Unlike the other silver halides, silver fluoride is positively charged in its saturated solution as determined by nonequilibrium electrophoresis measurements. In the absence of surface hydrolysis reactions, other fluoride salts (LiF, CaF2, and MgF2) also are positively charged in their saturated solutions. Furthermore, the electrokinetic behavior of these fluoride salts is rather insensitive to the fluoride ion activity in neutral or acidic solutions, and reversal of the sign of the surface charge by fluoride addition is not possible. Based on FTIR transmission spectra to describe the water structure of ionic solutions, in situ FTIR/internal reflection spectroscopy (FTIR/IRS) has been used to spectroscopically characterize interfacial water at fluoride salt surfaces. The experimental spectra were examined by consideration of the O-H stretching region (3000-3800 cm(-1)) associated with the vibrational spectra of interfacial water. These results reveal a unique hydration state for fluorides and explain the anomalous electrokinetic behavior of fluoride salts such as LiF, CaF2, and MgF2, which show an unexpected insensitivity to the fluoride ion concentration in solution. It appears that this insensitivity is due to the formation of strong hydrogen bonding of the fluoride ions with water molecules. This hydration state prevents the accommodation of excess fluoride ions at surface lattice sites and accounts for the observed electrokinetic behavior.