Chapter 13

413. In almost all the instances, as yet observed, which are governed by this law, the substances experimented with have been those which were not only compound bodies, but such as contain elements known to arrange themselves at the opposite poles; and were also such as could be _decomposed_ by the electrical current. When conduction took place, decomposition occurred; when decomposition ceased, conduction ceased also; and it becomes a fair and an important question, Whether the conduction itself may not, wherever the law holds good, be a consequence not merely of the capability, but of the act of decomposition? And that question may be accompanied by another, namely, Whether solidification does not prevent conduction, merely by chaining the particles to their places, under the influence of aggregation, and preventing their final separation in the manner necessary for decomposition?

414. But, on the other hand, there is one substance (and others may occur), the _per-iodide of mercury_, which, being experimented with like the others (400.), was found to insulate when solid, and to acquire conducting power when fluid; yet it did not seem to undergo decomposition in the latter case.

415. Again, there are many substances which contain elements such as would be expected to arrange themselves at the opposite poles of the pile, and therefore in that respect fitted for decomposition, which yet do not conduct. Amongst these are the iodide of sulphur, per-iodide of zinc, per-chloride of tin, chloride of arsenic, hydrated chloride of arsenic, acetic acid, orpiment, realgar, artificial camphor, &c.; and from these it might perhaps be assumed that decomposition is dependent upon conducting power, and not the latter upon the former. The true relation, however, of conduction and decomposition in those bodies governed by the general law which it is the object of this paper to establish, can only be satisfactorily made out from a far more extensive series of observations than those I have yet been able to supply[A].

[A] See 673, &c. &c.--_Dec. 1838._

416. The relation, under this law, of the conducting power for electricity to that for heat, is very remarkable, and seems to imply a natural dependence of the two. As the solid becomes a fluid, it loses almost entirely the power of conduction for heat, but gains in a high degree that for electricity; but as it reverts hack to the solid state, it gains the power of conducting heat, and loses that of conducting electricity. If, therefore, the properties are not incompatible, still they are most strongly contrasted, one being lost as the other is gained. We may hope, perhaps, hereafter to understand the physical reason of this very extraordinary relation of the two conducting powers, both of which appear to be directly connected with the corpuscular condition of the substances concerned.

417. The assumption of conducting power and a decomposable condition by liquefaction, promises new opportunities of, and great facilities in, voltaic decomposition. Thus, such bodies as the oxides, chlorides, cyanides, sulpho-cyanides, fluorides, certain vitreous mixtures, &c. &c., may be submitted to the action of the voltaic battery under new circumstances; and indeed I have already been able, with ten pairs of plates, to decompose common salt, chloride of magnesium, borax, &c. &c., and to obtain sodium, magnesium, boron, &c., in their separate states.

§ 10. _On Conducting Power generally._[A]

[A] In reference to this § refer to 983 in series viii., and the results connected with it.--_Dec. 1838._

418. It is not my intention here to enter into an examination of all the circumstances connected with conducting power, but to record certain facts and observations which have arisen during recent inquiries, as additions to the general stock of knowledge relating to this point of electrical science.

419. I was anxious, in the first place, to obtain some idea of the conducting power of ice and solid salts for electricity of high tension (392.), that a comparison might be made between it and the large accession of the same power gained upon liquefaction. For this purpose the large electrical machine (290.) was brought into excellent action, its conductor connected with a delicate gold-leaf electrometer, and also with the platina inclosed in the ice (383.), whilst the tin case was connected with the discharging train (292.). On working the machine moderately, the gold leaves barely separated; on working it rapidly, they could be opened nearly two inches. In this instance the tin case was five-eighths of an inch in width; and as, after the experiment, the platina plate was found very nearly in the middle of the ice, the average thickness of the latter had been five-sixteenths of an inch, and the extent of surface of contact with tin and platina fourteen square inches (384.). Yet, under these circumstances, it was but just able to conduct the small quantity of electricity which this machine could evolve (371.), even when of a tension competent to open the leaves two inches; no wonder, therefore, that it could not conduct any sensible portion of the electricity of the troughs (384.), which, though almost infinitely surpassing that of the machine in quantity, had a tension so low as not to be sensible to an electrometer.

420. In another experiment, the tin case was only four-eighths of an inch in width, and it was found afterwards that the platina had been not quite one-eighth of an inch distant in the ice from one side of the tin vessel. When this was introduced into the course of the electricity from the machine (419.), the gold leaves could be opened, but not more than half an inch; the thinness of the ice favouring the conduction of the electricity, and permitting the same quantity to pass in the same time, though of a much lower tension.

