Infrared spectra of cesium chloride aqueous solutions

The aqueous solutions of CsCl were studied at room temperature by infrared (IR) spectroscopy in the entire solubility range, 0-1200 g/L, using attenuated total reflection (ATR) sampling. The influence of anomalous dispersion on the IR-ATR spectra was evaluated by calculating the imaginary refractive index, k(nu), of each sample. Factor analysis (FA) was used to determine the number and abundance of species in the solutions. FA applied to both k(nu) spectra and IR-ATR spectra produced two principal spectra with a similar abundance of species. This result indicates that, even at high salt concentration, the optical effects do not influence the chemical analysis of IR-ATR spectra. The spectral modifications related to the salt concentrations are mainly first order. Second order effects were observed, but being weak, were not investigated. The two principal spectra are related to the two species present in the solution: pure water and CsCl-solvated water. From the latter, 2.8 +/-0.4 water molecules were calculated to be associated with each close-bound Cs+/Cl- ion pair. In the case of KCl and NaCl aqueous solutions, both of which showed the same number of species, the number of water molecules associated to an ion pair was 5.0 +/-0.4. That the latter number is different from that of CsCl indicates that the interaction between water molecules and ion pairs is different when cation Na or K in the chloride salt is replaced by Cs. (C) 2000 American Institute of Physics. [S0021-9606(00)51837-6].