Entropy Changes in Aqueous Solutions of Non-polar Substances and in Bio-complex Formation

• Published in: Journal of solution chemistry Vol. 37; no. 4; pp. 487 - 501
• Main Authors: Fisicaro, E., Compari, C., Duce, E., Braibanti, A.
• Format: Journal Article Conference Proceeding
• Language: English
• Published: Boston Springer US 01.04.2008; Springer
• Subjects: Chemistry; Chemistry and Materials Science; Condensed Matter Physics; Exact sciences and technology; General and physical chemistry; Geochemistry; Industrial Chemistry/Chemical Engineering; Inorganic Chemistry; Oceanography; Physical Chemistry; Simec'06; Solutions; Non-polar gases solubility; Entropy change; Enthalpy change; Cavity; Water structure; Protein-ligand complexes; Bio-complexes; Water; Enthalpy; Solubility; Entropy; Complexes; Protein; Gases; Cavity· Bio-complexes; Aqueous solution; Thermodynamic properties; Structure; Non-polar gases solubility, Entropy change
• DOI: 10.1007/s10953-008-9248-4
• ISSN: 0095-9782

The entropy changes, Δ S app , (i) for dissolution in water of non-polar substances and (ii) for protein-ligand complexation show linear dependences on the logarithm of the absolute temperature. For every compound, the slope m ( S ) =Δ C p for the line Δ S app = f (ln  T ) depends on the size of the molecule and is exactly equal to the slope m ( H ) =Δ C p found in the diagram Δ H app = f ( T ). This means that the slopes are rigorously proportional (with a ratio m ( S ) / n w = C p ,w ) where n w is the number of involved water molecules as determined from the enthalpy change Δ H app = f ( T ). It is also worth noting that the value of n w is positive (as well as m ( S ) and m ( H ) ) in the dissolution of non-polar substances, whereas it is negative (as well as m ( S ) and m ( H ) ) in bio-complex formation and in micelle formation. The number n w ( n w >0) involved in the dissolution of non-polar substances depends on the size of the cavity (excluded volume) formed in the structure of water. These water molecules that have been excluded from the structure of the solvent absorb thermal energy that compensates for the negative enthalpy change, whereas the formation of the cavity implies there should be a large negative entropy contribution. The low solubility of non-polar substances in water depends on the highly negative entropy effect due both to cavity formation and to loss of configurational entropy by the gas trapped in a cage of water molecules. In processes involving association, as in micelle formation and in protein complexation, the cavities surrounding the separate units coalesce and the resultant cavity is smaller than the sum of the previous ones. The n w water molecules ( n w <0) needed to fill the excess cavity return to the structure of the bulk solvent and release thermal energy, which compensates for the endothermic enthalpy. The affinity in the association processes is bound, for the most part, to the entropy produced by occupation of part of the cavity by condensation of water molecules. The association processes are therefore entropy driven.