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
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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
If we assume that the complex is decomposed so fast as to supply
new silver ions rapidly enough, to allow us to consider the
precipitation of silver and silver sulphide as direct actions of the
silver ions, then we may, conservatively, consider T_{Decomposition}
to be about 1 / 100 second. Then T_{Formation} would be only
1 / 10^{24} second. Considering the limiting results for the
dimensions of atoms (and ions) and taking account of the fact that
the formation of the complex ‹involves electrical changes›, that
is, in modern terms, changes in position of electrons,[470] Haber
finds, that to satisfy the above value for the time constant, such
changes must involve a motion of electrical charges at a speed
about a million times as great as the velocity of light. Such a
velocity is, unquestionably, incompatible with our knowledge of the
velocities of light and of electrical charges. We must draw the
conclusion that ‹the complex argenticyanide-ion probably cannot
decompose fast enough into its ions›, to enable the latter to be
the ‹only› components which make it possible to precipitate silver
sulphide or metallic silver from its solutions[471] (see above,
p. 232). That would make it necessary to assume ‹direct action›
[p235] (as given in equation II, p. 232) ‹between the complex› and
the ‹precipitating agent›, to some extent, at least, the extent
being dependent on the concentrations involved in a given case. If
further investigations should confirm such a view, we would probably
find that ‹both› the actions under consideration (equations I and
II, p. 232) must proceed ‹simultaneously›. The second one would
have the advantage of enormously greater concentrations of the
reacting components, ‹e.g.› of the complex ion; the first one would,
probably, be found to have the advantage of an enormously greater
velocity constant. The actual velocities of the two reactions have
never been measured[472] and no final explanation of the relations
can be offered. The problem is a very important one, involving
the whole question of the mode of ionic action (‹cf.› Chap. V,
especially p. 83).
Aside from the theoretical value of the problem that has been
raised, the question of immediate moment to us, from the point
of view of analytical chemistry, is the question whether such
conclusions would invalidate, in any way, the use we have made of
the theory of complex ions, in elucidating the question of the
precipitation and nonprecipitation of salts of simple ions from
solutions of their complex ions.
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