where D represents the coefficient of inter-diffusion of A into B, and
N1 the number of particles of A per cubic centimetre when the pressure
due to A is p1. Let us calculate by this equation the velocity with
which a molecule of hydrogen would move through hydrogen if it carried
the charge carried by an ion, which we shall prove shortly to be equal
to the charge carried by an atom of hydrogen in the electrolysis of
solutions. Since p1/N1 is independent of the pressure, it is equal to
[Pi]/N, where [Pi] is the atmospheric pressure and N the number of
molecules in a cubic centimetre of gas at atmospheric pressure. Now Ne
= 1.22 × 10^10, if e is measured in electrostatic units; [Pi] = 10^6
and D in this case is the coefficient of diffusion of hydrogen into
itself, and is equal to 1.7. Substituting these values we find
u = 1.97 × 10^4X.
If the potential gradient is 1 volt per centimetre, X = 1/300.
Substituting this value for X, we find u = 66 cm./sec, for the
velocity of a hydrogen molecule. We have seen that the velocity of the
ion in hydrogen is only about 5 cm./sec, so that the ion moves more
slowly than it would if it were a single molecule. One way of
explaining this is to suppose that the ion is bigger than the
molecule, and is in fact an aggregation of molecules, the charged ion
acting as a nucleus around which molecules collect like dust round a
charged body. This view is supported by the effect produced by
moisture in diminishing the velocity of the negative ion, for, as C.
T. R. Wilson (_Phil. Trans._ 193, p. 289) has shown, moisture tends to
collect round the ions, and condenses more easily on the negative than
on the positive ion. In connexion with the velocities of ions in the
gases drawn from flames, we find other instances which suggest that
condensation takes place round the ions. An increase in the size of
the system is not, however, the only way by which the velocity might
fall below that calculated for the hydrogen molecule, for we must
remember that the hydrogen molecule, whose coefficient of diffusion is
1.7, is not charged, while the ion is. The forces exerted by the ion
on the other molecules of hydrogen are not the same as those which
would be exerted by a molecule of hydrogen, and as the coefficient of
diffusion depends on the forces between the molecules, the coefficient
of diffusion of a charged molecule into hydrogen might be very
different from that of an uncharged one.
Wellisch (_loc. cit._) has shown that the effect of the charge on the
ion is sufficient in many cases to explain the small velocity of the
ions, even if there were no aggregation.
Public-domain text, read in full here on John Shaqi.
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