Abstract
17O-NMR spin-lattice relaxation timesT 1 of D2O molecules were measured at 5–85°C in D2O solutions of alkali metal halides (LiCl∼CsCl, KBr, and KI), DCl, KOD, Ph4PCl, NaPh4B, and tetraalkylammonium bromides (Me4NBr∼Am4NBr) in the concentration range 0.1–1.4 mol-kg−1 TheB-coefficients of the electrolytes obtained from the concentration dependence of relaxation ratesR 1=1/T1 were divided into the ionicB-coefficients by three methods: (i) the assumption ofB (K+)=B(Cl−), (ii) the assumption ofB(Ph4P+)=B(Ph4B−), and (iii) the use ofB(Br−) obtained from a series ofB(R4NBr). It was found that Methods (ii) and (iii) resulted in an abnormal temperature dependence of theB-coefficients of alkali metal ions and a negative values of rotational correlation times τc at lower temperatures for hydroxide and halide ions. These results suggest that the methods based on the van der Waals volume are not adequate for the ionic separation of NMRB-coefficients. From the analysis using the assumption ofB(K+)=B(Cl−), it was found that D3O+, OD−, and Me4N+ ions are the intermediates between structure makers and breakers, and that the hydrophobicity of phenyl groups is weaker than that of alkyl groups due to the interactions between water molecules and π-electrons in phenyl groups.
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Yoshida, K., Ibuki, K. & Ueno, M. Estimated ionicB-coefficients from NMR measurements in aqueous electrolyte solutions. J Solution Chem 25, 435–453 (1996). https://doi.org/10.1007/BF00972991
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DOI: https://doi.org/10.1007/BF00972991