In 1826 he described the prismatically-coloured films of metal, known as Nobili's' rings, deposited electrolytically from solutions of lead and other salts when the anode is a polished iron plate and the cathode is a fine wire placed vertically above it.
If in a vessel of nitric acid are placed a large platinum plate and a platinum electrode of very small surface such as that produced when an extremely fine platinum wire is slightly immersed in the liquid, and if a current from a single voltaic cell is passed through the electrolytic cell so that the fine wire is the anode or positive pole, then the small surface will be polarized or covered with a film of gas due to electrolysis (fig.
In the case we have chosen, the solution becomes stronger near the anode, or electrode at which the current enters, and weaker near the cathode, or electrode at which it leaves the solution.
If, instead of using copper electrodes, we take plates of platinum, copper is still deposited on the cathode; but, instead of the anode dissolving, free sulphuric acid appears in the neighbouring solution, and oxygen gas is evolved at the surface of the platinum plate.
Thus, with a dilute solution of sulphuric acid and platinum electrodes, hydrogen gas is evolved at the cathode, while, as the result of a secondary action on the anode, sulphuric acid is there re-formed, and oxygen gas evolved.
Again, with the solution of a salt such as sodium chloride, the sodium, which is primarily liberated at the cathode, decomposes the water and evolves hydrogen, while the chlorine may be evolved as such, may dissolve the anode, or may liberate oxygen from the water, according to the nature of the plate and the concentration of the solution.
Into the solution dips a silver plate wrapped in filter paper, and the current is passed from the silver plate as anode to the bowl as cathode.
If the anode consist of platinum, cyanogen gas is evolved thereat from the anion Ag(CN) 2, and the platinum becomes covered with the insoluble silver cyanide, AgCN, which soon stops the current.
Jahn, 2 the processes at the anode can be represented by the equations 2CH 3 000+H 2 0 =2CH3 000H+0 2 C H 3.
Many organic compounds can be prepared by taking advantage of secondary actions at the electrodes, such as reduction by the cathodic hydrogen, or oxidation at the anode (see Electrochemistry).
Under the influence of an applied electric force, he imagined that the B part of the first molecule was liberated at the anode, and that the A part thus isolated united with the B part of the second molecule, which, in its turn, passed on its A to the B of the third molecule.
If we assume that no other cause is at work, it is easy to prove that, with non-dissolvable electrodes, the ratio of salt lost at the anode to the salt lost at the cathode must be equal to the ratio of the velocity of the cation to the velocity of the anion.
If some of the anions, instead of being simple iodine ions represented chemically by the symbol I, are complex structures formed by the union of iodine with unaltered cadmium iodide - structures represented by some such chemical formula as I(CdI 2), the concentration of the solution round the anode would be increased by the passage of an electric current, and the phenomena observed would be explained.
Zinc dissolves at the anode, an equal amount of zinc replaces an equivalent amount of copper on the other side of the porous partition, and the same amount of copper is deposited on the cathode.
But the internal rearrangements which accompany the production of a current do not cause any change in the original nature of the electrodes, fresh zinc being exposed at the anode, and copper being deposited on copper at the cathode.
But, on the other hand, if a few drops of acid be placed in the vessel with the platinum, bubbles of hydrogen appear, and a current flows, zinc dissolving at the anode, and hydrogen being liberated at the cathode.
The concentration of the simple copper ions is then so much diminished that the copper plate becomes an anode with regard to zinc. Thus the cell - copper I potassium cyanide solution I potassium sulphate solution - zinc sulphate solution I zinc - gives a current which carries copper into solution and deposits zinc. In a similar way silver could be made to act as anode with respect to cadmium.
Very irregular surfaces may require the use of specially shaped anodes in order that the distance between the electrodes may be fairly uniform, otherwise the portion of the cathode lying nearest to the anode may receive an undue share of the current, and therefore a greater thickness of coat.
Large metallic surfaces (especially external surfaces) are sometimes plated by means of a "doctor," which, in its simplest form, is a brush constantly wetted with the electrolyte, with a wire anode buried amid the hairs or bristles; this brush is painted slowly over the surface of the metal to be coated, which must be connected to the negative terminal of the electrical generator.
