Metastable zone significance

Figure 9-2 Concentration profile for reverse addition (solute solution to antisolvent) with reference to equilibrium saturation and the metastable zone. As solution is added to the antisolvent, the solute concentration can rapidly exceed the solubility limit and the metastable zone boundary, resulting in significant nucleation.

Experimental techniques for determining the metastable zone width, the amount of undercooling that a solution will tolerate before nucleating, are described in section 5.3. The significance of the metastable zone and the interpretation of metastable zone width measurements are somewhat contentious subjects. Experimental values depend very strongly on the method of detection of the onset of nucleation, but it is still possible to extract kinetic information on the nucleation process as well as on the growth behaviour of very small crystals. These topics are discussed in some detail in section 5.3. 

The precipitation boundary may or may not coincide with the solubility curve since its position in the diagram depends on the time and method of detection of the onset of precipitation. In effect, it establishes the metastable zone for the given system. If a stable precipitate is formed at low levels of supersaturation the precipitation boundary and solubility curve may be assumed to be virtually coincident. In cases where they do not coincide, the composition of the critical nuclei may be determined from the slopes of the precipitation boundary while the compositions of the corresponding bulk equilibrium solid phases may be obtained from the solubility curve. Hence, comparison of the two curves can yield information as to whether the composition of both nuclei and precipitate is the same or if the bulk solid phase is formed by a solid-state transformation from a metastable precursor. A useful account of the significance of the zones on a precipitation diagram has also been given by Nielsen (1979). 

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