Application of Kirkwood's theory of the dielectric constant to solutes hydrogen-bonded in the water network

In a quasi-thermodynamic treatment, the partial molar polarization of a solute in a network liquid is expressed in terms of dipole moments, molalities. Kirkwood's formal correlation factors, and solute-induced changes in the correlation factors. The formal correlation factors are then resolved into explicit terms for solvent-solvent, solvent-solute and solute-solute dipole correlation, which convey specific (though limited) information about the stoichiometry and geometry of the respective hydrogen-bonding. Experimental partial molar polarizations are analyzed for aqueous solutions of p-dioxane, pyrazine, quinoxaline, acetone, pyridine, N,N,N,N-tetramethylurea, acetonitrile, and dimethylsulfoxide. The treatment does not yield unique hydrogen-bonded structures but, when combined with other evidence, it greatly limits the possibilities. Water molecules appear to donate hydrogen bonds exhaustively to ether and carbonyl oxygen atoms, and to aza-aromatic nitrogen atoms. Water molecules also appear to donate hydrogen bonds to aza-aromatic -systems, and to the triple bond in acetonitrile.