Effect of Counter-ions on the Thermodynamic Properties of Alkali Dodecyl Sulfates in Monomeric and Micellar Dispersions
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概要
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In order to elucidate the behavior of ionic portion as well as hydrophobic one of surfactant at solution and micelle formation with the view-point of enthalpy and heat capacity changes, the molar standard enthalpies of solution and micelle formation of lithium, sodium and potassium dodecyl sulfates (generically abr. as DMS), Δ_<sol>H^^-<M^^oDS> and Δ_mH^^-<M^^oDS>, were determined by calorimetry at various temperatures from 20° to 50°, and also their critical micelle concentrations, CMC's by electric conductivity measurement. The molar standard Gibbs free energy and entropy of micelle formation as well as the degree of counter-ion dissociation in micelle were calculated using thermodynamic relations from the values of CMC at various temperatures and Δ_mH^^-<M^^oDS>. On the basis of Born's theory, Δ_<sol>H^^-<M^^oDS> was expressed in the terms, explicitly containing the ionic radii of both dodecylsulfate anion and counter-cation, Li^+, Na^+, and K^+, in MDS crystal and in water, and the terms, representing the hydrophobic contributions of MDS to lattice and hydration energies. The substitution of experimental and literary values into the above-mentioned expression gives, e.g. 2.2 A and 2.0 A as ionic radii of dodecylsulfate ion in crystal and in water, respectively. Also, Δ_mH^^-<M^^oDS> and its corresponding heat capacity, Δ_mC^^-<p^^o.MDS>, were analyzed with respect to the hydrophobic and ionic contributions to micelle formation.
- 公益社団法人日本薬学会の論文
- 1976-06-25
著者
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岸本 博
名古屋市立大学薬学部
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岸本 博
Faculty Of Pharmaceutical Sciences Nagoya City University
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住田 国治
Faculty of Pharmaceutical Sciences, Nagoya City University
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住田 国治
Faculty Of Pharmaceutical Sciences Nagoya City University
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