Atomistry » Sulphur » Compounds
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Compounds of Sulphur

Although sulphur in the compact form appears to be a comparatively inactive element, yet when in a fine state of division it reacts with many metals, and at elevated temperatures it combines directly with nearly all other elements (exceptions being nitrogen, iodine, beryllium, gold, platinum and iridium) to form stable binary compounds, the reactions often occurring with great vigour.

In its most stable compounds with hydrogen and the metals, sulphur in Compounds of Sulphur is usually bivalent, but it possesses the property of combining with these elements in proportions exceeding the valency requirements, forming series of polysulphides of the type R2Sx, where x may be as high as 6. The polysulphides of hydrogen are unstable oily liquids of uncertain freezing-points, and on heating undergo decomposition.

Towards the halogens, sulphur is electropositive. Combination with fluorine and chlorine takes place at ordinary temperatures, the product in the former case being the hexafluoride, SF6, whilst with chlorine, sulphur monochloride, S2Cl2, is first formed, then the dichloride, S2Cl2, and finally the tetrachloride, SCl4. A monofluoride and a mono- bromide are also known, but no compound of sulphur and iodine has been isolated.

Sulphur is also electropositive towards oxygen, and in the oxides and their derivatives the element usually exhibits a valency of 4 or 6. The two stable oxides, SO2 and SO3, are strongly acidic, giving rise to sulphurous and sulphuric acids, respectively, from which numerous other oxyacids are derived. An intermediate unstable sesquioxide, S2O3, is known, but it does not appear to be the anhydride of hydro-sulphurous acid, H2S2O4, as its formula would suggest, since this acid cannot be obtained from it. Products have also been described purporting to contain a higher oxide variously formulated as S2O7, SO4 and S3O11, from which the peracids are derived, but the identity of such an oxide has not yet been satisfactorily established.

The following is a list of the oxyacids of sulphur; those in brackets are only known in the form of their derivatives, whilst those marked

with an asterisk are known in solution, but have not been isolated:

(Sulphoxylic acid, H2SO2).
*Hydrosulphurous acid, H2S2O4.
*Sulphurous acid, H2SO3.
Sulphuric acid, H2SO4.
Pyrosulphuric acid, H2S2O7.
*Thiosulphuric acid, H2S2O3.
Permonosulphuric acid, H2SO5.
Perdisulphuric acid, H2S2O8.
*Dithionic acid, H2S2O6.
*Trithionic acid, H2S3O6.
*Tetrathionic acid, H2S4O6.
*Pentathionic acid, H2S5O6.
(Hexathionic acid, H2S6O6).

Arranged in order of increasing strength, the sulphur acids are as follows:

H2S, H2SO3, H2S2O4, H2S2O3, H2SO4, H2S2O6, H2S3O6.

Hydrogen sulphide is the weakest acid, di- and tri-thionic acids are approximately of equal strength, whilst sulphurous acid is the weakest oxyacid in the list.

On replacement of one hydroxyl group in sulphuric acid, SO2(OH)2, by such univalent radicals as -NH2, -NO2, -F or -Cl, a series of sulphonic acids may be obtained, from which a large number of derivatives, both inorganic and organic, have been prepared.

Sulphur and Hydrogen

The most important and the most stable compound of sulphur and hydrogen is the well-known hydrogen sulphide, but, in addition, at least three well-defined compounds, H2S2, H2S3 and H2S5, are known, and there is evidence that a hexasulphide, H2S6, also exists.

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