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
(5) The displacement of an acid (or base) in salts by another acid
(or base) is subject always to the law that equilibrium is reached,
when all the equilibrium constants are satisfied in the system. Very
frequently, the application of the law will lead, apparently, to the
incorrect conclusion that the stronger acid (or base) will ‹always›
displace, more or less completely, the weaker[222]—an inference, out
of which grew, indeed, the characterization of acids and bases as
strong and weak. Yet, when the laws of equilibrium, as the result
of the peculiar values of constants, demand that, on the contrary,
a strong acid or base should be displaced by a weak, or even a
feeble one, we find that the change in this direction occurs with
equal ease. Numerous instances will be given where a weak acid (or
a weak base) does this to a certain extent (Chap. X), and others
where precipitation of salts facilitates the action of weaker acids
greatly by the introduction of new, physical constants. The following
case of the liberation of hydrochloric acid by the exceedingly weak
acid, hydrocyanic acid, is important because it shows a reversal
of the common action without the formation of any precipitate, and
especially because it brings out most strikingly the relations
between ionization and chemical activity in a case of special
importance to analytical chemists.
«The Exceptional Ionization of Mercuric Cyanide and Its
Consequences.»—We have found that practically all salts are very
readily ionized. But it was mentioned that there are a few exceptions
to this rule, and mercuric chloride and especially mercuric cyanide
were named as the most important exceptions from the point of view
of analytical chemistry. The difference in ionization between these
two salts and ordinary salts may be shown readily by the apparatus
previously used to demonstrate the difference in the ionization of
various bases and acids.
EXP. Into the parallel tubes of the conductivity apparatus (p. 77)
equivalent quantities[223] of solutions of mercuric cyanide[224]
Hg(CN)_{2}, mercuric chloride [p116] HgCl_{2}, and barium chloride
BaCl_{2}, are introduced. The barium chloride represents an ordinary
salt of the same type as the mercury salts, and the current passing
through its solution makes the little lamp glow. The electrodes
in the mercuric chloride solution must be brought ‹quite close›
together before sufficient current will pass through the solution to
bring its little lamp to redness. In the case of the cyanide we can,
at most, get a faint, dull glow by bringing the electrodes together
as closely as we can, without allowing them to touch each other and
short-circuit the current.
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