Reichsanstalt is given in the Report of the British Association Committee on Electrical Standards, presented at the Edinburgh Meeting in 1892. For the design and construction of standards of electric resistances adapted for employment in the comparison and measurement of very low or very high resistances, the reader may be referred to standard treatises on electric measurements.
Bibliography.—See also J. A. Fleming, A Handbook for the Electrical Laboratory and Testing Room, vol. i. (London, 1901); Reports of the British Association Committee on Electrical Standards, edited by Fleeming Jenkin (London, 1873); A. Matthiessen and C. Vogt, “On the Influence of Temperature on the Conducting Power of Alloys,” Phil. Trans., 1864, 154, p. 167, and Phil. Mag., 1865, 29, p. 363; A. Matthiessen and M. Holtzmann, “On the Effect of the Presence of Metals and Metalloids upon the Electric Conducting Power of Pure Copper,” Phil. Trans., 1860, 150, p. 85; T. C. Fitzpatrick, “On the Specific Resistance of Copper,” Brit. Assoc. Report, 1890, p. 120, or Electrician, 1890, 25, p. 608; R. Appleyard, The Conductometer and Electrical Conductivity; Clark, Forde and Taylor, Temperature Coefficients of Copper (London, 1901). (J. A. F.)
Through liquid metals, such as mercury at ordinary temperatures and other metals at temperatures above their melting points, the electric current flows as in solid metals without changing the state of the conductor, except in so far as heat is developed by the electric resistance. But another class of liquid conductors exists, and in them the phenomena are quite different. The conductivity of fused salts, and of solutions of salts and acids, although less than that of metals, is very great compared with the traces of conductivity found in so-called non-conductors. In fused salts and conducting solutions the passage of the current is always accompanied by definite chemical changes; the substance of the conductor or electrolyte is decomposed, and the products of the decomposition appear at the electrodes, i.e. the metallic plates by means of which the current is led into and out of the solution. The chemical phenomena are considered in the article Electrolysis; we are here concerned solely with the mechanism of this electrolytic conduction of the current.
To explain the appearance of the products of decomposition at the electrodes only, while the intervening solution is unaltered, we suppose that, under the action of the electric forces, the opposite parts of the electrolyte move in opposite directions through the liquid. These opposite parts, named ions by Faraday, must therefore be associated with electric charges, and it is the convective movement of the opposite streams of ions carrying their charges with them that, on this view, constitutes the electric current.
In metallic conduction it is found that the current is proportional to the applied electromotive force—a relation known by the name of Ohm’s law. If we place in a circuit with a small electromotive force an electrolytic cell consisting of two platinum electrodes and a solution, the initial current soon dies away, and we shall find that a certain minimum electromotive force must be applied to the circuit before any considerable permanent current passes. The chemical changes which are initiated on the surfaces of the electrodes set up a reverse electromotive force of polarization, and, until this is overcome, only a minute current, probably due to the slow but steady removal of the products of decomposition from the electrodes by a process of diffusion, will pass through the cell. Thus it is evident that, considering the electrolytic cell as a whole, the passage of the current through it cannot conform to Ohm’s law. But the polarization is due to chemical changes, which are confined to the surfaces of the electrodes; and it is necessary to inquire whether, if the polarization at the electrodes be eliminated, the passage of the current through the bulk of the solution itself is proportional to the electromotive force actually applied to that solution. Rough experiment shows that the current is proportional to the excess of the electromotive force over a constant value, and thus verifies the law approximately, the constant electromotive force to be overcome being a measure of the polarization. A more satisfactory examination of the question was made by F. Kohlrausch in the years 1873 to 1876. Ohm’s law states that the current C is proportional to the electromotive force E, or C = kR, where k is a constant called the conductivity of the circuit. The equation may also be written as C = E/R, where R is a constant, the reciprocal of k, known as the resistance of the circuit. The essence of the law is the proportionality between C and E, which means that the ratio E/C is a constant. But E/C = R, and thus the law may be tested by examining the constancy of the measured resistance of a conductor when different currents are passing through it. In this way Ohm’s law has been confirmed in the case of metallic conduction to a very high degree of accuracy. A similar principle was applied by Kohlrausch to the case of electrolytes, and he was the first to show that an electrolyte possesses a definite resistance which has a constant value when measured with different currents and by different experimental methods.
Measurement of the Resistance of Electrolytes.—There are two effects of the passage of an electric current which prevent the possibility of measuring electrolytic resistance by the ordinary methods with the direct currents which are used in the case of metals. The products of the chemical decomposition of the electrolyte appear at the electrodes and set up the opposing electromotive force of polarization, and unequal dilution of the solution may occur in the neighbourhood of the two electrodes. The chemical and electrolytic aspects of these phenomena are treated in the article Electrolysis, but from our present point of view also it is evident that they are again of fundamental importance. The polarization at the surface of the electrodes will set up an opposing electromotive force, and the unequal dilution of the solution will turn the electrolyte into a concentration cell and produce a subsidiary electromotive force either in the same direction as that applied or in the reverse according as the anode or the cathode solution becomes the more dilute. Both effects thus involve internal electromotive forces, and prevent the application of Ohm’s law to the electrolytic cell as a whole. But the existence of a definite measurable resistance as a characteristic property of the system depends on the conformity of the system to Ohm’s law, and it is therefore necessary to eliminate both these effects before attempting to measure the resistance.
The usual and most satisfactory method of measuring the resistance of electrolytes consists in eliminating the effects of polarization by the use of alternating currents, that is, currents that are reversed in direction many times a second. The chemical action produced by the first current is thus reversed by the second current in the opposite direction, and the polarization caused by the first current on the surface of the electrodes is destroyed before it rises to an appreciable value. The polarization is also diminished in another way. The electromotive force of polarization is due to the deposition of films of the products of chemical decomposition on the surface of the electrodes, and only reaches its full value when a continuous film is formed. If the current be stopped before such a film is completed, the reverse electromotive force is less than its full value. A given current flowing for a given time deposits a definite amount of substance on the electrodes, and therefore the amount per unit area is inversely proportional to the area of the electrodes—to the area of contact, that is, between the electrode and the liquid. Thus, by increasing the area of the electrodes, the polarization due to a given current is decreased. Now the area of free surface of a platinum plate can be increased enormously by coating the plate with platinum black, which is metallic platinum in a spongy state, and with such a plate as electrode the effects of polarization are diminished to a very marked extent. The coating is effected by passing an electric current first one way and then the other between two platinum plates immersed in a 3% solution of platinum chloride to which a trace of lead acetate is sometimes added. The platinized plates thus obtained are quite satisfactory for the investigation of strong solutions. They have the power, however, of absorbing a certain amount of salt from the solutions and of giving it up again when water or more dilute solution is placed in contact with them. The measurement of very dilute solutions is thus made difficult, but, if the plates be heated to
- F. Kohlrausch and L. Holborn, Das Leitvermögen der Elektrolyte (Leipzig, 1898).