Preferential interactions in aqueous solutions of urea and KCl.

A quantitative characterization of the thermodynamic effects due to interactions of salt ions and urea in aqueous solution is needed for rigorous analyses of the effects of changing urea concentration on biopolymer processes in solutions that also contain salt. Therefore, we investigate preferential interactions in aqueous solutions containing KCl and urea by using vapor pressure osmometry (VPO) to measure osmolality as a function of the molality of urea (component 3) over the range 0.09<or=m(3)<or=1.65 m at two fixed molalities of KCl (component 2) (m(2)=0.212 and 0.427 m). With this experimental input and corresponding VPO measurements on solutions that contain only urea or KCl, we evaluate approximately the chemical potential derivative micro(23)=( partial differential micro(KCl)/ partial differential m(urea))(T,P,m(KCl))=( partial differential micro(urea)/ partial differential m(KCl))(T,P,m(urea))= micro(32) and hence the preferential interaction coefficients Gammamicro(3) and Gammamicro(1),micro(3). These results show that for water-KCl-urea solutions neither of these coefficients is determined primarily by contributions from thermodynamic nonideality to micro(23). In aqueous solutions containing a biopolymer and a small solute, the contribution of ideal mixing entropy to micro(23) is negligible in comparison with the experimental uncertainty, whereas in KCl-urea solutions the contribution due to ideal mixing entropy accounts for at least half of the magnitude of micro(23). For comparison, we analyze literature data for NaCl-urea interactions and find again that nonideality makes a smaller contribution to micro(23) than does ideal mixing entropy. In contrast, for aqueous solutions of urea and the protein bovine serum albumin, the experimentally determined contribution of nonideality to micro(23) exceeds the contribution of ideal mixing by a factor of approximately 2 x 10(2).