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
[513] To a certain extent, the effect of the acid may be to
coagulate and precipitate the ‹colloidal› sulphide. Possibly, also,
the concentrated acid renders inactive a considerable portion of
the water present (forming oxonium salts OH_{3}Cl, etc., see p.
238), which tends, by hydrolysis, to reverse the formation of the
chloride As(OH)_{5} + 5 HCl ⇄ AsCl_{5} + 5 H_{2}O. Possibly, the
formation of the pentasulphide is not wholly an ‹ionic reaction›,
its precipitation being always a more or less ‹slow process›,
and there may be intermediate products whose formation could be
‹accelerated› by the presence of acids (see Bredig and Walton, ‹Z.
Elektrochem.›, «9», 114 (1903) for the study of a simple inorganic
action involving such ‹catalytic› effects of acids).
[p251]
CHAPTER XIV
«OXIDATION AND REDUCTION REACTIONS. I»
Oxidation and reduction reactions are frequently met with in
analysis, and we shall turn now to the consideration of such
reactions, from the point of view of the modern theory of solution
and the laws of equilibrium.
Leaving until later the discussion of the most important and most
common oxidizing agents, such as oxygen, nitric acid, permanganate,
etc., we shall, in order to develop the subject most simply, confine
ourselves, for the moment, to the ‹qualitative› study of some
oxidations and reductions met with early in the study of analytical
reactions. One such reaction is the reduction of ferric salts by
hydrogen sulphide, and the simultaneous oxidation of the latter to
sulphur (‹exp.›). The reaction may be expressed by the equation
2 FeCl_{3} + H_{2}S → 2 FeCl_{2} + 2 HCl + S ↓.
If the action is considered to be the result of the interaction
of the ionized ferric chloride and hydrogen sulphide, it would be
represented by the equation
2 Fe^{3+} + 6 Cl^{−} + 2 H^{+} + S^{2−} →
2 Fe^{2+} + 6 Cl^{−} + 2 H^{+} + S ↓.
It is then clear that the reacting components, according to such a
conception, are the ferric and the sulphide ions, whose electrical
charges mutually discharge each other. Considering only those
components whose charges are changed, we have
2 Fe^{3+} + S^{2−} → 2 Fe^{2+} + S ↓.
The reduction of a ferric to a ferrous salt would then be
accomplished by the discharge of one of the three positive charges on
the ferric ions; the oxidation of hydrogen sulphide to sulphur would
be accomplished by the complete discharge of the sulphide ions.
Ferric salts are reduced, much in the same way, by iodides (‹exp.›),
iodine being liberated: 2 Fe^{3+} + 2 I^{−} → 2 Fe^{2+} + I_{2}.
Reduction then appears to involve a loss of positive charges by ions,
oxidation a loss of negative charges. [p252]
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