The Principles of Leather ManufactureProcter, H. R. (Henry Richardson)
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The Principles of Leather Manufacture
Procter, H. R. (Henry Richardson)
Leather
In the first stage, very slight acidification is required, and if the
skins have been chromed with excess of hydrochloric acid, may be
altogether dispensed with. The skins become brownish from the conversion
of the chromic acid into so-called “chromium dioxide” (probably really a
basic chromic chromate, Cr₂CrO₄(OH)₄, which on ignition leaves Cr₃O₆);
no sulphurous acid is liberated, or sulphur deposited, but sodium
tetrathionate is formed in the bath, and the reaction may be represented
as follows:
(1) 3CrO₃ + 6HCl + 6Na₂S₂O₃ = 3Na₂S₄O₆ + 6NaCl + 3OH₂ + Cr₃O₆.
Further addition of hydrochloric acid brightens the colour of the skins,
while the liquid still remains clear, and chromium chloride is formed
instead of chromic chromate, the main reaction being:
(2) 2CrO₃ + 12HCl + 6Na₂S₂O₃ = 3Na₂S₄O₆ + 2CrCl₃ + 6NaCl + 6OH₂.
On still further addition of hydrochloric acid, sulphur is separated
according to the following equation, and is deposited partly in the
skins, and partly in the bath:
(3) 2CrO₃ + 6HCl + 3Na₂S₂O₃ = 3Na₂SO₄ + 3S + 2CrCl₃ + 3OH₂.
After complete reduction, and consumption of the free hydrochloric acid,
further reactions take place at the expense of the excess of
thiosulphate which should be present, resulting in the production of
basic chromic salts, and the further deposition of sulphur, mostly
within the skin, as shown in the following equations:
(4) Cr₂(SO₄)₃ + Na₂S₂O₃ + OH₂ = 2CrOH.SO₄ + SO₂ + S + Na₂SO₄.
(5) 2CrCl₃ + Na₂S₂O₃ + OH₂ = 2CrOH.Cl₂ + SO₂ + S + 2NaCl.
The thiosulphate bath therefore not only reduces, but precipitates
sulphur in the skin, and reduces the chromic salt to a basic state. In
boiling solution, thiosulphate precipitates the whole of the chromium as
chromic oxide, but in the cold, and in presence of free sulphurous acid,
it only reduces to a basic salt. Eitner does not consider the
possibility, which certainly requires investigation, that instead of
basic salts, sulphite-sulphates are formed at least in the first
instance. Such salts of one base and two acids are quite possible, and
it is very probable that in the use of chroming baths containing organic
acids, they have considerable influence on the tannage.
The free sulphur which is liberated is partially deposited on and among
the fibres of the leather, and adds to its softness, and also acts
chemically on the oils used in “fatliquoring,” so that it is probably
one of the main causes of difference between the products of the Schultz
or “two-bath” method, and the “one-bath” processes subsequently to be
described.
Public-domain text, read in full here on John Shaqi.
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