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Any evolved gas must be examined. Oxygen, recognized by its power of igniting a glowing splinter, results from the decomposition of oxides of the noble metals, peroxides, chlorates, nitrates and other highly oxygenized salts. Sulphur dioxide, recognized by its smell and acid reaction, results from the ignition of certain sulphites, sulphates, or a mixture of a sulphate with a sulphide. Nitrogen oxides, recognized by their odour and brown-red colour, result from the decomposition of nitrates. Carbon dioxide, recognized by turning lime-water milky, indicates decomposable carbonates or oxalates. Chlorine, bromine, and iodine, each recognizable by its colour and odour, result from decomposable haloids; iodine forms also a black sublimate. Cyanogen and hydrocyanic acid, recognizable by their odour, indicate decomposable cyanides. Sulphuretted hydrogen, recognized by its odour, results from sulphides containing water, and hydrosulphides. Ammonia, recognizable by its odour and alkaline reaction, indicates ammoniacal salts or cyanides containing water.

A sublimate may be formed of: sulphur—reddish-brown drops, cooling to a yellow to brown solid, from sulphides or mixtures; iodine—violet vapour, black sublimate, from iodides, iodic acid, or mixtures; mercury and its compounds—metallic mercury forms minute globules, mercuric sulphide is black and becomes red on rubbing, mercuric chloride fuses before subliming, mercurous chloride does not fuse, mercuric iodide gives a yellow sublimate; arsenic and its compounds—metallic arsenic gives a grey mirror, arsenious oxide forms white shining crystals, arsenic sulphides give reddish-yellow sublimates which turn yellow on cooling; antimony oxide fuses and gives a yellow acicular sublimate; lead chloride forms a white sublimate after long and intense heating.

If the substance does not melt but changes colour, we may have present: zinc oxide—from white to yellow, becoming white on cooling; stannic oxide—white to yellowish brown, dirty white on cooling; lead oxide—from white or yellowish-red to brownish-red, yellow on cooling; bismuth oxide—from white or pale yellow to orange-yellow or reddish-brown, pale yellow on cooling; manganese oxide—from white or yellowish white to dark brown, remaining dark brown on cooling (if it changes on cooling to a bright reddish-brown, it indicates cadmium oxide); copper oxide—from bright blue or green to black; ferrous oxide—from greyish-white to black; ferric oxide—from brownish-red to black, brownish-red on cooling; potassium chromate—yellow to dark orange, fusing at a red heat.

2. Heat the substance on a piece of charcoal in the reducing flame of the blowpipe.

(α) The substance may fuse and be absorbed by the charcoal; this indicates more particularly the alkaline metals.

(β) An infusible white residue may be obtained, which may denote barium, strontium, calcium, magnesium, aluminium or zinc. The first three give characteristic flame colorations (see below); the last three, when moistened with cobalt nitrate and re-ignited, give coloured masses; aluminium (or silica) gives a brilliant blue; zinc gives a green; whilst magnesium phosphates or arsenate (and to a less degree the phosphates of the alkaline earths) give a violet mass.

A metallic globule with or without an incrustation may be obtained. Gold and copper salts give a metallic bead without an incrustation. If the incrustation be white and readily volatile, arsenic is present, if more difficultly volatile and beads are present, antimony; zinc gives an incrustation yellow whilst hot, white on cooling, and volatilized with difficulty; tin gives a pale yellow incrustation, which becomes white on cooling, and does not volatilize in either the reducing or oxidizing flames; lead gives a lemon-yellow incrustation turning sulphur-yellow on cooling, together with metallic malleable beads; bismuth gives metallic globules and a dark orange-yellow incrustation, which becomes lemon-yellow on cooling; cadmium gives a reddish-brown incrustation, which is removed without leaving a gleam by heating in the reducing flame; silver gives white metallic globules and a dark-red incrustation.

3. Heat the substance with a bead of microcosmic salt or borax on a platinum wire in the oxidizing flame.

(α) The substance dissolves readily and in quantity, forming a bead which is clear when hot. If the bead is coloured we may have present: cobalt, blue to violet; copper, green, blue on cooling; in the reducing flame, red when cold; chromium, green, unaltered in the reducing flame; iron, brownish-red, light-yellow or colourless on cooling; in the reducing flame, red while hot, yellow on cooling, greenish when cold; nickel, reddish to brownish-red, yellow to reddish-yellow or colourless on cooling, unaltered in the reducing flame; bismuth, yellowish-brown, light-yellow or colourless on cooling; in the reducing flame, almost colourless, blackish-grey when cold; silver, light yellowish to opal, somewhat opaque when cold; whitish-grey in the reducing flame; manganese, amethyst red, colourless in the reducing flame. If the hot bead is colourless and remains clear on cooling, we may suspect the presence of antimony, aluminium, zinc, cadmium, lead, calcium and magnesium. When present in sufficient quantity the five last-named give enamel-white beads; lead oxide in excess gives a yellowish bead. If the hot colourless bead becomes enamel-white on cooling even when minute quantities of the substances are employed, we may infer the presence of barium or strontium.

