Na+/K+ selectivity in the formation of ion pairs in aqueous solutions

The integral equations of liquids (RISM) and molecular dynamics method were used to calculate the mean force potential for the SO₃ and COO hydrophilic groups and the CH₃ hydrophobic group in the acetate, methyl sulfonate, and hydrosulfate anions, which form ion pairs with sodium and potassium cations in water. The carboxyl group selectively binds sodium ions from solutions containing Na⁺ and K⁺ ions, in spite of their equal charges, because the potassium ion experiences stronger steric hindrances near this group compared with sodium. The biophysical consequences of the revealed selectivity are discussed.