Chapter 7

The square plate had a resistance of 35.5 Siemens units, and the reticulated ring one of 32.5. From the first figure we deduce k = 1/91.12, that is to say, the specific conductivity of river-water is 1:91120000. Calculation, then, gives as the resistance of the earth in Siemens units:

Calculated. Observed. Square plate. 33.5 33.5 Annular ring. 31.76 32.5

These figures prove the accuracy of the calculations that had been made in an approximate way.

The experiments were performed upon the Elba, above Dresden. Other experiments still had reference to the influence of immersion. In order to diminish polarization, only instantaneous currents from the measuring pile were employed. It was to be supposed that the current of water through which the bubbles of gas were removed from the electrodes would not have permitted of a notable resistance of polarization. Later measurements, made upon a ribbon buried, like the plates, in the earth, gave likewise most favorable results.

As a result of these experiments, the State railways of Saxony have, in such cases as were practicable, introduced the annular network of copper. There are some manufacturers, too, who seem desirous of adopting this system, although it has hardly emerged from the period of experiment. The pecuniary advantages that will result from an application of it ought, it would seem, to dispel a large proportion of the criticisms directed against the erection of lightning rods, from the standpoint of expense, and contribute to extend an arrangement which may be considered as a very happy one.

If we compare the square plate with the equivalent annular network, constructed as above indicated, and which should possess, according to the author an external diameter of 1.26 m. and of 3.45 m., we find that:

The square plate, 1 mm. thick weighs 8.9 kilos. " 2 " " " 17.8 " The annular network " 1.64 "

The cost of reticulated ribbon per meter amounts to about 4.4 francs, supposing it to be arranged as shown in the cut.

As term of comparison, we may admit that the following forms are nearly the equivalent of a horizontal, unburied plate one meter square.

Length. Diameter. Vertical cylinder buried 1.40 m. 0.13 m. " " " 1.80 m. 0.06 m. Vertical bar " 2.60 m. 0.013 m. Horizontal bar " 5.20 m. 0.013 m.

Horizontal flat ring 1.32 m. in external diameter, and 1.08 m. internal.

Horizontal network 1.01 m. square, and having meshes of the same size as those of the reticulated ribbon.

Horizontal reticulated ribbon 3 m. in length and of the structure described.

Horizontal annular ring 1.26 m. in external diameter, 0.94 m. internal.

In conclusion, let us meet an objection that might be made to the accuracy of the hypotheses that serve as a base to the preceding calculations, in cases where ground plates for lightning rods and not for telegraphs are concerned. Between the two ground plates of a telegraph line there is generally a distance such that the curves of the current undergo no deviation in the vicinity of one of the electrodes (the only part important for integrations) through the influence of the other. But it might be admitted that such would prove the case with a lightning rod in a storm, at the time of the passage of the fluid into the earth. The ground plate here is one of the electrodes, and the other is replaced by the surface of the earth strongly charged to a great distance under the storm clouds. If we suppose (what may be admitted in a good lightning rod) that there no longer occurs any spark from the point downward, the curves of the current, in starting perpendicularly from the ground plate, would be obliged to leave their rectilinear trajectory and strike the surface of the earth at right angles. When the electricity flows through a plane surface into an infinite body, it is only when such surface presents a very great development that the respective potentials decrease very slowly in the vicinity of the said surface. No notable modification occurs, then, in the curves of equal potential, in the vicinity of the ground plate through the action of this extended charge, nor consequently any modification in the curves of the current; but the electricity which spreads has but a short distance to travel in order to overcome the most important resistances.

The calculations of resistances given above have, then, the same value for discharges of atmospheric electricity.--_Bull. du Musee de l'Industrie._

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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._

* * * * *

THE ELECTRO-CHEMICAL EQUIVALENT OF SILVER.

A very careful and important determination of the electrochemical equivalent of silver has been made at the observatory of the Physical Institute of Würzbourg, and the results are that an ampere current flowing for a second, or a coulomb of electricity deposits 1.1183 milligrammes of silver or 0.3281 milligramme of copper, and decomposes 0.09328 milligramme of water, a result agreeing closely with that of Lord Rayleigh recently communicated to the Physical Society. An ampere therefore deposits 4.0259 grammes of silver per hour; Kohlrausch's value is 4.0824, a value hitherto accepted universally. This value is so useful in measuring electric currents with accuracy, and free from the disturbances of magnetism, etc., that it is eminently satisfactory to find the German value agree with that of Lord Rayleigh, which will probably be adopted by English electricians.

* * * * *

A NEW STANDARD LIGHT.

