Studies of the Sodium Salts of Homologues of Alkyl Sulfates in Aqueous Solutions in Relation to the Water Structure

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<jats:title>Abstract</jats:title> <jats:p>The adiabatic compressibility (β) and the partial molar volume at an infinite dilution (\barV0) were obtained for aqueous solutions of the sodium alkylsulfates (SAS) of homologues. The sound velocity (U) and the density (ρ) were determined by the use of an ultrasonic interferometer and the float-balance method respectively. The results indicate that the slope at an infinite dilution (dβ⁄dC)0 of β vs. the concentration (C) diagram is in a linear relation with the carbon number (φ) of SAS. A similar relation was obtained between \barV0 and φ. We have derived these two relations by a statistical thermodynamical treatment based on the interstitial model of water, consisting of two species, one constituting the framework of an extended ice-1 structure with many cavities, and the other species, non-hydrogen-bonded water, occupying part of these cavities. The occupancy of the cavity with alkyl radical leads to a decrease in the structural compressibility, while the hydration of the ionic parts of the solute leads to a decrease in the compressibility due to the electrostriction. According to the calculations, the theoretical dependency of (dβ⁄dC)0 on φ is about three times larger than the experimental value. The theoretical dependency of \barV0 on φ is nearly in agreement with the experimental value, while the constant-addivite term is different.</jats:p>

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