421. Iodide of potassium which had been fused and cooled was introduced into the course of the electricity from the machine. There were two pieces, each about a quarter of an inch in thickness, and exposing a surface on each side equal to about half a square inch; these were placed upon platina plates, one connected with the machine and electrometer (419.), and the other with the discharging train, whilst a fine platina wire connected the two pieces, resting upon them by its two points. On working the electrical machine, it was possible to open the electrometer leaves about two-thirds of an inch.

422. As the platina wire touched only by points, the facts show that this salt is a far better conductor than ice; but as the leaves of the electrometer opened, it is also evident with what difficulty conduction, even of the small portion of electricity produced by the machine, is effected by this body in the solid state, when compared to the facility with which enormous quantities at very low tensions are transmitted by it when in the fluid state.

423. In order to confirm these results by others, obtained from the voltaic apparatus, a battery of one hundred and fifty plates, four inches square, was well-charged: its action was good; the shock from it strong; the discharge would _continue_ from copper to copper through four-tenths of an inch of air, and the gold-leaf electrometer before used could be opened nearly a quarter of an inch.

424. The ice vessel employed (420.) was half an inch in width; as the extent of contact of the ice with the tin and platina was nearly fourteen square inches, the whole was equivalent to a plate of ice having a surface of seven square inches, of perfect contact at each side, and only one fourth of an inch thick. It was retained in a freezing mixture during the experiment.

425. The order of arrangement in the course of the electric current was as follows. The positive pole of the battery was connected by a wire with the platina plate in the ice; the plate was in contact with the ice, the ice with the tin jacket, the jacket with a wire, which communicated with a piece of tin foil, on which rested one end of a bent platina wire (312.), the other or decomposing end being supported on paper moistened with solution of iodide of potassium (316.): the paper was laid flat on a platina spatula connected with the negative end of the battery. All that part of the arrangement between the ice vessel and the decomposing wire point, including both these, was insulated, so that no electricity might pass through the latter which had not traversed the former also.

426. Under these circumstances, it was found that, a pale brown spot of iodine was slowly formed under the decomposing platina point, thus indicating that ice could conduct a little of the electricity evolved by a voltaic battery charged up to the degree of intensity indicated by the electrometer. But it is quite evident that notwithstanding the enormous quantity of electricity which the battery could furnish, it was, under present circumstances, a very inferior instrument to the ordinary machine; for the latter could send as much through the ice as it could carry, being of a far higher intensity, i.e. able to open the electrometer leaves half an inch or more (419. 420.).

427. The decomposing wire and solution of iodide of potassium were then removed, and replaced by a very delicate galvanometer (205.); it was so nearly astatic, that it vibrated to and fro in about sixty-three beats of a watch giving one hundred and fifty beats in a minute. The same feebleness of current as before was still indicated; the galvanometer needle was deflected, but it required to break and make contact three or four times (297.), before the effect was decided.

428. The galvanometer being removed, two platina plates were connected with the extremities of the wires, and the tongue placed between them, so that the whole charge of the battery, so far as the ice would let it pass, was free to go through the tongue. Whilst standing on the stone floor, there was shock, &c., but when insulated, I could feel no sensation. I think a frog would have been scarcely, if at all, affected.

429. The ice was now removed, and experiments made with other solid bodies, for which purpose they were placed under the end of the decomposing wire instead of the solution of iodide of potassium (125.). For instance, a piece of dry iodide of potassium was placed on the spatula connected with the negative pole of the battery, and the point of the decomposing wire placed upon it, whilst the positive end of the battery communicated with the latter. A brown spot of iodine very slowly appeared, indicating the passage of a little electricity, and agreeing in that respect with the results obtained by the use of the electrical machine (421.). When the galvanometer was introduced into the circuit at the same time with the iodide, it was with difficulty that the action of the current on it could be rendered sensible.

430. A piece of common salt previously fused and solidified being introduced into the circuit was sufficient almost entirely to destroy the action on the galvanometer. Fused and cooled chloride of lead produced the same effect. The conducting power of these bodies, _when fluid_, is very great (395. 402.).

431. These effects, produced by using the common machine and the voltaic battery, agree therefore with each other, and with the law laid down in this paper (394.); and also with the opinion I have supported, in the Third Series of these Researches, of the identity of electricity derived from different sources (360.).

432. The effect of heat in increasing the conducting power of many substances, especially for electricity of high tension, is well known. I have lately met with an extraordinary case of this kind, for electricity of low tension, or that of the voltaic pile, and which is in direct contrast with the influence of heat upon metallic bodies, as observed and described by Sir Humphry Davy[A].

[A] Philosophical Transactions, 1821, p. 131.

