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 barium. The solution contains magnesium, sodium and potassium, which are separately distinguished by the methods given under their own headings.

We now proceed with the examination of the various group precipitates. The white precipitate formed by cold hydrochloric acid is boiled with water, and the solution filtered while hot. Any lead chloride dissolves, and may be identified by the yellow precipitate formed with potassium chromate. To the residue add ammonia, shake, then filter. Silver chloride goes into solution, and may be precipitated by dilute nitric acid. The residue, which is black in colour, consists of mercuroso-ammonium chloride, in which mercury can be confirmed by its ordinary tests.

The precipitate formed by sulphuretted hydrogen may contain the black mercuric, lead, and copper sulphides, dark-brown bismuth sulphide, yellow cadmium and arsenious sulphides, orange-red antimony sulphide, brown stannous sulphide, dull-yellow stannic sulphide, and whitish sulphur, the last resulting from the oxidation of sulphuretted hydrogen by ferric salts, chromates, &c. Warming with ammonium sulphide dissolves out the arsenic, antimony and tin salts, which are reprecipitated by the addition of hydrochloric acid to the ammonium sulphide solution. The precipitate is shaken with ammonium carbonate, which dissolves the arsenic. Filter and confirm arsenic in the solution by its particular tests. Dissolve the residue in hydrochloric acid and test separately for antimony and tin. The residue from the ammonium sulphide solution is warmed with dilute nitric acid. Any residue consists of black mercuric sulphide (and possibly white lead sulphate), in which mercury is confirmed by its usual tests. The solution is evaporated with a little sulphuric acid and well cooled. The white precipitate consists of lead sulphate. To the filtrate add ammonia in excess; a white precipitate indicates bismuth; if the solution be blue, copper is present. Filter from the bismuth hydrate, and if copper is present, add potassium cyanide till the colour is destroyed, then pass sulphuretted hydrogen, and cadmium is precipitated as the yellow sulphide. If copper is absent, then sulphuretted hydrogen can be passed directly into the solution.

The next group precipitate may contain the white gelatinous aluminium hydroxide, the greenish chromium hydroxide, reddish ferric hydroxide, and possibly zinc and manganese hydroxides. Treatment with casutic soda dissolves out aluminium hydroxide, which is reprecipitated by the addition of ammonium chloride. The remaining metals are tested for separately.

The next group may contain black nickel and cobalt sulphides, flesh-coloured manganese sulphide, and white zinc sulphide. The last two are dissolved out by cold, very dilute hydrochloric acid, and the residue is tested for nickel and cobalt. The solution is boiled till free from sulphuretted hydrogen and treated with excess of sodium hydrate. A white precipitate rapidly turning brown indicates manganese. The solution with ammonium sulphide gives a white precipitate of zinc sulphide.

The next group may contain the white calcium, barium and strontium carbonates. The flame coloration (see above) may give information as to which elements are present. The carbonates are dissolved in hydrochloric acid, and calcium sulphate solution is added to a portion of the solution. An immediate precipitate indicates barium; a precipitate on standing indicates strontium. If barium is present, the solution of the carbonates in hydrochloric acid is evaporated and digested with strong alcohol for some time; barium chloride, which is nearly insoluble in alcohol, is thus separated, the remainder being precipitated by a few drops of hydrofluosilicic acid, and may be confirmed by the ordinary tests. The solution free from barium is treated with ammonia and ammonium sulphate, which precipitates strontium, and the calcium in the solution may be identified by the white precipitate with ammonium oxalate.

Having determined the bases, it remains to determine the acid radicals. There is no general procedure for these operations, and it is customary to test for the acids separately by special tests; these are given in the articles on the various acids. A knowledge of the solubility of salts considerably reduces the number of acids likely to be present, and affords evidence of great value to the analyst (see A. M. Comey, Dictionary of Chemical Solubilities.) In the above account we have indicated the procedure adopted in the analysis of a complex mixture of salts. It is unnecessary here to dwell on the precautions which can only be conveniently acquired by experience; a sound appreciation of analytical methods is only possible after the reactions and characters of individual substances have been studied, and we therefore refer the reader to the articles on the particular elements and compounds for more information on this subject.

Quantitative Inorganic Analysis.

Quantitative methods are divided into four groups, which we now pass on to consider in the following sequence: gravimetric,  volumetric,  electrolytic,  colorimetric.

