Quantitative Inorganic Analysis.
Quantitative methods are divided into four groups, which we now pass on to consider in the following sequence: (α) gravimetric, (β) volumetric, (γ) electrolytic, (δ) colorimetric.
(α) 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 [Weighing Machines]. (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.
(β) 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, sodium hydrate, &c., it is necessary to check or re-standardize it periodically.
(2) The preparation of the solution of the substance consists in dissolving an accurately determined weight, and making up the volume in a graduated cylinder or flask to a known volume.
(3) The titration is conducted by running the standard solution from a burette into a known volume of the test solution, which is usually transferred from the stock-bottle to a beaker or basin by means of a pipette. Various artifices are employed to denote the end of the reaction. These may be divided into two groups: (1) those in which a change in appearance of the reacting mixture occurs; (2) those in which it is necessary to use an indicator which, by its change in appearance, shows that an excess of one reagent is present. In the first group, we have to notice the titration of a cyanide with silver nitrate, when a milkiness shows how far the reaction has gone; the titration of iron with permanganate, when the faint pink colour shows that all the iron is oxidized. In the second group, we may notice the application of litmus, methyl orange or phenolphthalein in alkalimetry, when the acid or alkaline character of the solution commands the colour which it exhibits; starch paste, which forms a blue compound with free iodine in iodometry; potassium chromate, which forms red silver chromate after all the hydrochloric acid is precipitated in solutions of chlorides; and in the estimation of ferric compounds by potassium bichromate, the indicator, potassium ferricyanide, is placed in drops on a porcelain plate, and the end of the reaction is shown by the absence of a blue coloration when a drop of the test solution is brought into contact with it.
(γ) Electrolytic.—This method consists in decomposing a solution of a salt of the metal by the electric current and weighing the metal deposited at the cathode.
It is only by paying great attention to the current density that good results are obtained, since metals other than that sought for may be deposited. In acid copper solutions, mercury is deposited before the copper with which it subsequently amalgamates; silver is thrown down simultaneously; bismuth appears towards the end; and after all the copper has been precipitated, arsenic and antimony may be deposited. Lead and manganese are partially separated as peroxides, but the remaining metals are not deposited from acid solutions. It is therefore necessary that the solution should be free from metals which may vitiate the results, or special precautions taken by which the impurities are rendered harmless. In such cases the simplicity of manipulation and the high degree of accuracy of the method have made it especially valuable. The electrolysis is generally conducted with platinum electrodes, of which the cathode takes the form of a piece of foil bent into a cylindrical form, the necessary current being generated by one or more Daniell cells.