Part 65

Ibid. 1821, p. 431.

1340. I formerly described a substance, sulphuret of silver, whose conducting power was increased by heat (433. 437. 438.); and I have since then met with another as strongly affected in the same way: this is fluoride of lead. When a piece of that substance, which had been fused and cooled, was introduced into the circuit of a voltaic battery, it stopped the current. Being heated, it acquired conducting powers before it was visibly red-hot in daylight; and even sparks could be taken against it whilst still solid. The current alone then raised its temperature (as in the case of sulphuret of silver) until it fused, after which it seemed to conduct as well as the metallic vessel containing it; for whether the wire used to complete the circuit touched the fused fluoride only, or was in contact with the platina on which it was supported, no sensible difference in the force of the current was observed. During all the time there was scarcely a trace of decomposing action of the fluoride, and what did occur, seemed referable to the air and moisture of the atmosphere, and not to electrolytic action.

1341. I have now very little doubt that periodide of mercury (414. 448. 691.) is a case of the same kind, and also corrosive sublimate (692.). I am also inclined to think, since making the above experiments, that the anomalous action of the protoxide of antimony, formerly observed and described (693. 801.), may be referred in part to the same cause.

1342. I have no intention at present of going into the particular relation of heat and electricity, but we may hope hereafter to discover by experiment the law which probably holds together all the above effects with those of the evolution and the disappearance of heat by the current, and the striking and beautiful results of thermo-electricity, in one common bond.

¶ viii. Electrolytic discharge.

1343. I have already expressed in a former paper (1164.), the view by which I hope to associate ordinary induction and electrolyzation. Under that view, the discharge of electric forces by electrolyzation is rather an effect superadded, in a certain class of bodies, to those already described as constituting induction and insulation, than one independent of and distinct from these phenomena.

1344. Electrolytes, as respects their insulating and conducting forces, belong to the general category of bodies (1320. 1334.); and if they are in the solid state (as nearly all can assume that state), they retain their place, presenting then no new phenomenon (426. &c.); or if one occur, being in so small a proportion as to be almost unimportant. When liquefied, they also belong to the same list whilst the electric intensity is below a certain degree; but at a given intensity (910. 912. 1007.), fixed for each, and very low in all known cases, they play a new part, causing discharge in proportion (783.) to the development of certain chemical effects of combination and decomposition; and at this point, move out from the general class of insulators and conductors, to form a distinct one by themselves. The former phenomena have been considered (1320. 1338.); it is the latter which have now to be revised, and used as a test of the proposed theory of induction.

1345. The theory assumes, that the particles of the dielectric (now an electrolyte) are in the first instance brought, by ordinary inductive action, into a polarized state, and raised to a certain degree of tension or intensity before discharge commences; the inductive state being, in fact, a necessary preliminary to discharge. By taking advantage of those circumstances which bear upon the point, it is not difficult to increase the tension indicative of this state of induction, and so make the state itself more evident. Thus, if distilled water be employed, and a long narrow portion of it placed between the electrodes of a powerful voltaic battery, we have at once indications of the intensity which can be sustained at these electrodes by the inductive action through the water as a dielectric, for sparks may be obtained, gold leaves diverged, and Leyden bottles charged at their wires. The water is in the condition of the spermaceti (1322. 1323.) a bad conductor and a bad insulator; but what it does insulate is by virtue of inductive action, and that induction is the preparation for and precursor of discharge (1338.).

1346. The induction and tension which appear at the limits of the portion of water in the direction of the current, are only the sums of the induction and tension of the contiguous particles between those limits; and the limitation of the inductive tension, to a certain degree shows (time entering in each case as an important element of the result), that when the particles have acquired a certain relative state, discharge, or a transfer of forces equivalent to ordinary conduction, takes place.

1347. In the inductive condition assumed by water before discharge comes on, the particles polarized are the particles of the water that being the dielectric used; but the discharge between particle and particle is not, as before, a mere interchange of their powers or forces at the polar parts, but an actual separation of them into their two elementary particles, the oxygen travelling in one direction, and carrying with it its amount of the force it had acquired during the polarization, and the hydrogen doing the same thing in the other direction, until they each meet the next approaching particle, which is in the same electrical state with that they have left, and by association of their forces with it, produce what constitutes discharge. This part of the action may be regarded as a carrying one (1319. 1572. 1622.), performed by the constituent particles of the dielectric. The latter is always a compound body (664. 823.); and by those who have considered the subject and are acquainted with the philosophical view of transfer which was first put forth by Grotthuss, its particles may easily be compared to a series of metallic conductors under inductive action, which, whilst in that state, are divisible into these elementary moveable halves.

