Experimental researches in electricity/New law of electric conduction

§ 9. _On a new Law of Electric Conduction._ § 10. _On Conducting Power generally._

Received April 24,--Read May 23, 1833.

§ 9. _On a new Law of Electric Conduction._[A]

[A] In reference to this law see further considerations at 910. 1358. 1705.--_Dec. 1838._

380. It was during the progress of investigations relating to electro-chemical decomposition, which I still have to submit to the Royal Society, that I encountered effects due to a very _general law_ of electric conduction not hitherto recognised; and though they prevented me from obtaining the condition I sought for, they afforded abundant compensation for the momentary disappointment, by the new and important interest which they gave to an extensive part of electrical science.

381. I was working with ice, and the solids resulting from the freezing of solutions, arranged either as barriers across a substance to be decomposed, or as the actual poles of a voltaic battery, that I might trace and catch certain elements in their transit, when I was suddenly stopped in my progress by finding that ice was in such circumstances a non-conductor of electricity; and that as soon as a thin film of it was interposed, in the circuit of a very powerful voltaic battery, the transmission of electricity was prevented, and all decomposition ceased.

382. At first the experiments were made with common ice, during the cold freezing weather of the latter end of January 1833; but the results were fallacious, from the imperfection of the arrangements, and the following more unexceptionable form of experiment was adopted.

383. Tin vessels were formed, five inches deep, one inch and a quarter wide in one direction, of different widths from three eighths to five eighths of an inch in the other, and open at one extremity. Into these were fixed by corks, plates of platina, so that the latter should not touch the tin cases; and copper wires having previously been soldered to the plate, these were easily connected, when required, with a voltaic pile. Then distilled water, previously boiled for three hours, was poured into the vessels, and frozen by a mixture of salt and snow, so that pure transparent solid ice intervened between the platina and tin; and finally these metals were connected with the opposite extremities of the voltaic apparatus, a galvanometer being at the same time included in the circuit.

384. In the first experiment, the platina pole was three inches and a half long, and seven eighths of an inch wide; it was wholly immersed in the water or ice, and as the vessel was four eighths of an inch in width, the average thickness of the intervening ice was only a quarter of an inch, whilst the surface of contact with it at both poles was nearly fourteen square inches. After the water was frozen, the vessel was still retained in the frigorific mixture, whilst contact between the tin and platina respectively was made with the extremities of a well-charged voltaic battery, consisting of twenty pairs of four-inch plates, each with double coppers. Not the slightest deflection of the galvanometer needle occurred.

385. On taking the frozen arrangement out of the cold mixture, and applying warmth to the bottom of the tin case, so as to melt part of the ice, the connexion with the battery being in the mean time retained, the needle did not at first move; and it was only when the thawing process had extended so far as to liquefy part of the ice touching the platina pole, that conduction took place; but then it occurred effectually, and the galvanometer needle was permanently deflected nearly 70°.

386. In another experiment, a platina spatula, five inches in length and seven eighths of an inch in width, had four inches fixed in the ice, and the latter was only three sixteenths of an inch thick between one metallic surface and the other; yet this arrangement insulated as perfectly as the former.

387. Upon pouring a little water in at the top of this vessel on the ice, still the arrangement did not conduct; yet fluid water was evidently there. This result was the consequence of the cold metals having frozen the water where they touched it, and thus insulating the fluid part; and it well illustrates the non-conducting power of ice, by showing how thin a film could prevent the transmission of the battery current. Upon thawing parts of this thin film, at _both_ metals, conduction occurred.

388. Upon warming the tin case and removing the piece of ice, it was found that a cork having slipped, one of the edges of the platina had been all but in contact with the inner surface of the tin vessel; yet, notwithstanding the extreme thinness of the interfering ice in this place, no sensible portion of electricity had passed.

389. These experiments were repeated many times with the same results. At last a battery of fifteen troughs, or one hundred and fifty pairs of four-inch plates, powerfully charged, was used; yet even here no sensible quantity of electricity passed the thin barrier of ice.

390. It seemed at first as if occasional departures from these effects occurred; but they could always be traced to some interfering circumstances. The water should in every instance be well-frozen; for though it is not necessary that the ice should reach from pole to pole, since a barrier of it about one pole would be quite sufficient to prevent conduction, yet, if part remain fluid, the mere necessary exposure of the apparatus to the air or the approximation of the hands, is sufficient to produce, at the _upper surface_ of the water and ice, a film of fluid, extending from the platina to the tin; and then conduction occurs. Again, if the corks used to block the platina in its place are damp or wet within, it is necessary that the cold be sufficiently well applied to freeze the water in them, or else when the surfaces of their contact with the tin become slightly warm by handling, that part will conduct, and the interior being ready to conduct also, the current will pass. The water should be pure, not only that unembarrassed results may be obtained, but also that, as the freezing proceeds, a minute portion of concentrated saline solution may not be formed, which remaining fluid, and being interposed in the ice, or passing into cracks resulting from contraction, may exhibit conducting powers independent of the ice itself.

