An Introductory Course of Quantitative Chemical Analysis: With Explanatory NotesTalbot, Henry Paul
Science
An Introductory Course of Quantitative Chemical Analysis: With Explanatory Notes
Talbot, Henry Paul
Chemistry, Analytic -- Quantitative
From these data it is evident that in order to deposit copper from a
normal solution of copper sulphate a minimum potential equal to the
algebraic sum of the deposition-potentials of copper ions and sulphate
ions must be applied, that is, +1.56 volts. The deposition of zinc
from a solution of zinc sulphate would require +2.67 volts, but, since
the deposition of hydrogen from sulphuric acid solution requires only
+1.90 volts, the quantitative deposition of zinc by electrolysis from
a sulphuric acid solution of a zinc salt is not practicable. On the
other hand, silver, if present in a solution of copper sulphate, would
deposit with the copper.
The foregoing examples suffice to illustrate the application of the
principle of deposition potentials, but it must further be noted
that the values stated apply to normal solutions of the compounds in
question, that is, to solutions of considerable concentrations. As the
concentration of the ions diminishes, and hence fewer ions approach
the electrodes, somewhat higher voltages are required to attract and
discharge them. From this it follows that the concentrations should be
kept as high as possible to effect complete deposition in the least
practicable time, or else the potentials applied must be progressively
increased as deposition proceeds. In practice, the desired result is
obtained by starting with small volumes of solution, using as large an
electrode surface as possible, and by stirring the solution to bring
the ions in contact with the electrodes. This is, in general, a more
convenient procedure than that of increasing the potential of the
current during electrolysis, although that method is also used.
As already stated, those ions in a solution of electrolytes will first
be discharged which have the lowest deposition potentials, and so
long as these ions are present around the electrode in considerable
concentration they, almost alone, are discharged, but, as their
concentration diminishes, other ions whose deposition potentials are
higher but still within that of the current applied, will also begin
to separate. For example, from a nitric acid solution of copper
nitrate, the copper ions will first be discharged at the cathode, but
as they diminish in concentration hydrogen ions from the acid (or
water) will be also discharged. Since the hydrogen thus liberated is a
reducing agent, the nitric acid in the solution is slowly reduced to
ammonia, and it may happen that if the current is passed through for a
long time, such a solution will become alkaline. Oxygen is liberated
at the anode, but, since there is no oxidizable substance present
around that electrode, it escapes as oxygen gas. It should be noted
that, in general, the changes occurring at the cathode are reductions,
while those at the anode are oxidations.
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