NMR studies on reorientational motion of hydrated D2O molecules in tetraalkylammonium bromide dilute aqueous solutions.
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概要
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The spin-lattice relaxation times of D and <SUP>17</SUP>O nuclei of hydrated D<SUB>2</SUB>O molecules in tetraalkylammonium bromide (Me<SUB>4</SUB>NBr, Et<SUB>4</SUB>NBr, Pr<SUB>4</SUB>NBr, and Bu<SUB>4</SUB>NBr) dilute aqueous solutions in the concentration range of 0.2 to 1.0 mol kg<SUP>−1</SUP> at 25°C were measured by NMR spectroscopy. The relaxation rates of D and <SUP>17</SUP>O nuclei varied linearly with increasing the concentration below 1.0 mol kg<SUP>−1</SUP>. The dynamic hydration number, <I>B</I><SUB>x</SUB><SUP>+</SUP>, is defined by <I>B</I><SUB>x</SUB><SUP>+</SUP>=(<I>k</I>·τ<SUB>x</SUB><SUP>+</SUP>⁄τ<SUB>x</SUB><SUP>0</SUP>−1)<I>n</I><SUB>x</SUB><SUP>+</SUP>⁄50.0, where τ<SUB>x</SUB><SUP>+</SUP> and τ<SUB>x</SUB><SUP>0</SUP> (X=D or <SUP>17</SUP>O) are the reorientational correlation times of hydrated D<SUB>2</SUB>O molecules (<I>n</I><SUB>x</SUB><SUP>+</SUP>) in R<SUB>4</SUB>N<SUP>+</SUP> (R: alkyl group) and pure D<SUB>2</SUB>O molecule. The <I>B</I><SUB>x</SUB><SUP>+</SUP> increases with increasing the alkyl chain length of R<SUB>4</SUB>N<SUP>+</SUP> ions. The abnormally large <I>B</I><SUB>x</SUB><SUP>+</SUP> values, compared with those of alkali metal ions, are caused by the hydrophobic hydration around the alkyl group of the R<SUB>4</SUB>N<SUP>+</SUP> ion. The reorientational motion of a hydrated D<SUB>2</SUB>O molecule in the hydration sphere of R<SUB>4</SUB>N<SUP>+</SUP> ions is isotropic, though the motion of a D<SUB>2</SUB>O molecule in the ionic hydration of alkali metal ions is anisotropic.
- 公益社団法人 日本化学会の論文
著者
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Taniguchi Yoshihiro
Department Of Applied Chemistry Faculty Of Science And Engineering Ritsumeikan University
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Shimizu Akio
Department of Bioengincering Facutly of Engineering,Soka University
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