The Bakerian Lecture: On Electrolysis

Humphrey Davy

Read November 19, 1807.

I. Introduction.

In the Bakerian Lecture which I had the honour of presenting to the Royal Society last year, I described a number of decompositions and chemical changes produced in substances of known composition by electricity, and I ventured to conclude from the general principles on which the phenomena were capable of being explained, that the new methods of investigation promised to lead to a more intimate knowledge than had hitherto been obtained, concerning the true elements of bodies.

This conjecture, then sanctioned only by strong analogies, I am now happy to be able to support by some conclusive facts. In the course of a laborious experimental application of the powers of electro-chemical analysis, to bodies which have appeared simple when examined by common chemical agents, or which at least have never been decomposed, it has been my good fortune to obtain new and singular results. [p.363]

Such of the series of experiments as are in a tolerably mature state, and capable of being arranged in a connected order, I shall detail in the following sections, particularly those which demonstrate the decomposition and composition of the fixed alkalies, and the production of the new and extraordinary bodies which constitute their bases.

In speaking of novel methods of investigation, I shall not fear to be minute. When the common means of chemical research have been employed, I shall mention only results. A historical detail of the progress of the investigation, of all the difficulties that occurred, and of the manner in which they were overcome, and of all the manipulations employed, would far exceed the limits assigned to this Lecture. It is proper to state, however, that when general facts are mentioned, they are, such only as have been deduced from processes carefully performed and often repeated.

II. On the Methods used for the Decomposition of the fixed Alkalies.

The researches I had made on the decomposition of acids, and of alkaline and earthy neutral compounds, proved that the powers of electrical decomposition were proportional to the strength of the opposite electricities in the circuit, and to the conducting power and degree of concentration of the materials employed.

In the first attempts, that I made on the decomposition of the fixed alkalies, I acted upon aqueous solutions of potash and soda, saturated at common temperatures, by the highest electrical power I could command, and which was produced by a combination of Voltaic batteries belonging to the Royal Institution, containing 24 plates of copper and zinc of 12 inches square, 100 plates of 6 inches, and 150 of 4 inches square, charged with solutions of alum and nitrous acid; but in these cases, though there was a high intensity of action, the water of the solutions alone was affected, and hydrogen and oxygen disengaged with the production of much heat and violent effervescence.

The presence of water appearing thus to prevent any decomposition, I used potash in igneous fusion. By means of a stream of oxygen gas from a gasometer applied to the flame of a spirit lamp, which was thrown on a platina spoon containing potash, this alkali was kept for some minutes in a strong red heat, and in a state of perfect fluidity. The spoon was preserved in communication with the positive side of the battery of the power of 100 of 6 inches, highly charged; and the connection from the negative side was made by a platina wire.

By this arrangement some brilliant phenomena were produced. The potash appeared a conductor in a high degree, and as long as the communication was preserved, a most intense light was exhibited at the negative wire, and a column of flame, which seemed to be owing to the development of combustible matter, arose from the point of contact.

When the order was changed, so that the platina spoon was made negative, a vivid and constant light appeared at the opposite point: there was no effect of inflammation round it; but aeriform globules, which inflamed in the atmosphere, rose through the potash.

The platina, as might have been expected, was considerably acted upon; and in the cases when it had been negative, in the highest degree.

The alkali was apparently dry in this experiment; and it seemed probable that the inflammable matter arose from its decomposition. The residual potash was unaltered; it contained indeed a number of dark grey metallic particles, but these proved to be derived from the platina.

I tried several experiments on the electrization of potash rendered fluid by heat, with the hopes of being able to collect the combustible matter, but without success; and I only attained mv object by employing electricity as the common agent for fusion and decomposition.

Though potash, perfectly dried by ignition, is a non-conductor, yet it is rendered a conductor by a very slight addition of moisture, which does not perceptibly destroy its aggregation; and in this state it readily fuses and decomposes by strong electrical powers.

A small piece of pure potash, which had been exposed for a few seconds to the atmosphere, so as to give conducting power to the surface, was placed upon an insulated disc of platina, connected with the negative side of the battery of the power of 250 of 6 and 4, in a state of intense activity; and a platina wire, communicating with the positive side, was brought in contact with the upper surface of the alkali. The whole apparatus was in the open atmosphere.

Under these circumstances a vivid action was soon observed to take place. The potash began to fuse at both its points of electrization. There was a violent effervescence at the upper surface; at the lower, or negative surface, there was no liberation of elastic fluid; but small globules having a high metallic lustre, and being precisely similar in visible characters to quicksilver, appeared, some of which burnt with explosion and bright flame, as soon as they were formed, and others remained, and were merely tarnished, and finally covered by a white film which formed on their surfaces.

These globules, numerous experiments soon showed to be the substance I was in search of, and a peculiar inflammable principle the basis of potash. I found that the platina was in no way connected with the result, except as the medium for exhibiting the electrical powers of decomposition; and a substance of the same kind was produced when pieces of copper, silver, gold, plumbago, or even charcoal were employed for completing the circuit.

