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Chemical speciation in concentrated aqueous solutions of CuCl2 using thin-film UV–visible spectroscopy combined with DFT calculations
Journal article   Open access   Peer reviewed

Chemical speciation in concentrated aqueous solutions of CuCl2 using thin-film UV–visible spectroscopy combined with DFT calculations

N. Zhang, D. Zeng, G. Hefter and Q. Chen
Journal of Molecular Liquids, Vol.198, pp.200-203
2014
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Abstract

In this work, a thin-film UV-visible spectroscopic technique has been developed and combined with time-dependent density functional theory (TD-DFT) calculations for the study of the chemical speciation in concentrated aqueous solutions of Cu(II) + Cl-. When the CuCl2 concentration changed from 0.05 mol·kg- 1 to 5 mol·kg- 1, the UV peak shifted from ~ 250 nm to ~ 262 nm. Similar shifts were recorded for CuCl2 solutions containing up to 5 mol·kg- 1 NaCl. Combination of the spectral data with our previous TD-DFT calculations provided a consistent model of the chemical speciation in the Cu(II)/Cl- system up to high concentrations of both components. The results obtained indicate that many of the previous conclusions regarding these solutions, drawn from a variety of techniques are unreliable. Under the present conditions, the only species detected were innersphere complexes with one or two Cl- ions bound to the aquated Cu(II) ion. For all the solutions, no remarkable peaks at ~ 280 nm or 380 nm, indicative of CuCl3 - (aq) and CuCl4 2 - (aq) respectively, were observed.

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Collaboration types
Domestic collaboration
International collaboration
Citation topics
2 Chemistry
2.89 Ionic, Molecular & Complex Liquids
2.89.677 Liquid Water
Web Of Science research areas
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
ESI research areas
Chemistry
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