Herr Hefner-Alteneck has suggested a new standard light for photometric purposes, which promises to be very simple and effective in operation. The light is produced by an open flame of amyl-acetate burning from a wick of cotton fiber which fills a tube of German silver 1 in. long and 316 mils. internal diameter; the external diameter being 324 mils. The flame is 1.58 in. high from top to bottom; and it should be lighted at least ten minutes before using the light for testing. A cylindrical glass chimney surrounds it to ward off air currents. About 2 per cent. of the light is absorbed by the glass. The power of the flame is that of a standard English candle; and experiments have shown that amyl acetate, which besides is not expensive, is the best fuel for steadiness and brilliance. Neither the substitution of commercial amyl-acetate for pure nor the use of a wick of cotton thread for loose cotton fiber alters the illuminating power; but the wick should be trimmed square across the mouth of the tube, for if it project and droop the illuminating power is increased.

* * * * *

[NATURE.]

DR. FEUSSNER'S NEW POLARIZING PRISM.

In a recent number of the _Zeitschrift fur Instrumentenkunde_ (iv., 42-50, February, 1884), Dr. K. Feussner of Karlsruhe has given a detailed description of a polarizing prism lately devised by him, which presents several points of novelty, and for which certain advantages are claimed. The paper also contains an account, although not an exhaustive one, of the various polarizing prisms which have from time to time been constructed by means of different combinations of Iceland spar. The literature of this subject is scattered and somewhat difficult of access, and moreover only a small part of it has hitherto been translated into English; and it would appear therefore that a brief abstract of the paper may not be without service to those among the readers of _Nature_ who may be unacquainted with the original memoirs, or who may not have the necessary references at hand.

Following the order adopted by Dr. Feussner, the subject may be divided into two parts:

I.--OLDER FORMS OF POLARIZING PRISMS.

In comparing the various forms of polarizing prisms, the main points which need attention are--the angular extent of the field of view, the direction of the emergent polarized ray, whether it is shifted to one side of, or remains symmetrical to the long axis of the prism; the proportion which the length of the prism bears to its breadth; and lastly, the position of the terminal faces, whether perpendicular or inclined to the long axis. These requirements are fulfilled in different degrees by the following methods of construction:

1. _The Nicol Prism_ (_Edin. New Phil. Journal_, 1828, vi., 83).--This (Fig. 1), as is well known, is constructed from a rhombohedron of Iceland spar, the length of which must be fully three times as great as the width. The end faces are cut off in such a manner that the angle of 72° which they originally form with the lateral edge of the rhombohedron is reduced to 68°. The prism is then cut in two in a plane perpendicular to the new end surfaces, the section being carried obliquely from one obtuse corner of the prism to the other, in the direction of its length. The surfaces of this section, after having been carefully polished, are cemented together again by means of Canada balsam. A ray of light, on entering the prism, is separated by the double refraction of the calc-spar into an ordinary and an extraordinary ray; the former undergoes total reflection at the layer of balsam at an incidence which allows the extraordinary ray to be transmitted; the latter, therefore, passes through unchanged. This principle of obtaining a single polarized ray by means of total reflection of the other is common to all the forms of prism now to be described.

Dr. Feussner gives a mathematical analysis of the paths taken by the two polarized rays within the Nicol prism, and finds that the emergent extraordinary ray can include an angular field of 29°, but that this extreme value holds good only for rays incident upon that portion of the end surface which is near to the obtuse corner, and that from thence it gradually decreases until the field includes an angle of only about half the previous amount. He finds, moreover, that, although of course the ray emerges parallel to its direction of incidence, yet that the zone of polarized light is shifted to one side of the central line. Also that the great length of the Nicol--3.28 times its breadth--is not only an inconvenience, but owing to the large pieces of spar thus required for its construction, prisms of any but small size become very expensive. To this it may be added that there is a considerable loss of light by reflection from the first surface, owing to its inclined position in regard to the long axis of the prism.

It is with the view of obviating these defects that the modifications represented in Figs. 2 to 6 have been devised.

2. _The Shortened Nicol Prism_.--This arrangement of the Nicol prism is constructed by Dr. Steeg and Reuter of Homburg v.d.H. For the sake of facility of manufacture, the end surfaces are cleavage planes, and the oblique cut, instead of being perpendicular, makes with these an angle of about 84°. By this alteration the prism becomes shorter, and is now only 2.83 times its breadth; but if Canada balsam is still used as the cement, the field will occupy a very unsymmetrical position in regard to the long axis. If balsam of copaiba is made use of, the index of refraction of which is 1.50, a symmetrical field of about 24° will be obtained. A prism of this kind has also been designed by Prof. B. Hasert of Eisenach (_Pogg. Ann._, cxiii., 189), but its performance appears to be inferior to the above.

3. _The Nicol Prism with Perpendicular Ends._--The terminal surfaces in this prism are perpendicular to the long axis, and the sectional cut makes with them an angle of about 75°. The length of the prism is 3.75 times its breadth, and if the cement has an index of refraction of 1.525, the field is symmetrically disposed, and includes an angle of 27°. Prisms of this kind have been manufactured by Dr. Steeg, Mr. C.D. Ahrens, and others.