Thermodynamics from Free Volumes

As discussed, the intuitive notion that there should be a connection between the statistics of the free volumes of a fluid and its measurable macroscopic properties has a long history in studies of the liquid state. In fact, it turns out that this connection is precise in the case of the thermodynamics of the single-component hard-sphere fluid. Specifically, Hoover, Ashurst, and Grover77 and Speedy82 have provided independent derivations that predict the relationship between the hard-sphere compressibility factor Z = P/pksT and the geometric properties of its free volumes, as follows  

Can the geometric properties on the right-hand side of Eq. [8] be predicted theoretically (i.e., rather than just measured from simulation) Krekelberg, Ganesan, and Truskett85 (KGT) have taken a step in this direction 

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Given this background, we can now provide several examples of how free volumes have been related to thermodynamic and dynamic properties of liquids, and how their measurement has been employed in computer simulations to derive microscopic insights that are otherwise not accessible from experiment. We consider first how to compute thermodynamic values from free volumes and follow that with the relationship of free volumes to dynamics. 

McMaster " demonstrated that LOST behavior arises from free volume effects. In particular, if the pure component thermal expansion coefficients are sufficiently different, LCST behavior becomes more likely. It should be noted again that the normal entropic effects are very small. By using Flory s equation-of-state thermodynamics, it can be demonstrated that LCST behavior should generally be expected for high-molecular-weight mixtures. Although the detailed thermodynamic arguments are beyond the scope of this chapter, the theory has been reviewed recently. " ... 

P rtl IMol r Properties. The properties of individual components in a mixture or solution play an important role in solution thermodynamics. These properties, which represent molar derivatives of such extensive quantities as Gibbs free energy and entropy, are called partial molar properties. For example, in a Hquid mixture of ethanol and water, the partial molar volume of ethanol and the partial molar volume of water have values that are, in general, quite different from the volumes of pure ethanol and pure water at the same temperature and pressure (21). If the mixture is an ideal solution, the partial molar volume of a component in solution is the same as the molar volume of the pure material at the same temperature and pressure. 

StoKes-Einstein and Free-Volume Theories The starting point for many correlations is the Stokes-Einstein equation. This equation is derived from continuum fluid mechanics and classical thermodynamics for the motion of large spherical particles in a liqmd. 

The standard entropy difference between the reactant(s) of a reaction and the activated complex of the transition state, at the same temperature and pressure. Entropy of activation is symbolized by either A5 or and is equal to (A// - AG )IT where A// is the enthalpy of activation, AG is the Gibbs free energy of activation, and T is the absolute temperature (provided that all rate constants other than first-order are expressed in temperature-independent concentration units such as molarity). Technically, this quantity is the entropy of activation at constant pressure, and from this value, the entropy of activation at constant volume can be deduced. See Transition-State Theory (Thermodynamics) Gibbs Free Energy of Activation Enthalpy of Activation Volume of Activation Entropy and Enthalpy of Activation (Enzymatic)... 

A modified version of the free-volume theory is used to calculate the viscoelastic scaling factor or the Newtonian viscosity reduction where the fractional free volumes of pure polymer and polymer-SCF mixtures are determined from thermodynamic data and equation-of-state models. The significance of the combined EOS and free-volume theory is that the viscoelastic scaling factor can be predicted accurately without requiring any mixture rheological data. 

Abstract. Free-volume structure in the lanthanum salt of laurinic acid in crystalline and liquid-crystalline states and an effect of dissolved Cgo molecules on the mean nanovoid radius and concentration were studied by means of the positron annihilation technique. La(Ci2H25COO)3 clathrate compound with dissolved C6o molecules was obtained, which is thermodynamically more stable than a simple mixture of components. Increased mean nanovoid radius (from 0.28 to 0.39 nm) after the inclusion of C6o molecules and concomitant decrease of the positronium annihilation rate by a factor of 2.7 indicate the decrease of the smallest nanovoid concentration. 

One of the simplest early free-volume diffusion models was formulated in (51,52,60). The concept of this model was considered an advance, because some of the parameters required to describe the concentration dependence of the diffusion coefficient could be obtained from the physico-chemical properties of the polymer and penetrant. The relation proposed for the calculation of the thermodynamic diffusion coefficient, DT, was (51,60) ... 

The Kauzmann temperature plays an important role in the most widely applied phenomenological theories, namely the configurational entropy [100] and the free-volume theories [101,102]. In the entropy theory, the excess entropy ASex obtained from thermodynamic studies is related to the temperature dependence of the structural relaxation time xa. A similar relation is derived in the free-volume theory, connecting xa with the excess free volume AVex. In both cases, the excess quantity becomes zero at a distinguished temperature where, as a consequence, xa(T) diverges. Although consistent data analyses are sometimes possible, the predictive power of these phenomenological theories is limited. In particular, no predictions about the evolution of relaxation spectra are made. Essentially, they are theories for the temperature dependence of x.-jT) and r (T). 

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