Scientific American Supplement, No. 288, July 9, 1881Various
Science
Scientific American Supplement, No. 288, July 9, 1881
Various
Science -- Periodicals
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,
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