Electrical double layer

When a metal electrode is placed in an electrolyte

solution, an equilibrium difference usually becomes
established between the metal and solution. Equilibrium
is reached when the electrons left in the metal contribute
to the formation of a layer of ions whose charge is equal
and opposite to that of the cations in solution at the
interface. The positive charges of cations in the solution
and the negative charges of electrons in the metal
electrode form the electrical double layer.The solution
side of the double layer is made up of several layers as
shown in Fig. 2.7. The inner layer, which is closest to the
electrode, consists of solvent and other ions, which are
called specifically adsorbed ions. This inner layer is
called the compact Helmholtz layer, and the locus of the
electrical centers of this inner layer is called the inner
Helmholtz plane, which is at a distance of d1 from the
metal electrode surface. The solvated ion can approach
the electrode only to a distance d2. The locus of the
centers of the nearest solvated ion is called the outer
Helmholtz plane. The interaction of the solvated ion with
metal electrode only involves electrostatic force and is
independent of the chemical properties of the ions.
These ions are called non-specifically adsorbed ions.
These ions are distributed in the 3D region called
diffusion layer whose thickness depends on the ionic
concentration in the electrolyte. The structure of the
double layer affects the rate of electrode reactions.
Figure 2.7.

The excess charge stored on both sides of the double

layer depends on the electrode potential; therefore the
double layer can be represented by a capacitor in
equivalent circuits; the interfacial capacity can be
described as two capacitors in series. The resulting
potential drop across the interface due to this
capacitance is termed as double layer potential. The
effects of double layer may be neglected in ECM at the
macrolevel, which utilizes electrolytes with higher
velocity.