vapour density shows a considerable lowering in value, due to the dissociation of the complex molecule.

By condensing arsenic vapour in a glass tube, in a current of an indifferent gas, such as hydrogen, amorphous arsenic is obtained, the deposit on the portion of the tube nearest to the source of heat being crystalline, that farther along (at a temperature of about 210° C.) being a black amorphous solid, while still farther along the tube a grey deposit is formed. These two latter forms possess a specific gravity of 4.710 (14° C.) [A. Bettendorff, Annalen, 1867, 144, p. 110], and by heating at about 358°–360° C. pass over into the crystalline variety. Arsenic burns on heating in a current of oxygen, with a pale lavender-coloured flame, forming the trioxide. It is easily oxidized by heating with concentrated nitric acid to arsenic acid, and with concentrated sulphuric acid to arsenic trioxide; dilute nitric acid only oxidizes it to arsenious acid. It burns in an atmosphere of chlorine forming the trichloride; it also combines directly with bromine and sulphur on heating, while on fusion with alkalis it forms arsenites.

Arsenic and most of its soluble compounds are very poisonous, and consequently the methods used for the detection of arsenic are very important. For full accounts of methods used in detecting minute traces of arsenic in foods, &c., see “Report to Commission to Manchester Brewers’ Central Association,” the Analyst, 1900, 26, p. 8; “Report of Conjoint Committee of Society of Chemical Industry and Society of Public Analysts,” the Analyst, 1902, 27, p. 48; T. E. Thorpe, Journal of the Chemical Society, 1903, 83, p. 774; O. Hehner and others, Journal of Society of Chemical Industry, 1902, 21, p. 94; also Adulteration.

Arsenic and arsenical compounds generally can be detected by (a) Reinsch’s test: A piece of clean copper is dipped in a solution of an arsenious compound which has been previously acidified with pure hydrochloric acid. A grey film is produced on the surface of the copper, probably due to the formation of a copper arsenide. The reaction proceeds better on heating the solution. On removing, washing and gently drying the metal and heating it in a glass tube, a white crystalline sublimate is formed on the cool part of the tube; under the same conditions antimony does not produce a crystalline sublimate.

(b) Fleitmann’s test and Marsh’s test depend on the fact that arsenic and its compounds, when present in a solution in which hydrogen is being generated, are converted into arseniuretted hydrogen, which can be readily detected either by its action on silver nitrate solution or by its decomposition on heating. In Fleitmann’s test, the solution containing the arsenious compound is mixed with pure potassium hydroxide solution and a piece of pure zinc or aluminium foil dropped in and the whole then heated. A piece of bibulous paper, moistened with silver nitrate, is held over the mouth of the tube, and if arsenic be present, a grey or black deposit is seen on the paper, due to the silver nitrate being reduced by the arseniuretted hydrogen. Antimony gives no reaction under these conditions, so that the method can be used to detect arsenic in the presence of antimony, but the test is not so delicate as either Reinsch’s or Marsh’s method.

In the Marsh test the solution containing the arsenious compounds is mixed with pure hydrochloric acid and placed in an apparatus in which hydrogen is generated from pure zinc and pure sulphuric acid. The arseniuretted hydrogen produced is passed through a tube containing lead acetate paper and soda-lime, and finally through a narrow glass tube, constricted at various points, and heated by a very small flame. As the arseniuretted hydrogen passes over