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Iron in nonoxidizing hydrochloric acid principally gives an iron(II) solution; tin in oxidizing aqua regia principally gives a tin(IV) solution. These are the two preparations paired most directly by “respectively”. Their contrast is clearer when the other acid treatment of each metal is considered as well. “Nitrohydrochloric acid” is the historical name for aqua regia, containing nitric and hydrochloric acids.

For iron in dilute hydrochloric acid,The fresh solution is typically pale green when sufficiently concentrated. Hydroxide gives a pale green precipitate of iron(II) hydroxide, which darkens and turns brown on exposure to air as oxidation proceeds. Ammonia can similarly precipitate a ferrous hydroxide rather than forming a stable soluble excess-ammonia complex under the usual test conditions. Ferricyanide gives a deep blue product; the modern structural account of this blue material should not be replaced by an overly literal formula inferred solely from the reagent names. Ferrous solution also reduces a suitable oxidant such as acidic permanganate:

If instead oxidizing acid treatment produces iron(III), the solution exhibits ferric reactions: hydroxide or Ammonia gives red-brown iron(III) hydroxide; thiocyanate gives a strong red colour; and ferrocyanide gives Prussian blue. Chloride complex formation affects colour and some equilibria, so “yellow” is not a universal iron(III) identity test. Oxidizing aqua regia supplies this ferric comparison rather than merely generating more of the same ferrous salt.

Tin in ordinary hydrochloric acid gives a tin(II) solution with hydrogen evolution:Its characteristic property is reducing power. With mercury(II) chloride, controlled addition can first form white mercury(I) chloride and then, with further reductant, grey metallic Mercury:The chloride formulae are useful net bookkeeping, not a complete statement of all aqueous chloro-complexes.

In aqua regia, tin is oxidized predominantly to tin(IV). A representative balance, choosing nitrogen monoxide as the nitrate-reduction product, isActual gas products depend on the acid conditions. Sufficient chloride and acidity retain tin in solution; dilution can cause hydrolysis and precipitation of hydrated tin(IV) oxide. This differs from the simple expectation that every dilution leaves unchanged molecular ${\mathrm{SnCl}}_4$ in water. Hydrogen sulfide in suitable acidic conditions gives yellow tin(IV) sulfide, compared with brown tin(II) sulfide from a stannous solution. Tin(IV) does not reproduce the characteristic reducing reaction of fresh tin(II) with mercuric chloride; reduction to tin(II) is needed first. Oxidation during storage can therefore change the reactions of a nominally stannous preparation.

In a suitably dilute, nonoxidizing chemical acid, hydrogen sulfide precipitates the sufficiently insoluble sulfides, including those of copper, lead, Mercury, bismuth, cadmium, arsenic, antimony and tin. “Sulphuretted hydrogen” is the historical name for hydrogen sulfide, ${\mathrm{H}}_2\mathrm{S}$. Oxidation state and acidity must be specified: the statement is not independent of every possible chemical solution condition.

Arsenic is now classed as a metalloid; the historical analytical grouping was not a rigorous modern division into metals and nonmetals. Dissolved silver also gives black ${\mathrm{Ag}}_2\mathrm{S}$ in acidic conditions. It is often absent from the conventional second analytical group because a preceding hydrochloric acid treatment has already removed it as silver chloride. Suitable gold and platinum solutions can likewise yield dark sulfide precipitates, although their speciation and reduction chemistry make a simple universal colour rule inappropriate. Thus an analytical group is a separation convention, not a list of every ion that can possibly react.

For a divalent metal ion, a useful net balance isThe selectivity follows from two coupled chemical equilibrium conditions. Hydrogen sulfide is a weak acid; increasing $[{\mathrm{H}}^{+}]$ suppresses its ionization. Approximately,Even this small sulfide activity can exceed the solubility product of very insoluble sulfides. More soluble sulfides, such as those of zinc and manganese, generally require less acidic or alkaline conditions. Consequently an excessively strong chemical acid, complex formation or an oxidizing medium can change the result. Colours alone are preliminary indications, not final identification.^[ref]

The traditional preparation treats iron(II) sulfide with a dilute nonoxidizing chemical acid:A gas-generating flask with controlled acid entry and a delivery outlet conducts the product to the test solution. The apparatus must permit gas flow and contain the effluent rather than accumulating pressure in a sealed vessel. Sulfuric acid in dilute form can replace hydrochloric acid; concentrated oxidizing acids are unsuitable for this simple preparation. Hydrogen sulfide is acutely toxic, and loss of odour perception makes smell an unreliable warning: the historical apparatus describes a laboratory principle, not a household test.^[ref]

The brown or brown-black sulfide formed from suitable tin(II) solutions.