Part 28 (1/2)

[A] In connexion with this part of the subject refer now to Series XI.

1164, Series XII. 1343-1358, and Series XIII. 1621. &c.--_Dec. 1838._

947. We seem to have the power of deciding to a certain extent in numerous cases of chemical affinity, (as of zinc with the oxygen of water, &c. &c.) which of _two modes of action of the attractive power_ shall be exerted (996.). In the one mode we can transfer the power onwards, and make it produce elsewhere its equivalent of action (867. 917.); in the other, it is not transferred, but exerted wholly at the spot. The first is the case of volta-electric excitation, the other ordinary chemical affinity: but both are chemical actions and due to one force or principle.

948. The general circ.u.mstances of the former mode occur in all instances of voltaic currents, but may be considered as in their perfect condition, and then free from those of the second mode, in some only of the cases; as in those of plates of zinc and platina in solution of pota.s.sa, or of amalgamated zinc and platina in dilute sulphuric acid.

949. a.s.suming it sufficiently proved, by the preceding experiments and considerations, that the electro-motive action depends, when zinc, platina, and dilute sulphuric acid are used, upon the mutual affinity of the metal zinc and the oxygen of the water (921. 924.), it would appear that the metal, when alone, has not power enough, under the circ.u.mstances, to take the oxygen and expel the hydrogen from the water; for, in fact, no such action takes place. But it would also appear that it has power so far to act, by its attraction for the oxygen of the particles in contact with it, as to place the similar forces already active between these and the other particles of oxygen and the particles of hydrogen in the water, in a peculiar state of tension or polarity, and probably also at the same time to throw those of its own particles which are in contact with the water into a similar but opposed state. Whilst this state is retained, no further change occurs; but when it is relieved, by completion of the circuit, in which case the forces determined in opposite directions, with respect to the zinc and the electrolyte, are found exactly competent to neutralize each other, then a series of decompositions and recompositions takes place amongst the particles of oxygen and hydrogen const.i.tuting the water, between the place of contact with the platina and the place where the zinc is active; these intervening particles being evidently in close dependence upon and relation to each other. The zinc forms a direct compound with those particles of oxygen which were, previously, in divided relation to both it and the hydrogen: the oxide is removed by the acid, and a fresh surface of zinc is presented to the water, to renew and repeat the action.

950. Practically, the state of tension is best relieved by dipping a metal which has less attraction for oxygen than the zinc, into the dilute acid, and making it also touch the zinc. The force of chemical affinity, which has been influenced or polarized in the particles of the water by the dominant attraction of the zinc for the oxygen, is then transferred, in a most extraordinary manner, through the two metals, so as to re-enter upon the circuit in the electrolytic conductor, which, unlike the metals in that respect, cannot convey or transfer it without suffering decomposition; or rather, probably, it is exactly balanced and neutralized by the force which at the same moment completes the combination of the zinc with the oxygen of the water. The forces, in fact, of the two particles which are acting towards each other, and which are therefore in opposite directions, are the origin of the two opposite forces, or directions of force, in the current.

They are of necessity equivalent to each other. Being transferred forward in contrary directions, they produce what is called the voltaic current: and it seems to me impossible to resist the idea that it must be preceded by a _state of tension_ in the fluid, and between the fluid and the zinc; the _first consequence_ of the affinity of the zinc for the oxygen of the water.

951. I have sought carefully for indications of a state of tension in the electrolytic conductor; and conceiving that it might produce something like structure, either before or during its discharge, I endeavoured to make this evident by polarized light. A gla.s.s cell, seven inches long, one inch and a half wide, and six inches deep, had two sets of platina electrodes adapted to it, one set for the ends, and the other for the sides. Those for the _sides_ were seven inches long by three inches high, and when in the cell were separated by a little frame of wood covered with calico; so that when made active by connexion with a battery upon any solution in the cell, the bubbles of gas rising from them did not obscure the central parts of the liquid.

952. A saturated solution of sulphate of soda was put into the cell, and the electrodes connected with a battery of 150 pairs of 4-inch plates: the current of electricity was conducted across the cell so freely, that the discharge was as good as if a wire had been used. A ray of polarized light was then transmitted through this solution, directly across the course of the electric current, and examined by an a.n.a.lysing plate; but though it penetrated seven inches of solution thus subject to the action of the electricity, and though contact was sometimes made, sometimes broken, and occasionally reversed during the observations, not the slightest trace of action on the ray could be perceived.

