Chemical elements
  Sulphur
    Isotopes
    Energy
    Extraction
    Refining
    Applications
    Allotropy
    Crystalline
    Amorphous Sulphur
    Colloidal Sulphur
    Physical Properties
    Chemical Properties
    Detection
    Estimation
    Compounds
      Hydrogen Sulphide
      Metal Polysulphides
      Hydrogen Polysulphides
      Hydrogen Pentasulphide
      Hydrogen Trisulphide
      Hydrogen Disulphide
      Sulphur Monofluoride
      Sulphur Tetrafluoride
      Sulphur Hexafluoride
      Sulphur Monochloride
      Sulphur Dichloride
      Sulphur Tetrachloride
      Sulphur Monobromide
      Thionyl Fluoride
      Sulphuryl Fluoride
      Fluorosulphonic Acid
      Thionyl Chloride
      Sulphuryl Chloride
      Sulphur Oxytetrachloride
      Pyrosulphuryl Chloride
      Chlorosulphonic Acid
      Thionyl Bromide
      Sodium Sulphoxylate
      Sulphur Dioxide
      Sulphurous Acid
      Sulphites
      Sulphur Trioxide
      Pyrosulphuric Acid
      Pyrosulphates
      Sulphuric Acid
      Persulphuric Anhydride
      Persulphuric Acid or Perdisulphuric Acid
      Perdisulphates
      Permonosulphuric Acid
      Amidopermonosulphuric Acid
      Thiosulphuric Acid
      Thiosulphates
      Polythionic Acids
      Dithionic Acid
      Trithionic Acid
      Trithionates
      Tetrathionic Acid
      Tetrathionates
      Pentathionic Acid
      Pentathionates
      Wackenroders Solution
      Hexathionic Acid
      Polythionic Acids
      Sulphur Sesquioxide
      Hydrosulphurous Acid
      Hydrosulphites
      Nitrogen Sulphide
      Nitrogen Persulphide
      Nitrogen Pentasulphide
      Sulphammonium
      Hexasulphamide
      Nitrogen Chlorosulphide
      Trithiazyl Chloride
      Thiotrithiazyl Chloride
      Dithiotetrathiazyl Chloride
      Nitrogen Bromosulphide
      Thiotrithiazyl Bromide
      Thiotrithiazyl Iodide
      Thiotrithiazyl Nitrate
      Thiotrithiazyl Hydrogen Sulphate
      Thiotrithiazyl Thiocyanate
      Thionylamide
      Sulphamide
      Imidodisulphamide
      Sulphimide
      Sulphonic Acids
      Amidosulphonic Acid
      Imidosulphonic Acid
      Nitrilosulphonic Acid
      Hydroxylamine-monosulphonic Acid
      Nitrososulphonic Acid
      Hydroxylamine-disulphonic Acid
      Hydroxylamine-isodisulphonic Acid
      Hydroxylamine-trisulphonic Acid
      Dihydroxylamidosulphonic Acid
      Sulphazinic Acid
      Sulphazotinic Acid
      Dehydrosulphazotinic Acid
      Nitrosulphonic Acid
      Nitrosulphonyl Chloride
      Nitrosulphonic Anhydride
      Nitrosulphuric Acid
      Nitrosodisulphonic Acid
      Sulphonitronic Acid
      Sulphates of Hydroxylamine
      Hydroxylamine Dithionate
      Hydrazine Dithionate
      Hydrazine Amidosulphonate
      Carbon Subsulphide
      Carbon Monosulphide
      Carbon Disulphide
      Thioformaldehyde
      Thiocarbonic Acid
      Ammonium thiocarbonate
      Thiolcarbonic Acid
      Xanthic Acid
      Perthiocarbonic Acid
      Sodium perthiocarbonate
      Carbonyl Sulphide
      Thiocarbonyl Chloride
      Thiocarbonyl Tetrachloride or
      Carbon Hexachlorosulphide
      Trichloromethyl Disulphide
      Thiocarbonyl Sulphochloride
      Carbon Bromosulphide
      Amino-derivatives of Thiocarbonic Acid
      Dithiocarbamic Acid
      Thiocarbamide
      Azidodithiocarbonic Acid
      Thiocyanogen
      Cyanogen Monosulphide
      Cyanogen Trisulphide
      Sulphur Thiocyanate
      Disulphur Dithiocyanate
      Thiocyanic Acid
      Thiocyanates
      Dithiocyanic Acid
      Trithiocyanuric Acid
      Perthiocyanic Acid
      Perthiocyanogen
      Sulphates

Sulphites






Sulphurous acid gives rise to normal sulphites of the type M2SO3 and acid salts of the type MHSO3, where M represents a univalent metal atom. The normal salts are odourless and do not resemble the free acid or sulphur dioxide in their very harmful effect on living organisms. On the other hand, the acid sulphites readily yield sulphur dioxide; they have an acid reaction towards phenolphthalein, but are neutral towards methyl orange.

Other saline derivatives of sulphur dioxide are known corresponding with a hypothetical acid H2S2O5; for example, alkali metabisulphites or pyrosulphites of the composition M2S2O5 are known, which may be considered as structurally derived from two molecules of the hydrogen sulphites MHSO3 by elimination of one molecule of water. They are well-defined compounds obtained by crystallisation from aqueous solutions of the sulphites of the alkali metals in the presence of excess of sulphur dioxide.