Sherard Cowper Coles patented a process in which, working with a high current density, a lead anode is used, and powdered zinc is kept suspended in the solution to maintain the proportion of zinc in the electrolyte, and so to guard against the gradual acidification of the bath.
Canvas diaphragms were used to prevent the acid formed by electrolysis at the anode from mixing with the cathode liquor, and so hindering deposition.
13,336 of 1894) a rapidly rotating cathode is used in a chloride solution, a porous partition separating the tank into anode and cathode compartments, and the chlorine generated by electrolysis at the anode being recovered.
On passing a current of electricity, of which the volume and pressure are adjusted to the conditions of the electrolyte and electrodes, the anode slowly dissolves, leaving the insoluble impurities in the form of a sponge, if the proportion be considerable, but otherwise as a mud or slime which becomes detached from the anode surface and must be prevented from coming into contact with the cathode.
From these and other considerations it is obvious that (I) the electrolyte must be such as will freely dissolve the metal to be refined; (2) the electrolyte must be able to dissolve the major portion of the anode, otherwise the mass of insoluble matter on the outer layer will prevent access of electrolyte to the core, which will thus escape refining; (3) the electrolyte should, if possible, be incapable of dissolving metals more electro-negative than that to be refined; (4) the proportion of soluble electro-positive impurities must not be excessive, or these substances will accumulate too rapidly in the solution and necessitate its frequent purification; (5) the current density must be so adjusted to the strength of the solution and to other conditions that no relatively electro-positive metal is deposited, and that the cathode deposit is physically suitable for subsequent treatment; (6) the current density should be as high as is consistent with the production of a pure and sound deposit, without undue expense of voltage, so that the operation may be rapid and the "turnover" large; (7) the electrolyte should be as good a conductor of electricity as possible, and should not, ordinarily, be altered chemically by exposure to air; and (8) the use of porous partitions should be avoided, as they increase the resistance and usually require frequent renewal.
The solution of the iron anode was intended to afford the necessary energy.
If, however, no porous division be used to prevent the intermingling by diffusion of the anode and cathode solutions, a complicated set of subsidiary reactions takes place.
The chlorine reacts with the caustic soda, forming sodium hypochlorite, and this in turn, with an excess of chlorine and at higher temperatures, becomes for the most part converted into chlorate, whilst any simultaneous electrolysis of a hydroxide or water and a chloride (so that hydroxyl and chlorine are simultaneously liberated at the anode) also produces oxygen-chlorine compounds direct.
Hypochlorites were made, at ordinary temperatures, and chlorates at higher temperatures, in a cell without a partition in which the cathode was placed horizontally immediately above the anode, to favour the mixing of the ascending chlorine with the descending caustic solution.
Kellner, who in 1886 patented the use of cathode (caustic soda) and anode (chlorine) liquors in the manufacture of cellulose from wood-fibre, and has since evolved many similar processes, has produced an apparatus that has been largely used.
Similarly, the formation of organic halogen products may be effected by electrolytic chlorine, as, for example, in the production of chloral by the gradual introduction of alcohol into an anode cell in which the electrolyte is a strong solution of potassium chloride.
Many electrolytic methods have been proposed for the purification of sugar; in some of them soluble anodes are used for a few minutes in weak alkaline solutions, so that the caustic alkali from the cathode reaction may precipitate chemically the hydroxide of the anode metal dissolved in the liquid, the precipitate carrying with it mechanically some of the impurities present, and thus clarifying the solution.
In the " dry " methods the silver is converted into sulphide or chloride, the gold remaining unaltered; in the " wet " methods the silver is dissolved by nitric acid or boiling sulphuric acid; and in the electrolytic processes advantage is taken of the fact that under certain current densities and other circumstances silver passes from an anode composed of a gold-silver alloy to the cathode more readily than gold.
One process depends upon the fact that, with a suitable current density, if a very dilute solution of silver nitrate be electrolysed between an auriferous silver anode and a silver cathode, the silver of the anode is dissolved out and deposited at the cathode, the gold remaining at the anode.
