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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.

(δ) Colorimetric.—This method is adopted when it is necessary to determine minute traces (as in the liquid obtained in the electrolytic separation of copper) of substances which afford well-defined colour reactions.

The general procedure is to make a series of standard solutions containing definite quantities of the substance which it is desired to estimate; such a series will exhibit tints which deepen as the quantity of the substance is increased. A known weight of the test substance is dissolved and a portion of the solution is placed in a tube similar to those containing the standard solutions. The colour-producing reagent is added and the tints compared. In the case of copper, the colour reactions with potassium ferrocyanide or ammonia are usually employed; traces of ammonia are estimated with Nessler’s reagent; sulphur in iron and steel is determined by the tint assumed by a silver-copper plate suspended in the gases liberated when the metal is dissolved in sulphuric acid (Eggertz’s test) (see W. Crookes, Select Methods in Analytical Chemistry).

Organic Analysis.

The elements which play important parts in organic compounds are carbon, hydrogen, nitrogen, chlorine, bromine, iodine, sulphur, phosphorus and oxygen. We shall here consider the qualitative and quantitative determination of these elements.

Qualitative.—Carbon is detected by the formation of carbon dioxide, which turns lime-water milky, and hydrogen by the formation of water, which condenses on the tube, when the substance is heated with copper oxide. Nitrogen may be detected by the evolution of ammonia when the substance is heated with soda-lime. A more delicate method is that due to J. L. Lassaigne and improved by O. Jacobsen and C. Graebe. The substance is heated with metallic sodium or potassium (in excess if sulphur be present) to redness, the residue treated with water, filtered, and ferrous sulphate, ferric chloride and hydrochloric acid added. A blue coloration indicates nitrogen, and is due to the formation of potassium (or sodium) cyanide during the fusion, and subsequent interaction with the iron salts. The halogens may be sometimes detected by fusing with lime, and testing the solution for a bromide, chloride and iodide in the usual way. F. Beilstein determines their presence by heating the substance with pure copper oxide on a platinum wire in the Bunsen flame; a green coloration is observed if halogens be present. Sulphur is detected by heating the substance with sodium, dissolving the product in water, and adding sodium nitroprusside; a bluish-violet coloration indicates sulphur (H. Vohl). Or we may use J. Horbaczewski’s method, which consists in boiling the substance with strong potash, saturating the cold solution with chlorine, adding hydrochloric acid, and boiling till no more chlorine is liberated, and then testing for sulphuric acid with barium chloride. Phosphorus is obtained as a soluble phosphate (which can be examined in the usual way) by lixiviating the product obtained when the substance is ignited with potassium nitrate and carbonate.

Quantitative.—Carbon and hydrogen are generally estimated by the combustion process, which consists in oxidizing the substance and absorbing the products of combustion in suitable apparatus. The oxidizing agent in commonest use isCarbon and hydrogen. copper oxide, which must be freshly ignited before use on account of its hygroscopic nature. Lead chromate is sometimes used, and many other substances, such as platinum, manganese dioxide, &c., have been suggested. The procedure for a combustion is as follows:—

EB1911 Chemistry - Fig. 1.jpg

EB1911 Chemistry - Figs. 2-4.jpg

A hard glass tube slightly longer than the furnace and 12 to 15 mm. in diameter is thoroughly cleansed and packed as shown in fig. 1. The space a must allow for the inclusion of a copper spiral if the substance contains nitrogen, and a silver spiral if halogens be present, for otherwise nitrogen oxides and the halogens may be condensed in the absorption apparatus; b contains copper oxide; c is a space for the insertion of a porcelain or platinum boat containing a weighed quantity of the substance; d is a copper spiral. The end d is connected to an air or oxygen supply with an intermediate drying apparatus. The other end is connected with the absorption vessels, which consist of a tube (e) containing calcium chloride, and a set of bulbs (f) containing potash solution. Various forms of potash bulbs are employed; fig. 2 is Liebig’s, fig. 3 Mohr’s or Geissler’s, fig. 4 is a more recent form, of which special variations have been made by Anderson, Gomberg, Delisle and others. After having previously roasted the tube and copper oxide, and reduced the copper spiral a, the weighed calcium chloride tube and potash bulbs are put in position, the boat containing the substance is inserted (in the case of a difficultly combustible substance it is desirable to mix it with cupric oxide or lead chromate), the copper spiral (d) replaced, and the air and oxygen supply connected up. The apparatus is then tested for leaks. If all the connexions are sound, the copper oxide is gradually heated from the end a, the gas-jets under the spiral d are lighted, and a slow current of oxygen is passed through the tube. The success of the operation depends upon the slow burning of the substance. Towards the end the heat and the oxygen supply are increased. When there is no more absorption in the potash bulbs, the oxygen supply is cut off and air passed through. Having replaced the oxygen in the absorption vessels by air, they are disconnected and weighed, after having cooled down to the temperature of the room. The increase in weight of the calcium chloride tube gives the weight of water formed, and of the potash bulbs the carbon dioxide.

Liquids are amenable to the same treatment, but especial care must be taken so that they volatilize slowly. Difficultly volatile liquids may be weighed directly into the boat; volatile liquids are weighed in thin hermetically sealed bulbs, the necks of which are broken just before they are placed in the combustion tube.

The length of time and other disadvantages attending the combustion method have caused investigators to devise other processes. In 1855 C. Brunner described a method for oxidizing the carbon to carbon dioxide, which could be estimated by the usual methods, by heating the substance with potassium bichromate and sulphuric acid. This process has been considerably developed by J. Messinger, and we may hope that with subsequent improvements it may be adapted to all classes of organic compounds. The oxidation, which is effected by chromic acid and sulphuric acid, is conducted in a flask provided with a funnel and escape tube, and the carbon dioxide formed is swept by a current of dry air, previously freed from carbon dioxide, through a drying tube to a set of potash bulbs and a tube containing soda-lime; if halogens are present, a small wash bottle containing potassium iodide, and a U tube containing glass wool moistened with silver nitrate on one side and strong sulphuric acid on the other, must be inserted between the flask and the drying tube. The increase in weight of the potash bulbs and soda-lime tube gives