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- W2038445767 abstract "A novel method for investigating solute–solvent H/D exchange equilibria in aqueous solution is described. The ‘‘first-order difference’’ neutron diffraction method of Enderby and co-workers is combined with a variation of the isotopic composition of the solvent, ideally from pure D2O to that D2O–H2O mixture in which the average neutron scattering length of the H and D species vanishes. The new technique can give the location of the exchange site with respect to a particular atom as well as the H/D exchange constant for the site with reference to the bulk solvent. The relevant solution thermodynamic data are reviewed to identify systems for which the proposed neutron diffraction experiment is feasible. The literature data are complemented by new calculations of the effect of an ion on the O–H stretch vibration and the libration of the neighboring water. For +3 ions the dominant isotope effect is associated with the O–H stretch of the water; the shift to lower frequencies is proportional to the square of the ionic charge z in the sequence Na+, Mg2+, Al3+, while the libration frequency increases linearly with z in the same series. The reported free energy data for H2O to D2O transfers of various Mz+ ions can be understood on the basis of these observations. Finally, while the question of feasibility of the new technique invites examination of the details of ionic hydration, the main point is that such details could be elucidated by the proposed diffraction technique." @default.
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- W2038445767 title "A proposed neutron diffraction experiment to measure hydrogen isotope fractionation in solution" @default.
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