Gold is left in the anode slime when copper or silver are refined by the usual processes, but if the gold preponderate in the anode these processes are inapplicable.
In this process all the anode metals pass into solution except iridium and other refractory metals of that group, which remain as metals, and silver, which is converted into insoluble chloride; lead and bismuth form chloride and oxychloride respectively, and these dissolve until the bath is saturated with them, and then precipitate with the silver in the tank.
Platinum and palladium dissolved from the anode accumulate in the solution, and are removed at intervals of, say, a few months by chemical precipitation.
In art-work of this nature the principal points to be looked to in depositing are the electrical connexions to the cathode, the shape of the anode (to secure uniformity of deposition), the circulation of the electrolyte, and, in some cases, the means for escape of anode oxygen.
The Edison electric meter, like those of Sprague and Lane-Fox, was based upon the principle that when an electric current flows through an electrolyte, such as sulphate of copper or sulphate of zinc, the electrodes being plates of copper or zinc, metal is dissolved off one plate (the anode) and deposited on the other plate (the cathode).
In this meter the electrolyte is a solution of mercurous nitrate which is completely enclosed in a glass tube of a particular form, having a mercury anode and a platinum or carbon cathode.
Henri Moissan obtained the metal of 99% purity by electrolysing calcium iodide at a low red heat, using a nickel cathode and a graphite anode; he also showed that a more convenient process consisted in heating the iodide with an excess of sodium, forming an amalgam of the product, and removing the sodium by means of absolute alcohol (which has but little action on calcium), and the mercury by distillation.
Filr Electrochemie, 1902, p. 8757) obtained the metal of 90% purity by electrolysing calcium chloride at a temperature of about 780°, using an iron cathode, the anode being the graphite vessel in which the electrolysis was carried out.
1902, 35, p. 3612) employed a mixture of calcium chloride (ioo parts) and fluorspar (16.5 parts), which was fused in a porcelain crucible and electrolysed with a carbon anode and an iron cathode.
The fluorine, which is liberated as a gas at the anode, is passed through a well cooled platinum vessel, in order to free it from any acid fumes that may be carried over, and finally through two platinum tubes containing sodium fluoride to remove the last traces of hydrofluoric acid; it is then collected in a platinum tube closed with fluor-spar plates.
Among the difficulties here to be contended with are the destructive action of fused chlorides and of the reduced alkali metals upon most non-metallic substances available for the containing vessel and its partition, and also of the anode chlorine upon metals; also the low fusing-point (95° C. for sodium, and 62° C. for potassium) and the low specific gravity of the metals, so that the separated metal floats as a fused layer upon the top of the melted salt.
Borchers endeavoured to contend against the first difficulty by employing an iron cathode vessel and a chamotte (fire-clay) anode chamber united by a specially constructed water-cooled joint.
During electrolysis, oxygen is evolved at the anode and escapes from the outer vessel, while the sodium deposited in globules on the cathode floats upwards into the iron cylinder, within which it accumulates, and from which it may be removed at intervals by means of a perforated iron ladle, the fused salt, but not the metal, being able to pass freely through the perforations.
Sodium hydroxide has certain advantages compared with chloride, although it is more costly; its fusing-point is only 320° C., and no anode chlorine is produced, so that both containing vessel and anode may be of iron, and no porous partition is necessary.
Then, by the use of another piece of platinum as anode, mercury is electrolytically deposited upon the platinum, which may also be amalgamated by making it white hot in a Bunsen flame and plunging it in mercury.
Borchers also used an externally heated metal vessel as the cathode; it is provided with a supporting collar or flange a little below the top, so that the upper part of the vessel is exposed to the cooling influence of the air, in order that a crust of solidified salt may there be formed, and so prevent the creeping of the electrolyte over the top. The carbon anode passes through the cover of a porcelain cylinder, open at the bottom, and provided with a side-tube at the top to remove the chlorine formed during electrolysis.
His attention was at first divided between two processes - the chemical method of reducing the chloride with potassium, and an electrolytic method of decomposing it with a carbon anode and a platinum cathode, which was simultaneously imagined by himself and R.