Quantitative Determination of Selective Solvation by the X-Ray Diffraction with Isomorphous Substitution Technique

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1) X-ray diffraction measurements using the imaging plate(IP) detector were demonstrated to be useful for transition metal systems if fluorescent X-rays are removed by the zirconium filter.2) X-ray diffraction method with the isomorphous substitution were demonstrated to be useful for the determination of solvent compositions in the 1st sphere of metal ions dissolved in aqueous mixed solvents such as water-amide systems.3) Solvation power of the solvents for CoィイD12+ィエD1 in water-amide mixtures was clarified to be the order FA>NMF≧DEF>HィイD22ィエD2O>DMF≫NMA【approximately equal】DMA>DMP.4) Factors controlling selective solvation of CoィイD12+ィエD1 in water-amide mixtures were revealed to be the steric hindrance for metal-oxygen interactions, the effective mole fraction controlled by water-amide interactions, and the ability of solvents as the electron donor. Ability as the electron acceptor is also important, especially for the effective mole fraction.5) Solvation power of TMP in water-TMP mixtures was found to be similar to that of NMA or DMA and dominantly controlled by the steric hindrance.