433. The substance presenting this effect is sulphuret of silver. It was made by fusing a mixture of precipitated silver and sublimed sulphur, removing the film of silver by a file from the exterior of the fused mass, pulverizing the sulphuret, mingling it with more sulphur, and fusing it again in a green glass tube, so that no air should obtain access during the process. The surface of the sulphuret being again removed by a file or knife, it was considered quite free from uncombined silver.

434. When a piece of this sulphuret, half an inch in thickness, was put between surfaces of platina, terminating the poles of a voltaic battery of twenty pairs of four-inch plates, a galvanometer being also included in the circuit, the needle was slightly deflected, indicating a feeble conducting power. On pressing the platina poles and sulphuret together with the fingers, the conducting power increased as the whole became warm. On applying a lamp under the sulphuret between the poles, the conducting power rose rapidly with the heat, and at last-the galvanometer needle jumped into a fixed position, and the sulphuret was found conducting in the manner of a metal. On removing the lamp and allowing the heat to fall, the effects were reversed, the needle at first began to vibrate a little, then gradually left its transverse direction, and at last returned to a position very nearly that which it would take when no current was passing through the galvanometer.

435. Occasionally, when the contact of the sulphuret with the platina poles was good, the battery freshly charged, and the commencing temperature not too low, the mere current of electricity from the battery was sufficient to raise the temperature of the sulphuret; and then, without any application of extraneous heat, it went on increasing conjointly in temperature and conducting power, until the cooling influence of the air limited the effects. In such cases it was generally necessary to cool the whole purposely, to show the returning series of phenomena.

436. Occasionally, also, the effects would sink of themselves, and could not be renewed until a fresh surface of the sulphuret had been applied to the positive pole. This was in consequence of peculiar results of decomposition, to which I shall have occasion to revert in the section on Electro-chemical Decomposition, and was conveniently avoided by inserting the ends of two pieces of platina wire into the opposite extremities of a portion of sulphuret fused in a glass tube, and placing this arrangement between the poles of the battery.

437. The hot sulphuret of silver conducts sufficiently well to give a bright spark with charcoal, &c. &c., in the manner of a metal.

438. The native grey sulphuret of silver, and the ruby silver ore, both presented the same phenomena. The native malleable sulphuret of silver presented precisely the same appearances as the artificial sulphuret.

439. There is no other body with which I am acquainted, that, like sulphuret of silver, can compare with metals in conducting power for electricity of low tension when hot, but which, unlike them, during cooling, loses in power, whilst they, on the contrary, gain. Probably, however, many others may, when sought for, be found[A].

[A] See now on this subject, 1340, 1341.--_Dec. 1838._

440. The proto-sulphuret of iron, the native per-sulphuret of iron, arsenical sulphuret of iron, native yellow sulphuret of copper and iron, grey artificial sulphuret of copper, artificial sulphuret of bismuth, and artificial grey sulphuret of tin, all conduct the voltaic battery current when cold, more or less, some giving sparks like the metals, others not being sufficient for that high effect. They did not seem to conduct better when heated, than before; but I had not time to enter accurately into the investigation of this point. Almost all of them became much heated by the transmission of the current, and present some very interesting phenomena in that respect. The sulphuret of antimony does not conduct the same current sensibly either hot or cold, but is amongst those bodies acquiring conducting power when fused (402.). The sulphuret of silver and perhaps some others decompose whilst in the solid state; but the phenomena of this decomposition will be reserved for its proper place in the next series of these Researches.

441. Notwithstanding the extreme dissimilarity between sulphuret of silver and gases or vapours, I cannot help suspecting the action of heat upon them to be the same, bringing them all into the same class as conductors of electricity, although with those great differences in degree, which are found to exist under common circumstances. When gases are heated, they increase in conducting power, both for common and voltaic electricity (271.); and it is probable that if we could compress and condense them at the same time, we should still further increase their conducting power. Cagniard de la Tour has shown that a substance, for instance water, may be so expanded by heat whilst in the liquid state, or condensed whilst in the vaporous state, that the two states shall coincide at one point, and the transition from one to the other be so gradual that no line of demarcation can be pointed out[A]; that, in fact, the two states shall become one;--which one state presents us at different times with differences in degree as to certain properties and relations; and which differences are, under ordinary circumstances, so great as to be equivalent to two different states.

[A] Annales de Chimie, xxi. pp. 127, 178.

442. I cannot but suppose at present that at that point where the liquid and the gaseous state coincide, the conducting properties are the same for both; but that they diminish as the expansion of the matter into a rarer form takes place by the removal of the necessary pressure; still, however, retaining, as might be expected, the capability of having what feeble conducting power remains, increased by the action of heat.

