Publication Details (including relevant citation information):
Journal of Solution Chemistry 2010, 39, 301-317. http://dx.doi.org/10.1007/s10953-010-9503-3
Contrary to widely held beliefs, many concentrated aqueous solutions of strong electrolytes and nonelectrolytes are shown to behave ideally by calculating the activity of water (aw) from vapor pressure data. The mole fraction of water (xw) is equal to the water activity aw (Raoult’s Law) when the mole fraction of water is calculated by accounting for water strongly bound to the solute, which is then not available to act as solvent. In this case xw = (55.51− mHT)/(55.51 − mHT + im), where m is the molality of the solute particles, i is the stoichiometric number of solute particles produced per mole of dissolved solute, and HT is the thermodynamic hydration number. Published reservations about previous work of this type are addressed. The values of HT vary little over wide ranges of concentration and correlate with the Hofmeister series, the B coefficient of the Jones-Dole viscosity equation, and other properties of water. Activity coefficients of the bulk or “free” water remain at unity even at high concentrations.
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