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
[14] As a result of numerous vain endeavors, as well as of much
direct evidence of a positive character, the scientific world has,
for many years, held the opinion that any sort of "perpetual motion
machine" is impossible. Every one now admits that a machine which
would be able to work continuously, without consuming energy, is
an impossibility—that is, that a "‹perpetuum mobile of the first
class›," as it is called, is impossible (law of the conservation of
energy or ‹first law› of thermodynamics). From this law it does not
of necessity follow, however, that it would be impossible to make a
machine or device that would convert ‹continuously› into available
energy or work, say, the enormous amounts of heat energy of the
earth or of large bodies of water ("dissipated energy") which would
thereby be ‹cooled below› the temperatures of their surroundings.
Such a hypothetical process has been termed a "‹perpetuum mobile of
the second class›"; it has never been realized and is universally
conceded to be an impossibility; the so-called "‹second law› of
thermodynamics" gives expression to this fact.
Now van 't Hoff [‹Z. phys. Chem.›, «1», 481 (1887)] showed, first,
that a gas like oxygen, nitrogen, hydrogen, etc., which is soluble
in proportion to its gas pressure (Henry's law), must exert, in
solution, an osmotic pressure equal to the gas pressure, which it
would have, if present in the same quantity as a gas in the same
volume at the same temperature; for, if such were not the case,
the solution and gas could be used to produce a ‹perpetuum mobile
of the second class›, which, according to the above law, is an
impossibility. Similar proofs were given by Rayleigh [‹Nature›,
«55», 253 (1897)] and by Larmor [‹Phil. Trans.›, «190», 266 (1897),
‹Nature›, «55», 545 (1897)] that the principle applies to solutions
of other solutes.
Provided, then, that we have (1) perfect semipermeable membranes,
(2) sufficiently dilute solutions, and (3) none but negligible
heats of dilution (p. 12), van 't Hoff's generalization, concerning
the relation of osmotic pressure and the laws of gases, must hold,
if the ‹perpetuum mobile of the second class› is impossible, as is
demanded by the second law of thermodynamics.
[15] See p. 15 in regard to the relation for concentrated solutions.
[16] The pressure ‹P›_{0} of a given quantity (weight) of a gas
at 0° C., in a given constant volume, is also a given number and
consequently ‹P›_{0}/273 is a constant under these conditions.
[17] The slight differences in the ionization of copper sulphate
solutions of 14% and 17% and at 20° and 80° are not included in the
calculation, ionization being unknown, when van 't Hoff made his
calculations.
[18] ‹Am. Chem. J.›, 41, 258 (1909).
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