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
«Gaseous Dissociation.»—The discrepancy between the two conclusions
and any doubt as to the universal soundness of the great
generalization expressed in Avogadro's hypothesis disappear, however,
in the light of a closer study of the composition of ammonium
chloride vapor. It was suggested simultaneously by Cannizzaro, by
Kopp and by Kékulé[52] that the abnormally low result, obtained
for the molecular weight of ammonium chloride from a study of its
vapor density, is due to the ‹dissociation› of the salt at high
temperatures into its components, ammonia and hydrogen chloride, the
‹average› of whose ‹molecular weights› is, in fact, (17 + 36.5) / 2,
or 26.75, the value found experimentally for the vapor of ammonium
chloride. Proof of the correctness of this interpretation was
furnished by Pébal,[53] who showed that ammonium chloride vapor does
consist of the two gases, the lighter of which, ammonia, diffuses
more rapidly through porous walls (Pébal used an asbestos stopper)
than does the heavier, hydrogen chloride. The dissociation may be
easily demonstrated by using an air cushion as a porous wall.[54]
From the mixture produced by vaporizing ammonium chloride,[55] the
ammonia will diffuse more rapidly through the layer of air than will
the hydrogen [p036] chloride, and the gases may be recognized in
succession by their action on litmus paper (‹exp.›).
The ‹gaseous dissociation› of other ammonium salts, of phosphorus
pentachloride and pentabromide (PX_{5} ⇄ PX_{3} + X_{2}), and of a
number of less common compounds, has been demonstrated in similar
ways. As a result of the study of each case, the important conclusion
has been reached that, as far as our knowledge goes, there are no
exceptions to Avogadro's hypothesis, and this hypothesis seems
therefore to represent a universal truth.[56]
«Molecular Weight Determinations in Solution.»—Van 't Hoff's
extension of the Avogadro Hypothesis, so that it shall apply to
solutes in dilute solutions, is the basis of another general method
of greatest value for determining molecular weights. Equal volumes
of dilute solutions of the same osmotic pressure and the same
temperature contain, according to van 't Hoff, the same numbers of
dissolved molecules, irrespective of the solvent used. Furthermore,
the number of dissolved molecules is identical with that which a
gas of the same pressure and at the same temperature would contain
in the same volume. To determine the molecular weight of a solute,
therefore, we may calculate, from the osmotic pressure, the
temperature and the concentration of the solution,[57] that weight of
the solute which, in 22.4 liters of the solution, at 0° would give
760 mm. osmotic pressure; the weight found represents, in grams, the
‹molecular weight› of the solute ‹in the solution used›. [p037]
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