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Pure Appl. Chem., 2011, Vol. 83, No. 5, pp. 1163-1214

Published online 2011-03-29

Chemical speciation of environmentally significant metals with inorganic ligands. Part 4: The Cd2+ + OH, Cl, CO32–, SO42–, and PO43– systems (IUPAC Technical Report)

Kipton J. Powell1*, Paul L. Brown2, Robert H. Byrne3, Tamás Gajda4, Glenn Hefter5, Ann-Kathrin Leuz6, Staffan Sjöberg7 and Hans Wanner6

1 Department of Chemistry, University of Canterbury, Christchurch, New Zealand
2 Rio Tinto Technology and Innovation, 1 Research Avenue, Bundoora VIC 3083, 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 Chemical and Mathematical Sciences, Murdoch University, Murdoch, WA 6150, Australia
6 Swiss Federal Nuclear Safety Inspectorate, CH-5200 Brugg, Switzerland
7 Department of Chemistry, Umeå University, S-901 87 Umeå, Sweden

Abstract: The numerical modeling of CdII speciation amongst the environmental inorganic ligands Cl, OH, CO32–, SO42–, and PO43– requires reliable values for the relevant stability (formation) constants. This paper compiles and provides a critical review of these constants and related thermodynamic data. It recommends values of log10 βp,q,r° valid at Im = 0 mol kg–1 and 25 °C (298.15 K), along with the equations and empirical reaction ion interaction coefficients, ∆ε , required to calculate log10 βp,q,r values at higher ionic strengths using the Brønsted–Guggenheim–Scatchard specific ion interaction theory (SIT). Values for the corresponding reaction enthalpies, ∆rH, are reported where available. Unfortunately, with the exception of the CdII-chlorido system and (at low ionic strengths) the CdII-sulfato system, the equilibrium reactions for the title systems are relatively poorly characterized. In weakly acidic fresh water systems (–log10 {[H+]/c°} < 6), in the absence of organic ligands (e.g., humic substances), CdII speciation is dominated by Cd2+(aq), with CdSO4(aq) as a minor species. In this respect, CdII is similar to CuII [2007PBa] and PbII [2009PBa]. However, in weakly alkaline fresh water solutions, 7.5 < –log10 {[H+]/c°} < 8.6, the speciation of CdII is still dominated by Cd2+(aq), whereas for CuII [2007PBa] and PbII [2009PBa] the carbonato- species MCO3(aq) dominates. In weakly acidic saline systems (–log10 {[H+]/cϒ} < 6; –log10 {[Cl]/c°} < 2.0) the speciation is dominated by CdCln(2–n)+ complexes, (n = 1–3), with Cd2+(aq) as a minor species. This is qualitatively similar to the situation for CuII and PbII. However, in weakly alkaline saline solutions, including seawater, the chlorido- complexes still dominate the speciation of CdII because of the relatively low stability of CdCO3(aq). In contrast, the speciation of CuII [2007PBa] and PbII [2009PBa] in seawater is dominated by the respective species MCO3(aq). There is scope for additional high-quality measurements in the Cd2+ + H+ + CO32– system as the large uncertainties in the stability constants for the Cd2+-carbonato complexes significantly affect the speciation calculations.