In a former memoir1 we showed that it was possible to decompose anhydrous hydrofluoric acid by the action of an electric current. At the negative pole hydrogen collects; at the positive pole a gaseous body is disengaged, having novel properties. The experiment was performed in a platinum U tube, closed by stoppers of fluorite, and having at the upper part of each branch a small delivery tube, also of platinum. Through the stopper passes a platinum rod, which acts as electrode. The metal employed for the positive pole is an alloy containing 10 per cent. of iridium.

To obtain pure anhydrous hydrofluoric acid, we begin by preparing fluorhydrate of fluoride of potassium, taking all the precautions pointed out by M. Fremy. When the salt is obtained pure, it is dried on a water bath at 100°, and the platinum capsule containing it is then placed in a vacuum in the presence of concentrated sulphuric acid, and two or three sticks of potash fused in a silver crucible. The acid and potash are renewed every morning for a fortnight, and the vacuum is kept at 2 cm. of mercury. Care must be taken during this desiccation to pulverize the salt every day in an iron mortar, so as to renew the surface. When the fluorhydrate contains no more water it falls to powder, and is then fit to serve for the preparation of fluoric acid; the fluorhydrate of fluoride of potassium, if well prepared, is much less deliquescent than the fluoride.

When the fluoride is quite dry, it is quickly introduced into a platinum alembic, which has just been dried by heating it to redness. The whole is kept at a gentle temperature for an hour or an hour and a half, so as to allow the decomposition to commence very slowly; the first portions of acid which come over are rejected as they carry with them traces of water remaining in the salt. The platinum receiver is then attached, and the heat increased, allowing the decomposition to proceed with a certain degree of slowness. The receiver is then surrounded with a mixture of ice and salt, and from this moment all the hydrofluoric acid is condensed as a limpid liquid, boiling at 19.5°, very hygroscopic, and, as is well known, giving abundant fumes in presence of the atmospheric moisture.

During this operation the platinum U tube, dried with the greatest care, has been fixed with a cork in a cylindrical glass vessel surrounded with chloride of methyl. Up to the moment of introducing the hydrofluoric acid, the leading tubes are attached to drying tubes containing fused caustic potash. To introduce the hydrochloric acid into the apparatus, it may be absorbed through one of the lateral tubes in the receiver in which it is condensed.

In some experiments we have directly condensed the hydrofluoric acid in the U tube surrounded with chloride of methyl; but in this case care must be taken that the tubes are not clogged up by small quantities of fluoride carried over, which would infallibly lead to an explosion and projections, which are always dangerous with so corrosive a liquid.

When we have introduced in advance in the small platinum apparatus a determined amount of hydrofluoric acid cooled with chloride of methyl, in tranquil ebullition at a temperature of -23°, the current of 20 cells of Bunsen large size, arranged in series, is passed through by means of the electrodes. An amperemeter in the circuit admits of the intensity of the current being observed.

If the hydrofluoric acid contains a small quantity of water, either by accident or design, there is always disengaged at the positive pole ozone, which has no action on crystallized silicium. In proportion as the water contained in the acid is thus decomposed, it is seen by the amperemeter that the conductivity of the liquid rapidly decreases. With absolutely anhydrous hydrofluoric acid the current will no longer pass. In many of our experiments we have succeeded in obtaining an acid so anhydrous that a current of 25 amperes was entirely arrested.

To render the liquid conducting, we have added before each experiment a small quantity of dried and fused fluorhydrate of fluoride of potassium. In this case, decomposition proceeds in a continuous manner; we obtain at the negative pole hydrogen, and at the positive pole a regular disengagement of a colorless gas in which crystallized silicium in the cold burns with great brilliancy, becoming fluoride of silicium. This latter gas has been collected over mercury, and accurately characterized.

Deville's adamantine boron burns in the same manner, but with more difficulty, becoming fluoride or boron. The small quantity of carbon and aluminum which it contains impedes the combination. Arsenic and antimony in powder combine with this gaseous body with incandescence. Sulphur takes fire in it, and iodine combines with a pale flame, losing its color. We have already remarked that it decomposes cold water, producing ozone and hydrofluoric acid.

The metals are attacked with much less energy. This is due, we think, to the small quantity of metallic fluoride formed preventing the action being very deep. Iron and manganese in powder, slightly heated, burn with sparks. Organic bodies are violently attacked. A piece of cork placed near the end of the platinum tube, where the gas is evolved, immediately carbonizes and inflames. Alcohol, ether, benzol, spirit of turpentine, and petroleum take fire on contact.

The gas evolved at the negative pole is hydrogen, burning with a pale flame, and producing none of these reactions.

When the experiment has lasted several hours, and there is not enough hydrofluoric acid left at the bottom of the tube to separate the two gases, they recombine in the apparatus in the cold, with violent detonation.

We have satisfied ourselves, by direct experiment, that a mixture of ozone and hydrofluoric acid produces none of the reactions described above.

It is the same with gaseous hydrofluoric acid. Finally we may add that the hydrofluoric acid employed, as well as the hydrofluorate of fluoride, were absolutely free from chlorine.

The gas obtained in our experiments is therefore either fluorine or a perfluoride of hydrogen.

New experiments are necessary to settle this last point. We hope soon to lay the results before the Academy. - Comptes Mendus, vol. ciii., p. 202, July 19, 1886; Chem. News.


Comptes Rendus, vol. cii., p. 1543, and Chemical News, vol. liv., p. 36.