¶ iv. On some general conditions of Electro-chemical Decomposition.

669. From the period when electro-chemical decomposition was first effected to the present time, it has been a remark, that those elements which, in the ordinary phenomena of chemical affinity, were the most directly opposed to each other, and combined with the greatest attractive force, were those which were the most readily evolved at the opposite extremities of the decomposing bodies (549.).

670. If this result was evident when water was supposed to be essential to, and was present in, almost every case of such decomposition (472.), it is far more evident now that it has been shown and proved that water is not necessarily concerned in the phenomena (474.), and that other bodies much surpass it in some of the effects supposed to be peculiar to that substance.

671. Water, from its constitution and the nature of its elements, and from its frequent presence in cases of electrolytic action, has hitherto stood foremost in this respect. Though a compound formed by very powerful affinity, it yields up its elements under the influence of a very feeble electric current; and it is doubtful whether a case of electrolyzation can occur, where, being present, it is not resolved into its first principles.

672. The various oxides, chlorides, iodides, and salts, which I have shown are decomposable by the electric current when in the liquid state, under the same general law with water (402.), illustrate in an equally striking manner the activity, in such decompositions, of elements directly and powerfully opposed to each other by their chemical relations.

¶ v. On a new measure of Volta-electricity.

704. I have already said, when engaged in reducing common and voltaic electricity to one standard of measurement (377.), and again when introducing my theory of electro-chemical decomposition (504. 505. 510.), that the chemical decomposing action of a current is constant for a constant quantity of electricity, notwithstanding the greatest variations in its sources, in its intensity, in the size of the electrodes used, in the nature of the conductors (or non-conductors (307.)) through which it is passed, or in other circumstances. The conclusive proofs of the truth of these statements shall be given almost immediately (783, &c.).

705. I endeavoured upon this law to construct an instrument which should measure out the electricity passing through it, and which, being interposed in the course of the current used in any particular experiment, should serve at pleasure, either as a comparative standard of effect, or as a positive measurer of this subtile agent.

706. There is no substance better fitted, under ordinary circumstances, to be the indicating body in such an instrument than water; for it is decomposed with facility when rendered a better conductor by the addition of acids or salts; its elements may in numerous cases be obtained and collected without any embarrassment from secondary action, and, being gaseous, they are in the best physical condition for separation and measurement. Water, therefore, acidulated by sulphuric acid, is the substance I shall generally refer to, although it may become expedient in peculiar cases or forms of experiment to use other bodies (843.).

707. The first precaution needful in the construction of the instrument was to avoid the recombination of the evolved gases, an effect which the positive electrode has been found so capable of producing (571.). For this purpose various forms of decomposing apparatus were used. The first consisted of straight tubes, each containing a plate and wire of platina soldered together by gold, and fixed hermetically in the glass at the closed extremity of the tube (Plate V. fig. 60.). The tubes were about eight inches long, 0.7 of an inch in diameter, and graduated. The platina plates were about an inch long, as wide as the tubes would permit, and adjusted as near to the mouths of the tubes as was consistent with the safe collection of the gases evolved. In certain cases, where it was required to evolve the elements upon as small a surface as possible, the metallic extremity, instead of being a plate, consisted of the wire bent into the form of a ring (fig. 61.). When these tubes were used as measurers, they were filled with the dilute sulphuric acid, inverted in a basin of the same liquid (fig. 62.), and placed in an inclined position, with their mouths near to each other, that as little decomposing matter should intervene as possible; and also, in such a direction that the platina plates should be in vertical planes (720).

708. Another form of apparatus is that delineated (fig. 63.). The tube is bent in the middle; one end is closed; in that end is fixed a wire and plate, a, proceeding so far downwards, that, when in the position figured, it shall be as near to the angle as possible, consistently with the collection, at the closed extremity of the tube, of all the gas evolved against it. The plane of this plate is also perpendicular (720.). The other metallic termination, b, is introduced at the time decomposition is to be effected, being brought as near the angle as possible, without causing any gas to pass from it towards the closed end of the instrument. The gas evolved against it is allowed to escape.

709. The third form of apparatus contains both electrodes in the same tube; the transmission, therefore, of the electricity, and the consequent decomposition, is far more rapid than in the separate tubes. The resulting gas is the sum of the portions evolved at the two electrodes, and the instrument is better adapted than either of the former as a measurer of the quantity of voltaic electricity transmitted in ordinary cases. It consists of a straight tube (fig. 64.) closed at the upper extremity, and graduated, through the sides of which pass platina wires (being fused into the glass), which are connected with two plates within. The tube is fitted by grinding into one mouth of a double-necked bottle. If the latter be one-half or two-thirds full of the dilute sulphuric acid (706.), it will, upon inclination of the whole, flow into the tube and fill it. When an electric current is passed through the instrument, the gases evolved against the plates collect in the upper portion of the tube, and are not subject to the recombining power of the platina.