391. On one occasion I was surprised to find that after thawing much of the ice the conducting power had not been restored; but I found that a cork which held the wire just where it joined the platina, dipped so far into the ice, that with the ice itself it protected the platina from contact with the melted part long after that contact was expected.

392. This insulating power of ice is not effective with electricity of exalted intensity. On touching a diverged gold-leaf electrometer with a wire connected with the platina, whilst the tin case was touched by the hand or another wire, the electrometer was instantly discharged (419.).

393. But though electricity of an intensity so low that it cannot diverge the electrometer, can still pass (though in very limited quantities (419.),) through ice; the comparative relation of water and ice to the electricity of the voltaic apparatus is not less extraordinary on that account, Or less important in its consequences.

394. As it did not seem likely that this _law of the assumption of conducting power during liquefaction, and loss of it during congelation_, would be peculiar to water, I immediately proceeded to ascertain its influence in other cases, and found it to be very general. For this purpose bodies were chosen which were solid at common temperatures, but readily fusible; and of such composition as, for other reasons connected with electrochemical action, led to the conclusion that they would be able when fused to replace water as conductors. A voltaic battery of two troughs, or twenty pairs of four-inch plates (384.), was used as the source of electricity, and a galvanometer introduced into the circuit to indicate the presence or absence of a current.

395. On fusing a little chloride of lead by a spirit lamp on a fragment of a Florence flask, and introducing two platina wires connected with the poles of the battery, there was instantly powerful action, the galvanometer was most violently affected, and the chloride rapidly decomposed. On removing the lamp, the instant the chloride solidified all current and consequent effects ceased, though the platina wires remained inclosed in the chloride not more than the one-sixteenth of an inch from each other. On renewing the heat, as soon as the fusion had proceeded far enough to allow liquid matter to connect the poles, the electrical current instantly passed.

396. On fusing the chloride, with one wire introduced, and then touching the liquid with the other, the latter being cold, caused a little knob to concrete on its extremity, and no current passed; it was only when the wire became so hot as to be able to admit or allow of contact with the liquid matter, that conduction took place, and then it was very powerful.

397. When chloride of silver and chlorate of potassa were experimented with, in a similar manner, exactly the same results occurred.

398. Whenever the current passed in these cases, there was decomposition of the substances; but the electro-chemical part of this subject I purpose connecting with more general views in a future paper[A].

[A] In 1801, Sir H. Davy knew that "dry nitre, caustic potash, and soda are conductors of galvanism when rendered fluid by a high degree  of heat," (Journals of the Royal Institution, 1802, p. 53,) but was not aware of the general law which I have been engaged in developing. It is remarkable, that eleven years after that, he should say, "There are no fluids known except such as contain water, which are capable of  being made the medium of connexion between the metal or metals of the  voltaic apparatus."--Elements of Chemical Philosophy, p. 169.

399. Other substances, which could not be melted on glass, were fused by the lamp and blowpipe on platina connected with one pole of the battery, and then a wire, connected with the other, dipped into them. In this way chloride of sodium, sulphate of soda, protoxide of lead, mixed carbonates of potash and soda, &c. &c., exhibited exactly the same phenomena as those already described: whilst liquid, they conducted and were decomposed; whilst solid, though very hot, they insulated the battery current even when four troughs were used.

400. Occasionally the substances were contained in small bent tubes of green glass, and when fused, the platina poles introduced, one on each side. In such cases the same general results as those already described were procured; but a further advantage was obtained, namely, that whilst the substance was conducting and suffering decomposition, the final arrangement of the elements could be observed. Thus, iodides of potassium and lead gave iodine at the positive pole, and potassium or lead at the negative pole. Chlorides of lead and silver gave chlorine at the positive, and metals at the negative pole. Nitre and chlorate; of potassa gave oxygen, &c., at the positive, and alkali, or even potassium, at the negative pole.

[Illustration]

401. A fourth arrangement was used for substances requiring very high temperatures for their fusion. A platina wire was connected with one pole of the battery; its extremity bent into a small ring, in the manner described by Berzelius, for blowpipe experiments; a little of the salt, glass, or other substance, was melted on this ring by the ordinary blowpipe, or even in some cases by the oxy-hydrogen blowpipe, and when the drop, retained in its place by the ring, was thoroughly hot and fluid, a platina wire from the opposite pole of the battery was made to touch it, and the effects observed.

402. The following are various substances, taken from very different classes chemically considered, which are subject to this law. The list might, no doubt, be enormously extended; but I have not had time to do more than confirm the law by a sufficient number of instances.

First, _water_.

Amongst _oxides_;--potassa, protoxide of lead, glass of antimony, protoxide of antimony, oxide of bismuth.

