Theory of the hydrophobic effect

A microscopic theory is developed which can describe many of the structural and thermodynamic properties of infinitely dilute solutions of apolar solutes in liquid water. The theory is based on an integral equation for the pair correlation functions associated with spherical apolar species dissolved in water. It requires as input the experimentally determined oxygen–oxygen correlation function for pure liquid water. The theory is tested by computing thermodynamic properties for aqueous solutions of apolar solute species. The predictions of both the Henry’s Law constant and the entropy of solution are in good agreement with experiment. The calculation of the latter quantity is essentially independent of any adjustable parameters. It is shown how the correlation functions we have calculated can be used to predict the solubility of more complicated, aspherical, and nonrigid solutes in liquid water. For the more complex molecules it is convenient to study the difference between the excess chemical potential o...

[1]  Joel H. Hildebrand,et al.  Solubility of Non-Electrolytes , 1936, Nature.

[2]  C. F. Curtiss,et al.  Molecular Theory Of Gases And Liquids , 1954 .

[3]  John S. Rowlinson,et al.  Liquids and liquid mixtures , 1959 .

[4]  W. Kauzmann.  Some factors in the interpretation of protein denaturation. , 1959, Advances in protein chemistry.

[5]  S. Rundqvist,et al.  The Solubility of Methane in Hydrocarbons, Alcohols, Water, and Other Solvents. , 1960 .

[6]  Harold A. Scheraga,et al.  Structure of Water and Hydrophobic Bonding in Proteins. I. A Model for the Thermodynamic Properties of Liquid Water , 1962 .

[7]  F. Richards.  STRUCTURE OF PROTEINS. , 1963, Annual review of biochemistry.

[8]  John S. Rowlinson,et al.  The triplet distribution function in a fluid of hard spheres , 1963 .

[9]  E. Whalley,et al.  The PVT properties of water , 1965, Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences.

[10]  D. A. Mcquarrie,et al.  High‐Temperature Equation of State , 1966 .

[11]  Harold A. Scheraga,et al.  Conformational Analysis of Macromolecules. II. The Rotational Isomeric States of the Normal Hydrocarbons , 1966 .

[12]  C. McAuliffe,et al.  Solubility in Water of Paraffin, Cycloparaffin, Olefin, Acetylene, Cycloolefin, and Aromatic Hydrocarbons1 , 1966 .

[13]  G. Kell,et al.  Precise representation of volume properties of water at one atmosphere , 1967 .

[14]  J. Barker,et al.  Perturbation Theory and Equation of State for Fluids. II. A Successful Theory of Liquids , 1967 .

[15]  A. Siegert,et al.  Statistical Mechanics of Hard‐Particle Systems , 1968 .

[16]  G. Fasman,et al.  Structure and stability of biological macromolecules , 1969 .

[17]  M. Volkenstein,et al.  Statistical mechanics of chain molecules , 1969 .

[18]  W. Jencks.  Catalysis in chemistry and enzymology , 1969 .

[19]  David Chandler,et al.  Perturbation Theory of the Thermodynamic Properties of Simple Liquids , 1971 .

[20]  H. A. Levy,et al.  Liquid Water: Molecular Correlation Functions from X‐Ray Diffraction , 1971 .

[21]  L. Verlet,et al.  Perturbation theory for the thermodynamic properties of simple liquids , 1972 .

[22]  L. Verlet,et al.  Equilibrium Theory of Simple Liquids , 1972 .

[23]  A. Ben-Naim.  Statistical Mechanical Study of Hydrophobic Interaction. IV. The Behavior of the Function y(R) at Short Distances , 1972 .

[24]  Felix Franks,et al.  Water:A Comprehensive Treatise , 1972 .

[25]  W. Streett,et al.  Three Atom Correlations in the Lennard‐Jones Fluid , 1972 .

[26]  T. Higuchi,et al.  Thermodynamic group contributions from ion pair extraction equilibriums for use in the prediction of partition coefficients. Correlation of surface area with group contributions , 1973 .

[27]  David Chandler,et al.  Derivation of an integral equation for pair correlation functions in molecular fluids , 1973 .

[28]  Frank H. Stillinger,et al.  Structure in aqueous solutions of nonpolar solutes from the standpoint of scaled-particle theory , 1973 .

[29]  D. Chandler,et al.  Solution of a new integral equation for pair correlation functions in molecular liquids , 1973 .

[30]  A. Ben-Naim.  Water and Aqueous Solutions: Introduction to a Molecular Theory , 1974 .

[31]  C. Tanford,et al.  Empirical correlation between hydrophobic free energy and aqueous cavity surface area. , 1974, Proceedings of the National Academy of Sciences of the United States of America.

[32]  R. B. Hermann.  Theory of hydrophobic bonding. III. Method for the calculation of the hydrophobic interaction based on liquid state perturbation theory and a simple liquid model , 1975 .

[33]  Jean-Paul Ryckaert,et al.  Molecular dynamics of liquid n-butane near its boiling point , 1975 .

[34]  R. Pierotti,et al.  A scaled particle theory of aqueous and nonaqueous solutions , 1976 .

[35]  I. R. Mcdonald,et al.  Theory of simple liquids , 1998 .

[36]  Jerome Percus,et al.  Model for density variation at a fluid surface , 1976 .

[37]  David Chandler,et al.  Statistical mechanics of chemical equilibria and intramolecular structures of nonrigid molecules in condensed phases , 1976 .

[38]  D. Chandler,et al.  Interaction site cluster series for the Helmholtz free energy and variational principle for chemical equilibria and intramolecular structures , 1977 .