Gravimetric.—This method is made up of four operations: (1) a weighed quantity of the substance is dissolved in a suitable solvent; (2) a particular reagent is added which precipitates the substance it is desired to estimate; (3) the precipitate is filtered, washed and dried; (4) the filter paper containing the precipitate is weighed either as a tared filter, or incinerated and ignited either in air or in any other gas, and then weighed.

(1) Accurate weighing is all-important: for details of the various appliances and methods see. (2) No general directions can be given as to the method of precipitation. Sometimes it is necessary to allow the solution to stand for a considerable time either in the warm or cold or in the light or dark; to work with cold solutions and then boil; or to use boiling solutions of both the substance and reagent. Details will be found in the articles on particular metals. (3) The operation of filtration and washing is very important. If the substance to be weighed changes in composition on strong heating, it is necessary to employ a tared filter, i.e. a filter paper which has been previously heated to the temperature at which the substance is to be dried until its weight is constant. If the precipitate settles readily, the supernatant liquor may be decanted through the filter paper, more water added to the precipitate and again decanted. By this means most of the washing, i.e.freeing from the other substances in the solution, can be accomplished in the precipitating vessel. If, however, the precipitate refuses to settle, it is directly transferred to the filter paper, the last traces being removed by washing and rubbing the sides of the vessel with a piece of rubber, and the liquid is allowed to drain through. It is washed by ejecting a jet of water, ammonia or other prescribed liquid on to the side of the filter paper until the paper is nearly full. It can be shown that a more efficient washing results from alternately filling and emptying the funnel than by endeavouring to keep the funnel full. The washing is continued until the filtrate is free from salts or acids. (4) After washing, the funnel containing the filter paper is transferred to a drying oven. In the case of a tared filter it is weighed repeatedly until the weight suffers no change; then knowing the weight of the filter paper, the weight of the precipitate is obtained by subtraction. If the precipitate may be ignited, it is transferred to a clean, weighed and recently ignited crucible, and the filter paper is burned separately on the lid, the ash transferred to the crucible, and the whole ignited. After ignition, it is allowed to cool in a desiccator and then weighed. Knowing the weight of the crucible and of the ash of the filter paper, the weight of the precipitate is determined. The calculation of the percentage of the particular constituent is simple. We know the amount present in the precipitate, and since the same amount is present in the quantity of substance experimented with, we have only to work out a sum in proportion.

Volumetric.—This method is made up of three operations:—(1) preparation of a standard solution; (2) preparation of a solution of the substance; (3) titration, or the determination of what volume of the standard solution will occasion a known and definite reaction with a known volume of the test solution.

(1) In general analytical work the standard solution contains the equivalent weight of the substance in grammes dissolved in a litre of water. Such a solution is known as normal. Thus a normal solution of sodium carbonate contains 53 grammes per litre, of sodium hydrate 40 grammes, of hydrochloric acid 36.5 grammes, and so on. By taking 1/10th or 1/100th of these quantities, decinormal or centinormal solutions are obtained. We see therefore that 1 cubic centimetre of a normal sodium carbonate solution will exactly neutralize 0.049 gramme of sulphuric acid, 0.0365 gramme of hydrochloric acid (i.e. the equivalent quantities), and similarly for decinormal and centinormal solutions. Unfortunately, the term normal is sometimes given to solutions which are strictly decinormal; for example, iodine, sodium thiosulphate, &c. In technical analysis, where a solution is used for one process only, it may be prepared so that 1 cc. is equal to .01 gramme of the substance to be estimated. This saves a certain amount of arithmetic, but when the solution is applied in another determination additional calculations are necessary. Standard solutions are prepared by weighing out the exact amount of the pure substance and dissolving it in water, or by forming a solution of approximate normality, determining its exact strength by gravimetric or other means, and then correcting it for any divergence. This may be exemplified in the case of alkalimetry. Pure sodium carbonate is prepared by igniting the bicarbonate, and exactly 53 grammes are dissolved in water, forming a strictly normal solution. An approximate normal sulphuric acid is prepared from 30 ccs. of the pure acid (1.84 specific gravity) diluted to 1 litre. The solutions are titrated (see below) and the acid solution diluted until equal volumes are exactly equivalent. A standard sodium hydrate solution can be prepared by dissolving 42 grammes of sodium hydrate, making up to a litre, and diluting until one cubic centimetre is exactly equivalent to one cubic centimetre of the sulphuric acid. Similarly, normal solutions of hydrochloric and nitric acids can be prepared. Where a solution is likely to change in composition on keeping, such as potassium permanganate, iodine,