Sulphurous acid and the alkali sulphites show a marked tendency to react with sulphites of the heavier metals to form complexes in which the ordinary reactions of the heavy metal are often more or less obscured. The alkali sulphites and bisulphites are produced on the large scale by treating lime and magnesia or dolomitic limestone with sulphur dioxide in the presence of water, then adding the requisite amount of alkali sulphate to the filtrate and filtering off any insoluble sulphate; or, alkali carbonate or bicarbonate may be treated directly with sulphur dioxide.

The action of heat on sulphites varies both with the temperature and with the nature of the metal concerned. With sodium sulphite, Na2SO3, the chief reaction at 700° C. in vacuo is

4Na2SO3 ⇔ 3Na2SO4 + Na2S,

and apparently lithium sulphite behaves similarly. In the case of calcium sulphite an analogous reaction takes place at about 650° C., but at 1100° C. the dissociation

CaSO3CaO + SO2

is practically complete. The residue contains calcium sulphate in addition to the oxide, probably because the equilibrium

3SO2 ⇔ 2SO3 + S

becomes effective at higher temperatures. Magnesium sulphite decomposes at 300° C. according to the equation:

4MgSO3 = 2MgSO4 + MgS2O3 + MgO.

At higher temperatures the following also occurs:

MgS2O3 = MgSO3 + S,
MgSO3 = MgO + SO2.

The decomposition of the alkali pyrosulphites under the influence of heat follows a very complicated course. At 150° C. the potassium salt yields trithionate and sulphate, the ionic reaction being:

  1. 2S2O5S3O6' + SO4';

    above 200° C. sulphur dioxide is liberated, and if the partial pressure of the sulphur dioxide (from (iii)) is kept low, the reaction
  2. S2O5' ⇔ SO3' + SO2

    proceeds from left to right. The main reaction at 250° C., however, produces thiosulphate, thus:
  3. 3S2O5' → S2O3' + 2SO2 + 2SO2.

    A number of side reactions also occur, depending largely on concentration and temperature; the thiosulphate gradually disappears and the final state may be represented:
  4. 2S2O5' → 2SO4' + SO2 + S.

    The sodium salt behaves somewhat similarly, but the main reaction at 150° C. is that indicated in equation (ii).
The sulphites, both normal and acid, are easily oxidised, and in solution readily undergo atmospheric oxidation with the formation of sulphates. The oxidation proceeds more readily in neutral than in acid solution, and is accelerated by warming. The change in SO2- content of a solution of potassium metabisulphite (0.1 per cent.) kept in a stoppered bottle, observed by titration at intervals of aliquot portions with standard iodine solution, has been observed to be as follows:

Time interval (hours)024487296144
Relative SO2-content10098.294.693.592.291.3


The oxidation can be considerably checked by the addition of certain organic compounds, such as sucrose, alcohols, quinol, and some organic acids. On the other hand it is accelerated by dextrose and certain other sugars, and also by the presence of Cu•• or Fe••• ions in solutions of PH value 4 to 12.

Aqueous solutions of normal alkali sulphites are oxidised to dithionate by heating with lead dioxide, the latter being reduced to red lead. Manganese dioxide does not react in this way.

Analogous to the action of oxygen is that of sulphur, which slowly converts a sulphite in hot aqueous solution into the corresponding thio-sulphate, some trithionate being formed simultaneously. The reaction goes to completion with excess of sulphur, and is accelerated by the presence of sodium sulphide.

Crystalline hydrazine derivatives of certain sulphites, for example of zinc, cadmium, manganese, cobalt and nickel sulphites, have been prepared. When aqueous manganous sulphite containing excess of sulphurous acid is neutralised with hydrazine hydrate, a white crystalline compound, MnSO3.N2H4.H2SO3, is formed. A solution of cobalt hydrogen sulphite similarly treated yields a red compound of composition 5CoSO3.9N2H4.6H2O, but if the hydrogen sulphite is added to an excess of concentrated hydrazine hydrate solution, a buff-coloured compound, CoSO3.2N2H4.H2O, results. A suspension of the latter salt treated with sulphur dioxide gives two red sulphites, CoSO3.2N2H4.H2SO3.2H2O and CoSO3.N2H4.H2SO3.0.5H2O. The other (red) compound similarly treated yields a brown substance, 2CoSO3.N2H4.3H2O. Similar products from sulphites of the other metals mentioned may be obtained.

By the action of alkali hydrogen sulphites on alkali nitrites, compounds are obtained the structure of which may be derived from that of ortho-nitrous acid, N(OH)3, by substituting the sulphonic acid group, -SO2.OH, for one or more hydroxyl groups.

The acid sulphites possess the property of forming crystalline additive compounds with aldehydes and ketones. Sodium hydrogen sulphite is therefore largely used for the purification of compounds of these classes; the sulphite adds on at the carbonyl group, >C:O, forming the grouping , and the original organic substance can be liberated

by suitable treatment with acid or alkali.

Calcium bisulphite is largely used in the manufacture of "sulphite pulp," from which paper and viscose silk may be produced. Wood chips or shavings are boiled with the bisulphite under pressure and so yield cellulose, which at the same time is bleached. The bisulphites of magnesium and the alkali metals are also sometimes used.

It is of interest that there is a frequent occurrence of isomorphism between the sulphites and the corresponding carbonates; this would appear, at first sight, to indicate quadrivalency of sulphur in the sulphites, but the evidence is untrustworthy and insufficient.


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