Aqueous solutions of calcium ions: hydration numbers and the effect of temperature.

Hydration numbers of calcium ions are determined from extensive measurements of colligative properties of water solutions of calcium salts. The hydration numbers reported refer to the average number of water molecules that are bound sufficiently strongly to calcium ions so as to be removed from the solvent and become part of the solute. Contrary to common descriptions of deviations from ideal behavior for concentrated solutions, ideal behavior is demonstrated when mole fractions are calculated by taking account of such bound water. Measurements over wide concentration and temperature ranges are used to obtain the effect of temperature on the average hydration number of Ca(2+). Freezing point depression measurements yield a hydration number of 12.0 +/- 0.8. Boiling point elevations yield 6.7 +/- 0.6. Consistent with this, vapor pressure measurements from 0 to 200 degrees C show a gradual decrease in hydration number with increasing temperature, with a value of 5.0 at 200 degrees C.