(β) The substance dissolves slowly and in small quantity, and forms a colourless bead which remains so on cooling. Either silica or tin may be present. If silica be present, it gives the iron bead when heated with a little ferric oxide; if tin is present there is no change. Certain substances, such as the precious metals, are quite insoluble in the bead, but float about in it.

4. Hold a small portion of the substance moistened with hydrochloric acid on a clean platinum wire in the fusion zone of the Bunsen burner, and note any colour imparted to the flame.

Potassium gives a blue-violet flame which may be masked by the colorations due to sodium, calcium and other elements. By viewing the flame through an indigo prism it appears sky-blue, violet and ultimately crimson, as the thickness of the prism is increased. Other elements do not interfere with this method. Sodium gives an intense and persistent yellow flame; lithium gives a carmine coloration, and may be identified in the presence of sodium by viewing through a cobalt glass or indigo prism; from potassium it may be distinguished by its redder colour; barium gives a yellowish-green flame, which appears bluish-green when viewed through green glass; strontium gives a crimson flame which appears purple or rose when viewed through blue glass; calcium gives an orange-red colour which appears finch-green through green glass; indium gives a characteristic bluish-violet flame; copper gives an intense emerald-green coloration.

5. Film Reactions.—These reactions are practised in the following manner:—A thread of asbestos is moistened and then dipped in the substance to be tested; it is then placed in the luminous point of the Bunsen flame, and a small porcelain basin containing cold water placed immediately over the asbestos. The formation of a film is noted. The operation is repeated with the thread in the oxidizing flame.

Any film formed in the first case is metallic, in the second it is the oxide. The metallic film is tested with 20% nitric acid and with bleaching-powder solution. Arsenic is insoluble in the acid, but immediately dissolves in the bleaching-powder. The black films of antimony and bismuth and the grey mottled film of mercury are slowly soluble in the acid, and untouched by bleaching-powder. The black films of tin, lead and cadmium dissolve at once in the acid, the lead film being also soluble in bleaching-powder. The oxide films of antimony, arsenic, tin and bismuth are white, that of bismuth slightly yellowish; lead yields a very pale yellow film, and cadmium a brown one; mercury yields no oxide film. The oxide films (the metallic one in the case of mercury) are tested with hydriodic acid, and with ammonium sulphide, and from the changes produced the film can be determined (see F. M. Perkin, Qualitative Chemical Analysis, 1905).

Having completed the dry analysis we may now pass on to the wet and more accurate investigation. It is first necessary to get the substance into solution. Small portions Wet methods.should be successively tested with water, dilute hydrochloric acid, dilute nitric acid, strong hydrochloric acid, and a mixture of hydrochloric and nitric acids, first in the cold and then with warming. Certain substances are insoluble in all these reagents, and other methods, such as the fusion with sodium carbonate and potassium nitrate, and subsequent treatment with an acid, must be employed. Some of these insoluble compounds can be detected by their colour and particular reactions. For further information on this subject, we refer the readers to Fresenius’s Qualitative Analysis.

The procedure for the detection of metals in solution consists of first separating them into groups and then examining each group separately. For this purpose the cold solution is treated with hydrochloric acid, which precipitates lead, silver and mercurous salts as chlorides. The solution is filtered and treated with an excess of sulphuretted hydrogen, either in solution or by passing in the gas; this precipitates mercury (mercuric), any lead left over from the first group, copper, bismuth, cadmium, arsenic, antimony and tin as sulphides. The solution is filtered off, boiled till free of sulphuretted hydrogen, and ammonium chloride and ammonia added. If phosphoric acid is absent, aluminium, chromium and ferric hydrates are precipitated. If, however, phosphoric acid is present in the original substance, we may here obtain a precipitate of the phosphates of the remaining metals, together with aluminium, chromium and ferric hydrates. In this case, the precipitate is dissolved in as little as possible hydrochloric acid and boiled with ammonium acetate, acetic acid and ferric chloride. The phosphates of aluminium, chromium and iron are precipitated, and the solution contains the same metals as if phosphoric acid had been absent. To the filtrate from the aluminium, iron and chromium precipitate, ammonia and ammonium sulphide are added; the precipitate may contain nickel, cobalt, zinc and manganese sulphides. Ammonium carbonate is added to the filtrate; this precipitates calcium, strontium and