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This paper describes the main thermodynamic concepts related to the construction of supplemented phase (or state) diagrams (SPDs) for aqueous solutions containing vitrifying agents used in the cryo-and dehydro-preservation of natural (foods, seeds, etc.) and synthetic (pharmaceuticals) products. It also reviews the empirical and theoretical equations employed to predict equilibrium transitions (ice freezing, solute solubility) and non-equilibrium transitions (glass transition and the extrapolated freezing curve). The comparison with experimental results is restricted to carbohydrate aqueous solutions, because these are the most widely used cryoprotectant agents. The paper identifies the best standard procedure to determine the glass transition curve over the entire water-content scale, and how to determine the temperature and concentration of the maximally freeze-concentrated solution.

Supplemented temperature/composition phase diagrams include the non-equilibrium glass-transition temperature (T g ) curve and equilibrium ice-melting and solubility curves. The inclusion of the non-equilibrium curve allows one to establish relationships with the time coordinate and, thus, with the dynamic behavior of systems, provided that the thermal history of such systems is known.The objective of this report is to contribute to the potential applications of supplemented state diagrams for aqueous glass-formers, in order to describe the influence of water content, nature of vitrifying agents, and temperature on the physico-chemical properties of foods and biological and pharmaceutical products. These data are helpful to develop formulations, processing strategies, or storage procedures in order to optimize the stability of food ingredients and pharmaceutical formulations. Reported experimental data on phase and state transitions for several food and pharmaceutical systems were analyzed. Some methodological aspects and the effect of phase and state transitions on the main potential chemical reactions that can alter those systems during processing and/or storage are discussed.

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