Abstract

We apply our previously developed deconvolution method and interpretation to analyze changes in the OH stretching band [nu(OH) band] of low-concentration (< or =0.2 m) aqueous solutions of NaCl and KCl. We treat these simple, monovalent ions as defects in the hydrogen-bond network of pure water and quantify the changes in the spectra at low defect concentration with an "order parameter". Order-parameter analysis of difference spectra of the two solutions leads to hydration numbers of 7.0+/-1.0 and 5.9+/-0.3 for K(+) and Na(+), respectively. Additionally, we find that changes in the nu(OH) band due to low concentrations of ions result from changes in the topology of the hydrogen-bond network.

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