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
Science
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
‹In all these cases the use of the conception of the degree of
ionization of the electrolytes› makes possible a much broader
and more general application of the principle of the independent
migration or mobility of the ions than was possible before the
theory of Arrhenius was proposed, and marks a distinct advance in
the theory of conductivity, over what was possible on the basis of
the theory of Clausius. [p058]
«Faraday's Law.»—If a definite quantity of electricity, a
faraday,[93] or 96,600 coulombs, is passed through a solution of
hydrochloric acid, a definite quantity (36.5 grams, one mole) of
the hydrogen chloride is decomposed, and one gram of hydrogen and
35.5 grams of chlorine are liberated by the discharge of one gram
(‹i.e.› one gram-ion) of the hydrogen-ion and 35.5 grams or one
gram-ion of the chloride-ion. In a solution of cupric chloride, the
chloride-ion is identical in every respect with the chloride-ion
found in a solution of hydrochloric acid. In the solution of
cupric chloride, however, a molecule of the salt, when it is
completely ionized, produces two chloride ions for every cupric ion
(CuCl_{2} ⇄ Cu^{2+} + 2 Cl^{−}). Since the solution never shows the
presence of an excess of either form of electricity, and the negative
charge on each chloride ion is the same as on a chloride ion formed
by the dissociation of hydrogen chloride, a cupric ion must hold
‹exactly› double the positive charge that a hydrogen ion does. In
modern terms, each hydrogen atom, present as an ion, has lost one
electron, and each copper atom present in the form of a cupric ion
has lost two electrons. Our unit quantity of electricity, 96,600
coulombs, can discharge therefore ‹only half as many of the cupric›
as of the hydrogen ions, and since each cupric ion is 63.6 times
as heavy as the hydrogen-ion (Cu = 63.6, H = 1), 63.6 / 2 grams of
copper, the ‹equivalent weight›, will be deposited in place of one
gram of hydrogen. Similarly, from a solution of ferrous chloride
FeCl_{2}, 55.9 / 2 grams of iron (Fe = 55.9) will be deposited, the
ferrous ion being Fe^{2+}; while from a solution of ferric chloride
FeCl_{3}, only 55.9 / 3 grams of iron will be deposited by 96,600
coulombs, the ferric ion, Fe^{3+}, holding three times the charge
that a hydrogen ion does. In other words, a given quantity of current
will decompose ‹equivalent› quantities of electrolytes and deposit
‹equivalent quantities› of metals. This is the well-known law of
Faraday. The theory of Arrhenius agrees with it, as did the theory
of Clausius. It cannot be considered as evidence bearing on the
question of the preference to be given to either of the theories of
ionization, since the degree of ionization of electrolytes is not
involved in the relations covered by the law. But any other relation
would have been incompatible with the theory of Arrhenius. The law
is of particular importance in giving us [p059] the best clew that
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