Solution

ID: past-exam-of-the-medicine-course-of-the-university-of-oxford/1866/first-examination/chemistry/4/solution

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, . Oxidation state and acidity must be specified: the statement is not independent of every possible chemical solution condition.
Representative dissolved speciesPrincipal precipitateUsual appearance
Copper(II)Black
Lead(II)Black
Mercury(II)Black when freshly precipitated
Bismuth(III)Brown-black
Cadmium(II)Yellow
Arsenic(III)Yellow
Antimony(III)Orange
Tin(II)Brown or brown-black
Tin(IV)Yellow
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 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 is
The selectivity follows from two coupled chemical equilibrium conditions. Hydrogen sulfide is a weak acid; increasing 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]

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