953. The large electrodes were then removed, and others introduced which fitted the _ends_ of the cell. In each a slit was cut, so as to allow the light to pa.s.s. The course of the polarized ray was now parallel to the current, or in the direction of its axis (517.); but still no effect, under any circ.u.mstances of contact or disunion, could be perceived upon it.

954. A strong solution of nitrate of lead was employed instead of the sulphate of soda, but no effects could be detected.

955. Thinking it possible that the discharge of the electric forces by the successive decompositions and recompositions of the particles of the electrolyte might neutralize and therefore destroy any effect which the first state of tension could by possibility produce, I took a substance which, being an excellent electrolyte when fluid, was a perfect insulator when solid, namely, borate of lead, in the form of a gla.s.s plate, and connecting the sides and the edges of this ma.s.s with the metallic plates, sometimes in contact with the poles of a voltaic battery, and sometimes even with the electric machine, for the advantage of the much higher intensity then obtained, I pa.s.sed a polarized ray across it in various directions, as before, but could not obtain the slightest appearance of action upon the light. Hence I conclude, that notwithstanding the new and extraordinary state which must be a.s.sumed by an electrolyte, either during decomposition (when a most enormous quant.i.ty of electricity must be traversing it), or in the state of tension which is a.s.sumed as preceding decomposition, and which might be supposed to be retained in the solid form of the electrolyte, still it has no power of affecting a polarized ray of light; for no kind of structure or tension can in this way be rendered evident.

956. There is, however, one beautiful experimental proof of a state of tension acquired by the metals and the electrolyte before the electric current is produced, and _before contact_ of the different metals is made (915.); in fact, at that moment when chemical forces only are efficient as a cause of action. I took a voltaic apparatus, consisting of a single pair of large plates, namely, a cylinder of amalgamated zinc, and a double cylinder of copper. These were put into a jar containing dilute sulphuric acid[A], and could at pleasure be placed in metallic communication by a copper wire adjusted so as to dip at the extremities into two cups of mercury connected with the two plates.

[A] When nitro-sulphuric acid is used, the spark is more powerful, but local chemical action can then commence, and proceed without requiring metallic contact.

957. Being thus arranged, there was no chemical action whilst the plates were not connected. On _making_ the connexion a spark was obtained[A], and the solution was immediately decomposed. On breaking it, the usual spark was obtained, and the decomposition ceased. In this case it is evident that the first spark must have occurred before metallic contact was made, for it pa.s.sed through an interval of air; and also that it must have tended to pa.s.s before the electrolytic action began; for the latter could not take place until the current pa.s.sed, and the current could not pa.s.s before the spark appeared. Hence I think there is sufficient proof, that as it is the zinc and water which by their mutual action produce the electricity of this apparatus, so these, by their first contact with each other, were placed in a state of powerful tension (951.), which, though it could not produce the actual decomposition of the water, was able to make a spark of electricity pa.s.s between the zinc and a fit discharger as soon as the interval was rendered sufficiently small. The experiment demonstrates the direct production of the electric spark from pure chemical forces.

[A] It has been universally supposed that no spark is produced on making the contact between a single pair of plates. I was led to expect one from the considerations already advanced in this paper. The wire of communication should be short; for with a long wire, circ.u.mstances strongly affecting the spark are introduced.

958. There are a few circ.u.mstances connected with the production of this spark by a single pair of plates, which should be known, to ensure success to the experiment[B]. When the amalgamated surfaces of contact are quite clean and dry, the spark, on making contact, is quite as brilliant as on breaking it, if not even more so. When a film of oxide or dirt was present at either mercurial surface, then the first spark was often feeble, and often failed, the breaking spark, however, continuing very constant and bright. When a little water was put over the mercury, the spark was greatly diminished in brilliancy, but very regular both on making and breaking contact. When the contact was made between clean platina, the spark was also very small, but regular both ways. The true electric spark is, in fact, very small, and when surfaces of mercury are used, it is the combustion of the metal which produces the greater part of the light. The circ.u.mstances connected with the burning of the mercury are most favourable on breaking contact; for the act of separation exposes clean surfaces of metal, whereas, on making contact, a thin film of oxide, or soiling matter, often interferes. Hence the origin of the general opinion that it is only when the contact is broken that the spark pa.s.ses.

