the deposition of a given
quantity of an electrolyte from solution, it must be remembered that
the law expresses what occurs when the concentration of the ions in
the solution is kept constant, as, for example, when the anode in
a silver salt solution is a plate of metallic silver. Under the
conditions of electro-analysis the concentration of the ions is
constantly diminishing as deposition proceeds and the time actually
required for complete deposition of a given weight of material by
a current of constant strength is, therefore, greater than that
calculated on the basis of the law as stated above.
The electrodes employed in electro-analysis are almost exclusively
of platinum, since that metal alone satisfactorily resists chemical
action of the electrolytes, and can be dried and weighed without
change in composition. The platinum electrodes may be used in the
form of dishes, foil or gauze. The last, on account of the ease of
circulation of the electrolyte, its relatively large surface in
proportion to its weight and the readiness with which it can be washed
and dried, is generally preferred.
Many devices have been described by the use of which the electrode
upon which deposition occurs can be mechanically rotated. This has an
effect parallel to that of greatly increasing the electrode surface
and also provides a most efficient means of stirring the solution.
With such an apparatus the amperage may be increased to 5 or even 10
amperes and depositions completed with great rapidity and accuracy. It
is desirable, whenever practicable, to provide a rotating or stirring
device, since, for example, the time consumed in the deposition of the
amount of copper usually found in analysis may be reduced from the
20 to 24 hours required with stationary electrodes, and unstirred
solutions, to about one half hour.
DETERMINATION OF COPPER AND LEAD
PROCEDURE.--Weigh out two portions of about 0.5 gram each (Note 1)
into tall, slender lipless beakers of about 100 cc. capacity. Dissolve
the metal in a solution of 5 cc. of dilute nitric acid (sp. gr. 1.20)
and 5 cc. of water, heating gently, and keeping the beaker covered.
When the sample has all dissolved (Note 2), wash down the sides of the
beaker and the bottom of the watch-glass with water and dilute the
solution to about 50 cc. Carefully heat to boiling and boil for a
minute or two to expel nitrous fumes.
Meanwhile, four platinum electrodes, two anodes and two cathod
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