Entropy molecular view

As we have seen, the third law of thermodynamics is closely tied to a statistical view of entropy. It is hard to discuss its implications from the exclusively macroscopic view of classical themiodynamics, but the problems become almost trivial when the molecular view of statistical themiodynamics is introduced. Guggenlieim (1949) has noted that the usefiihiess of a molecular view is not unique to the situation of substances at low temperatures, that there are other limiting situations where molecular ideas are helpfid in interpreting general experimental results ... 

From a molecular view, the decrease of entropy upon hydrophobic hydration is not mitigated by a large hydration enthalpy and this translates into an increase in the free energy of water. A system will tend to minimize this increase in free energy through association of the hydrophobic moieties. This phenomenon that explains the salting in of a neutral hydrophobic molecule by hydrophobic ions is expected to amplify with the sizes of the hydrophobic moieties [49]. Attractive forces between two hydrophobic ions and repulsive forces between hydrophilic and hydrophobic... 

Figure 9-2 Molecular view of mixing (a) pure component (b) component in mixture (c) component in mixture with the other components made invisible. In the mixed state a component has undergone isothermal expansion relative to the pure state. This gives rise to the entropy of mixing.

To gain insight into the thermodynamic properties of bioiogicai assembiies and a deeper understanding of what drives a spontaneous change, we need to develop a molecular view of entropy. 

The solvophobic model of Hquid-phase nonideaHty takes into account solute—solvent interactions on the molecular level. In this view, all dissolved molecules expose microsurface area to the surrounding solvent and are acted on by the so-called solvophobic forces (41). These forces, which involve both enthalpy and entropy effects, are described generally by a branch of solution thermodynamics known as solvophobic theory. This general solution interaction approach takes into account the effect of the solvent on partitioning by considering two hypothetical steps. Eirst, cavities in the solvent must be created to contain the partitioned species. Second, the partitioned species is placed in the cavities, where interactions can occur with the surrounding solvent. The idea of solvophobic forces has been used to estimate such diverse physical properties as absorbabiHty, Henry s constant, and aqueous solubiHty (41—44). A principal drawback is calculational complexity and difficulty of finding values for the model input parameters. 

Equation (1) can be viewed in an over-simplistic manner and it might be assumed that it would be relatively easy to calculate the retention volume of a solute from the distribution coefficient, which, in turn, could be calculated from a knowledge of the standard enthalpy and standard entropy of distribution. Unfortunately, these properties of a distribution system are bulk properties. They represent, in a single measurement, the net effect of a large number of different types of molecular interactions which, individually, are almost impossible to separately identify and assess quantitatively. 

Three types of methods are used to study solvation in molecular solvents. These are primarily the methods commonly used in studying the structures of molecules. However, optical spectroscopy (IR and Raman) yields results that are difficult to interpret from the point of view of solvation and are thus not often used to measure solvation numbers. NMR is more successful, as the chemical shifts are chiefly affected by solvation. Measurement of solvation-dependent kinetic quantities is often used (<electrolytic mobility, diffusion coefficients, etc). These methods supply data on the region in the immediate vicinity of the ion, i.e. the primary solvation sphere, closely connected to the ion and moving together with it. By means of the third type of methods some static quantities entropy and compressibility as well as some non-thermodynamic quantities such as the dielectric constant) are measured. These methods also pertain to the secondary solvation-sphere, in which the solvent structure is affected by the presence of ions, but the... 

The principle that different structural domains, moieties, or features of a molecular substance contribute separately and additively to a property of a substance. In 1840, G. H. Hess introduced the Law of Constant Heat Summation, a relation that allows one to calculate the heat of a reaction from collected measurements of seemingly different reactions, as long as the summation of a series of reactions yields the same overall chemical reaction as the one of interest. Thermodynamic additivity requires that if two components, A and B, contribute independently to some process, then the total change in free energy (or enthalpy or entropy) is the sum of components, AG = AGa + AGb. In view of its broad use in examining chemical and physical principles, Benson has even offered the view that additivity is the fourth law of thermodynamics. 

MOLECULAR RECOGNITION IN CHEMISTRY AND BIOLOGY AS VIEWED FROM ENTHALPY-ENTROPY COMPENSATION EFFECT ... 

In view of the compensatory enthalpy-entropy relationship observed for a wide variety of ionophore types, we may conclude that the cation-binding behavior, where the weak ion-dipole and dipole-dipole interaction is the major driving force for complexation, can be quantitatively analyzed and characterized by the slope and intercept of the AH-TAS plot without any exception. In this context, it is stimulating to extend the scope of this theory to the inclusion complexation of organic guests with molecular hosts. 

Finally, we wish to emphasize that, to the best of our knowledge, only the present theory can consistently explain the whole molecular recognition systems and present a global and unified view to understand the sophisticated supramolecular interactions in chemistry and biology. It is also said that the molecular recognition phenomenon through cooperative weak interactions is synonymous to entropy-governed chemistry. 

The standard entropies S° of gases are much larger than those of solids and liquids (Section 2.3). This may be understood by the somewhat simplistic view of S° as a measure of disorder at the molecular level. The molecules of gases have much greater freedom of translational motion, and hence are less ordered, than those of liquids and especially solids. Consequently, for oxidation of a solid metal to a solid oxide with consumption of gaseous oxygen... 

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