An empirical correlation between the enthalpy of solution of aqueous salts and their ability to form hydrates.

The ability of aqueous salt solutions to form hydrates by cooling them at ambient pressure is probed by infrared (IR) spectroscopy by examining the structure of the spectra in the OH-stretching region (3000-3800 cm(-1)). A collection of 75 organic and inorganic salts in saturated solutions are examined. We have found a correlation between the enthalpy of solution of the salt and its ability to form a hydrate, namely, that the salt's enthalpy of solution is lower than the standard enthalpy of fusion of ice (6 kJ/mol). This observation can serve as an empirical rule that determines whether a salt will form a hydrate upon cooling from its aqueous solution.

Time-resolved dynamics of the OH stretching vibration in aqueous NaCl hydrate.

We report on the first time-resolved study of the OH stretching vibration in NaCl dihydrate with the use of two-color IR spectroscopy. The sample is characterized by conventional FTIR spectroscopy. The water molecules bound in the hydrate show two well separated absorption bands at 3426 cm(-1) and 3541 cm(-1). The transient data display an ultrafast heating of the polycrystalline ice-hydrate samples after excitation of the OH stretching vibration and its transient relaxation. The relaxation time of the low-frequency OH stretching band in the NaCl hydrate is measured to be 6.8 +/- 1 ps. The dynamics are significantly slower than those measured in neat water. This fact, together with the reproducible crystalline environment reveals the potential of aqueous hydrates for a systematic investigation of the OH stretching vibration in varying hydrogen bonding environments.