Part 37

737. It can scarcely be needful to point out further than has been done how this instrument is to be used. It is to be introduced into the course of the electric current, the action of which is to be exerted anywhere else, and if 60° or 70° of electricity are to be measured out, either in one or several portions, the current, whether strong or weak, is to be continued until the gas in the tube occupies that number of divisions or hundredths of a cubical inch. Or if a quantity competent to produce a certain effect is to be measured, the effect is to be obtained, and then the indication read off. In exact experiments it is necessary to correct the volume of gas for changes in temperature and pressure, and especially for moisture. For the latter object the volta-electrometer (fig. 66.) is most accurate, as its gas can be measured over water, whilst the others retain it over acid or saline solutions.

For a simple table of correction for moisture, I may take the liberty of referring to my Chemical Manipulation, edition of 1830, p. 376.

738. I have not hesitated to apply the term degree (736.), in analogy with the use made of it with respect to another most important imponderable agent, namely, heat; and as the definite expansion of air, water, mercury, &c., is there made use of to measure heat, so the equally definite evolution of gases is here turned to a similar use for electricity.

739. The instrument offers the only actual measurer of voltaic electricity which we at present possess. For without being at all affected by variations in time or intensity, or alterations in the current itself, of any kind, or from any cause, or even of intermissions of action, it takes note with accuracy of the quantity of electricity which has passed through it, and reveals that quantity by inspection; I have therefore named it a VOLTA-ELECTROMETER.

740. Another mode of measuring volta-electricity may be adopted with advantage in many cases, dependent on the quantities of metals or other substances evolved either as primary or as secondary results; but I refrain from enlarging on this use of the products, until the principles on which their constancy depends have been fully established (791. 848.);

741. By the aid of this instrument I have been able to establish the definite character of electro-chemical action in its most general sense; and I am persuaded it will become of the utmost use in the extensions of the science which these views afford. I do not pretend to have made its detail perfect, but to have demonstrated the truth of the principle, and the utility of the application.

As early as the year 1811, Messrs. Gay-Lussac and Thénard employed chemical decomposition as a measure of the electricity of the voltaic pile. See Recherches Physico-chymiques, p. 12. The principles and precautions by which it becomes an exact measure were of course not then known.--Dec. 1838.

¶ vi. On the primary or secondary character of the bodies evolved at the Electrodes.

742. Before the volta-electrometer could be employed in determining, as a general law, the constancy of electro-decomposition, it became necessary to examine a distinction, already recognised among scientific men, relative to the products of that action, namely, their primary or secondary character; and, if possible, by some general rule or principle, to decide when they were of the one or the other kind. It will appear hereafter that great mistakes inspecting electro-chemical action and its consequences have arisen from confounding these two classes of results together.

743. When a substance under decomposition yields at the electrodes those bodies uncombined and unaltered which the electric current has separated, then they may be considered as primary results, even though themselves compounds. Thus the oxygen and hydrogen from water are primary results; and so also are the acid and alkali (themselves compound bodies) evolved from sulphate of soda. But when the substances separated by the current are changed at the electrodes before their appearance, then they give rise to secondary results, although in many cases the bodies evolved are elementary.

744. These secondary results occur in two ways, being sometimes due to the mutual action of the evolved substance and the matter of the electrode, and sometimes to its action upon the substances contained in the body itself under decomposition. Thus, when carbon is made the positive electrode in dilute sulphuric acid, carbonic oxide and carbonic acid occasionally appear there instead of oxygen; for the latter, acting upon the matter of the electrode, produces these secondary results. Or if the positive electrode, in a solution of nitrate or acetate of lead, be platina, then peroxide of lead appears there, equally a secondary result with the former, but now depending upon an action of the oxygen on a substance in the solution. Again, when ammonia is decomposed by platina electrodes, nitrogen appears at the anode; but though an elementary body, it is a secondary result in this case, being derived from the chemical action of the oxygen electrically evolved there, upon the ammonia in the surrounding solution (554.). In the same manner when aqueous solutions of metallic salts are decomposed by the current, the metals evolved at the cathode, though elements, are always secondary results, and not immediate consequences of the decomposing power of the electric current.

Annales de Chimie, 1801, tom. li. p. 167.

745. Many of these secondary results are extremely valuable; for instance, all the interesting compounds which M. Becquerel has obtained by feeble electric currents are of this nature; but they are essentially chemical, and must, in the theory of electrolytic action, be carefully distinguished from those which are directly due to the action of the electric current.

