This section is from "Scientific American Supplement Volumes 275, 286, 288, 299, 303, 312, 315, 324, 344 and 358". Also available from Amazon: Scientific American Reference Book.
By M. E. BOUTY.
In previous notes I have established, first, that the galvanic depositions experience a change of volume, from which there results a pressure exercised on the mould which receives them; second, that the Peltier phenomenon is produced at the surface of contact of an electrode and of an electrolyte. Fresh observations have caused me to believe that the two phenomena are connected, and that the first is a consequence of the second. The Peltier effect can clearly be proved when the electrolysis is not interfered with by energetic secondary actions, and particularly with the sulphate and nitrate of copper, the sulphate and chloride of zinc, and the sulphate and chloride of cadmium. For any one of these salts it is possible to determine a value, I, of the intensity of the current which produces the metallic deposit such that, for all the higher intensities the electrode becomes heated, and such that it becomes cold for less intensities. I will designate this intensity, I, under the name of neutral point of temperatures.
The new fact which I have observed is, that in the electrolysis of the same salts it is always possible to lower the intensity of the current below a limit, I', such that the compression produced by the deposit changes its direction, that is to say, instead of contracting the metal dilates in solidifying. This change, although unquestionable, is sufficiently difficult to produce with sulphate of copper. It is necessary to employ as a negative electrode a thermometer sensitive to 1/200 of a degree, and to take most careful precautions to avoid accidental deformations of the deposit; but the phenomenon can be observed very easily with nitrate of copper, the sulphate of zinc, and the chloride of cadmium. There is, therefore, a neutral point of compression in the same cases where there is a neutral point of temperatures. With the salts of iron, nickel, etc., for which the neutral point of temperatures cannot be arrived at, there is also no neutral point of compression; and the negative electrode always becomes heated, and the deposit obtained is always a compressing deposit.
I have determined, by the help of observations made with ten different current strengths, the constants of the formulæ which I have explained elsewhere, and which gives the apparent excess, y, of the thermometer electrode compressed by the metallic deposit in terms of the time, t, during which the metal was depositing:
A t (1) y = ------- B + t
The constant, A, is proportional to the variation of volume of the unit of volume of the metal. The values of A, without being exactly regular, are sufficiently well represented within practical limits by the formula:
(2) A = - a'i + b'i²,
of the same form as the expression E:
E = - ai + bi²,
of the heating of the thermometer electrode. Further, every cause which affects the coefficients, a or b, also affects in the same way a' and b': such causes being the greater or less dilution of the solution, the nature of the salt, etc. It is, therefore, impossible not to be struck by the direct relation of the thermic and mechanical phenomena of which the negative electrode is the origin. The following is the explanation which I offer: The thermometer indicates the mean temperature of the liquid just outside it; this temperature is not necessarily that of the metal which incloses it. The current, propagated almost exclusively by the molecules of the decomposed salt, does not act directly to cause a variation in the temperature of the dissolving molecules; these change heat with the molecules of the electrolyte, which should be in general hotter than those when a heating is noticed and colder when a cooling is observed. Suppose it is found, in the first case, that the metal, at the moment when it is deposited, is hotter than the liquid, and, consequently, than the thermometer; it becomes colder immediately after the deposit, and consequently contracts; the deposit is compressed. The reverse is the case when the metal is colder than the liquid; the deposit then dilates. If this hypothesis is correct, the excess, T, of the temperature of the metal over the liquid which surrounds the thermometer should be proportional to the contraction, A, represented by the formula (2), and the neutral point, I', of the contraction corresponds to the case where the temperature of the metal is precisely equal to that of the liquid.
It might be expected, perhaps, from the foregoing, that I' = I; this would take place if the excess of temperature of the metal, measured by the contraction, were rigorously proportional to the heating of the liquid, for then the two quantities would be null at the same time. Careful experiment proves that this is not the case. The sulphate of copper gives compressing deposits on a thermometer which is undoubtedly cooling; chloride of zinc of a density 200 can give expanding deposits on a thermometer which is heating. There is, therefore, no proportionality; but it must be remarked that the temperature of the metal which is deposited does not depend only on the quantities of heat disengaged in an interval of molecular thickness which is infinitely small compared with the thickness of the layer, of which the variations of temperature are registered by the thermometer. There is nothing surprising, therefore, that the two variations of temperature, according exactly with one another, do not follow identically the same laws.--Comptes Rendus.