710. Another form of the instrument is given at fig. 65.

711. A fifth form is delineated (fig. 66.). This I have found exceedingly useful in experiments continued in succession for days together, and where large quantities of indicating gas were to be collected. It is fixed on a weighted foot, and has the form of a small retort containing the two electrodes: the neck is narrow, and sufficiently long to deliver gas issuing from it into a jar placed in a small pneumatic trough. The electrode chamber, sealed hermetically at the part held in the stand, is five inches in length, and 0.6 of an inch in diameter; the neck about nine inches in length, and 0.4 of an inch in diameter internally. The figure will fully indicate the construction.

712. It can hardly be requisite to remark, that in the arrangement of any of these forms of apparatus, they, and the wires connecting them with the substance, which is collaterally subjected to the action of the same electric current, should be so far insulated as to ensure a certainty that all the electricity which passes through the one shall also be transmitted through the other.

* * * * *

713. Next to the precaution of collecting the gases, if mingled, out of contact with the platinum, was the necessity of testing the law of a definite electrolytic action, upon water at least, under all varieties of condition; that, with a conviction of its certainty, might also be obtained a knowledge of those interfering circumstances which would require to be practically guarded against.

714. The first point investigated was the influence or indifference of extensive variations in the size of the electrodes, for which purpose instruments like those last described (709. 710. 711.) were used. One of these had plates 0.7 of an inch wide, and nearly four inches long; another had plates only 0.5 of an inch wide, and 0.8 of an inch long; a third had wires 0.02 of an inch in diameter, and three inches long; and a fourth, similar wires only half an inch in length. Yet when these were filled with dilute sulphuric acid, and, being placed in succession, had one common current of electricity passed through them, very nearly the same quantity of gas was evolved in all. The difference was sometimes in favour of one and sometimes on the side of another; but the general result was that the largest quantity of gases was evolved at the smallest electrodes, namely, those consisting merely of platina wires.

715. Experiments of a similar kind were made with the single-plate, straight tubes (707.), and also with the curved tubes (708.), with similar consequences; and when these, with the former tubes, were arranged together in various ways, the result, as to the equality of action of large and small metallic surfaces when delivering and receiving the same current of electricity, was constantly the same. As an illustration, the following numbers are given. An instrument with two wires evolved 74.3 volumes of mixed gases; another with plates 73.25 volumes; whilst the sum of the oxygen and hydrogen in two separate tubes amounted to 73.65 volumes. In another experiment the volumes were 55.3, 55.3, and 54.4.

716. But it was observed in these experiments, that in single-plate tubes (707.) more hydrogen was evolved at the negative electrode than was proportionate to the oxygen at the positive electrode; and generally, also, more than was proportionate to the oxygen and hydrogen in a double-plate tube. Upon more minutely examining these effects, I was led to refer them, and also the differences between wires and plates (714.), to the solubility of the gases evolved, especially at the positive electrode.

717. When the positive and negative electrodes are equal in surface, the bubbles which rise from them in dilute sulphuric acid are always different in character. Those from the positive plate are exceedingly small, and separate instantly from every part of the surface of the metal, in consequence of its perfect cleanliness (633.); whilst in the liquid they give it a hazy appearance, from their number and minuteness; are easily carried down by currents, and therefore not only present far greater surface of contact with the liquid than larger bubbles would do, but are retained a much longer time in mixture with it. But the bubbles at the negative surface, though they constitute twice the volume of the gas at the positive electrode, are nevertheless very inferior in number. They do not rise so universally from every part of the surface, but seem to be evolved at different parts; and though so much larger, they appear to cling to the metal, separating with difficulty from it, and when separated, instantly rising to the top of the liquid. If, therefore, oxygen and hydrogen had equal solubility in, or powers of combining with, water under similar circumstances, still under the present conditions the oxygen would be far the most liable to solution; but when to these is added its well-known power of forming a compound with water, it is no longer surprising that such a compound should be produced in small quantities at the positive electrode; and indeed the blenching power which some philosophers have observed in a solution at this electrode, when chlorine and similar bodies have been carefully excluded, is probably due to the formation there, in this manner, of oxywater.

718. That more gas was collected from the wires than from the plates, I attribute to the circumstance, that as equal quantities were evolved in equal times, the bubbles at the wires having been more rapidly produced, in relation to any part of the surface, must have been much larger; have been therefore in contact with the fluid by a much smaller surface, and for a much shorter time than those at the plates; hence less solution and a greater amount collected.

