Solid–Liquid Metastable Equilibria for Solar Evaporation of Brines and Solubility Determination: A Critical Discussion

Abstract

Within the last two decades, a large number of articles were published that report, as the authors claim, ‘metastable phase equilibria’, or ‘metastable solubilities’. The main objective of these studies was to carry out experiments under conditions closely meeting those in solar evaporation ponds or industrial evaporation–crystallization processes. Occasionally, such studies were subject to controversial discussion and criticism and the question was raised whether metastable equilibrium data are worth being published at all. This paper provides a critical discussion of such evaporation experiments. The thermodynamic background of stable and metastable solubility and typical experimental difficulties in solubility determinations are discussed in detail. We also demonstrate that the knowledge of metastable equilibria is very useful in different research areas such as geochemistry or industrial application of solubility equilibria. Finally, it is shown that so-called ‘isothermal evaporation method’ used in the above-mentioned studies does not yield stable or metastable solubilities.