Mössbauer spectroscopic studies of frozen aqueous solutions of Fe3+ salts

Frozen aqueous solutions (FAS) of Fe3+ salts have been investigated by use of Mössbauer spectroscopy in order to study the conditions for formation of glasses. A general discussion of spin–spin relaxation in glasses is given, and we discuss how changes in the spin–spin relaxation time can be attributed to changes in the average separation between the iron ions. In the FeCl3–H2O system, it was found that homogeneous glasses are easily formed when the salt concentration is larger than 3.5 moles FeCl3 per 100 moles H2O. In more dilute samples, ice crystallizes during cooling, while the salt concentration of the solution increases. At low temperatures the crystallization terminates and the remaining liquid solidifies into a glass. During exposure at 200 K, the dilute samples change irreversibly. This is discussed in terms of a metastable phase diagram. The properties of frozen solutions with other glass forming agents such as NO3−, ClO4−, and glycerol are also discussed. In some systems it was found that the states obtained after cooling depend critically on the cooling rate.