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. — John Shaqi
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
These are instances of a very large class of apparent gross
discrepancies between the requirements of the Avogadro-van 't Hoff
principle and the generally accepted molecular weights of common
compounds. There are three ways, in particular, in which one might
be inclined to regard such results: in the first place, one might
be tempted to consider that van 't Hoff's extension of Avogadro's
hypothesis to solutions is justified in a considerable number of
cases, but not as a ‹universal› expression, applicable to ‹all›
dilute solutions. This seems, indeed, to have been van 't Hoff's own
attitude originally. Such a view, since it does not throw new light
on the matter, but simply shelves the question of the source of the
discrepancy, would be tenable only after all other explanations had
been found unsatisfactory.
In the second place, we might be inclined to consider whether a
molecule like hydrogen chloride is not dissociated in aqueous
solution into two smaller molecules, ‹h›‹cl›, in which hydrogen
and chlorine would appear as atoms with the weights ‹h› = 0.5
and ‹cl› = 17.75, which are half as large as the atomic weights
determined from a study of volatile compounds of hydrogen and
chlorine. If we remember that our atomic weights are confessedly
maximum weights, and not minimum weights—although they are almost
certainly also the true atomic weights—such a view would be, at
least, worthy of some consideration. But, in the first place,
it would be extraordinary that we should never have found, in
the thousands of [p039] hydrogen derivatives that have been
investigated, any compound, the molecule of which, in the gaseous
condition, contained a ‹single› such atom of hydrogen, with the
weight 0.5, or an ‹uneven› multiple of it: that only ‹even› multiples
or pairs ‹h›_{2}, corresponding to the atom H, should always
have been found. In the second place, such an explanation of the
results of the molecular weight determinations in aqueous solutions
given above, would soon lead to difficulties, which make the view
altogether untenable. For instance, the molecule of zinc chloride,
according to the data given, would have to break down into three
molecules and, if these were of uniform composition, we would have to
assume chlorine atoms two-thirds or one-third as large as Cl. Since a
moment ago we had to assume chlorine atoms one-half as large as Cl,
we would have to conclude that the atomic weight of chlorine could
be, at most, Cl / 6, which is the largest common divisor of Cl / 2
and Cl / 3. No chemist would seriously consider an atomic weight
for chlorine one-sixth as large as the accepted weight, for that
would mean that, in all the chlorine compounds investigated in the
condition of gases, we have always at least six such atoms occurring
together, and otherwise always multiples of six. Consequently such
an interpretation of the so-called "abnormal" behavior of solutions
of hydrogen chloride, sodium and zinc chlorides, etc., although at
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