Text 28 A
Interactions in Electrolyte Solutions
In a solution of an cicctrolytc, it is often ncccssary to have a detailed
knowledge of the spccics present. New ions or uncharged molcculcs
resulting from interactions in the solution may behave quite differently
from the constituent ions of the cicctrolytc. Some properties o f the
solutions will be profoundly affcctcd, and the chcmist, in order to
understand these phenomena, will require to know the nature of the
spccics present. There arc a number o f formidable difficulties in the
analysis of such systems and, during the past forty years or so, a great
deal of work has been done on the problem. The equilibrium properties
of cicctrolytc solutions and the way in which ion-pair and complex
formation can be dctcctcd and quantitatively studied arc of primary
importance. Although the application of new physical and chcmical
methods has produced significant contributions in this field, the
information obtained from measurements of a system at equilibrium is
to some extent limited, and in studying the phenomenon it is desirable to
know the relevant kinetic parameters. Without this understanding, it is
sometimes impossible to sketch the actual reaction mechanism by which
the system approaches equilibrium. In general, wc may regard the
elucidation of the structure of an cicctrolytc solution as a difficult problem
which requires as many independent lines of attack as possible.
A good deal of succcss in the study o f molcculcs in the gas phase
prompted chcmists to attempt to build up theories o f solutions in an
analogous way. The classical theories regarded the solvent as merely
providing spacc in which the solute particles moved and interactions
between the ions and the solvent molcculcs were neglected. This
0 assumption can be questioned on the basis of even the most elementary
electrostatic considerations.
As long ago as 1833, both Faraday and Danicll concluded that
electrolysis took placc through the transport of clcctricity by mobile charged
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