746. The nature of the substances evolved will often lead to a correct judgement of their primary or secondary character, but is not sufficient alone to establish that point. Thus, nitrogen is said to be attracted sometimes by the positive and sometimes by the negative electrode, according to the bodies with which it may be combined (554. 555.), and it is on such occasions evidently viewed as a primary result; but I think I shall show, that, when it appears at the positive electrode, or rather at the anode, it is a secondary result (748.). Thus, also, Sir Humphry Davy, and with him the great body of chemical philosophers, (including myself,) have given the appearance of copper, lead, tin, silver, gold, &c., at the negative electrode, when their aqueous solutions were acted upon by the voltaic current, as proofs that the metals, as a class, were attracted to that surface; thus assuming the metal, in each case, to be a primary result. These, however, I expect to prove, are all secondary results; the mere consequence of chemical action, and no proofs either of the attraction or of the law announced respecting their places.

Annales de Chimie, 1804, tom. li. p. 172.

Elements of Chemical Philosophy, pp. 144. 161.

It is remarkable that up to 1804 it was the received opinion that the metals were reduced by the nascent hydrogen. At that date the general opinion was reversed by Hisinger and Berzelius (Annales de Chimie, 1804, tom. li. p. 174,), who stated that the metals were evolved directly by the electricity: in which opinion it appears, from that time, Davy coincided (Philosophical Transactions, 1826, p. 388).

747. But when we take to our assistance the law of constant electro-chemical action already proved with regard to water (732.), and which I hope to extend satisfactorily to all bodies (821.), and consider the quantities as well as the nature of the substances set free, a generally accurate judgement of the primary or secondary character of the results may be formed: and this important point, so essential to the theory of electrolyzation, since it decides what are the particles directly under the influence of the current, (distinguishing them from such as are not affected,) and what are the results to be expected, may be established with such degree of certainty as to remove innumerable ambiguities and doubtful considerations from this branch of the science.

748. Let us apply these principles to the case of ammonia, and the supposed determination of nitrogen to one or the other electrode (554. 555,). A pure strong solution of ammonia is as bad a conductor, and therefore as little liable to electrolyzation, as pure water; but when sulphate of ammonia is dissolved in it, the whole becomes a conductor; nitrogen almost and occasionally quite pure is evolved at the anode, and hydrogen at the cathode; the ratio of the volume of the former to that of the latter varying, but being as 1 to about 3 or 4. This result would seem at first to imply that the electric current had decomposed ammonia, and that the nitrogen had been determined towards the positive electrode. But when the electricity used was measured out by the volta-electrometer (707. 736.), it was found that the hydrogen obtained was exactly in the proportion which would have been supplied by decomposed water, whilst the nitrogen had no certain or constant relation whatever. When, upon multiplying experiments, it was found that, by using a stronger or weaker solution, or a more or less powerful battery, the gas evolved at the anode was a mixture of oxygen and nitrogen, varying both in proportion and absolute quantity, whilst the hydrogen at the cathode remained constant, no doubt could be entertained that the nitrogen at the anode was a secondary result, depending upon the chemical action of the nascent oxygen, determined to that surface by the electric current, upon the ammonia in solution. It was the water, therefore, which was electrolyzed, not the ammonia. Further, the experiment gives no real indication of the tendency of the element nitrogen to either one electrode or the other; nor do I know of any experiment with nitric acid, or other compounds of nitrogen, which shows the tendency of this element, under the influence of the electric current, to pass in either direction along its course.

749. As another illustration of secondary results, the effects on a solution of acetate of potassa, may be quoted. When a very strong solution was used, more gas was evolved at the anode than at the cathode, in the proportion of 4 to 3 nearly: that from the anode was a mixture of carbonic oxide and carbonic acid; that from the cathode pure hydrogen. When a much weaker solution was used, less gas was evolved at the anode than at the cathode; and it now contained carburetted hydrogen, as well as carbonic oxide and carbonic acid. This result of carburetted hydrogen at the positive electrode has a very anomalous appearance, if considered as an immediate consequence of the decomposing power of the current. It, however, as well as the carbonic oxide and acid, is only a secondary result; for it is the water alone which suffers electro-decomposition, and it is the oxygen eliminated at the anode which, reacting on the acetic acid, in the midst of which it is evolved, produces those substances that finally appear there. This is fully proved by experiments with the volta-electrometer (707.); for then the hydrogen evolved from the acetate at the cathode is always found to be definite, being exactly proportionate to the electricity which has passed through the solution, and, in quantity, the same as the hydrogen evolved in the volta-electrometer itself. The appearance of the carbon in combination with the hydrogen at the positive electrode, and its non-appearance at the negative electrode, are in curious contrast with the results which might have been expected from the law usually accepted respecting the final places of the elements.

