Experimental Researches in Electricity, Volume 1

by Michael Faraday

¶ iv. On the Resistance of an Electrolyte to Electrolytic Action, and on Interpositions.

1007. I have already illustrated, in the simplest possible form of experiment (891. 910.), the resistance established at the place of decomposition to the force active at the exciting place. I purpose examining the effects of this resistance more generally; but it is rather with reference to their practical interference with the action and phenomena of the voltaic battery, than with any intention at this time to offer a strict and philosophical account of their nature. Their general and principal cause is the resistance of the chemical affinities to be overcome; but there are numerous other circumstances which have a joint influence with these forces (1034. 1040. &c.), each of which would require a minute examination before a correct account of the whole could be given.

1008. As it will be convenient to describe the experiments in a form different to that in which they were made, both forms shall first be explained. Plates of platina, copper, zinc, and other metals, about three quarters of an inch wide and three inches long, were associated together in pairs by means of platina wires to which they were soldered, fig. 88, the plates of one pair being either alike or different, as might be required. These were arranged in glasses, fig. 89, so as to form Volta's crown of cups. The acid or fluid in the cups never covered the whole of any plate; and occasionally small glass rods were put into the cups, between the plates, to prevent their contact. Single plates were used to terminate the series and complete the connexion with a galvanometer, or with a decomposing apparatus (899. 968. &c.), or both. Now if fig. 90 be examined and compared with fig. 91, the latter may be admitted as representing the former in its simplest condition; for the cups i, ii, and iii of the former, with their contents, are represented by the cells i, ii, and iii of the latter, and the metal plates Z and P of the former by the similar plates represented Z and P in the latter. The only difference, in fact, between the apparatus, fig. 90, and the trough represented fig. 91, is that twice the quantity of surface of contact between the metal and acid is allowed in the first to what would occur in the second.

1009. When the extreme plates of the arrangement just described, fig. 90, are connected metallically through the galvanometer g, then the whole represents a battery consisting of two pairs of zinc and platina plates urging a current forward, which has, however, to decompose water unassisted by any direct chemical affinity before it can be transmitted across the cell iii, and therefore before it can circulate. This decomposition of water, which is opposed to the passage of the current, may, as a matter of convenience, be considered as taking place either against the surfaces of the two platina plates which constitute the electrodes in the cell in, or against the two surfaces of that platina plate which separates the cells ii and iii, fig. 91, from each other. It is evident that if that plate were away, the battery would consist of two pairs of plates and two cells, arranged in the most favourable position for the production of a current. The platina plate therefore, which being introduced as at x, has oxygen evolved at one surface and hydrogen at the other (that is, if the decomposing current passes), may be considered as the cause of any obstruction arising from the decomposition of water by the electrolytic action of the current; and I have usually called it the interposed plate.

1010. In order to simplify the conditions, dilute sulphuric acid was first used in all the cells, and platina for the interposed plates; for then the initial intensity of the current which tends to be formed is constant, being due to the power which zinc has of decomposing water; and the opposing force of decomposition is also constant, the elements of the water being unassisted in their separation at the interposed plates by any affinity or secondary action at the electrodes (744.), arising either from the nature of the plate itself or the surrounding fluid.

1011. When only one voltaic pair of zinc and platina plates was used, the current of electricity was entirely stopped to all practical purposes by interposing one platina plate, fig. 92, i.e. by requiring of the current that it should decompose water, and evolve both its elements, before it should pass. This consequence is in perfect accordance with the views before given (910. 917. 973.). For as the whole result depends upon the opposition of forces at the places of electric excitement and electro-decomposition, and as water is the substance to be decomposed at both before the current can move, it is not to be expected that the zinc should have such powerful attraction for the oxygen, as not only to be able to take it from its associated hydrogen, but leave such a surplus of force as, passing to the second place of decomposition, should be there able to effect a second separation of the elements of water. Such an effect would require that the force of attraction between zinc and oxygen should under the circumstances be at least twice as great as the force of attraction between the oxygen and hydrogen.

1012. When two pairs of zinc and platina exciting plates were used, the current was also practically stopped by one interposed platina plate, fig. 93. There was a very feeble effect of a current at first, but it ceased almost immediately. It will be referred to, with many other similar effects, hereafter (1017.).

1013. Three pairs of zinc and platina plates, fig. 94, were able to produce a current which could pass an interposed platina plate, and effect the electrolyzation of water in cell iv. The current was evident, both by the continued deflection of the galvanometer, and the production of bubbles of oxygen and hydrogen at the electrodes in cell iv. Hence the accumulated surplus force of three plates of zinc, which are active in decomposing water, is more than equal, when added together, to the force with which oxygen and hydrogen are combined in water, and is sufficient to cause the separation of these elements from each other.

1014. The three pairs of zinc and platina plates were now opposed by two intervening platina plates, fig. 95. In this case the current was stopped.

1015. Four pairs of zinc and platina plates were also neutralized by two interposed platina plates, fig. 96.