ON ELECTROLYSIS.

By H. SCHUCHT.

Concerning the separations which take place at the positive pole, the composition of the peroxides, and the manner of their determination, relatively little has been done.

If solutions of the salts of lead, thallium, silver, bismuth, nickel, and cobalt are decomposed by the current between platinum electrodes, metal is deposited at the negative, and oxide at the positive electrode. Manganese is precipitated only as peroxide. The formation of peroxide is, of course, effected by the ozone found in the electrolytic oxygen at the positive pole; the oxide existing in solution is brought to a higher degree of oxidation, and is separated out. Its formation may be decreased or entirely prevented by the addition of readily oxidizible bodies, such as organic acids, lactose, glycerine, and preferably by an excess of oxalic acid; but only until the organic matter is transformed into carbonic acid. In this manner Classen separates other metals from manganese in order to prevent the saline solutions from being retained by the peroxide.

With solutions of silver, bismuth, nickel, and cobalt, it is often practicable to prevent the separation of oxide by giving the current a greater resistance—increasing the distance between the electrodes.

The proportion between the quantities of metal and of peroxide deposited is not constant, and even if we disregard the concentration of the solution, the strength of the current and secondary influences (action of nascent hydrogen) is different in acid and in alkaline solutions. In acid solutions much peroxide is formed; in alkaline liquids, little or none. The reason of the difference is that ozone is evolved principally in acid solutions, but appears in small quantities only in alkaline liquids, or under certain circumstances not at all. The quantity of peroxide deposited depends also on the temperature of the saline solution; at ordinary temperatures the author obtained more peroxide—the solution, the time, and the strength of current being equal—than from a heated liquid. The cause is that ozone is destroyed by heat and converted into ordinary oxygen. With the exception of lead and thallium the quantity of metal deposited from an acid solution is always greater than that of the peroxide.

Lead.—Luckow has shown that from acid solutions—no matter what may be the acid—lead is deposited at the anode as a mixture of anhydrous and hydrated peroxide of variable composition. Only very strongly acid solutions let all their lead fall down as peroxide; the precipitation is rapid immediately on closing the circuit, and complete separation is effected only in presence of at least 10 per cent. of free nitric acid. As the current becomes stronger with the increase of free acid, there is deposited upon the first compact layer a new stratum of loosely adhering peroxide.

In presence of small quantities of other metals which are thrown down by the current in the metallic state, such as copper, mercury, etc., peroxide alone is deposited from a solution of lead containing small quantities only of free nitric acid.

The lead peroxide deposited is at first light brown or dark red, and becomes constantly darker and finally taking a velvet-black. As its stratification upon the platinum is unequal, it forms beautifully colored rings.

Experiments show that the quantity of peroxide deposited depends on the nature of the solution and the strength of the current. In case of very feeble currents and slight acidity, its quantity is so small that it does not need to be taken into consideration. If the lead solution is very dilute scarcely any current is observed, lead solutions per se being very bad conductors of electricity.

Faintly acid concentrated lead solutions give loose peroxide along with much spongy metallic lead. Free alkali decreases the separation of peroxide; feebly alkaline solutions, concentrated and dilute, yield relatively much peroxide along with metallic lead, while strongly alkaline solutions deposit no peroxide.

Dried lead peroxide is so sparingly hygroscopic that it may be weighed as such; its weight remains constant upon the balance for a long time. In order to apply the peroxide for quantitative determinations, a large surface must be exposed to action. As positive electrode a platinum capsule is convenient, and a platinum disk as negative pole. The capsule shape is necessary because the peroxide when deposited in large quantities adheres only partially, and falls in part in thin loose scales. It is necessary to siphon off the nitric solution, since, like all peroxides, that of lead is not absolutely insoluble in nitric acid. The methods of Riche and May give results which are always too high, since portions of saline solution are retained by the spongy deposit and can be but very imperfectly removed by washing. This is especially the case in presence of free alkali.

The author has proceeded as follows: The lead peroxide is dried in the capsule, and there is passed over it pure dry gaseous sulphurous acid in a strong current from a rather narrow delivery tube. Lead sulphate is formed with evolution of heat; it is let cool under the exsiccator, and weighed as such. Or he ignites the peroxide along with finely pulverized ammonium sulphite; the mass must have a pure white color. After the conclusion of the reaction it is ignited for about 20 minutes. The results are too high. The proportion of actual lead peroxide in the deposit ranges from 94 to 94.76 per cent. The peroxide precipitated from a nitric solution may, under certain circumstances, be anhydrous. This result is due to the secondary influences at the positive pole, where the free acid gradually withdraws water from the peroxide.

