Water solubility is one of the most important and frequently used physical-chemical properties of chemicals. It is crucial within several industrial sectors, in research and in the regulatory sector e.g. for the risk and hazard assessment of chemicals. The most recent OECD guideline (Test No. 105) for measuring solubility is from 1995 and limited to mono-constituent, stable and non-volatile substances. This OECD guideline and the described methods are not suited for several groups of difficult-to-test substances, such as highly hydrophobic chemicals, volatile chemicals, surfactants and mixtures. The aim of this paper is to review solubility measurement methods for difficult-to-test substances on a technical, analytical and scientific level. Methods to handle highly hydrophobic chemicals and volatile chemicals, and methods to rapidly saturate water with fast degrading chemicals are reviewed. A decision tree is presented outlining the preferred choice of method for each chemical group. This review also includes measurement methods for critical micelle concentrations that set the upper concentration limit for freely dissolved surfactants. Finally, concepts and strategies to measure solubility parameters for mixtures, including multi-constituent substances and chemical substances of unknown or variable composition, are discussed.
Keywords: Hydrophobic chemicals; Passive dosing; Slow stir; Volatile chemicals; Water solubility.
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