History of Chemistry, Volume 2 (of 2): From 1850 to 1910Thorpe, T. E. (Thomas Edward)
History
History of Chemistry, Volume 2 (of 2): From 1850 to 1910
Thorpe, T. E. (Thomas Edward)
Chemistry -- History
The importance, of these observations in relation to the general theory
of solution was first recognised by Van ’t Hoff. Osmotic pressure was
regarded by him as analogous to gaseous pressure. Since P/C is constant
for any one substance, and since for a definite weight of the solute
the concentration is inversely as the volume of the solution, we obtain
an equation analogous to the statement of Boyle’s law, PV = constant.
Van ’t Hoff also found that the _osmotic pressure is proportional
to the absolute temperature_, like the gaseous pressure. From these
results, in conjunction with Avogadro’s hypothesis, it follows that
_the osmotic pressure exerted by any substance in solution is the
same as it would exert if present as gas in the same volume as that
occupied by the solution, provided that the solution is so dilute that
the volume occupied by the solute is negligible in comparison with
that occupied by the solvent_. Another important consequence is that
_solutes, when present in the ratio of their molecular weights in equal
volumes of the same solvent, exert the same osmotic pressure_. Such
solutions are said to be _isomotic_ or _isotonic_. It can be proved by
thermodynamical reasoning that depression of the vapour pressure and
freezing-point of a solution is proportional to its osmotic pressure.
The significance of this relation in connection with the determination
of the molecular weight of a soluble substance has already been
referred to.[6]
[6] See pp. 70–73.
Determinations of molecular freezing-point depressions by Raoult
and others showed that certain substances exerted only about half
the osmotic pressure calculated from their known formulæ, whereas
others have abnormally high osmotic pressures. The explanation of
the discrepancies in the latter case was given in 1887 by Arrhenius,
who pointed out that _only those solutions which have abnormally
high osmotic pressures are electrically conductive_. This pregnant
observation proved to be very fruitful in suggestiveness; and the
connection between conductivity and Van ’t Hoff’s theory of solution
was developed by Arrhenius into the doctrine of _electrolytic
dissociation_ or _ionisation_—one of the most important consequences
of Faraday’s electrolytic laws, the work of Hittorf, and the kinetic
conceptions of Williamson and Clausius to which the last quarter
of a century has given rise. Arrhenius showed that not only were
free ions present in an electrically conductive solution before
electrolysis, as maintained by Clausius, but that the proportion of
molecules dissociated into ions could be calculated from measurements
of electrical conductivity, as well as from measurements of osmotic
pressure. Both methods give concordant results—a strong confirmation of
the validity of the theory. In a solution of common salt, containing a
gramme equivalent of that substance in a litre, Arrhenius calculated
that only about three tenths of the salt exists as NaCl, the remaining
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