The phenomenon was independent of the presence of air; I found that it took place when the alkali was in the vacuum of an exhausted receiver.

The substance was likewise produced from potash fused by means of a lamp, in glass tubes confined by mercury, and furnished with hermetically inserted platina wires by which the electrical action was transmitted. But this operation could not be carried on for any considerable time; the glass was rapidly dissolved by the action of the alkali, and this substance soon penetrated through the body of the tube.

Soda, when acted upon in the same manner as potash, exhibited an analogous result; but the decomposition demanded greater intensity of action in the batteries, or the alkali was required to be in much thinner and smaller pieces. With the battery of 100 of 6 inches in full activity I obtained good results from pieces of potash weighing from 40 to 70 grains, and of a thickness which made the distance of the electrified metallic surfaces nearly a quarter of an inch; but with a similar power it was impossible to produce the effects of decomposition on pieces of soda of more than 15 or 20 grains in weight, and that only when the distance between the wires was about 1–8 or 1–10 of an inch.

The substance produced from potash remained fluid at the temperature of the atmosphere at the time of its production; that from soda, which was fluid in the degree of heat of the alkali during its formation, became solid on cooling, and appeared having the lustre of silver.

When the power of 250 was used, with a very high charge for the decomposition of soda, the globules often burnt at the moment of their formation, and sometimes violently exploded and separated into smaller globules, which flew with great velocity through the air in a state of vivid combustion, producing a beautiful effect of continued jets of fire.

III. Theory of the Decomposition of the fixed Alkalies; their Composition, and Production.

As in all decompositions of compound substances which I had previously examined, at the same time that combustible bases were developed at the negative surface in the electrical circuit, oxygen was [p.366] produced, and evolved or carried into combination at the positive surface, it was reasonable to conclude that this substance was generated in a similar manner by the electrical action upon the alkalies; and a number of experiments made above mercury, with the apparatus for excluding external air, proved that this was the case.

When solid potash, or soda in its conducting state, was included in glass tubes furnished with electrified platina wires, the new substances were generated at the negative surfaces; the gas given out at the other surface proved by the most delicate examination to be pure oxygen; and unless an excess of water was present, no gas was evolved from the negative surface.

In the synthetical experiments, a perfect coincidence likewise will be found.

I mentioned that the metallic lustre of the substance from potash immediately became destroyed in the atmosphere, and that a white crust formed upon it. This crust I soon found to be pure potash, which immediately deliquesced, and new quantities were formed, which in their turn attracted moisture from the atmosphere till the whole globule disappeared, and assumed the form of a saturated solution of potash.

When globules were placed in appropriate tubes containing common air or oxygen gas confined by mercury, an absorption of oxygen took place; a crust of alkali instantly formed upon the globule; but from the want of moisture for its solution, the process stopped, the interior being defended from the action of the gas.

With the substance from soda, the appearances and effects were analogous.

When the substances were strongly heated, confined in given proportions of oxygen, a rapid combustion with a brilliant white flame was produced, and the metallic globules were found converted into a white and solid mass, which in the case of the substance from potash was found to be potash, and in the case of that from soda, soda.

Oxygen gas was absorbed in this operation, and nothing emitted which affected the purity of the residual air.

The alkalies produced were apparently dry, or at least contained no more moisture than might well be conceived to exist in the oxygen gas absorbed; and their weights considerably exceeded those of the combustible matters consumed.

The processes on which these conclusions are rounded will be fully described hereafter, when the minute details which are necessary will be explained, and the proportions of oxygen, and of the respective inflammable substances which enter into union to form the fixed alkalies, will be given.

It appears, then, that in these facts there is the same evidence for the decomposition of potash and soda into oxygen and two peculiar substances, as there is for the decomposition of sulphuric and phosphoric acids and the metallic oxides into oxygen and their respective combustible bases.

In the analytical experiments, no substances capable of decomposition are present but the alkalies and a minute portion of moisture; which seems in no other way essential to the result, than in rendering them conductors at the surface: for the new substances are not generated till the interior, which is dry, begins to be fused; they explode when in rising through the fused alkali they come in contact with the heated moistened surface; they cannot be produced from crystallized alkalies, which contain much water; and the effect produced by the electrization of ignited potash, which contains no sensible quantity of water, confirms the opinion of their formation independently of the presence of this substance.

The combustible bases of the fixed alkalies seem to be repelled as other combustible substances, by positively electrified surfaces, and attracted by negatively electrified surfaces, and the oxygen follows the contrary order; or the oxygen being naturally possessed of the negative energy, and the bases of the positive, do not remain in combination when either of them is brought into an electrical state opposite to its natural one. In the synthesis, on the contrary, the natural energies or attractions come in equilibrium with each other; and when these are in a low state at common temperatures, a slow combination is effected; but when they are exalted by heat, a rapid union is the result; and as in other like cases with the production of fire. A number of circumstances relating to the agencies of the bases of the alkalies will be immediately stated, and will be found to offer confirmations of these general conclusions.