Nonelectrolyte
solubility in electrolyte solutions follow the Hofmeister
series, but the applicability of the series to salt solubility has
been less appreciated. This study, using solubility data for thirteen
sodium-bearing salts, shows that salts are consistently salted out
by electrolytes important to alkaline nuclear waste in the order NaOH
> NaCl > NaNO2 > NaNO3 at 298.15 K,
which is
the same order as the Hofmeister series. Graphical presentation allowed
for easy separation of the common ion effect (caused by the addition
of Na+) from the salting-out effect (caused by the presence
of anions) because there is a large difference between the solubility
of a given salt in different background electrolytes at a common Na+ molality. The trend persists even in very high electrolyte
concentrations where essentially all of the water molecules must be
in the coordination sphere of an ion, which means that the effect
of electrolytes on “bulk water” is not the cause of
the trend. These specific interactions more likely result from the
sharing of water molecules between ions, augmented by differences
in ion-pairing of the electrolytes. The Hofmeister series has practical
application to the management of alkaline high-level radioactive waste
created at nuclear fuel reprocessing facilities, where a predictive
understanding of salt solubility is essential for blending wastes
of disparate compositions prior to treatment.