The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.Stieglitz, Julius
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The Elements of Qualitative Chemical Analysis, vol. 1, parts 1 and 2.: With Special Consideration of the Application of the Laws of Equilibrium and of the Modern Theories of Solution.
Stieglitz, Julius
Chemistry, Analytic -- Qualitative
This simple fact, that the very solutions which give abnormally
low molecular weights for the dissolved compounds are also good
conductors of electricity, was explained by a theory of ‹electrolytic
dissociation› or of ‹ionization›, which Arrhenius had developed[62]
from a study of the conductivity of electrolytes. The same fact has
aided in establishing this theory which has led to the elucidation
of vital problems of ‹electrical conductivity› and to a successful
[p041] explanation of the problem of the apparently abnormal
‹osmotic pressures› (and ‹molecular weights›) of electrolyte solutes.
It has thus removed the last difficulty in the way of accepting
the van 't Hoff-Avogadro Hypothesis (p. 15) as true for all dilute
solutions, exactly as the discovery of ‹gaseous dissociation› made it
possible to recognize in the original Avogadro Hypothesis a universal
truth (p. 36) about gases. And to these results was added, chiefly
as the fruit of the work of Ostwald, with the aid of the theory
of Arrhenius, the most successful and accurate formulation of the
problem of the ‹chemical activity› of electrolytes, known in the
history of chemistry.
«Main Assumptions of Arrhenius's Theory of Ionization.»—The main
assumptions of the theory of electrolytic dissociation or ionization
are the following: (1) When an ionogen is dissolved in water, its
molecules are immediately, more or less completely, ‹dissociated by
the water› into smaller fragments or molecules of unlike composition.
(2) These new molecules are charged with ‹electricity›; the molecules
of the one product are charged with ‹positive›, the molecules of the
other product[63] with ‹negative electricity›, the unit positive
charge being equal in quantity, but opposite in kind, to the unit
negative charge; the sum of all the positive charges in a solution is
equal to the sum of all the negative charges, and the whole solution
is electrically neutral. (3) The dissociation is a reversible
reaction, and all electrolytes must be considered to be ‹completely
ionized at infinite dilution›. (4) Except for the dependence
resulting from the electrical charges and the consequent attractions
and repulsions between ions, the ions must be considered independent
molecules with their own ‹specific chemical› and ‹physical›
properties.
When a current is passed through the solution of an ionogen, the
electrified particles carry their charges to the electrodes (see
[p042] below). They are called the ‹ions›[64] of the electrolyte;
the positively charged ions are distinguished as ‹cations› from the
negatively charged ‹anions›, and the electrode toward which the
cations move is called the cathode (negative electrode), and the
electrode to which the anions move is called the ‹anode› (positive
electrode).
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