Page:EB1911 - Volume 09.djvu/225

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208
ELECTROCHEMISTRY


and v, the velocity of propagation, is equal to λ/T. As the means of a number of experiments Blondlot found v to be 3.02 × 1010 cm./sec., which, within the errors of experiment, is equal to 3 × 1010 cm./sec., the velocity of light. A second method used by Blondlot, and one which does not involve the calculation of the period, is as follows:—A and A′ (fig. 10) are two equal Leyden jars coated inside and outside with tin-foil. The outer coatings form two separate rings a, a1; a′, a1, and the inner coatings are connected with the poles of the induction coil by means of the metal pieces b, b′. The sharply pointed conductors p and p′, the points of which are about 1/2 mm. apart, are connected with the rings of the tin-foil a and a′, and two long copper wires pca1, pca1, 1029 cm. long, connect these points with the other rings a1, a1′. The rings aa′, a1a1′, are connected by wet strings so as to charge up the jars. When a spark passes between b and b′, a spark at once passes between pp′, and this is followed by another spark when the waves travelling by the paths a1cp, a1cp′ reach p and p′. The time between the passage of these sparks, which is the time taken by the waves to travel 1029 cm., was observed by means of a rotating mirror, and the velocity measured in 15 experiments varied between 2.92 × 1010 and 3.03 × 1010 cm./sec., thus agreeing well with that deduced by the preceding method. Other determinations of the velocity of electromagnetic propagation have been made by Lodge and Glazebrook, and by Saunders.

On Maxwell’s electromagnetic theory the velocity of propagation of electromagnetic disturbances should equal the velocity of light, and also the ratio of the electromagnetic unit of electricity to the electrostatic unit. A large number of determinations of this ratio have been made:—

Observer. Date. Ratio 1010 ×.
Klemenčič 1884 3.019 cm./sec.
Himstedt 1888 3.009 cm./sec.
Rowland 1889 2.9815 cm./sec.
Rosa 1889 2.9993 cm./sec.
J. J. Thomson and Searle   1890 2.9955 cm./sec.
Webster 1891 2.987 cm./sec.
Pellat 1891 3.009 cm./sec.
Abraham 1892 2.992 cm./sec.
Hurmuzescu 1895 3.002 cm./sec.
Rosa 1908 2.9963 cm./sec.

The mean of these determinations is 3.001 × 1010 cm./sec., while the mean of the last five determinations of the velocity of light in air is given by Himstedt as 3.002 × 1010 cm./sec. From these experiments we conclude that the velocity of propagation of an electromagnetic disturbance is equal to the velocity of light, and to the velocity required by Maxwell’s theory.

In experimenting with electromagnetic waves it is in general more difficult to measure the period of the oscillations than their wave length. Rutherford used a method by which the period of the vibration can easily be determined; it is based upon the theory of the distribution of alternating currents in two circuits ACB, ADB in parallel. If A and B are respectively the maximum currents in the circuits ACB, ADB, then

A = S2 + (N − M)2p2
B R2 + (L − M)2p2

when R and S are the resistances, L and N the coefficients of self-induction of the circuits ACB, ADB respectively, M the coefficient of mutual induction between the circuits, and p the frequency of the currents. Rutherford detectors were placed in the two circuits, and the circuits adjusted until they showed that A = B; when this is the case

p2 = R2 − S2 .
N2 − L2 − 2M (N − L)

If we make one of the circuits, ADB, consist of a short length of a high liquid resistance, so that S is large and N small, and the other circuit ACB of a low metallic resistance bent to have considerable self-induction, the preceding equation becomes approximately p = S/L, so that when S and L are known p is readily determined. (J. J. T.) 


ELECTROCHEMISTRY. The present article deals with processes that involve the electrolysis of aqueous solutions, whilst those in which electricity is used in the manufacture of chemical products at furnace temperatures are treated under Electrochemistry, although, strictly speaking, in some cases (e.g. calcium carbide and phosphorus manufacture) they are not truly metallurgical in character. For the theory and elemental laws of electro-deposition see Electrolysis; and for the construction and use of electric generators see Dynamo and Battery: Electric. The importance of the subject may be gauged by the fact that all the aluminium, magnesium, sodium, potassium, calcium carbide, carborundum and artificial graphite, now placed on the market, is made by electrical processes, and that the use of such processes for the refining of copper and silver, and in the manufacture of phosphorus, potassium chlorate and bleach, already pressing very heavily on the older non-electrical systems, is every year extending. The convenience also with which the energy of waterfalls can be converted into electric energy has led to the introduction of chemical industries into countries and districts where, owing to the absence of coal, they were previously unknown. Norway and Switzerland have become important producers of chemicals, and pastoral districts such as those in which Niagara or Foyers are situated manufacturing centres. In this way the development of the electrochemical industry is in a marked degree altering the distribution of trade throughout the world.

Electrolytic Refining of Metals.—The principle usually followed in the electrolytic refining of metals is to cast the impure metal into plates, which are exposed as anodes in a suitable solvent, commonly a salt of the metal under treatment. 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. The metal to be refined passing into solution is concurrently deposited at the cathode. Soluble impurities which are more electro-negative than the metal under treatment must, if present, be removed by a preliminary process, and the voltage and other conditions must be so selected that none of the more electro-positive metals are co-deposited with the metal to be refined. From these and other considerations it is obvious that (1) 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. For details of the practical methods see Gold; Silver; Copper and headings for other metals.

Electrolytic Manufacture of Chemical Products.—When an aqueous solution of the salt of an alkali metal is electrolysed, the