_Chlorides_ of potassium, sodium, barium, strontium, calcium, magnesium, manganese, zinc, copper (proto-), lead, tin (proto-), antimony, silver.

_Iodides_ of potassium, zinc and lead, protiodide of tin, periodide of mercury; _fluoride_ of potassium; _cyanide_ of potassium; _sulpho-cyanide_ of potassium.

_Salts._ Chlorate of potassa; nitrates of potassa, soda, baryta, strontia, lead, copper, and silver; sulphates of soda and lead, proto-sulphate of mercury; phosphates of potassa, soda, lead, copper, phosphoric glass or acid phosphate of lime; carbonates of potassa and soda, mingled and separate; borax, borate of lead, per-borate of tin; chromate of potassa, bi-chromate of potassa, chromate of lead; acetate of potassa.

_Sulphurets._ Sulphuret of antimony, sulphuret of potassium made by reducing sulphate of potassa by hydrogen; ordinary sulphuret of potassa.

Silicated potassa; chameleon mineral.

403. It is highly interesting in the instances of those substances which soften before they liquefy, to observe at what period the conducting power is acquired, and to what degree it is exalted by perfect fluidity. Thus, with the borate of lead, when heated by the lamp upon glass, it becomes as soft as treacle, but it did not conduct, and it was only when urged by the blowpipe and brought to a fair red heat, that it conducted. When rendered quite liquid, it conducted with extreme facility.

404. I do not mean to deny that part of the increased conducting power in these cases of softening was probably due to the elevation of temperature (432. 445.); but I have no doubt that by far the greater part was due to the influence of the general law already demonstrated, and which in these instances came gradually, instead of suddenly, into operation.

405. The following are bodies which acquired no conducting power upon assuming the liquid state:--

Sulphur, phosphorus; iodide of sulphur, per-iodide of tin; orpiment, realgar; glacial acetic acid, mixed margaric and oleic acids, artificial camphor; caffeine, sugar, adipocire, stearine of cocoa-nut oil, spermaceti, camphor, naphthaline, resin, gum sandarach, shell lac.

406. Perchloride of tin, chloride of arsenic, and the hydrated chloride of arsenic, being liquids, had no sensible conducting power indicated by the galvanometer, nor were they decomposed.

407. Some of the above substances are sufficiently remarkable as exceptions to the general law governing the former cases. These are orpiment, realgar, acetic acid, artificial camphor, per-iodide of tin, and the chlorides of tin and arsenic. I shall have occasion to refer to these cases in the paper on Electro-chemical Decomposition.

408. Boracic acid was raised to the highest possible temperature by an oxy-hydrogen flame (401.), yet it gained no conducting powers sufficient to affect the galvanometer, and underwent no apparent voltaic decomposition. It seemed to be quite as bad a conductor as air. Green bottle-glass, heated in the same manner, did not gain conducting power sensible to the galvanometer. Flint glass, when highly heated, did conduct a little and decompose; and as the proportion of potash or oxide of lead was increased in the glass, the effects were more powerful. Those glasses, consisting of boracic acid on the one hand, and oxide of lead or potassa on the other, show the assumption of conducting power upon fusion and the accompanying decomposition very well.

409. I was very anxious to try the general experiment with sulphuric acid, of about specific gravity 1.783, containing that proportion of water which gives it the power of crystallizing at 40° Fahr.; but I found it impossible to obtain it so that I could be sure the whole would congeal even at 0° Fahr. A ten-thousandth part of water, more or less than necessary, would, upon cooling the whole, cause a portion of uncongealable liquid to separate, and that remaining in the interstices of the solid mass, and moistening the planes of division, would prevent the correct observation of the phenomena due to entire solidification and subsequent liquefaction.

410. With regard to the substances on which conducting power is thus conferred by liquidity, the degree of power so given is generally very great. Water is that body in which this acquired power is feeblest. In the various oxides, chlorides, salts, &c. &c., it is given in a much higher degree. I have not had time to measure the conducting power in these cases, but it is apparently some hundred times that of pure water. The increased conducting power known to be given to water by the addition of salts, would seem to be in a great degree dependent upon the high conducting power of these bodies when in the liquid state, that state being given them for the time, not by heat but solution in the water[A].

[A] See a doubt on this point at 1356.--_Dec. 1838._

411. Whether the conducting power of these liquefied bodies is a consequence of their decomposition or not (413.), or whether the two actions of conduction and decomposition are essentially connected or not, would introduce no difference affecting the probable accuracy of the preceding statement.

412. This _general assumption of conducting power_ by bodies as soon as they pass from the solid to the liquid state, offers a new and extraordinary character, the existence of which, as far as I know, has not before been suspected; and it seems importantly connected with some properties and relations of the particles of matter which I may now briefly point out.

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.