To illustrate the matter, the case of a basic chrome alum liquor will be
considered. The chromium hydrate sol is primarily a positive sol, just
like ferric and aluminium hydrate sols: _i.e._ in water they are
somewhat exceptional in that they adsorb H+ rather than OH-. To cause
precipitation therefore it is necessary to make the sol less positive
and more negative. The positive charge of the sol, however, is greater
than in water, because of the free acid formed in the hydrolysis, which
results in the adsorption of more hydrions by the sol. Hence to ensure
precipitation steps must be taken to reduce the adsorption of hydrions
by the chromium hydrate sol. In practice such steps are taken, and to
such an extent that there can be little doubt that the chrome sol is not
far from its isoelectric point. Amongst these "steps" are (1) making the
liquor "basic," _i.e._ adding alkali to neutralize much of the free
acid, which involves a considerable reduction in the stabilizing effect
of the hydrions; (2) the adsorption of hydrions by the hide gel when
first immersed in approximately neutral condition; (3) the operation of
the "valency rule" that the predominant ionic effect in discharging is
due to the multivalent anions. In this case the divalent SO{4}-- ions
assist materially in discharging the positive charge on the chrome sol;
(4) the final process of neutralization in which still more alkali is
added. The operation of the valency rule is the most complex of these
factors, for there is also to be considered the stabilizing effect of
the kations, especially of the trivalent kation Cr+++ from the
unhydrolyzed chromium sulphate. It is quite possible also that in the
last stages of chrome tanning there are "zones of non-precipitation" due
to the total effect of multivalent ions, and it is quite conceivable
that the chrome sol may change its sign, _i.e._ become a negative sol
and thus give also a mutual precipitation with the hide-gel. This is
particularly probable where a local excess of alkali occurs in
neutralization. However that may be, it is probable that most of the
tannage is accomplished by chromium hydrate in acid solution, and it is
therefore legitimate to conclude that adsorption and gelation have a
relatively greater part in chrome tannage. The operation of the valency
rule makes it easy to understand why basic chlorides do not tan so well
as sulphates; the precipitating anion is only monovalent (Cl-) and
chromic chloride contains no substance analogous to the potassium
sulphate of chrome alum and hence contains a less concentration of the
precipitating anion. Hence also the stabilizing influence of common salt
added to a basic alum liquor, the effect being to replace partially the
divalent SO{4}-- by the monovalent Cl-. Lyotrope influence, however,
may be here at work.
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