Part 42

849. It is probable that all our present elementary bodies are ions, but that is not as yet certain. There are some, such as carbon, phosphorus, nitrogen, silicon, boron, alumium, the right of which to the title of ion it is desirable to decide as soon as possible. There are also many compound bodies, and amongst them alumina and silica, which it is desirable to class immediately by unexceptionable experiments. It is also possible, that all combinable bodies, compound as well as simple, may enter into the class of ions; but at present it does not seem to me probable. Still the experimental evidence I have is so small in proportion to what must gradually accumulate around, and bear upon, this point, that I am afraid to give a strong opinion upon it.

850. I think I cannot deceive myself in considering the doctrine of definite electro-chemical action as of the utmost importance. It touches by its facts more directly and closely than any former fact, or set of facts, have done, upon the beautiful idea, that ordinary chemical affinity is a mere consequence of the electrical attractions of the particles of different kinds of matter; and it will probably lead us to the means by which we may enlighten that which is at present so obscure, and either fully demonstrate the truth of the idea, or develope that which ought to replace it.

851. A very valuable use of electro-chemical equivalents will be to decide, in cases of doubt, what is the true chemical equivalent, or definite proportional, or atomic number of a body; for I have such conviction that the power which governs electro-decomposition and ordinary chemical attractions is the same; and such confidence in the overruling influence of those natural laws which render the former definite, as to feel no hesitation in believing that the latter must submit to them also. Such being the case, I can have, no doubt that, assuming hydrogen as 1, and dismissing small fractions for the simplicity of expression, the equivalent number or atomic weight of oxygen is 8, of chlorine 36, of bromine 78.4, of lead 103.5, of tin 59, &c., notwithstanding that a very high authority doubles several of these numbers.

§ 13. On the absolute quantity of Electricity associated with the particles or atoms of Matter.

852. The theory of definite electrolytical or electro-chemical action appears to me to touch immediately upon the absolute quantity of electricity or electric power belonging to different bodies. It is impossible, perhaps, to speak on this point without committing oneself beyond what present facts will sustain; and yet it is equally impossible, and perhaps would be impolitic, not to reason upon the subject. Although we know nothing of what an atom is, yet we cannot resist forming some idea of a small particle, which represents it to the mind; and though we are in equal, if not greater, ignorance of electricity, so as to be unable to say whether it is a particular matter or matters, or mere motion of ordinary matter, or some third kind of power or agent, yet there is an immensity of facts which justify us in believing that the atoms of matter are in some way endowed or associated with electrical powers, to which they owe their most striking qualities, and amongst them their mutual chemical affinity. As soon as we perceive, through the teaching of Dalton, that chemical powers are, however varied the circumstances in which they are exerted, definite for each body, we learn to estimate the relative degree of force which resides in such bodies: and when upon that knowledge comes the fact, that the electricity, which we appear to be capable of loosening from its habitation for a while, and conveying from place to place, whilst it retains its chemical force, can be measured out, and being so measured is found to be as definite in its action as any of those portions which, remaining associated with the particles of matter, give them their chemical relation; we seem to have found the link which connects the proportion of that we have evolved to the proportion of that belonging to the particles in their natural state.

853. Now it is wonderful to observe how small a quantity of a compound body is decomposed by a certain portion of electricity. Let us, for instance, consider this and a few other points in relation to water. One grain of water, acidulated to facilitate conduction, will require an electric current to be continued for three minutes and three quarters of time to effect its decomposition, which current must be powerful enough to retain a platina wire 1/104 of an inch in thickness, red-hot, in the air during the whole time; and if interrupted anywhere by charcoal points, will produce a very brilliant and constant star of light. If attention be paid to the instantaneous discharge of electricity of tension, as illustrated in the beautiful experiments of Mr. Wheatstone, and to what I have said elsewhere on the relation of common and voltaic electricity (371. 375.), it will not be too much to say that this necessary quantity of electricity is equal to a very powerful flash of lightning. Yet we have it under perfect command; can evolve, direct, and employ it at pleasure; and when it has performed its full work of electrolyzation, it has only separated the elements of a single grain of water.

I have not stated the length of wire used, because I find by experiment, as would be expected in theory, that it is indifferent. The same quantity of electricity which, passed in a given time, can heat an inch of platina wire of a certain diameter red-hot, can also heat a hundred, a thousand, or any length of the same wire to the same degree, provided the cooling circumstances are the same for every part in all cases. This I have proved by the volta-electrometer. I found that whether half an inch or eight inches were retained at one constant temperature of dull redness, equal quantities of water were decomposed in equal times. When the half-inch was used, only the centre portion of wire was ignited. A fine wire may even be used as a rough but ready regulator of a voltaic current; for if it be made part of the circuit, and the larger wires communicating with it be shifted nearer to or further apart, so as to keep the portion of wire in the circuit sensibly at the same temperature, the current passing through it will be nearly uniform.

Literary Gazette, 1833, March 1 and 8. Philosophical Magazine, 1833, p. 201. L'Institut, 1833, p.261.

