ISSN:
1572-8927
Keywords:
Hydrogen-bond acceptors
;
aqueous solutions
;
dielectric constants
;
hydration-shell structures
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract 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 π-systems, and to the triple bond in acetonitrile.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF00656772
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