750. If the salt in solution be an acetate of lead, then the results at both electrodes are secondary, and cannot be used to estimate or express the amount of electro-chemical action, except by a circuitous process (843.). In place of oxygen or even the gases already described (749.), peroxide of lead now appears at the positive, and lead itself at the negative electrode. When other metallic solutions are used, containing, for instance, peroxides, as that of copper, combined with this or any other decomposable acid, still more complicated results will be obtained; which, viewed as direct results of the electro-chemical action, will, in their proportions, present nothing but confusion, but will appear perfectly harmonious and simple if they be considered as secondary results, and will accord in their proportions with the oxygen and hydrogen evolved from water by the action of a definite quantity of electricity.

751. I have experimented upon many bodies, with a view to determine whether the results were primary or secondary. I have been surprised to find how many of them, in ordinary cases, are of the latter class, and how frequently water is the only body electrolyzed in instances where other substances have been supposed to give way. Some of these results I will give in as few words as possible.

752. Nitric acid.--When very strong, it conducted well, and yielded oxygen at the positive electrode. No gas appeared at the negative electrode; but nitrous acid, and apparently nitric oxide, were formed there, which, dissolving, rendered the acid yellow or red, and at last even effervescent, from the spontaneous separation of nitric oxide. Upon diluting the acid with its bulk or more of water, gas appeared at the negative electrode. Its quantity could be varied by variations, either in the strength of the acid or of the voltaic current: for that acid from which no gas separated at the cathode, with a weak voltaic battery, did evolve gas there with a stronger; and that battery which evolved no gas there with a strong acid, did cause its evolution with an acid more dilute. The gas at the anode was always oxygen; that at the cathode hydrogen. When the quantity of products was examined by the volta-electrometer (707.), the oxygen, whether from strong or weak acid, proved to be in the same proportion as from water. When the acid was diluted to specific gravity 1.24, or less, the hydrogen also proved to be the same in quantity as from water. Hence I conclude that the nitric acid does not undergo electrolyzation, but the water only; that the oxygen at the anode is always a primary result, but that the products at the cathode are often secondary, and due to the reaction of the hydrogen upon the nitric acid.

753. Nitre.--A solution of this salt yields very variable results, according as one or other form of tube is used, or as the electrodes are large or small. Sometimes the whole of the hydrogen of the water decomposed may be obtained at the negative electrode; at other times, only a part of it, because of the ready formation of secondary results. The solution is a very excellent conductor of electricity.

754. Nitrate of ammonia, in aqueous solution, gives rise to secondary results very varied and uncertain in their proportions.

755. Sulphurous acid.--Pure liquid sulphurous acid does not conduct nor suffer decomposition by the voltaic current, but, when dissolved in water, the solution acquires conducting power, and is decomposed, yielding oxygen at the anode, and hydrogen and sulphur at the cathode.

See also De la Rive, Bibliothèque Universelle, tom. xl. p. 205; or Quarterly Journal of Science, vol. xxvii. p, 407.

756. A solution containing sulphuric acid in addition to the sulphurous acid, was a better conductor. It gave very little gas at either electrode: that at the anode was oxygen, that at the cathode pure hydrogen. From the cathode also rose a white turbid stream, consisting of diffused sulphur, which soon rendered the whole solution milky. The volumes of gases were in no regular proportion to the quantities evolved from water in the voltameter. I conclude that the sulphurous acid was not at all affected by the electric current in any of these cases, and that the water present was the only body electro-chemically decomposed; that, at the anode, the oxygen from the water converted the sulphurous acid into sulphuric acid, and, at the cathode, the hydrogen electrically evolved decomposed the sulphurous acid, combining with its oxygen, and setting its sulphur free. I conclude that the sulphur at the negative electrode was only a secondary result; and, in fact, no part of it was found combined with the small portion of hydrogen which escaped when weak solutions of sulphurous acid were used.