Page:EB1911 - Volume 09.djvu/234

 (see ), or from chemical action when part of the circuit is an electrolytic conductor, or from the movement of lines of magnetic force across the conductor.

 ELECTROLIER, a fixture, usually pendent from the ceiling, for holding electric lamps. The word is analogous to chandelier, from which indeed it was formed.

 ELECTROLYSIS (formed from Gr. , to loosen). When the passage of an electric current through a substance is accompanied by definite chemical changes which are independent of the heating effects of the current, the process is known as electrolysis, and the substance is called an electrolyte. As an example we may take the case of a solution of a salt such as copper sulphate in water, through which an electric current is passed between copper plates. We shall then observe the following phenomena. (1) The bulk of the solution is unaltered, except that its temperature may be raised owing to the usual heating effect which is proportional to the square of the strength of the current. (2) The copper plate by which the current is said to enter the solution, i.e. the plate attached to the so-called positive terminal of the battery or other source of current, dissolves away, the copper going into solution as copper sulphate. (3) Copper is deposited on the surface of the other plate, being obtained from the solution. (4) Changes in concentration are produced in the neighbourhood of the two plates or electrodes. In the case we have chosen, the solution becomes stronger near the anode, or electrode at which the current enters, and weaker near the cathode, or electrode at which it leaves the solution. If, instead of using copper electrodes, we take plates of platinum, copper is still deposited on the cathode; but, instead of the anode dissolving, free sulphuric acid appears in the neighbouring solution, and oxygen gas is evolved at the surface of the platinum plate.

With other electrolytes similar phenomena appear, though the primary chemical changes may be masked by secondary actions. Thus, with a dilute solution of sulphuric acid and platinum electrodes, hydrogen gas is evolved at the cathode, while, as the result of a secondary action on the anode, sulphuric acid is there re-formed, and oxygen gas evolved. Again, with the solution of a salt such as sodium chloride, the sodium, which is primarily liberated at the cathode, decomposes the water and evolves hydrogen, while the chlorine may be evolved as such, may dissolve the anode, or may liberate oxygen from the water, according to the nature of the plate and the concentration of the solution.

Early History of Electrolysis.—Alessandro Volta of Pavia discovered the electric battery in the year 1800, and thus placed the means of maintaining a steady electric current in the hands of investigators, who, before that date, had been restricted to the study of the isolated electric charges given by frictional electric machines. Volta’s cell consists essentially of two plates of different metals, such as zinc and copper, connected by an electrolyte such as a solution of salt or acid. Immediately on its discovery intense interest was aroused in the new invention, and the chemical effects of electric currents were speedily detected. W. Nicholson and Sir A. Carlisle found that hydrogen and oxygen were evolved at the surfaces of gold and platinum wires connected with the terminals of a battery and dipped in water. The volume of the hydrogen was about double that of the oxygen, and, since this is the ratio in which these elements are combined in water, it was concluded that the process consisted essentially in the decomposition of water. They also noticed that a similar kind of chemical action went on in the battery itself. Soon afterwards, William Cruickshank decomposed the magnesium, sodium and ammonium chlorides, and precipitated silver and copper from their solutions—an observation which led to the process of electroplating. He also found that the liquid round the anode became acid, and that round the cathode alkaline. In 1804 W. Hisinger and J. J. Berzelius stated that neutral salt solutions could be decomposed by electricity, the acid appearing at one pole and the metal at the other. This observation showed that nascent hydrogen was not, as had been supposed, the primary cause of the separation of metals from their solutions, but that the action consisted in a direct decomposition into metal and acid. During the earliest investigation of the subject it was thought that, since hydrogen and oxygen were usually evolved, the electrolysis of solutions of acids and alkalis was to be regarded as a direct decomposition of water. In 1806 Sir Humphry Davy proved that the formation of acid and alkali when water was electrolysed was due to saline impurities in the water. He had shown previously that decomposition of water could be effected although the two poles were placed in separate vessels connected by moistened threads. In 1807 he decomposed potash and soda, previously considered to be elements, by passing the current from a powerful battery through the moistened solids, and thus isolated the metals potassium and sodium.

The electromotive force of Volta’s simple cell falls off rapidly when the cell is used, and this phenomenon was shown to be due to the accumulation at the metal plates of the products of chemical changes in the cell itself. This reverse electromotive force of polarization is produced in all electrolytes when the passage of the current changes the nature of the electrodes. In batteries which use acids as the electrolyte, a film of hydrogen tends to be deposited on the copper or platinum electrode; but, to obtain a constant electromotive force, several means were soon devised of preventing the formation of the film. Constant cells may be divided into two groups, according as their action is chemical (as in the bichromate cell, where the hydrogen is converted into water by an oxidizing agent placed in a porous pot round the carbon plate) or electrochemical (as in Daniell’s cell, where a copper plate is surrounded by a solution of copper sulphate, and the hydrogen, instead of being liberated, replaces copper, which is deposited on the plate from the solution).

Faraday’s Laws.—The first exact quantitative study of electrolytic phenomena was made about 1830 by Michael Faraday (Experimental Researches, 1833). When an electric current flows round a circuit, there is no accumulation of electricity anywhere in the circuit, hence the current strength is everywhere the same, and we may picture the current as analogous to the flow of an incompressible fluid. Acting on this view, Faraday set himself to examine the relation between the flow of electricity round the circuit and the amount of chemical decomposition. He passed the current driven by a voltaic battery ZnPt (fig. 1) through two branches containing the two electrolytic cells A and B. The reunited current was then led through another cell C, in which the strength of the current must be the sum of those in the arms A and B. Faraday found that the mass of substance liberated at the electrodes in the cell C was equal to the sum of the masses liberated in the cells A and B. He also found that, for the same current, the amount of chemical action was independent of the size of the electrodes and proportional to the time that the current flowed. Regarding the current as the passage of a certain amount of electricity per second, it will be seen that the results