719. There was also another effect produced, especially by the use of large electrodes, which was both a consequence and a proof of the solution of part of the gas evolved there. The collected gas, when examined, was found to contain small portions of nitrogen. This I attribute to the presence of air dissolved in the acid used for decomposition. It is a well-known fact, that when bubbles of a gas but slightly soluble in water or solutions pass through them, the portion of this gas which is dissolved displaces a portion of that previously in union with the liquid: and so, in the decompositions under consideration, as the oxygen dissolves, it displaces a part of the air, or at least of the nitrogen, previously united to the acid; and this effect takes place most extensively with large plates, because the gas evolved at them is in the most favourable condition for solution,

720. With the intention of avoiding this solubility of the gases as much as possible, I arranged the decomposing plates in a vertical position (707. 708.), that the bubbles might quickly escape upwards, and that the downward currents in the fluid should not meet ascending currents of gas. This precaution I found to assist greatly in producing constant results, and especially in experiments to be hereafter referred to, in which other liquids than dilute sulphuric acid, as for instance solution of potash, were used.

721. The irregularities in the indications of the measurer proposed, arising from the solubility just referred to, are but small, and may be very nearly corrected by comparing the results of two or three experiments. They may also be almost entirely avoided by selecting that solution which is found to favour them in the least degree (728.); and still further by collecting the hydrogen only, and using that as the indicating gas; for being much less soluble than oxygen, being evolved with twice the rapidity and in larger bubbles (717.), it can be collected more perfectly and in greater purity.

722. From the foregoing and many other experiments, it results that variation in the size of the electrodes causes no variation in the chemical action of a given quantity of electricity upon water.

723. The next point in regard to which the principle of constant electro-chemical action was tested, was variation of intensity. In the first place, the preceding experiments were repeated, using batteries of an equal number of plates, strongly and weakly charged; but the results were alike. They were then repeated, using batteries sometimes containing forty, and at other times only five pairs of plates; but the results were still the same. Variations therefore in the intensity, caused by difference in the strength of charge, or in the number of alternations used, produced no difference as to the equal action of large and small electrodes.

724. Still these results did not prove that variation in the intensity of the current was not accompanied by a corresponding variation in the electro-chemical effects, since the actions at all the surfaces might have increased or diminished together. The deficiency in the evidence is, however, completely supplied by the former experiments on different-sized electrodes; for with variation in the size of these, a variation in the intensity must have occurred. The intensity of an electric current traversing conductors alike in their nature, quality, and length, is probably as the quantity of electricity passing through a given sectional area perpendicular to the current, divided by the time (360. note); and therefore when large plates were contrasted with wires separated by an equal length of the same decomposing conductor (714.), whilst one current of electricity passed through both arrangements, that electricity must have been in a very different state, as to tension, between the plates and between the wires; yet the chemical results were the same.

725. The difference in intensity, under the circumstances described, may be easily shown practically, by arranging two decomposing apparatus as in fig. 67, where the same fluid is subjected to the decomposing power of the same current of electricity, passing in the vessel A. between large platina plates, and in the vessel B. between small wires. If a third decomposing apparatus, such as that delineated fig. 66. (711.), be connected with the wires at ab, fig. 67, it will serve sufficiently well, by the degree of decomposition occurring in it, to indicate the relative state of the two plates as to intensity; and if it then be applied in the same way, as a test of the state of the wires at a'b', it will, by the increase of decomposition within, show how much greater the intensity is there than at the former points. The connexions of P and N with the voltaic battery are of course to be continued during the whole time.

726. A third form of experiment, in which difference of intensity was obtained, for the purpose of testing the principle of equal chemical action, was to arrange three volta-electrometers, so that after the electric current had passed through one, it should divide into two parts, each of which should traverse one of the remaining instruments, and should then reunite. The sum of the decomposition in the two latter vessels was always equal to the decomposition in the former vessel. But the intensity of the divided current could not be the same as that it had in its original state; and therefore variation of intensity has no influence on the results if the quantity of electricity remain the same. The experiment, in fact, resolves itself simply into an increase in the size of the electrodes (725.).

727. The third point, in respect to which the principle of equal electro-chemical action on water was tested, was variation of the strength of the solution used. In order to render the water a conductor, sulphuric acid had been added to it (707.); and it did not seem unlikely that this substance, with many others, might render the water more subject to decomposition, the electricity remaining the same in quantity. But such did not prove to be the case. Diluted sulphuric acid, of different strengths, was introduced into different decomposing apparatus, and submitted simultaneously to the action of the same electric current (714.). Slight differences occurred, as before, sometimes in one direction, sometimes in another; but the final result was, that exactly the same quantity of water was decomposed in all the solutions by the same quantity of electricity, though the sulphuric acid in some was seventy-fold what it was in others. The strengths used were of specific gravity 1.495, and downwards.

