Chemical elements
    Amorphous Sulphur
    Colloidal Sulphur
    Physical Properties
    Chemical Properties
      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
      Sulphur Trioxide
      Pyrosulphuric Acid
      Sulphuric Acid
      Persulphuric Anhydride
      Persulphuric Acid or Perdisulphuric Acid
      Permonosulphuric Acid
      Amidopermonosulphuric Acid
      Thiosulphuric Acid
      Polythionic Acids
      Dithionic Acid
      Trithionic Acid
      Tetrathionic Acid
      Pentathionic Acid
      Wackenroders Solution
      Hexathionic Acid
      Polythionic Acids
      Sulphur Sesquioxide
      Hydrosulphurous Acid
      Nitrogen Sulphide
      Nitrogen Persulphide
      Nitrogen Pentasulphide
      Nitrogen Chlorosulphide
      Trithiazyl Chloride
      Thiotrithiazyl Chloride
      Dithiotetrathiazyl Chloride
      Nitrogen Bromosulphide
      Thiotrithiazyl Bromide
      Thiotrithiazyl Iodide
      Thiotrithiazyl Nitrate
      Thiotrithiazyl Hydrogen Sulphate
      Thiotrithiazyl Thiocyanate
      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
      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
      Azidodithiocarbonic Acid
      Cyanogen Monosulphide
      Cyanogen Trisulphide
      Sulphur Thiocyanate
      Disulphur Dithiocyanate
      Thiocyanic Acid
      Dithiocyanic Acid
      Trithiocyanuric Acid
      Perthiocyanic Acid

Pyrosulphuric Acid, H2S2O7

Although the substance of the composition H2S2O7 is capable of definite existence, the commercial products deviate from the composition expressed by the formula and contain variable quantities of sulphuric acid with pyrosulphuric acid or of pyrosulphuric acid with sulphur trioxide. For the purpose of including all varieties of impure pyrosulphuric acid, the somewhat vague terms "oleum," "fuming sulphuric acid" and "Nordhausen sulphuric acid " are advantageous.


  1. At one time fuming sulphuric acid was largely prepared by the dry distillation of basic ferric sulphate which had been obtained by submitting ferrous sulphate to atmospheric oxidation and subsequently dehydrating the oxidation product fairly completely:

    12FeSO4 + 3O2 = 4Fe2(SO4)3 + 2Fe2O3,
    Fe2(SO4)3 + 2H2O = Fe2O3 + H2S2O7 + H2SO4.

    The acid obtained will naturally vary in composition according to the extent of the previous dehydration.

    In the fifteenth and sixteenth centuries the alchemists obtained sulphuric acid in this manner, frequently aiding the process by the addition of silica, and the process was worked on a commercial scale until the end of the nineteenth century. From the fact that much of the fuming acid was distributed from Nordhausen in Prussia, the name "Nordhausen sulphuric acid" originated, but little if any of the acid was manufactured in this town.
  2. The present method of manufacture is to treat ordinary sulphuric acid with the necessary amount of sulphur trioxide, by which procedure any desired degree of concentration may be attained. The trioxide may be introduced in the liquid condition, but commercially it is simpler to pass the trioxide vapours from the contact chambers directly into sulphuric acid of 98 to 99 per cent, concentration. The latter is usually contained in bubbling vessels or circulated in towers. The vapours meet the most concentrated acid in the first vessel, and then pass through slightly weaker acid, and so on until the trioxide is completely absorbed. The acid in the last absorption vessel should contain 98 to 99 per cent.H2SO4; if stronger than this the acid has the same vapour pressure as the trioxide and the latter is not absorbed; if weaker, a mist is formed which is difficult to absorb.
Ordinary commercial "oleum" is 20 per cent, oleum, that is, it contains 80 per cent, of H2SO4 and 20 per cent, of "free" SO3. 100 parts of such "oleum," i.e. 80 parts of H2SO4 + 20 parts of SO3, can take up 18/80×20 = 4.5 parts of H2O, yielding 80 + 24.5 = 104.5 parts of H2SO4. Sulphuric acid containing high percentages of additional sulphur trioxide is frequently manufactured by distilling acid containing 20 to 30 per cent, of the trioxide.

Physical Properties

Pure pyrosulphuric acid is a colourless crystalline solid of melting-point 35° C.; the addition of a little water or of sulphur trioxide lowers the melting-point; the colour of the acid is frequently brown, due to the presence of traces of organic matter.

