Application of the mobile order theory to the prediction of aqueous solubility of chlorinated benzenes and biphenyls

The Hydrophobic Propensity of Water toward Amphiprotic Solutes: Predicton and Molecular Origin of the Aqueous Solubility of Aliphatic Alcohols

“…Such approximation is essentially based on the observed unimportance of that contribution in calculating the solubility of solutes able to interact specifically with the solvent. 18,19,22 :…”

“…The water-water self-association through the hydrophobic effect is the main factor responsible of the experimentally observed limited aqueous solubility of hydrophobes and of their hydrophobicity. [18][19][20][21][22] According to eq 4, hydrophobicity becomes more pronounced as the size of the solute increases. Now, what becomes of the hydrophobic propensity of water if instead of adding an inert substance ones dissolves an alcohol (i.e., what is the influence of an alcohol on the selfassociation of water and how is the alcohol solubility affected)?…”

“…13,14 Accordingly, the non-ergodic thermodynamics of the mobile order developed by Huyskens and co-workers 9,15,16 for H-bonded liquids considers not the static configurations within the liquid, but the fractions of time during which the system is found in a particular state; that is, the fraction of time during which the molecule escapes from H-bonding (γ) and the fraction of time when the molecule is bonded (1 -γ). The correctness of this approach is partly evidenced by the fact that the derived solubility equation 17 allows real predictions of solubility of hydrocarbons in alcohols and in water [18][19][20][21] where classical theories have failed. Although the equation does not involve any adjustable or regression parameter, the agreement between apriori calculated and measured molar solubilties over >10 orders of magnitude is remarkable.…”

“…By now, the mobile order theory has successfully been applied to predict the solubility of low-polarity substances in nonpolar, polar, and H-bonded solvents as well as in binary solvent mixtures. [18][19][20][21][22][23][24][25][26][27] Included in these works is the demonstration that alcohol or aqueous solubility of inert systems is essentially ruled by the hydrophobic effect. The same model was also used to predict the solubility of water in hydrocarbons 28 and the solubility of solid crystalline proton-acceptor substances in proton-donor solvents.…”

Prediction of solubilities, the effect of temperature on the solubility of n‐alkanes, and the mobile order theory

“…This solubility equation (in the volume fraction of a solute) has been applied successfully to predict the solubility of inert substances such as aliphatic and aromatic hydrocarbons, polychlorinated aromatic hydrocarbons, solid nitriles, tertiary amides, biphenyl, and pyrene in nonpolar, polar, and hydrogen-bonded liquids including alcohols. 1,[5][6][7][8][9] Furthermore, this equation has been used to highlight the significance of proton-acceptor sites of drugs on their solubility in protondonor solvents 8,9 and solid ketones and esters. 9 The utility of the predictive equation (eq 1) stems from the fact that it takes account of all the contributions to the free-energy change when a solid solute (B) passes into a solvent (S).…”