728. When an acid having a specific gravity of about 1.336 was employed, the results were most uniform, and the oxygen and hydrogen (716.) most constantly in the right proportion to each other. Such an acid gave more gas than one much weaker acted upon by the same current, apparently because it had less solvent power. If the acid were very strong, then a remarkable disappearance of oxygen took place; thus, one made by mixing two measures of strong oil of vitriol with one of water, gave forty-two volumes of hydrogen, but only twelve of oxygen. The hydrogen was very nearly the same with that evolved from acid of the specific gravity 1.232. I have not yet had time to examine minutely the circumstances attending the disappearance of the oxygen in this case, but imagine it is due to the formation of oxywater, which Thenard has shown is favoured by the presence of acid.

729. Although not necessary for the practical use of the instrument I am describing, yet as connected with the important point of constant chemical action upon water, I now investigated the effects produced by an electro-electric current passing through aqueous solutions of acids, salts, and compounds, exceedingly different from each other in their nature, and found them to yield astonishingly uniform results. But many of them which are connected with a secondary action will be more usefully described hereafter (778.).

730. When solutions of caustic potassa or soda, or sulphate of magnesia, or sulphate of soda, were acted upon by the electric current, just as much oxygen and hydrogen was evolved from them as from the diluted sulphuric acid, with which they were compared. When a solution of ammonia, rendered a better conductor by sulphate of ammonia (554.), or a solution of subcarbonate of potassa was experimented with, the hydrogen evolved was in the same quantity as that set free from the diluted sulphuric acid with which they were compared. Hence changes in the nature of the solution do not alter the constancy of electrolytic action upon water.

731. I have already said, respecting large and small electrodes, that change of order caused no change in the general effect (715.). The same was the case with different solutions, or with different intensities; and however the circumstances of an experiment might be varied, the results came forth exceedingly consistent, and proved that the electro-chemical action was still the same.

732. I consider the foregoing investigation as sufficient to prove the very extraordinary and important principle with respect to WATER, that when subjected to the influence of the electric current, a quantity of it is decomposed exactly proportionate to the quantity of electricity which has passed, notwithstanding the thousand variations in the conditions and circumstances under which it may at the time be placed; and further, that when the interference of certain secondary effects (742. &c.), together with the solution or recombination of the gas and the evolution of air, are guarded against, the products of the decomposition may be collected with such accuracy, as to afford a very excellent and valuable measurer of the electricity concerned in their evolution.

733. The forms of instrument which I have given, figg. 64, 65, 66. (709. 710. 711.), are probably those which will be found most useful, as they indicate the quantity of electricity by the largest volume of gases, and cause the least obstruction to the passage of the current. The fluid which my present experience leads me to prefer, is a solution of sulphuric acid of specific gravity about 1.336, or from that to 1.25; but it is very essential that there should be no organic substance, nor any vegetable acid, nor other body, which, by being liable to the action of the oxygen or hydrogen evolved at the electrodes (773. &c.), shall diminish their quantity, or add other gases to them.

734. In many cases when the instrument is used as a comparative standard, or even as a measurer, it may be desirable to collect the hydrogen only, as being less liable to absorption or disappearance in other ways than the oxygen; whilst at the same time its volume is so large, as to render it a good and sensible indicator. In such cases the first and second form of apparatus have been used, figg. 62, 63. (707. 708.). The indications obtained were very constant, the variations being much smaller than in those forms of apparatus collecting both gases; and they can also be procured when solutions are used in comparative experiments, which, yielding no oxygen or only secondary results of its action, can give no indications if the educts at both electrodes be collected. Such is the case when solutions of ammonia, muriatic acid, chlorides, iodides, acetates or other vegetable salts, &c., are employed.

735. In a few cases, as where solutions of metallic salts liable to reduction at the negative electrode are acted upon, the oxygen may be advantageously used as the measuring substance. This is the case, for instance, with sulphate of copper.

736. There are therefore two general forms of the instrument which I submit as a measurer of electricity; one, in which both the gases of the water decomposed are collected (709. 710. 711.); and the other, in which a single gas, as the hydrogen only, is used (707. 708.). When referred to as a comparative instrument, (a use I shall now make of it very extensively,) it will not often require particular precaution in the observation; but when used as an absolute measurer, it will be needful that the barometric pressure and the temperature be taken into account, and that the graduation of the instruments should be to one scale; the hundredths and smaller divisions of a cubical inch are quite fit for this purpose, and the hundredth may be very conveniently taken as indicating a DEGREE of electricity.