[B] See in relation to precautions respecting a spark, 1074.--_Dec.

1838._

959. With reference to the other set of cases, namely, those of local action (947.) in which chemical affinity being exerted causes no transference of the power to a distance where no electric current is produced, it is evident that forces of the most intense kind must be active, and in some way balanced in their activity, during such combinations; these forces being directed so immediately and exclusively towards each other, that no signs of the powerful electric current they can produce become apparent, although the same final state of things is obtained as if that current had pa.s.sed. It was Berzelius, I believe, who considered the heat and light evolved in cases of combustion as the consequences of this mode of exertion of the electric powers of the combining particles. But it will require a much more exact and extensive knowledge of the nature of electricity, and the manner in which it is a.s.sociated with the atoms of matter, before we can understand accurately the action of this power in thus causing their union, or comprehend the nature of the great difference which it presents in the two modes of action just distinguished. We may imagine, but such imaginations must for the time be cla.s.sed with the great ma.s.s of _doubtful knowledge_ (876.) which we ought rather to strive to diminish than to increase; for the very extensive contradictions of this knowledge by itself shows that but a small portion of it can ultimately prove true[A].

[A] Refer to 1738, &c. Series XIV.--_Dec. 1838._

960. Of the two modes of action in which chemical affinity is exerted, it is important to remark, that that which produces the electric current is as _definite_ as that which causes ordinary chemical combination; so that in examining the _production_ or _evolution_ of electricity in cases of combination or decomposition, it will be necessary, not merely to observe certain effects dependent upon a current of electricity, but also their _quant.i.ty_: and though it may often happen that the forces concerned in any particular case of chemical action may be partly exerted in one mode and partly in the other, it is only those which are efficient in producing the current that have any relation to voltaic action. Thus, in the combination of oxygen and hydrogen to produce water, electric powers to a most enormous amount are for the time active (861. 873.); but any mode of examining the flame which they form during energetic combination, which has as yet been devised, has given but the feeblest traces. These therefore may not, cannot, be taken as evidences of the nature of the action; but are merely incidental results, incomparably small in relation to the forces concerned, and supplying no information of the way in which the particles are active on each other, or in which their forces are finally arranged.

961. That such cases of chemical action produce no _current of electricity_, is perfectly consistent with what we know of the voltaic apparatus, in which it is essential that one of the combining elements shall form part of, or be in direct relation with, an electrolytic conductor (921. 923.). That such cases produce _no free electricity of tension_, and that when they are converted into cases of voltaic action they produce a current in which the opposite forces are so equal as to neutralize each other, prove the equality of the forces in the opposed acting particles of matter, and therefore the equality of electric power in those quant.i.ties of matter which are called _electro-chemical equivalents_ (824). Hence another proof of the definite nature of electro-chemical action (783. &c.), and that chemical affinity and electricity are forms of the same power (917. &c.).

962. The direct reference of the effects produced by the voltaic pile at the place of experimental decomposition to the chemical affinities active at the place of excitation (891. 917.), gives a very simple and natural view of the cause why the bodies (or _ions_) evolved pa.s.s in certain directions; for it is only when they pa.s.s in those directions that their forces can consist with and compensate (in direction at least) the superior forces which are dominant at the place where the action of the whole is determined. If, for instance, in a voltaic circuit, the activity of which is determined, by the attraction of zinc for the oxygen of water, the zinc move from right to left, then any other _cation_ included in the circuit, being part of an electrolyte, or forming part of it at the moment, will also move from right to left: and as the oxygen of the water, by its natural affinity for the zinc, moves from left to right, so any other body of the same cla.s.s with it (i.e. any other _anion_), under its government for the time, will move from left to right.

