he elucidation of the electrical behavior of electrolytes owes much to Arrhenius, who was

the originator of the theory of electrolytic dissociation, generally, known as the ionic theory.

The main postulates of the theory are enumerated in the following:

1. Nearly all the molecules of an electrolyte are spontaneously dissociated into charged

ions. The ions carrying positive charge are called cations, while those carrying negative

charge are called anions. The number of electrical charges carried by an ion is equal to

the valence of the atom or the radical from which the ion originates. The process of the

spontaneous splitting up of an electrolyte into ions, when dissolved in a solvent, is called

electrolytic dissociation or ionization.

2. Cations are generally metallic radicals obtained by loss of electrons from metal atoms

(M (metal) → Mn+ (cation) + n e– (electrons)), while anions are nonmetallic ions or radicals (a group of
atoms of two or more elements) obtained by the acquisition of electrons

by nonmetallic atoms (A (nonmetal) + m e– → Am– (anion).

3. The sum of the charges on the cations in a solution must always equal the sum of the

charges on the anions, since the whole solution is uncharged (e.g., Cu2+ and SO4 2– and

2 Na+ and SO

2–

).

4. A state of dynamic equilibrium exists between the ionized and the non-ionized molecules (XY (non-
ionized molecule) X+ (cation) + Y– (anion)). The process of electrolytic dissociation is reversible.

5. The ions are free to move and under influence of an electric field they are directed

towards oppositely charged electrodes.

6. The properties of electrolytes in solution are the properties of the ions produced.

7. The electrolyte at a given dilution may not be completely ionized, and the fraction of the

total molecules ionized is termed the degree of ionization or dissociation. It may be

added here that some of these postulates embodied in the Arrehenius concept have

appeared in some form or another in the two preceding sections.

The degree of ionization of an electrolyte in solution depends upon a number of factors, of

which the nature of the solute is perhaps the most important. The nature of the solvent also

affects ionization to a marked degree. The solvent weakens the force binding two ions and

6.3 Electrolytes606 6 Electrometallurgy

thus separates them; this effect of the solvent is measured by its dielectric constant. The

dielectric constant of a solvent may be defined as its capacity to weaken the force of attraction between
the electrical charges immersed in that solvent. The third important factor is

the concentration of the electrolyte in the solution. The extent of ionization of an electrolyte

is inversely proportional to the concentration of its solution. The less concentrated the solution, the
greater will be the ionization of the electrolyte; this ensues from the fact that in a

dilute solution the ratio of the number of solvent molecules to the number of solute molecules

is large, and the greater the number of solvent molecules, the greater will be the number of

solute molecules which will be separated into ions. The fourth factor to influence ionization

is temperature; the higher the temperature, the greater is the ionization.

A molecule HA of a weak electrolyte is now considered. It is assumed to dissociate in its

aqueous solution according to the equation HA H+ + A–. The application of the law of

mass action to the above equation gives

[H ][A ]

[HA]

where K

a is called the dissociation constant or the ionization constant of the electrolyte. If α

is the degree of dissociation of the electrolyte in a solution containing 1 gram-molecule of it

in V liters, then at equilibrium the gram-molecular concentration of the non-ionized electrolyte, and the
gram-ionic concentrations of the ions, are respectively, (1 – α)/V, α/V, and

α/V. Substituting these values in the expression for Ka, one obtains

2
a

(1 )

αα

or

(1 )

Kα

where C is the concentration in moles per liter (C is equal to 1/V). For a weak electrolyte, α

is small compared with 1 (α « 1), so that the term (1 – α) may be taken to be approximately

equal to 1. In this situation,

Ka

αV

= or 0.5 0.5

α==()(/)KVKCaa

i.e., the degree of ionization of a weak electrolyte is proportional to the square-root of dilution (the
volume of the solution containing 1 mole of the solute) or inversely proportional

to the square-root of concentration.

Any one of these expressions for Ka represents what is known as Ostwald’s dilution law,

which has essentially been obtained by applying the law of mass action to solutions of weak
electrolytes. It deals with the variation in the degree of dissociation with concentration or

dilution of solutions of weak electrolytes. It is not applicable to solutions of strong electrolytes. The
failure of strong electrolytes to obey Ostwald’s dilution law is known as the anomaly

of strong electrolytes.