| -- | -- -- |
| SO_4 | SO_4 SO_4 SO_4 SO_4 SO_4 |
- | | | +
| ++ | ++ ++ |
| Cu Cu Cu Cu | Cu Cu |
| | |
+---------------------------+---------------------------------+
FIG. 2.--After the passage of the current.
_Velocity of the Ions._--If the electrolytic cell is divided into two
segments by means of a porous diaphragm, we shall find after a time an
unequal distribution of the solute on the two sides. For instance, with a
solution of sulphate of copper, after the current has passed for some time
there will be a diminution of concentration in the liquid on both sides of
the diaphragm, but the loss will be very unequally divided. Two-thirds of
the loss of concentration will be on the side of the negative electrode and
only one-third on the positive side. In 1853, Hittorf gave the following
ingenious explanation of this phenomenon:-- {30}
Fig. 1 represents an electrolytic vessel containing a solution of sulphate
of copper, the vertical line indicating a porous partition separating the
vessel into two parts. Fig. 2 shows the same vessel after the passage of
the current. The acid radical has travelled twice as fast as the metal. For
each copper ion which has passed through the porous plate towards the
cathode two acid radicals have passed through it towards the anode. Three
ions have been liberated at either electrode, but in consequence of the
difference of velocity with which the positive and the negative ions have
travelled, the negative side of the vessel contains only one molecule of
copper sulphate and has lost two-thirds of its molecular concentration,
while the positive side contains two molecules of copper sulphate and has
only lost one-third of its concentration. This proves clearly that the ions
move in different directions with different velocities. Let u be the
velocity of the anions, and v the velocity of the cations. Let n be the
loss of concentration at the cathode, and 1 - n the loss of concentration
at the anode. Then
u / v = n / (1 - n),
_i.e._ the loss of concentration at the cathode is to the loss of
concentration at the anode as the velocity of the anions is to that of the
cations. Hence by measuring the loss of concentration at the two
electrodes, we have an easy means of determining the comparative velocity
of different ions.
Public-domain text, read in full here on John Shaqi.
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