963. This I may ill.u.s.trate by reference to fig. 83, the double circle of which may represent a complete voltaic circuit, the direction of its forces being determined by supposing for a moment the zinc _b_ and the platina _c_ as representing plates of those metals acting upon water, _d, e_, and other substances, but having their energy exalted so as to effect several decompositions by the use of a battery at _a_ (989.). This supposition may be allowed, because the action in the battery will only consist of repet.i.tions of what would take place between _b_ and _c_, if they really const.i.tuted but a single pair. The zinc _b_, and the oxygen _d_, by their mutual affinity, tend to unite; but as the oxygen is already in a.s.sociation with the hydrogen _e_, and has its inherent chemical or electric powers neutralized for the time by those of the latter, the hydrogen _e_ must leave the oxygen _d_, and advance in the direction of the arrow head, or else the zinc _b_ cannot move in the same direction to unite to the oxygen _d_, nor the oxygen _d_ move in the contrary direction to unite to the zinc _b_, the relation of the _similar_ forces of _b_ and _c_, in contrary directions, to the _opposite_ forces of _d_ being the preventive. As the hydrogen _e_ advances, it, on coming against the platina _c, f_, which forms a part of the circuit, communicates its electric or chemical forces through it to the next electrolyte in the circuit, fused chloride of lead, _g, h_, where the chlorine must move in conformity with the direction of the oxygen at _d_, for it has to compensate the forces disturbed in its part of the circuit by the superior influence of those between the oxygen and zinc at _d, b_, aided as they are by those of the battery _a_; and for a similar reason the lead must move in the direction pointed out by the arrow head, that it may be in right relation to the first moving body of its own cla.s.s, namely, the zinc _b_. If copper intervene in the circuit from _i_ to _k_, it acts as the platina did before; and if another electrolyte, as the iodide of tin, occur at _l, m_, then the iodine _l_, being an _anion_, must move in conformity with the exciting _anion_, namely, the oxygen _d_, and the _cation_ tin _m_ move in correspondence with the other _cations b, e_, and _h_, that the chemical forces may be in equilibrium as to their direction and quant.i.ty throughout the circuit.

Should it so happen that the anions in their circulation can combine with the metals at the _anodes_ of the respective electrolytes, as would be the case at the platina _f_ and the copper _k_, then those bodies becoming parts of electrolytes, under the influence of the current, immediately travel; but considering their relation to the zinc _b_, it is evidently impossible that they can travel in any other direction than what will accord with its course, and therefore can never tend to pa.s.s otherwise than _from_ the anode and _to_ the cathode.

964. In such a circle as that delineated, therefore, all the known _anions_ may be grouped within, and all the _cations_ without. If any number of them enter as _ions_ into the const.i.tution of _electrolytes_, and, forming one circuit, are simultaneously subject to one common current, the anions must move in accordance with each other in one direction, and the cations in the other. Nay, more than that, equivalent portions of these bodies must so advance in opposite directions: for the advance of every 32.5 parts of the zinc _b_ must be accompanied by a motion in the opposite direction of 8 parts of oxygen at _d_, of 36 parts of chlorine at _g_, of 126 parts of iodine at _l_; and in the same direction by electro-chemical equivalents of hydrogen, lead, copper and tin, at _e, h, k_. and _m_.

965. If the present paper be accepted as a correct expression of facts, it will still only prove a confirmation of certain general views put forth by Sir Humphry Davy in his Bakerian Lecture for 1806[A], and revised and re-stated by him in another Bakerian Lecture, on electrical and chemical changes, for the year 1826[B]. His general statement is, that ”_chemical and electrical attractions were produced by the same cause, acting in one case on particles, in the other on ma.s.ses, of matter; and that the same property, under different modifications, was the cause of all the phenomena exhibited by different voltaic combinations_[C].” This statement I believe to be true; but in admitting and supporting it, I must guard myself from being supposed to a.s.sent to all that is a.s.sociated with it in the two papers referred to, or as admitting the experiments which are there quoted as decided proofs of the truth of the principle. Had I thought them so, there would have been no occasion for this investigation. It may be supposed by some that I ought to go through these papers, distinguis.h.i.+ng what I admit from what I reject, and giving good experimental or philosophical reasons for the judgment in both cases. But then I should be equally bound to review, for the same purpose, all that has been written both for and against the necessity of metallic contact,--for and against the origin of voltaic electricity in chemical action,--a duty which I may not undertake in the present paper[D].