Abstract
The structure of supercritical water and aqueous solutions has been examined up to 510°C and 40 MPa with in situ laser Raman spectroscopy. Just near the critical point, the maximal concentration of the symmetric OH stretching is obtained although the breakdown of the hydrogen-bonding network occurs. Consequently, short-lived tetrahedral configurations accompanied by large fluctuations of the structure are significantly formed and become possible along with dimers monomers. The spectra of an aqueous zinc nitrate solution reveal that the replacement of H2O molecules in the solvation shell of Zn2+ by a nitrate ion is significantly promoted at higher temperatures above 300°C at 30 MPa. The average number of water molecules bound to the zinc ion is decreased to about 3 at 380°C from 6.
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