Coefficient of Dissociation.—We have seen that in order to obtain values which accord with experiment we have to multiply the number of gramme-molecules of the solute by the coefficient i, which is called the Coefficient of Dissociation.
This coefficient of dissociation, i, may be found by observing the lowering of the freezing point of a normal solution, and dividing it by 1.85. i = t/1.85.
The coefficient of dissociation varies with the degree of concentration of the solution, rising to a maximum when the solution is sufficiently diluted.
If we know i, the coefficient of dissociation for a given solute, contained in a solution of a definite concentration, we can find n′, the number of particles present in a solution containing n gramme-molecules of the solute per litre, since n′ = in. On the other hand, if from a consideration of its freezing point and other constants we find that an electrolytic solution appears to contain n′ gramme-molecules per litre, the real number of chemical gramme-molecules in one litre of the solution will be only n′ / i = n.
Very concentrated solutions do not conform to these laws. In this they resemble gases, which as they approach their point of condensation tend less and less to conform to the laws of gaseous pressure.
Electrolysis.—If we take a solution of an acid, a salt, or a base, and dip into it two metallic rods, one connected to the positive and the other to the negative pole of a battery, we
find that the metals or metallic radicals of the solution are liberated at the negative pole, while the acid radicals of the salts and acids and the hydroxyl of the bases are liberated at the positive pole. The liberated substances may either be discharged unchanged, or they may enter into new combinations, causing a series of secondary reactions.
Electrolytes.—Solutions which conduct electricity are called Electrolytes, and the conducting metallic rods dipping into the solution are the Electrodes. Faraday gave the names of Ions to the atoms or atom-groups liberated at either electrode. The ions liberated at the positive electrode are the Anions, and those at the negative electrode are the Cations. The only solutions which possess any notable degree of electrical conductivity are the aqueous solutions of the various salts, acids, and bases, and in these solutions only do we meet with those phenomena of dissociation which are evidenced by anomalies of osmotic pressure, freezing point and the like,—anomalies which show that the solution contains a greater number of molecules than that indicated by its molecular concentration. These anomalies are due to dissociation, the division of some of the molecules into fragments, each of which plays the part of a separate molecule, contributing its quota to the osmotic tension and vapour pressure of the solution, in fact to all the phenomena which are dependent on the degree of molecular concentration. The electrical conductivity of a solution is therefore proved to be dependent on its molecular dissociation.
Arrhenius' Theory of Electrolysis.—In 1885, Arrhenius brought forward his theory of the transport of electricity by an electrolyte. According to this hypothesis, the electric current is carried by the ions, the positive charges by the cations, and the negative charges by the anions. In virtue of the attraction between charges of different sign, and repulsion between charges of like sign, the cations are repelled by the positive charge on the anode, and attracted by the negative charge on the cathode. Similarly the anions are repelled by the cathode and attracted by the anode.