The Principles of Leather ManufactureProcter, H. R. (Henry Richardson)
History
The Principles of Leather Manufacture
Procter, H. R. (Henry Richardson)
Leather
The following may be suggested as a working hypothesis. As both water
and hydrochloric acid can pass freely in and out of the jelly, it must
be in osmotic equilibrium with the outer solution in every respect, and
neither the un-ionised hydrochloric acid of the solution, nor the small
amount which may be formed by hydrolysis of the gelatine compound can
have any effect on the swelling. So long as the outer solution is very
dilute, by far the greater part of the acid present is absorbed and
fixed by the gelatine, and almost the whole of the outer acid will be
ionised, as well as a portion of that in combination with the gelatine.
In the latter case, however, the ions will be unable to pass out of the
jelly, and will therefore cause an internal osmotic pressure, and the
gelatine will swell till the Cl-ions are in osmotic equilibrium with
those of the outer solution. At the same time, this internal pressure of
Cl-ions will oppose the entry of the Cl-ions (and therefore also of
their associated H-ions) from the outer solution, and the acid solution
absorbed mechanically will be somewhat less concentrated than that
outside. As the concentration of the outer solution is increased, the
pressure of the outer Cl-ions will repress the ionisation of the
gelatine-chloride, and at the same time its tendency to hydrolyse. Thus
the acid actually combined with the gelatine should somewhat increase,
but the swelling should diminish, as is actually the case.[57] It is
impossible to carry the concentration of the hydrochloric acid much
above 5 grm. per liter without causing solution of the gelatine, but the
addition of common salt to the outer solution should equally increase
the pressure of its Cl-ions, and cause further diminution of swelling,
the Na-ions in this case increasing the outside pressure in the same way
as the hydrogen ions. In fact the addition of salt in sufficient
quantity will reduce the swelling till the gelatine becomes quite solid,
and retains only about its own weight of water, while at the same time
the apparently combined acid largely increases. This cannot be
attributed to any direct dehydrating action of the salt, since
concentrated sodium chloride solutions have no dehydrating, but rather a
swelling effect on gelatine in the absence of acid, and the
concentration of the salt in the outer solution and in the jelly proves
precisely the same within the limits of experimental error. Several
other facts may be noted, tending to support the explanation which has
been given. The tendency to swell gelatine is common to all acids of
appreciable strength, and in all cases where the concentration of the
acid could be increased to a moderate extent without causing solution of
the jelly, the effect of a maximum swelling, diminishing as the
concentration of the acid increased, has been observed. Other salts also
produce similar effects to sodium chloride; thus the swelling caused by
sulphuric acid is repressed by sodium sulphate.
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