The peroxide thrown down from alkaline solutions retains alkali so obstinately that it cannot be removed by washing; the peroxide plays here the part of an acid. The lead nitrate mechanically inclosed in the peroxide is resolved by ignition into oxide, hyponitric acid, and oxygen; this small proportion of lead oxide does not exert an important influence on the final result. The quantity of matter mechanically inclosed is relatively high, as in the precipitation of much lead peroxide there is relatively more saline matter occluded than when a few centigrammes are deposited. The peroxide incloses also more foreign matter if it is thrown down upon a small surface than if it is deposited in a thin layer over a broad surface. From numerous analyses the author concludes that in presence of much free nitric acid the proportion of water is increased; with free alkali the reverse holds good.

Thallium behaves similarly to lead. From a nitric acid solution it is thrown down, according to the proportion of free acid, either as sesquioxide only or in small quantities as silvery, metallic leaflets; from alkaline solutions it is deposited as sesquioxide and metal, the latter of a lead-gray color. Thallium solutions conduct the electric current badly. Thallium oxide resembles lead peroxide in color; at a strong heat it melts, becomes darker, and is converted into peroxide, in which state it can be weighed.

Silver.—All solutions of silver salts, except the nitrate, and those containing a very large quantity of free nitric acid or nitrates, deposit electrolytically merely metallic silver. In the above mentioned exceptional cases there is formed a small quantity of peroxide which adheres to the anode as a blackish-gray deposit. The greatest quantity of peroxide is obtained on employing a concentrated, strongly acid solution of the nitrate, and a strong current. If the solution is very dilute we obtain no peroxide, or mere traces which disappear again toward the end of the process. The peroxide is deposited at first in small, dark, shining octahedral crystals; subsequently, in an amorphous state. At 110° it evolves oxygen suddenly, and is converted into metallic silver. It dissolves in ammonia with a violent escape of nitrogen. In nitric acid it dissolves without decomposition and with a red color.

The author uses a galvanic current for reducing silver residues, consisting of sulphocyanide. The salt is mixed with sulphuric acid in a roomy platinum capsule, and a fine platinum wire gauze is used as positive electrode.

Bismuth.—The current resolves bismuth solutions into metal and bismutic acid. The latter is deposited at the positive pole, and in thin layers appears of a golden-yellow, but in thick strata is darker, approaching to red. Its formation is very gradual, and in time it disappears again, owing to secondary actions of the current. On ignition it becomes lemon yellow, and transitorily darker, even brown, and passes into the sexquioxide.

Nickel and Cobalt.—On the electrolysis of the ammonical solution the sesquioxide appears at the positive pole. Its formation is prevented by an excess of ammonia. The author never obtains more than 3½ per cent. of the quantity of the metal. The sesquioxides dissolve in ammonia without escape of nitrogen, and are usually anhydrous.

Manganese.—Manganese is the only metal which is precipitated only as peroxide. It is deposited at once on closing the circuit, and is at first brown, then black and shining. Organic acids, ferrous oxide, chromic oxide, ammonium salts, etc., prevent the formation of peroxide and the red color produced by permanganic acid. In very dilute strongly acid nitric solutions there is formed only permanganic acid, which according to Riche is plainly visible in solutions containing 1/1000000 grm. manganese. On electrolyzing a manganiferous solution of copper nitrate, red permanganic acid appeared in a stratum floating above the platinum disk coated with brown peroxide. No manganese peroxide was deposited. The peroxide adheres firmly to the platinum when the proportion of free acid is small, not exceeding 3 per cent., and the current is not too strong. If the action of the current is prolonged after the peroxide is thrown down, it falls off in laminæ. According to Riche, in a nitric solution the manganese is deposited as peroxide, also at the negative pole. This formation is not directly due to the current, but is a precipitate occasioned by the production of ammonia by the reduction of nitric acid. To determine the manganese in peroxide electrolytically precipitated, it is heated to bright redness in the platinum capsule until the weight becomes constant. The results are too high.

Selenium and Tellurium.—Both these bodies are readily and completely reduced by the current either in acid or alkaline solutions. Selenium is thrown down at first of a fine brownish red, which gradually becomes darker. The deposit of tellurium is of a bluish black color. If the current is feeble, the deposit of selenium is moderately compact; that of tellurium is always loose, and it often floats on the liquid. A strong current precipitates both as powders. The positive pole is coated during electrolysis with a film of a dark color in case of selenium, but of a lemon yellow with tellurium. As in case of arsenic and antimony, the hydrogen evolved at the negative pole combines with the reduced substances, forming hydrogen, selenide, or telluride, which remain in part in solution in the liquid. The reduced metal separates out at the anode in a friable condition.—Zeitschrift fur Analytische Chemie, and Chemical News.