See 1699-1708.--Dec. 1838

Annales de Chimie, lviii. 60. and lxiii, 20.

1348. Electrolytic discharge depends, of necessity, upon the non-conduction of the dielectric as a whole, and there are two steps or acts in the process: first a polarization of the molecules of the substance and then a lowering of the forces by the separation, advance in opposite directions, and recombination of the elements of the molecules, these being, as it were, the halves of the originally polarized conductors or particles.

1349. These views of the decomposition of electrolytes and the consequent effect of discharge, which, as to the particular case, are the same with those of Grotthuss (481.) and Davy (482.), though they differ from those of Biot (487.), De la Rive (490.), and others, seem to me to be fully in accordance not merely with the theory I have given of induction generally (1165.), but with all the known facts of common induction, conduction, and electrolytic discharge; and in that respect help to confirm in my mind the truth of the theory set forth. The new mode of discharge which electrolyzation presents must surely be an evidence of the action of contiguous particles; and as this appears to depend directly upon a previous inductive state, which is the same with common induction, it greatly strengthens the argument which refers induction in all cases to an action of contiguous particles also (1295, &c.).

1350. As an illustration of the condition of the polarized particles in a dielectric under induction, I may describe an experiment. Put into a glass vessel some clear rectified oil of turpentine, and introduce two wires passing through glass tubes where they coincide with the surface of the fluid, and terminating either in balls or points. Cut some very clean dry white silk into small particles, and put these also into the liquid: then electrify one of the wires by an ordinary machine and discharge by the other. The silk will immediately gather from all parts of the liquid, and form a band of particles reaching from wire to wire, and if touched by a glass rod will show considerable tenacity; yet the moment the supply of electricity ceases, the band will fall away and disappear by the dispersion of its parts. The conduction by the silk is in this case very small; and after the best examination I could give to the effects, the impression on my mind is, that the adhesion of the whole is due to the polarity which each filament acquires, exactly as the particles of iron between the poles of a horse-shoe magnet are held together in one mass by a similar disposition of forces. The particles of silk therefore represent to me the condition of the molecules of the dielectric itself, which I assume to be polar, just as that of the silk is. In all cases of conductive discharge the contiguous polarized particles of the body are able to effect a neutralization of their forces with greater or less facility, as the silk does also in a very slight degree. Further we are not able to carry the parallel, except in imagination; but if we could divide each particle of silk into two halves, and let each half travel until it met and united with the next half in an opposite state, it would then exert its carrying power (1347.), and so far represent electrolytic discharge.

1351. Admitting that electrolytic discharge is a consequence of previous induction, then how evidently do its numerous cases point to induction in curved lines (521. 1216.), and to the divergence or lateral action of the lines of inductive force (1231.), and so strengthen that part of the general argument in the former paper! If two balls of platina, forming the electrodes of a voltaic battery, are put into a large vessel of dilute sulphuric acid, the whole of the surfaces are covered with the respective gases in beautifully regulated proportions, and the mind has no difficulty in conceiving the direction of the curved lines of discharge, and even the intensity of force of the different lines, by the quantity of gas evolved upon the different parts of the surface. From this condition of the lines of inductive force arise the general effects of diffusion; the appearance of the anions or cathions round the edges and on the further side of the electrodes when in the form of plates; and the manner in which the current or discharge will follow all the forms of the electrolyte, however contorted. Hence, also, the effects which Nobili has so well examined and described in his papers on the distribution of currents in conducting masses. All these effects indicate the curved direction of the currents or discharges which occur in and through the dielectrics, and these are in every case preceded by equivalent inductive actions of the contiguous particles.

Bibliothèque Universelle, 1835, lix. 263. 416.

1352. Hence also the advantage, when the exciting forces are weak or require assistance, of enlarging the mass of the electrolyte; of increasing the size of the electrodes; of making the coppers surround the zincs:--all is in harmony with the view of induction which I am endeavouring to examine; I do not perceive as yet one fact against it.

