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Pure Appl. Chem., 2007, Vol. 79, No. 5, pp. 895-950


Chemical speciation of environmentally significant metals with inorganic ligands Part 2: The Cu2+-OH-, Cl-, CO32-, SO42-, and PO43- systems (IUPAC Technical Report)

Kipton J. Powell1, Paul L. Brown2, Robert H. Byrne3, Tamás Gajda4, Glenn Hefter5, Staffan Sjöberg6 and Hans Wanner7

1 Department of Chemistry, University of Canterbury, Christchurch, New Zealand
2 Rio Tinto Technical Services, 1 Research Avenue, Bundoora VIC3083, Australia
3 College of Marine Science, University of South Florida, 140 Seventh Avenue South, St. Petersburg, FL 33701-5016, USA
4 Department of Inorganic and Analytical Chemistry, A. József University, P.O. Box 440, Szeged 6701, Hungary
5 School of Mathematical and Physical Sciences, Murdoch University, Murdoch, WA 6150, Australia
6 Department of Inorganic Chemistry, Umeå University, S-901 87 Umeå, Sweden
7 Swiss Federal Nuclear Safety Inspectorate, CH-5232 Villigen, Switzerland

Abstract: Complex formation between CuII and the common environmental ligands Cl-, OH-, CO32-, SO42-, and PO43- can have a significant effect on CuII speciation in natural waters with low concentrations of organic matter. Copper(II) complexes are labile, so the CuII distribution amongst these inorganic ligands can be estimated by numerical modeling if reliable values for the relevant stability (formation) constants are available. This paper provides a critical review of such constants and related thermodynamic data. It recommends values of log10βp,q,r° valid at Im = 0 mol kg-1 and 25 °C (298.15 K), along with the equations and specific ion interaction coefficients required to calculate log10βp,q,r values at higher ionic strengths. Some values for reaction enthalpies, ΔrHm, are also reported where available. In weakly acidic fresh water systems, in the absence of organic ligands, CuII speciation is dominated by the species Cu2+(aq), with CuSO4(aq) as a minor species. In seawater, it is dominated by CuCO3(aq), with Cu(OH)+, Cu2+(aq), CuCl+, Cu(CO3)OH-, Cu(OH)2(aq), and Cu(CO3)22- as minor species. In weakly acidic saline systems, it is dominated by Cu2+(aq) and CuCl+, with CuSO4(aq) and CuCl2(aq) as minor species.