Prevailing classification of salts based on their effect in solubility and stability of proteins in aqueous solution predicts that tetraalkylammonium salts, guanidinium chloride (GnCl), LiClO 4 act as salting-in (S/I) and LiCl, NaCl act as salting-out (S/O) in aqueous conditions. In the same context the behaviour of GnCl, LiClO 4 and LiCl are contradictory in polar solvents like ethylene glycol and formamide. In these solvents, expected salt effect shows just opposite nature from their usual expectation. However, in the aqueous solution salts like tetraalkylammonium halide (R 4 NX, R = alkyl group, X = Br group) behave like salting-in salts. The physicochemical origin of the salting in effect of R 4 NX type of salts has been discussed elaborately in the present work. The role of cations in terms of substitution of various alkyl groups on R 4 NX has been systematically presented here on the basis of experimental kinetic and thermodynamic studies. The abnormal behaviour of R 4 NX salts in aqueous solution has also been explained by the Setschenov equation (k s ) and Δμ solvation values, which highlights their individual nature out of common properties of R 4 NX.
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