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

Abstract

The numerical modeling of CdIIspeciation 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 log10βp,q,r° valid atIm= 0 mol kg–1and 25 °C (298.15 K), along with the equations and empirical reaction ion interaction coefficients, ∆ε, required to calculate log10βp,q,rvalues 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), CdIIspeciation is dominated by Cd2+(aq), with CdSO4(aq) as a minor species. In this respect, CdIIis similar to CuII[2007PBa] and PbII[2009PBa]. However, in weakly alkaline fresh water solutions, 7.5 < –log10{[H+]/c°} < 8.6, the speciation of CdIIis 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 CuIIand PbII. However, in weakly alkaline saline solutions, including seawater, the chlorido- complexes still dominate the speciation of CdIIbecause 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.