The complete effectiveness of various
inorganic salts (NaCl, KCl,
NaBr, KBr, Na2CO3, and Na2SO4) to form two-phase systems was systematically evaluated for
separating nicotine from its aqueous solutions. The binodal curve
and tie lines for nicotine + salt + water ternary systems were experimentally
determined at 298.15 K and atmospheric pressure. The salting-out effectiveness
was accounted for by phase diagrams, as well as partition coefficients
and recovery percentages of nicotine. The binodal curves obtained
experimentally were successfully fitted to the Merchuk model, and
the reliability of tie-line data was evaluated using the Othmer–Tobias
and Bancroft equations. The results clearly show that all investigated
salts, as salting-out media, cause the expansion of the two-phase
region and have high partition yield for the separation of nicotine
from its aqueous solutions. It is also observed that both cations
and anions present an influence on the liquid–liquid equilibrium.
The relative tendency of anions to form two-phase systems, CO3
2– > SO4
2– >
Cl– > Br–, follows the position
of anions in the Hofmeister series. Due to the stronger interaction
of Na+ with the nicotine nitrogen than K+, the
effectiveness order of cations (K+ > Na+)
follows
the opposite trend with the Hofmeister series. Furthermore, the order
Na2CO3 > Na2SO4 >
KCl
> NaCl > KBr > NaBr for the effective excluded volume (EEV)
of different
salts is consistent with the size order of the heterogeneous region.
Thus, EEV can be used as a predictive tool for the biphase-forming
ability of salts. The partition coefficients and recovery percentages
of nicotine are found to increase with the increase of temperature
and pH. The calculated entropy of the cloud point indicates that the
high positive entropy is the driving force for the two-phase formation.