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
«Summary.»—Van 't Hoff's theory of solution—that the osmotic
pressure of substances in solution obeys the laws of gases, and
that equal volumes of the most varied dilute solutions, having
the same temperature and osmotic pressure, contain the same
number of dissolved molecules, that number, namely, which would
be found in the same volume of a gas at the same temperature
and gas pressure,—accords thus, not only with the demands of
thermodynamics,[27] but is also, within the limits demanded by the
theory itself, in agreement with the best experimental measurements
of osmotic pressures that have been made in recent years. The
apparent exceptions, as in the cases just described and, as we shall
find, in the case of electrolytic dissociation, are found to be no
exceptions, when the conclusions, reached on the assumption that
[p020] the theory is correct, are tested rigorously by independent
methods of investigation.[28]
The fundamental laws of gases and the Avogadro Hypothesis may be
condensed into the following general equation, expressing all
of the laws, viz.: ‹P› ‹V› = ‹n› ‹R› ‹T›. This equation applies
equally to the osmotic pressures of dilute solutions, the osmotic
pressure being substituted for the gas pressure. In the equation,
‹T› is the absolute temperature of the gas or solution, ‹P› the
gaseous or osmotic pressure, ‹V› the free space of the gas volume,
‹i.e.› the volume of the gas less the volume occupied by the gas
molecules, or the volume of the pure solvent in the solution used,
‹i.e.› the volume of the solution less the volume of the solute.
‹R› is the so-called ‹gas-constant›, and represents ‹the work›
done against the external pressure when one gram molecule, or
mole, of the gas is heated one degree and allowed to expand, say
at constant pressure ‹P›, against an external pressure ‹P›; ‹n›
represents the number of gram molecules or moles of gas or solute
used (the total weight of solute or gas, divided by the average
weight of a mole in the gas or solute). If a given weight of a
gas or solute is taken, and no dissociation or association occurs
(such as would involve appreciable heats of dilution), then ‹n›
is a given number; and, therefore, at a given temperature ‹T›,
all the factors on the right side of the general equation being
given numbers, ‹P› ‹V› ‹is a constant› (Boyle's law). For a given
quantity of gas or solute (‹n› is a given number), kept at ‹constant
volume› ‹V›, the pressure must vary as the absolute temperature
(Gay-Lussac's law); ‹P› / ‹T› = ‹n› ‹R› / ‹V› = ‹a constant›. When
the pressure, volume and temperature of two gases, or two dilute
solutions, are equal, ‹n›, the number of gas or solute molecules
present, must be the same (Avogadro-van 't Hoff Hypothesis);
‹n› = ‹P› ‹V› / (‹R› ‹T›), and all the factors of the right side
are the same for the gases and solutions which we are comparing.
Finally, if the pressure is expressed in atmospheres, the volume in
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