Abstract
Abstract Concentration fluctuations play an important role in the statistical description of the stability of liquids, particularly in the neighborhood of phase transitions. Classical thermodynamics is blind to fluctuations, and statistical thermodynamics is required to fully understand quantities such as the isothermal compressibility or heat capacity, by linking them to fluctuations of appropriate statistical microscopic quantities and showing that they are response functions. This is illustrated by the seminal Kirkwood–Buff theory of solutions. However, the existence of micro-heterogeneous structures, particularly in aqueous mixtures, which leads to large Kirkwood–Buff integrals, suggest that micro-heterogeneity is a form of concentration fluctuation. This interpretation becomes difficult to accept when extrapolated to larger micro-heterogeneous structures such as micellar aggregates in micro-emulsions. By analyzing how different methods, experimental, computer experiments and theoretical approaches deal with the underlying duality behind these two physical manifestations, we put in evidence the need to reconsider the description of liquids by incorporating the description of emergent “objects”, such as the micro-heterogeneous structures from a molecular point of view. On this path, the concept of “molecular emulsion” allows to describe in a unified way all type of disordered liquids, from solutions to the organized liquids of soft matter.
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