Now recent investigations have shown that the essential physical
properties of water are affected by dissolved substances in a definite
manner and to a fixed extent, and that these substances exhibit a
sequence in order of their effect. This sequence is also exhibited in
the essential properties of water as solvent and as dispersion medium
for colloid sols. The sequence is known as the "lyotrope series." Thus
the numerical value of the compressibility of aqueous solutions is
reduced below that of water by salts which, with the same kation,
exhibit an effect in the following order:--
CO{3} > SO{4} > Cl > Br > NO{3} > I
This same order is observed, in the effect on the increased values for
the surface tension, density and viscosity of these solutions. On the
other hand, the kations have a similar sequence of effects,
Mg < NH{4} < Li < K < Na < Rb < Cs
which appears when salts of the same anion are chosen. It is not
surprising to find that this lyotrope series exhibit an analogous
influence on the chemical reactions of water, _e.g._ the hydrolysis of
esters. In the hydrolysis by acids SO{4} retards the action, the other
anions and the kations accelerate it, in the lyotrope order. In the
hydrolysis by bases the series is reversed. Similarly the lyotrope
series exert the same order of effect upon the inversion of cane sugar
and other reactions.
This lyotrope influence has also been shown to exert considerable effect
in the behaviour of lyophile sols. With the lyophobe sols the addition of
foreign substances apparently affects the disperse phase only, but with
the lyophile sols the effect on the continuous phase is also important,
and may overshadow the other. Now, in gelatine and in hide gels and
tanning sols we are dealing with lyophile systems, and there are many
points of behaviour in which lyotrope influences become prominent.
Similar effects are observed upon other lyophile sols (_e.g._ albumin,
agar-agar, etc.) which differ widely in chemical nature. Thus the
salting out of albumin (reversible precipitation) is influenced by
sodium salts in lyotropic sequence as follows. The anions hinder
precipitation; in order of precipitating power they are:
citrate > tartrate > SO{4} > acetate > Cl > NO{3} > ClO{3} > I > CNS
The sulphates illustrate the kation effect, which is independent and
which favours precipitation:
Li > K > Na > NH{4} > Mg
If the experiments be carried out in faintly acid solution this order of
effect is exactly reversed, iodide and thiocyanate having the greatest
effect and citrates the least. The coagulation temperature of albumin
and the coagulation by other organic substances are similarly influenced
by the lyotrope series.
Lyotrope influence also exerts a powerful effect on the behaviour of
gelatine sols and gels. The gelation temperature is influenced thus:--
raised by SO{4} > citrate > tartrate > acetate
lowered by Cl < ClO{3} < NO{3} < Br < I
The kation effect (small) is Na > K > NH{4} > Mg
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