AI Article Synopsis
- The study examines the inconsistency of categorizing ions as "water structure makers" or "breakers," suggesting a critical threshold of water molecules per ion influences solution properties.
- Raman spectra of hydroxide solutions were analyzed to observe how OH ion vibrations change with varying dilutions, revealing two distinct contributions related to ion concentration.
- The findings indicate significant structural and dynamic changes in the solution when the water-to-solute ratio drops below approximately 20 molecules, regardless of the type of ion present.
Article Abstract
The concept of ions being either water "structure makers" or water "breakers" seems to be inconsistent with the existence of a critical number of water molecules per ion dictating the properties of an aqueous solution, independent of the ion identity. To investigate this issue, Raman spectra of hydroxide aqueous solutions in the region of the OH stretching mode have been obtained under ambient conditions and at concentrations ranging from extreme dilution to the solubility limit. Spectra have been analyzed with a relatively model-free approach, in terms of a superposition of contributions due to the vibrations of the OH ions, with two contributions due to the solvent. One of these latter contributions falls at wavenumbers very close to that of the OH stretching band, sharing with it its concentration dependence of the full width at half maximum (FWHM). The other contribution due to the solvent is very broad, with increasing FWHM with increasing ion concentration. In the light of these observations, an interpretation of the Raman spectra, based on the possibility of distinguishing the self and distinct contributions, is proposed. The present analysis is supported by structural data on the same solutions and puts into evidence relevant structural and dynamical changes occurring when the number of water molecules available per solute is below ∼20, irrespective of the ion identity.
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| http://dx.doi.org/10.1021/acs.jpcb.8b01094 | DOI Listing |
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