Contacted Ion Pairs in Aqueous CuCl2 by the Combination of Ratio Spectra, Difference Spectra, Second Order Difference Spectra in the UV-Visible Spectra

Abstract

The microstructure of aqueous CuCl2 has been studied through lots of technologies for many years; however, it remains a controversial subject. In this study, a new spectroscopic method has been proposed to analyze the UV-visible spectra of thin film of CuCl2/H2O solutions at different concentrations. This method is the combination of ratio spectra, difference spectra and second order difference spectra. By using this method, two new bands at ~230 and ~380 nm are obviously observed. The bands are assigned as the contacted ion pairs[CuCl3(H2O)n]- or[CuCl4(H2O)n]2-, which demonstrates that ion pairs exist in the CuCl2/H2O solution. Such finding agrees with the recent theoretical spectra obtained by time-dependent density functional theory. Furthermore, the populations of the contacted ion pairs are discussed. This study not only offers the direct spectroscopic evidence of[CuCl3(H2O)n]- or[CuCl4(H2O)n]2- in aqueous CuCl2, but also suggests that the spectroscopic analysis method is powerful to extract the weak bands in a strong overlapping spectrum.