854. On the other hand, the relation between the conduction of the electricity and the decomposition of the water is so close, that one cannot take place without the other. If the water is altered only in that small degree which consists in its having the solid instead of the fluid state, the conduction is stopped, and the decomposition is stopped with it. Whether the conduction be considered as depending upon the decomposition, or not (443. 703.), still the relation of the two functions is equally intimate and inseparable.

855. Considering this close and twofold relation, namely, that without decomposition transmission of electricity does not occur; and, that for a given definite quantity of electricity passed, an equally definite and constant quantity of water or other matter is decomposed; considering also that the agent, which is electricity, is simply employed in overcoming electrical powers in the body subjected to its action; it seems a probable, and almost a natural consequence, that the quantity which passes is the equivalent of, and therefore equal to, that of the particles separated; i.e. that if the electrical power which holds the elements of a grain of water in combination, or which makes a grain of oxygen and hydrogen in the right proportions unite into water when they are made to combine, could be thrown into the condition of a current, it would exactly equal the current required for the separation of that grain of water into its elements again.

856. This view of the subject gives an almost overwhelming idea of the extraordinary quantity or degree of electric power which naturally belongs to the particles of matter; but it is not inconsistent in the slightest degree with the facts which can be brought to bear on this point. To illustrate this I must say a few words on the voltaic pile.

By the term voltaic pile, I mean such apparatus or arrangement of metals as up to this time have been called so, and which contain water, brine, acids, or other aqueous solutions or decomposable substances (476.), between their plates. Other kinds of electric apparatus may be hereafter invented, and I hope to construct some not belonging to the class of instruments discovered by Volta.

857. Intending hereafter to apply the results given in this and the preceding series of Researches to a close investigation of the source of electricity in the voltaic instrument, I have refrained from forming any decided opinion on the subject; and without at all meaning to dismiss metallic contact, or the contact of dissimilar substances, being conductors, but not metallic, as if they had nothing to do with the origin of the current,

I still am fully of opinion with Davy, that it is at least continued by chemical action, and that the supply constituting the current is almost entirely from that source.

858. Those bodies which, being interposed between the metals of the voltaic pile, render it active, are all of them electrolytes (476.); and it cannot but press upon the attention of every one engaged in considering this subject, that in those bodies (so essential to the pile) decomposition and the transmission of a current are so intimately connected, that one cannot happen without the other. This I have shown abundantly in water, and numerous other cases (402. 476.). If, then, a voltaic trough have its extremities connected by a body capable of being decomposed, as water, we shall have a continuous current through the apparatus; and whilst it remains in this state we may look at the part where the acid is acting upon the plates, and that where the current is acting upon the water, as the reciprocals of each other. In both parts we have the two conditions inseparable in such bodies as these, namely, the passing of a current, and decomposition; and this is as true of the cells in the battery as of the water cell; for no voltaic battery has as yet been constructed in which the chemical action is only that of combination: decomposition is always included, and is, I believe, an essential chemical part.

859. But the difference in the two parts of the connected battery, that is, the decomposition or experimental cell, and the acting cells, is simply this. In the former we urge the current through, but it, apparently of necessity, is accompanied by decomposition: in the latter we cause decompositions by ordinary chemical actions, (which are, however, themselves electrical,) and, as a consequence, have the electrical current; and as the decomposition dependent upon the current is definite in the former case, so is the current associated with the decomposition also definite in the latter (862. &c.).

860. Let us apply this in support of what I have surmised respecting the enormous electric power of each particle or atom of matter (856.). I showed in a former series of these Researches on the relation by measure of common and voltaic electricity, that two wires, one of platina and one of zinc, each one-eighteenth of an inch in diameter, placed five-sixteenths of an inch apart, and immersed to the depth of five-eighths of an inch in acid, consisting of one drop of oil of vitriol and four ounces of distilled water at a temperature of about 60° Fahr., and connected at the other extremities by a copper wire eighteen feet long, and one-eighteenth of an inch in thickness, yielded as much electricity in little more than three seconds of time as a Leyden battery charged by thirty turns of a very large and powerful plate electric machine in full action (371.). This quantity, though sufficient if passed at once through the head of a rat or cat to have killed it, as by a flash of lightning, was evolved by the mutual action of so small a portion of the zinc wire and water in contact with it, that the loss of weight sustained by either would be inappreciable by our most delicate instruments; and as to the water which could be decomposed by that current, it must have been insensible in quantity, for no trace of hydrogen appeared upon the surface of the platina during those three seconds.

