Page 192 - Introduction to Colloid and Surface Chemistry

Charged interfaces 181

For an aqueous solution of a symmetrical electrolyte at 25°C,
equation (7.6) becomes

( 2 \{ (7,10)
10 1
K = 0.329xl0 -^J iif
^ mol dm )
For a 1-1 electrolyte the double layer thickness is, therefore, about
1
3
3
1 nm for a 10" mol dm~ solution and about 10 nm for a 10~ mol
dm~ 3 solution. For unsymmetrical electrolytes the double layer
thickness can be calculated by taking z to be the counter-ion charge
number.
The Poisson-Boltzmann distribution for a spherical interface takes
the form
.
2zen Q
- y-
»,= __ - = - - sm — ~ / 7 in
r 2 dr( dr ) e kT { j
where r is the distance from the centre of the sphere. This expression
cannot be integrated analytically without approximation to the
exponential terms. If the Debye-Hiickel approximation is made, the
equation reduces to

2
2
V ^ = K ^ (7.12)
which, on integration (with the boundary conditions, tf> = t}/ 0 at r = a
and $ = 0, di/r/dr = 0 at r = <», taken into account) gives

0= 0b exp[-ic)r - «)J (7.13)

Unfortunately, the Debye-Hiickel approximation (z^ <^ c. 25 mV) is
often not a good one in the treatment of colloid and surface
phenomena. Unapproximated, numerical solutions of equation
(7.11) have been computed. 88

The inner part of the double layer

The treatment of the diffuse double layer outlined in the last section
is based on an assumption of point charges in the electrolyte medium.
The finite size of the ions will, however, limit the inner boundary of
the diffuse part of the double layer, since the centre of an ion can only