1353. There are many points of electrolytic discharge which ultimately will require to be very closely considered, though I can but slightly touch upon them. It is not that, as far as I have investigated them, they present any contradiction to the view taken (for I have carefully, though unsuccessfully, sought for such cases), but simply want of time as yet to pursue the inquiry, which prevents me from entering upon them here.

1354. One point is, that different electrolytes or dielectrics require different initial intensities for their decomposition (912.). This may depend upon the degree of polarization which the particles require before electrolytic discharge commences. It is in direct relation to the chemical affinity of the substances concerned; and will probably be found to have a relation or analogy to the specific inductive capacity of different bodies (1252. 1296.). It thus promises to assist in causing the great truths of those extensive sciences, which are occupied in considering the forces of the particles of matter, to fall into much closer order and arrangement than they have heretofore presented.

1355. Another point is the facilitation of electrolytic conducting power or discharge by the addition of substances to the dielectric employed. This effect is strikingly shown where water is the body whose qualities are improved, but, as yet, no general law governing all the phenomena has been detected. Thus some acids, as the sulphuric, phosphoric, oxalic, and nitric, increase the power of water enormously; whilst others, as the tartaric and citric acids, give but little power; and others, again, as the acetic and boracic acids, do not produce a change sensible to the voltameter (739.). Ammonia produces no effect, but its carbonate does. The caustic alkalies and their carbonates produce a fair effect. Sulphate of soda, nitre (753.), and many soluble salts produce much effect. Percyanide of mercury and corrosive sublimate produce no effect; nor does iodine, gum, or sugar, the test being a voltameter. In many cases the added substance is acted on either directly or indirectly, and then the phenomena are more complicated; such substances are muriatic acid (758.), the soluble protochlorides (766.), and iodides (769.), nitric acid (752.), &c. In other cases the substance added is not, when alone, subject to or a conductor of the powers of the voltaic battery, and yet both gives and receives power when associated with water. M. de la Rive has pointed this result out in sulphurous acid, iodine and bromine; the chloride of arsenic produces the same effect. A far more striking case, however, is presented by that very influential body sulphuric acid (681.): and probably phosphoric acid also is in the same peculiar relation.

Quarterly Journal, xxvii. 407. or Bibliothèque Universelle, xl. 205. Kemp says sulphurous acid is a very good conductor, Quarterly Journal, 1831, p. 613.

Quarterly Journal, xxiv, 465. or Annales de Chimie, xxxv. 161.

1356. It would seem in the cases of those bodies which suffer no change themselves, as sulphuric acid (and perhaps in all), that they affect water in its conducting power only as an electrolyte; for whether little or much improved, the decomposition is proportionate to the quantity of electricity passing (727. 730.), and the transfer is therefore due to electrolytic discharge. This is in accordance with the fact already stated as regards water (984.), that the conducting power is not improved for electricity of force below the electrolytic intensity of the substance acting as the dielectric; but both facts (and some others) are against the opinion which I formerly gave, that the power of salts, &c. might depend upon their assumption of the liquid state by solution in the water employed (410.). It occurs to me that the effect may perhaps be related to, and have its explanation in differences of specific inductive capacities.

1357. I have described in the last paper, cases, where shell-lac was rendered a conductor by absorption of ammonia (1294.). The same effect happens with muriatic acid; yet both these substances, when gaseous, are non-conductors; and the ammonia, also when in strong solution (718.). Mr. Harris has mentioned instances in which the conducting power of metals is seriously altered by a very little alloy. These may have no relation to the former cases, but nevertheless should not be overlooked in the general investigation which the whole question requires.

Philosophical Transactions, 1827, p. 22.

1358. Nothing is perhaps more striking in that class of dielectrics which we call electrolytes, than the extraordinary and almost complete suspension of their peculiar mode of effecting discharge when they are rendered solid (380, &c.), even though the intensity of the induction acting through them may be increased a hundredfold or more (419.). It not only establishes a very general relation between the physical properties of these bodies and electricity acting by induction through them, but draws both their physical and chemical relations so near together, as to make us hope we shall shortly arrive at the full comprehension of the influence they mutually possess over each other.

¶ ix. Disruptive discharge and insulation.