In the following table are given the melting-points for ordinary sulphuric acid containing gradually increasing proportions of additional sulphur trioxide; the maxima for pure sulphuric acid and pure pyrosulphuric acid are evident at the values 0 per cent, and near 40 per cent.

Melting points of H2SO4-SO3 mixtures

Percentage SO2.Melting-point, ° C
0 + 10.5
5 + 3.5
10- 4.8
15- 11.2
20- 11.0
25- 0.6
30 + 15.2
35 + 26.0
40 + 33.8
45 + 34.8
50 + 28.5
55 + 18.4
60 + 0.7
65 + 0.8
70 + 9.0
75 + 17.2
80 + 22.0

The specific gravity of " fuming sulphuric acid " reaches a maximum in the neighbourhood of 50 to 60 per cent, of " free " trioxide, the composition of maximum density acid being dependent to some extent on the temperature. In the next table are given figures for the specific gravities of concentrated sulphuric acid and the fuming acid at 15° C., which show clearly the irregularity in the variation of this physical characteristic with gradual alteration in composition.

Investigation has also been made of the viscosity, vapour pressure, boiling-point, specific heat, heat of solution in water, electrical resistance

Specific gravities of concentrated and fuming sulphuric acids

H2SO4 (per cent.).Total SO3 (per cent.).Free SO3 (per cent.).Sp. Gr. at 15° C.Sp. Gr. at 45° C.
95.9878.35. . .1.8418. . .
96.6878.92. . .1.8429. . .
96.9979.18. . .1.8431. . .
97.6679.72. . .1.8434 max.. . .
98.6580.53. . .1.8403. . .
99.4081.14. . .1.8388 min.. . .
99.7681.44. . .1.8418. . .
. . .83.4610.01.8881.858
. . .85.3020.01.9201.887
. . .87.1430.01.9571.920
. . .88.9740.01.9791.945
. . .90.8150.02.0091.964 max.
. . .92.6560.02.020 max.1.959
. . .94.4870.02.0181.942
. . .96.3280.02.0081.890
. . .98.1690.01.9901.864
. . .100.00100.01.9841.814

and capillarity of fuming sulphuric acid of varying richness in sulphur trioxide.

Chemical Properties

Pyrosulphuric acid, whether pure or mixed with excess of sulphuric acid or sulphur trioxide, readily undergoes decomposition into sulphuric acid and the trioxide; indeed, the fumes evolved at the ordinary temperature are due to vaporisation of the trioxide from the molten acid or its solution in sulphuric acid. On heating the acid, sulphur trioxide is expelled until the mixture of sulphuric acid and water of minimum vapour pressure (98.3 per cent, sulphuric acid) remains. It is owing to this behaviour that pyrosulphuric acid and "fuming sulphuric acids" in general have no definite and constant boiling temperature.

In consequence of this readiness of "fuming sulphuric acid" to undergo fission into its two constituents, the chemical properties of the acid are largely a blend of those of sulphuric acid and its anhydride.

Platinum and lead are attacked more seriously by fuming sulphuric acid than by ordinary sulphuric acid, but of considerable technical value is the fact that although a weaker acid corrodes wrought iron, this metal becomes "passive" in acid containing more than 27 per cent, of "free" anhydride.

The fuming sulphuric acid of commerce contains less sulphur trioxide than corresponds with the formula H2S2O7, and therefore consists of a mixture of pyrosulphuric acid and sulphuric acid.


The constitution of pyrosulphuric acid is to be regarded as that of an anhydride of sulphuric acid produced by the elimination from two molecules of the latter of a single molecule of water; the structural formula is therefore OH.SO2.O.SO2.OH, where the SO2-group possesses the same character as in sulphuric acid.


The estimation of pyrosulphuric acid is generally effected by the addition of water to a definite quantity and determination of the amount of sulphuric acid formed. Various special forms of apparatus have been suggested to obviate loss of the trioxide during the earlier manipulations.

The amount of free trioxide in " fuming sulphuric acid " can be estimated by titration with water in a stoppered cylinder. The water is added until no further fuming occurs when air is blown through a glass tube on to the liquid surface. Each molecule of water added indicates the presence of one molecule of sulphur trioxide, thus:

H2O + SO3 = H2SO4.

A thermometric method of evaluating the "fuming acid" consists in adding excess of standard 80 per cent, sulphuric acid and titrating back with the "fuming acid"; the temperature of the solution rises with each addition of the "fuming acid" until the water content of the standard is exhausted.
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