443. I venture to give the following summary of the conditions of electric conduction in bodies, not however without fearing that I may have omitted some important points[A].

[A] See now in relation to this subject, 1320--1242.--_Dec. 1838._

444. All bodies conduct electricity in the same manner from metals to lac and gases, but in very different degrees.

445. Conducting power is in some bodies powerfully increased by heat, and in others diminished, yet without our perceiving any accompanying essential electrical difference, either in the bodies or in the changes occasioned by the electricity conducted.

446. A numerous class of bodies, insulating electricity of low intensity, when solid, conduct it very freely when fluid, and are then decomposed by it.

447. But there are many fluid bodies which do not sensibly conduct electricity of this low intensity; there are some which conduct it and are not decomposed; nor is fluidity essential to decomposition[A].

[A] See the next series of these Experimental Researches.

448. There is but one body yet discovered[A] which, insulating a voltaic current when solid, and conducting it when fluid, is not decomposed in the latter case (414.).

[A] It is just possible that this case may, by more delicate experiment, hereafter disappear. (See now, 1340, 1341, in relation to this note.--_Dec. 1838._)

449. There is no strict electrical distinction of conduction which can, as yet, be drawn between bodies supposed to be elementary, and those known to be compounds.

_Royal Institution, April 15, 1833_.

FIFTH SERIES.

§ 11. _On Electro-chemical Decomposition._ ¶ i. _New conditions of Electro-chemical Decomposition._ ¶ ii. _Influence of Water in Electro-chemical Decomposition._ ¶ iii. _Theory of Electro-chemical Decomposition._

Received June 18,--Read June 20, 1833.

§ 11. _On Electro-chemical Decomposition._[A]

[A] Refer to the note after 1047, Series viii.--_Dec. 1838._

450. I have in a recent series of these Researches (265.) proved (to my own satisfaction, at least,) the identity of electricities derived from different sources, and have especially dwelt upon the proofs of the sameness of those obtained by the use of the common electrical machine and the voltaic battery.

451. The great distinction of the electricities obtained from these two sources is the very high tension to which the small quantity obtained by aid of the machine may be raised, and the enormous quantity (371. 376.) in which that of comparatively low tension, supplied by the voltaic battery, may be procured; but as their actions, whether magnetical, chemical, or of any other nature, are essentially the same (360.), it appeared evident that we might reason from the former as to the manner of action of the latter; and it was, to me, a probable consequence, that the use of electricity of such intensity as that afforded by the machine, would, when applied to effect and elucidate electro-chemical decomposition, show some new conditions of that action, evolve new views of the internal arrangements and changes of the substances under decomposition, and perhaps give efficient powers over matter as yet undecomposed.

452. For the purpose of rendering the bearings of the different parts of this series of researches more distinct, I shall divide it into several heads.

¶ i. _New conditions of Electro-chemical Decomposition._

453. The tension of machine electricity causes it, however small in quantity, to pass through any length of water, solutions, or other substances classing with these as conductors, as fast as it can be produced, and therefore, in relation to quantity, as fast as it could have passed through much shorter portions of the same conducting substance. With the voltaic battery the case is very different, and the passing current of electricity supplied by it suffers serious diminution in any substance, by considerable extension of its length, but especially in such bodies as those mentioned above.

454. I endeavoured to apply this facility of transmitting the current of electricity through any length of a conductor, to an investigation of the transfer of the elements in a decomposing body, in contrary directions, towards the poles. The general form of apparatus used in these experiments has been already described (312. 316); and also a particular experiment (319.), in which, when a piece of litmus paper and a piece of turmeric paper were combined and moistened in solution of sulphate of soda, the point of the wire from the machine (representing the positive pole) put upon the litmus paper, and the receiving point from the discharging train (292. 316.), representing the negative pole, upon the turmeric paper, a very few turns of the machine sufficed to show the evolution of acid at the former, and alkali at the latter, exactly in the manner effected by a volta-electric current.

455. The pieces of litmus and turmeric paper were _now_ placed each upon a separate plate of glass, and connected by an insulated string four feet long, moistened in the same solution of sulphate of soda: the terminal decomposing wire points were placed upon the papers as before. On working the machine, the same evolution of acid and alkali appeared as in the former instance, and with equal readiness, notwithstanding that the places of their appearance were four feet apart from each other. Finally, a piece of string, seventy feet long, was used. It was insulated in the air by suspenders of silk, so that the electricity passed through its entire length: decomposition took place exactly as in former cases, alkali and acid appearing at the two extremities in their proper places.