Entropy hydrophobic interactions

D. E. Smith and A. D. J. Haymet. Free energy, entropy and internal energy of hydrophobic interactions computer simulations. J. Chem. P/iys., 98 6445-6454,... 

What distinguishes water from ordinary organic solvents and justifies the term hydrophobic interaction is the molecular origin of the effect, being entropy driven in pure water at room temperature and resulting primarily from the strong water-water interactions. 

Sutoh and Noda154 succeeded in proving, by synthesizing block copolymers of the structure (Gly-Pro-Pro)n(Gly-Ala-Pro)m-(Gly-Pro-Pro)n, that with increasing imino add content, AS° changes to higher positive values. They do, however, not relate this to lower entropy losses of conformation but to hydrophobic interactions of the proline residues in the helical state. 

Hydrophobic interactions of this kind have been assumed to originate because the attempt to dissolve the hydrocarbon component causes the development of cage structures of hydrogen-bonded water molecules around the non-polar solute. This increase in the regularity of the solvent would result in an overall reduction in entropy of the system, and therefore is not favoured. Hydrophobic effects of this kind are significant in solutions of all water-soluble polymers except poly(acrylic acid) and poly(acrylamide), where large heats of solution of the polar groups swamp the effect. 

Solvent effects also play an important role in the theory separating enthalpy and entropy into external and internal parts (134-136) or, in other terms, into reaction and hydration contributions (79). This treatment has been widely used (71, 73, 78, 137-141). The most general thermodynamic treatment of intermolecular interaction was given by Rudakov (6) for various states of matter and for solution enthalpy and entropy as well as for kinetics. A particular case is hydrophobic interaction (6, 89, 90). 

The most fundamental thermodynamic approach of Rudakov (6) applies to all condensed systems. The actual linear relationship is argued to exist between enthalpy (AH) and entropy (AS) of intermolecular interaction, as reflected in an approximately linear relationship between the total enthalpy and entropy. Special attention has been given to hydrophobic interaction (89, 90) in water solutions, which makes the isokinetic behavior more pronounced and markedly changes its slope. 

A similar effect may exist for hydrophobic interaction between solute and stationary phase, as one solute may adsorb more strongly to the stationary phase than another. It has also been remarked that a flexible polymer confined to a pore should be at a lower entropy than one in bulk solution, leading to exclusion in excess of that expected for a simple geometric solid.23 Even in the absence of interactions, a high concentration of a small component can lead to an excluded volume effect, since the effective volume inside the pore is reduced. 

The arguments presented above lead to the conclusion that the adsorption of nonionic compounds such as halogenated hydrocarbons results primarily from "hydrophobic bonding" or, perhaps more appropriately, the hydrophobic interaction (7). The thermodynamic driving force for hydrophobic interactions is the increase in entropy resulting from the removal, or decrease, in the amount of hydration water surrounding an organic solute in water. Studies have shown that the adsorption of aliphatic amines onto clays (8)... 

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