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Arrhenius is specially associated with the development of the theory of electrolytic dissociation, and his great paper on the subject, Recherches sur la conductibilite galvanique des electrolytes - (1) conductibilite galvanique des solutions aqueuses extremement diluees, (2) theorie chimique des electrolytes, was presented to the Stockholm Academy of Sciences in 1883.
With other electrolytes similar phenomena appear, though the primary chemical changes may be masked by secondary actions.
This reverse electromotive force of polarization is produced in all electrolytes when the passage of the current changes the nature of the electrodes.
If we eliminate the reverse electromotive forces of polarization at the two electrodes, the conduction of electricity through electrolytes is found to conform to Ohm's law; that is, once the polarization is overcome, the current is proportional to the electromotive force applied to the bulk of the liquid.
But when we pass to solutions of mineral salts and acids - to solutions of electrolytes in fact - we find that the observed values of the osmotic pressures and of the allied phenomena are greater than the normal values.
Arrhenius pointed out that these exceptions would be brought into line if the ions of electrolytes were imagined to be separate entities each capable of producing its own pressure effects just as would an ordinary dissolved molecule.
The theoretical value for the depression of the freezing point of a dilute solution per gramme-equivalent of solute per litre is 1857° C. Completely ionized solutions of salts with two ions should give double this number or 3.714°, while electrolytes with three ions should have a value of 5.57°.
Electrolytes with two Ions.
3.61 Ammonium nitrate 3'58 Electrolytes with three Ions.
Electrolytes possess the power of coagulating solutions of colloids such as albumen and arsenious sulphide.
Moreover, a study of the chemical relations of electrolytes indicates that it is always the electrolytic ions that are concerned in their reactions.
(See Arrhenius, loc. cit.) The simplest and most important case is that of two electrolytes having one ion in common, such as two acids.
A current can be obtained by the combination of two metals in the same electrolyte, of two metals in different electrolytes, of the same metal in different electrolytes, or of the same metal in solutions of the same electrolyte at different concentrations.
On the other hand, it is commonly thought that the single potentialdifferences at the surface of metals and electrolytes have been determined by methods based on the use of the capillary electrometer and on others depending on what is called a dropping electrode, that is, mercury dropping rapidly into an electrolyte and forming a cell with the mercury at rest in the bottom of the vessel.
The contact differences of potential at the interfaces of metals and electrolytes have been co-ordinated by Nernst with those at the surfaces of separation between different liquids.
Our views of the nature of the ions of electrolytes have been extended by the application of the ideas of the relations between matter and electricity obtained by the study of electric conduction through gases.
A group of bodies may, however, be yet discovered between alloys and electrolytes in which evidence may be found of some gradual change from wholly metallic to electrolytic conduction.
P. 316; " On the Dielectric Constant of Certain Frozen Electrolytes at and above the Temperature of Liquid Air," id.
P. 299-this paper describes the cone condenser and methods used; " Further Observations on the Dielectric Constants of Frozen Electrolytes at and above the Temperature of Liquid Air," id.
Now measurements of osmotic properties of these solutions show that their osmotic pressures are abnormally great and that, at extreme dilution, the ratio of their osmotic pressures to that of equivalent solutions of non-electrolytes is equal to the number of ions indicated by the electrolytic properties.
On the lines of Poynting's theory of solution, each ion in electrolytes must combine with one or more molecules of solvent.
In the case of electrolytes we can go further, and calculate the diffusion constant itself from the theory of electrolytic dissociation (see Electric conduction, § In Liquids).
One class, represented by gelatin, will redissolve on warming or diluting, while the other class, containing such substances as silica, albumen, and metallic, hydrosulphides, will solidify on heating or on the addition of electrolytes to form a solid "gel" which cannot be redissolved.
The power of coagulation of colloids shown by electrolytes depends in a curious manner on the chemical valency of the effective ion.
In the case of electrolytes, S.