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
Perhaps the most instructive case of this kind, that we can study,
is that of iron in ferrous and ferric salts. Exceedingly sensitive
tests are known for the ferrous and the ferric ions. Thiocyanates
produce an intensely red salt, Fe(SCN)_{3}, when added, for instance,
to ‹ferric› chloride; potassium ferrocyanide, K_{4}Fe(CN)_{6},
precipitates ferric ferrocyanide, Fe_{4}[Fe(CN)_{6}]_{3}, Prussian
blue, from ferric chloride solutions; ammonium hydroxide precipitates
quantitatively the insoluble red ferric hydroxide (exps.). With
‹ferrous› salts, potassium ferricyanide K_{3}Fe(CN)_{6} precipitates
ferro-ferricyanide Fe_{3}[Fe(CN)_{6}]_{2}, Turnbull's blue; ammonium
sulphide precipitates black ferrous sulphide (‹exps.›). Now, in
two of the reagents used, potassium ferro- and ferricyanide, iron
is present according to the formulæ given. If one should attempt
to demonstrate its presence by means of these tests—among the
most sensitive and most reliable tests known in analysis—one
would fail utterly. Thiocyanates do not produce even the faintest
tinge of pink in potassium ferricyanide solution[163]; ammonium
hydroxide does not precipitate any ferric hydroxide (‹exps.›).
Ammonium sulphide does not precipitate the least trace of a black
sulphide from a ferrocyanide solution, and when the latter is
mixed with the ferricyanide solution, no trace, either of Prussian
or Turnbull's blue, is shown (‹exps.›). The contrast between
the behavior of these salts and ferrous and ferric salts is now
sharply and definitely interpreted, as being the result of the
contrast in their ionization,—the color tests we use are extremely
sensitive tests only for the ‹ferric› and ‹ferrous ions›, Fe^{3+}
and Fe^{2+}, respectively,—but potassium ferrocyanide ionizes into
potassium ions and the negative ferrocyanide ions Fe(CN)_{6}^{4−},
and shows the actions of ferrous ions as little as chlorate ions
ClO_{3}^{−} exhibit the reactions of chloride ions Cl^{−}. Potassium
ferricyanide, in turn, gives rise to trivalent, negative ferricyanide
ions Fe(CN)_{6}^{3−} and not to ferric [p089] ions.[164] If any
doubts arise on this point, one can decide the question readily by
experiment. When a concentrated solution of potassium ferricyanide is
placed in a U-tube under a solution of some colorless electrolyte,
such as sodium sulphate, and plates connected with a battery are
inserted, there is no difficulty (‹exp.›) in seeing that the yellow
ion,[165] containing the iron, moves to the ‹positive› pole and ‹not›
to the ‹negative›. The iron is, therefore, as a matter of experiment,
‹part of a negatively charged substance›.
That iron is really present in these compounds can be shown most
effectively if we destroy the salts:
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