Near-critical behavior of aqueous systems

Publisher Summary The properties of near-critical water are so drastically different from those of liquid water that one could almost consider it a different fluid: one that is highly compressible and expandable, low in viscosity, a low dielectric, and a poor solvent for electrolytes, as opposed to liquid water with low compressibility and expansivity, but very high dielectric constant that makes it an excellent solvent for electrolytes. The presence of the critical point is the principal reason that the accurate formulation of properties of water and steam over large ranges of temperature and pressure is such an unwieldy undertaking, requiring large numbers of adjustable parameters, and/or a division into a large number of sub-regions. The so-called cubic equations are among those that can be expanded in a Taylor expansion everywhere, including at the critical point, and are called classical or mean-field equations. The critical behavior exhibited by mean-field theory, however, is not quantitatively correct. This chapter provides many examples of the anomalous behavior of water and steam due to the presence of a critical point. The formulation of aqueous electrolyte solutions near the water critical point is not in a satisfactory state. The customary method has a serious fundamental problem, in part due to the strong divergence of the second derivatives of the Gibbs energy at the water critical point and to the improper use of the Debye–Huckel limiting law in a solvent of very high compressibility. The last and major problem is non-classical treatment of aqueous electrolytes in a range around the water critical point.

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