Abstract
DPS distills information on transformation of stiffness (frequency shift), fraction (peak area) and fluctuation (FWHM) of HO bonds upon KCl, HCl and KOH solvation, which suggests the presence of H↔H fragilation, O:⇔:O compression and K++Cl− polarization in the solutions.
[Display omitted]
•HCl solvation derives H↔H point breakers that disrupt the solution surface stress.•KOH solvation derives O:⇔:O point compressors.•Electric fields of aqueous ions stretch and polarize the hydrogen bond.•Differential phonon spectrometrics resolves solute capabilities of transforming the solute-solvent interface bonds.
An incorporation of the hydrogen bond (O:HO or HB) cooperativity notion, contact angle detection, and the differential phonon spectrometrics (DPS) has enabled us to gain refined information on the HCl, KCl and KOH solvation resolved solute-solvent molecular interactions and the solution surface stresses. Results show that ionic polarization stiffens the solvent HO bond phonon from 3200 to 3480cm−1 in the hydration shells. The HO− in alkaline solution, however, shares not only the same HO phonon redshift of compressed water from 3200 to <3100cm−1 but also the dangling bonds of H2O surface featured at 3610cm−1. Salt and alkaline solvation enhances the solution surface stress by K+ and Cl− ionic polarization. The excessive H+ proton in acid solution forms a H↔H anti-HB that depresses the solution surface stress, instead. The solute capability of transforming the fraction of the O:HO bonds of the solvent matrix is featured by: fH=0 and fx ∝ 1-exp(-C/C0) (x=HO−,K+ and Cl−) towards saturation. Exercises not only confirm the presence of the H↔H anti-HB point fragilization, the O:⇔:O super-HB point compression, and ionic polarization dominating the performance of the respective HCl, KOH, and KCl solutions, but also demonstrate the power of the DPS that enables high resolution of solute-solute-solvent interactions and correlation between HB relaxation and solution surface stress.