Raman spectroscopy combined with component analysis and molecular dynamics simulation were used to study chemical species and their transformation in aqueous sodium solutions. Study shows that the characteristic vibrational frequency of nitrate ions (ν1-NO3-) blue-shifted from 1043.9 to 1046.9 cm-1, and the full width at half maximum increased from 6.8 to 10.8 cm-1 as the concentration increasing. When water/salt molar ratio (WSR) > 30, the relative concentration (RC) of free hydrated ions and solvent shared ion pair accounts for the vast majority, and there is almost no contact ion pair in solution. When WSR less than 30, due to the continuous reduction of the number of water molecules, the hydrated water molecules around the sodium ions and nitrate ions begin to decrease, and solvent shared ion pair or contact ion pair gradually forms. Sodium ions and nitrate ions mainly exist in a monodentate coordination. When WSR > 160, both the relative concentration of contact ion pair and complex structure is close to 0. This work proves that a lower RC of complex structure in solution, a smaller supersaturation of the solution is achieved, meaning aqueous sodium nitrate solution is easier to nucleate crystals.
Keywords: Ion pair; Molecular dynamics; Raman spectrum frequency; Sodium nitrate solution.
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