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Structural Chemistry

, Volume 30, Issue 1, pp 61–74 | Cite as

Determination of structures of cupric-chloro complexes in hydrochloric acid solutions by UV-Vis and X-ray absorption spectroscopy

  • Masahito UchikoshiEmail author
  • Kozo Shinoda
Original Research
  • 138 Downloads

Abstract

Ultrahigh-purity metals are indispensable to understanding the nature of materials, but the purity of contemporary metals is insufficient for determining their intrinsic properties. The fundamentals of the anion-exchange reaction must be clear in order to increase the refining efficiency of anion-exchange separation for purification of metals. The thermodynamic analysis of the anion-exchange reaction needs to take account of the distributions of metal-chloro complexes in the solution phase in addition to those between the resin and the solution phase. The structures of metal-chloro complexes in the solution phase must be determined as the first step in determining what species is adsorbed on the resin. Copper is one of the base metals most commonly used in modern society, and the anion-exchange behavior of cupric species is representative. The distribution and the molar attenuation coefficients of cupric-chloro complexes in hydrochloric acid solutions were obtained employing factor analysis followed by fitting a thermodynamic model to ultraviolet-visible absorption spectra. The cumulative formation constants were determined as follows: \(\log _{10}\beta _{1} = 0.599\), \(\log _{10}\beta _{2} = 0.343\), \(\log _{10}\beta _{3} = -1.88\), and \(\log _{10}\beta _{4} = -5.25\), and the Setchénow coefficient for the neutral species of [CuIICl2]0 is 0.188. Using the distribution assessed by the above thermodynamic parameters, the X-ray absorption spectra (XAS), consisting of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) of individual species, were assessed by factor analysis. EXAFS theoretical models were fitted to experimental spectra of individual species to determine their structures and coordination geometries for the first time, although it is generally very difficult to obtain the spectrum of the individual species in a matrix containing other species simultaneously. The structures of five cupric-chloro complexes were determined to be distorted octahedrons of \(\left [\mathrm {Cu^{II}(H_{2}O)_{4}^{eq}(H_{2}O)_{2}^{ax}}\right ]^{2+}, \left [\mathrm {Cu^{II}(H_{2}O)_{4}^{eq}(H_{2}O)^{ax}Cl^{ax}}\right ]^{+}\), and \(\left [\mathrm {Cu^{II}Cl_{2}^{ax}(H_{2}O)_{4}^{eq}}\right ]^{0}\), a planar triangle of \(\left [\mathrm {Cu^{II}Cl_{3}}\right ]^{-}\), and a tetrahedron of [CuIICl4]2−. The obtained spectra can be used as standards. The XANES spectra of cupric-chloro complexes were interpreted qualitatively. The Cl ligand in \(\left [\mathrm {Cu^{II}(H_{2}O)_{4}^{eq}(H_{2}O)^{ax}Cl^{ax}}\right ]^{+}\) is attracted to the center atom of CuII by electrostatic force, as the H2O ligands are. Contrastingly, the bonding system of the Cl ligands in the latter three species involves covalency.

Keywords

Cupric-chloro complexes Hydrochloric acid solution Factor analysis Multivariate curve resolution-alternating least squares Ultraviolet-visible absorption spectrum X-ray absorption spectrum Extended X-ray absorption fine structure X-ray absorption near edge structure 

Notes

Acknowledgements

The authors wish to thank Mr. Yuji Baba and Mr. Kouji Nagahashi for their great devotion to this experimental work. The synchrotron radiation experiments of X-ray absorption spectrometry were performed at BL14B2 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (Proposal No. 2008A1941). This work was performed under the Research Program of “The Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials” in “The Network Joint Research Center for Materials and Devices” and as one of the projects in the MSTeC Research Center at the Institute of Multidisciplinary Research for Advanced Materials, Tohoku University.

Author Contributions

The manuscript was composed by contributions of all authors. All authors have given approval to the final version of the manuscript.

Compliance with Ethical Standards

Conflict of interests

The authors declare that they have no conflict of interest.

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Institute of Multidisciplinary Research for Advanced MaterialsTohoku UniversitySendaiJapan

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