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
Pfeffer's results, on the osmotic pressure of sugar solutions
at different temperatures, were not sufficiently accurate to
enable van 't Hoff to use them to confirm positively the rigorous
thermodynamic proof (footnote 3, p. 12), that the osmotic pressure
must increase proportionally to the absolute temperature, as
required by Gay-Lussac's law. But the data did show, uniformly, a
marked increase of the osmotic pressure with the temperature and,
frequently, excellent agreement between theory and experiment.
More striking were the results obtained by van 't Hoff in testing
the correctness of this extension of Gay-Lussac's law by means of
Soret's results on the diffusion of a solute from a warmer to a
colder place. It was found that the concentrations, obtained by
Soret when equilibrium was reached, agreed closely with the demand
that the osmotic pressures in the colder and the warmer parts of the
solution should be equal, and that the osmotic pressure of a given
weight of solute in a given volume should increase proportionally
to the absolute temperature. An elevation of temperature, in a
portion of a uniform solution, will increase the osmotic pressure of
this part. Diffusion will follow, until the loss in concentration
of the solute, and therefore the loss of osmotic pressure (Boyle's
law), of the warmer part, and the increased concentration and
increased pressure of the colder portion result in all parts of the
solution having the same osmotic pressure. [p015] As an example,
a concentration of 17.33% copper sulphate at 20° was found to be
in equilibrium with a concentration of 14.03% at 80°. Now, if
the 17.33% solution had an osmotic pressure of ‹P› mm. at 20°, a
14.03% solution at the same temperature would have a pressure of
(14.03 / 17.33) × ‹P› mm. (Boyle's law), and this would increase
to (14.03 / 17.33) × ‹P› × (353 / 293) mm. at 80° C., or 0.975 ‹P›
mm.—a result showing that the osmotic pressure in the hot part
was practically the same as that, (‹P›), in the cold part of the
solution.[17]
It is a source of great satisfaction, that the recent very exact
and painstaking work of Morse and Frazer,[18] in measuring osmotic
pressures directly, completely confirms this fundamentally important
conclusion, that the osmotic pressure of a solution does increase
proportionally to its absolute temperature.
«The Avogadro-van 't Hoff Hypothesis.»—For chemists, the most
important part of van 't Hoff's work lies in the extension of ‹the
Avogadro Hypothesis› to solutions. As van 't Hoff expresses it,
"equal volumes of the most different solutions, having the same
osmotic pressure and the same temperature, contain the same number of
dissolved molecules,—that number, namely, which would be found in the
same volume of a gas at the same gas pressure and temperature."[19]
[p016]
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