| 1. |
- Powell, Kipton J., et al.
(författare)
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Chemical speciation of environmentally significant heavy metals with inorganic ligands - Part 1: The Hg2+-Cl-, OH-, CO32-, SO42-, and PO43- aqueous systems - (IUPAC technical report)
- 2005
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Ingår i: Pure and Applied Chemistry. - : Walter de Gruyter GmbH. - 0033-4545 .- 1365-3075. ; 77:4, s. 739-800
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Tidskriftsartikel (refereegranskat)abstract
- This document presents a critical evaluation of the equilibrium constants and reaction enthalpies for the complex formation reactions between aqueous Hg(II) and the common environmental inorganic ligands Cl-, OH-, CO32-, SO42-, and PO43-. The analysis used data from the IUPAC Stability Constants database, SC-Database, focusing particularly on values for 25 ° C and perchlorate media. Specific ion interaction theory (SIT) was applied to reliable data available for the ionic strength range I-c ≤ 3.0 mol dm(-3). Recommended values of log(10) β(p,q,r)° and the associated reaction enthalpies, &UDelta;H-r(m)°, valid at I-m = 0 mol kg(-1) and 25 ° C, were obtained by weighted linear regression using the SIT equations. Also reported are the equations and specific ion interaction coefficients required to calculate log(10) β(p,q,r) values at higher ionic strengths and other temperatures. A similar analysis is reported for the reactions of H+ with CO32- and PO43-. Diagrams are presented to show the calculated distribution of Hg(II) amongst these inorganic ligands in model natural waters. Under typical environmental conditions, Hg(II) speciation is dominated by the formation of HgCl2(aq), Hg(OH)Cl(aq), and Hg(OH)(2)(aq).
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| 2. |
- Powell, Kipton J., et al.
(författare)
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Chemical speciation of environmentally significant metals with inorganic ligands Part 2: The Cu2+-OH-, Cl-, CO32-, SO42-, and PO43- systems (IUPAC Technical Report)
- 2007
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Ingår i: Pure and Applied Chemistry. - : Walter de Gruyter GmbH. - 0033-4545 .- 1365-3075. ; 79:5, s. 895-950
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Forskningsöversikt (refereegranskat)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.
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| 3. |
- Powell, Kipton J, et al.
(författare)
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Chemical speciation of environmentally significant metals with inorganic ligands. Part 3: The Pb2+ + OH–, Cl–, CO32–, SO42–, and PO43– systems (IUPAC Technical Report)
- 2009
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Ingår i: Pure and Applied Chemistry. - 0033-4545 .- 1365-3075. ; 81:12, s. 2425-76
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Tidskriftsartikel (refereegranskat)abstract
- Complex formation between PbII and the common environmental inorganic ligands, Cl–, OH–, CO32–, SO42–, and PO43–, can be significant in natural waters with low concentrations of organic matter. Numerical modeling of the speciation of PbII amongst these inorganic ligands requires reliable values for the relevant stability (formation) constants. This paper provides a critical review of such 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 coefficients required to calculate log10 βp,q,r values at higher ionic strengths using the Brønsted–Guggenheim–Scatchard specific ion interaction theory (SIT). Some values for reaction enthalpies, ΔrH, are also reported. In weakly acidic fresh water systems (–log10 {[H+]/c°} < 6), the speciation of PbII is similar to that of CuII. In the absence of organic ligands, PbII speciation is dominated by Pb2+(aq), with PbSO4(aq) as a minor species. In weakly alkaline solutions, 8.0 < –log10 {[H+]/c°} < 9.0, the speciation is dominated by the carbonato species PbCO3(aq) and Pb(CO3)22–. In weakly acidic saline systems (–log10 {[H+]/c°} < 6), the speciation is dominated by PbCln(2–n)+ complexes, (n = 0–3), with Pb2+(aq) as a minor species. In this medium (and in seawater), the speciation contrasts with that of CuII because of the higher stability of the Pb2+-chlorido- complexes. In seawater at –log10 {[H+]/c°} = 8.2, the calculated speciation is less well defined, although it is clearly dominated by the uncharged species PbCO3(aq) (41 % of [Pb]T) with a significant contribution (16 %) from Pb(CO3)Cl– and minor contributions (5–10 %) from PbCln(2–n)+, (n = 0–3) and Pb(CO3)22–. The uncertainty in calculations of PbII speciation in seawater arises from (a) the large uncertainty in the stability constant for the apparently dominant species PbCO3(aq), (b) the reliance on statistical predictions for stability constants of the ternary species Pb(CO3)Cl– and Pb(CO3)OH–, and (c) the uncertainty in the stability constant for PbCl42–, the available value being considered "indicative" only. There is scope for additional detailed high-quality measurements in the Pb2+ + CO32– + Cl– system.
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