861. What an enormous quantity of electricity, therefore, is required for the decomposition of a single grain of water! We have already seen that it must be in quantity sufficient to sustain a platina wire 1/104 of an inch in thickness, red-hot, in contact with the air, for three minutes and three quarters (853.), a quantity which is almost infinitely greater than that which could be evolved by the little standard voltaic arrangement to which I have just referred (860. 871.). I have endeavoured to make a comparison by the loss of weight of such a wire in a given time in such an acid, according to a principle and experiment to be almost immediately described (862.); but the proportion is so high that I am almost afraid to mention it. It would appear that 800,000 such charges of the Leyden battery as I have referred to above, would be necessary to supply electricity sufficient to decompose a single grain of water; or, if I am right, to equal the quantity of electricity which is naturally associated with the elements of that grain of water, endowing them with their mutual chemical affinity.

862. In further proof of this high electric condition of the particles of matter, and the identity as to quantity of that belonging to them with that necessary for their separation, I will describe an experiment of great simplicity but extreme beauty, when viewed in relation to the evolution of an electric current and its decomposing powers.

863. A dilute sulphuric acid, made by adding about one part by measure of oil of vitriol to thirty parts of water, will act energetically upon a piece of zinc plate in its ordinary and simple state: but, as Mr. Sturgeon has shown, not at all, or scarcely so, if the surface of the metal has in the first instance been amalgamated; yet the amalgamated zinc will act powerfully with platina as an electromotor, hydrogen being evolved on the surface of the latter metal, as the zinc is oxidized and dissolved. The amalgamation is best effected by sprinkling a few drops of mercury upon the surface of the zinc, the latter being moistened with the dilute acid, and rubbing with the fingers or two so as to extend the liquid metal over the whole of the surface. Any mercury in excess, forming liquid drops upon the zinc, should be wiped off.

Recent Experimental Researches, &c., 1830, p.74, &c.

The experiment may be made with pure zinc, which, as chemists well know, is but slightly acted upon by dilute sulphuric acid in comparison with ordinary zinc, which during the action is subject to an infinity of voltaic actions. See De la Rive on this subject, Bibliothèque Universelle, 1830, p.391.

864. Two plates of zinc thus amalgamated were dried and accurately weighed; one, which we will call A, weighed 163.1 grains; the other, to be called B, weighed 148.3 grains. They were about five inches long, and 0.4 of an inch wide. An earthenware pneumatic trough was filled with dilute sulphuric acid, of the strength just described (863.), and a gas jar, also filled with the acid, inverted in it. A plate of platina of nearly the same length, but about three times as wide as the zinc plates, was put up into this jar. The zinc plate A was also introduced into the jar, and brought in contact with the platina, and at the same moment the plate B was put into the acid of the trough, but out of contact with other metallic matter.

The acid was left during a night with a small piece of unamalgamated zinc in it, for the purpose of evolving such air as might be inclined to separate, and bringing the whole into a constant state.

865. Strong action immediately occurred in the jar upon the contact of the zinc and platina plates. Hydrogen gas rose from the platina, and was collected in the jar, but no hydrogen or other gas rose from either zinc plate. In about ten or twelve minutes, sufficient hydrogen having been collected, the experiment was stopped; during its progress a few small bubbles had appeared upon plate B, but none upon plate A. The plates were washed in distilled water, dried, and reweighed. Plate B weighed 148.3 grains, as before, having lost nothing by the direct chemical action of the acid. Plate A weighed 154.65 grains, 8.45 grains of it having been oxidized and dissolved during the experiment.

866. The hydrogen gas was next transferred to a water-trough and measured; it amounted to 12.5 cubic inches, the temperature being 52°, and the barometer 29.2 inches. This quantity, corrected for temperature, pressure, and moisture, becomes 12.15453 cubic inches of dry hydrogen at mean temperature and pressure; which, increased by one half for the oxygen that must have gone to the anode, i.e. to the zinc, gives 18.232 cubic inches as the quantity of oxygen and hydrogen evolved from the water decomposed by the electric current. According to the estimate of the weight of the mixed gas before adopted (791.), this volume is equal to 2.3535544 grains, which therefore is the weight of water decomposed; and this quantity is to 8.45, the quantity of zinc oxidized, as 9 is to 32.31. Now taking 9 as the equivalent number of water, the number 32.5 is given as the equivalent number of zinc; a coincidence sufficiently near to show, what indeed could not but happen, that for an equivalent of zinc oxidized an equivalent of water must be decomposed.

The experiment was repeated several times with the same results.

867. But let us observe how the water is decomposed. It is electrolyzed, i.e. is decomposed voltaically, and not in the ordinary manner (as to appearance) of chemical decompositions; for the oxygen appears at the anode and the hydrogen at the cathode of the body under decomposition, and these were in many parts of the experiment above an inch asunder. Again, the ordinary chemical affinity was not enough under the circumstances to effect the decomposition of the water, as was abundantly proved by the inaction on plate B; the voltaic current was essential. And to prevent any idea that the chemical affinity was almost sufficient to decompose the water, and that a smaller current of electricity might, under the circumstances, cause the hydrogen to pass to the cathode, I need only refer to the results which I have given (807. 813.) to shew that the chemical action at the electrodes has not the slightest influence over the quantities of water or other substances decomposed between them, but that they are entirely dependent upon the quantity of electricity which passes.