Antimony is the brittle, silvery crystalline element , encountered especially in sulfide ores and in compounds of oxidation states and . Its historical treatment as a metal is understandable from appearance and alloying behaviour; modern classifications commonly call it a metalloid. It is too brittle to behave like a readily drawn, ductile metal and is used in suitable alloys to alter properties such as hardness.
The important ore is stibnite, . A historical reduction can use iron to bind the sulfur:Another route roasts suitable sulfide material to an oxide and then reduces that oxide with carbon. For an ideal trioxide product,Real ore processing requires control of impurities and volatile losses, so these balances do not alone constitute a complete extraction flowsheet.[ref]
Among its principal combinations, antimony(III) oxide is an amphoteric oxide. It dissolves under suitable acidic or alkaline conditions rather than fitting a universal rule that a metal oxide must be solely basic. Antimony(III) chloride, historically “butter of antimony”, hydrolyses on dilution and can deposit a white oxychloride-containing material. A useful simplified balance isAdded acid favours dissolution; a more extensively hydrolysed precipitate need not be pure . Pentavalent compounds include antimony(V) chloride and antimonate species; chloride-rich solutions and their hydrolysis require attention to the medium.
Antimony(III) sulfide can occur as the dark crystalline ore and as an orange precipitate obtained from a suitable solution with hydrogen sulfide:Its dissolution in suitable alkaline sulfide solutions forms thioantimony species, providing an analytical separation from some other sulfides. Acidification can reverse that operational separation. A volatile hydride, stibine, , can decompose to a dark antimony deposit and thus interfere with the Marsh test for arsenic.
Antimony potassium tartrate, “tartar emetic”, is a historically important complex salt, not merely an arbitrary mixture of an antimony salt and a potassium salt. It was used medicinally, but historical use is not proof of safety or a present indication; antimony-containing substances can cause serious poisoning. No dosage or treatment recommendation follows from describing them.[ref]
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 species | Principal precipitate | Usual 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 isThe 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]
Qualitative Analysis of Metal Ions in Solution by Williams College. Experiment 2–3, Introduction and Group II discussion, printed II & III-1–3 and II & III-9–10
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]
Hydrogen sulfide by the National Institute for Occupational Safety and Health. Physical Description, odour fatigue, Symptoms and Target Organs