Chemical speciation of environmentally significant metals with inorganic ligands. Part 5

The Zn2+ + OH-, Cl-, CO3 2-, SO4 2-, and PO4 3-systems (IUPAC Technical Report)

Kipton J. Powell, Paul L. Brown, Robert H. Byrne, T. Gajda, Glenn Hefter, Ann Kathrin Leuz, Staffan Sjöberg, Hans Wanner

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Abstract

The numerical modeling of ZnII speciation amongst the environmental inorganic ligands Cl-, OH-, CO3 2-, SO4 2-, and PO4 3-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 at Im = 0 mol·kg-1 and 25 °C (298.15 K), and reports the empirical reaction ion interaction coefficients, Δ∈required to calculate log10βp,q,r values at higher ionic strengths using the Brønsted-Guggenheim-Scatchard specific ion interaction theory (SIT). Values for the corresponding reaction enthalpies, ΔrH, are reported where available. There is scope for additional high-quality measurements for the Zn2+ + H+ + CO3 2-system and for the Zn2+ + OH-and Zn2+ + SO4 2-systems at I > 0. In acidic and weakly alkaline fresh water systems (pH II speciation is dominated by Zn2+(aq). In this respect, ZnII contrasts with CuII and PbII (the subjects of earlier reviews in this series) for which carbonato-and hydroxido-complex formation become important at pH > 7. The speciation of ZnII is dominated by ZnCO3(aq) only at pH > 8.4. In seawater systems, the speciation at pH = 8.2 is dominated by Zn2+(aq) with ZnCl+, Zn(Cl)2(aq), ZnCO3(aq), and ZnSO4(aq) as minor species. This behaviour contrasts with that for CuII and PbII for which at the pH of seawater in equilibrium with the atmosphere at 25 °C (log10 {[H+]/c°} ≈ 8.2) the MCO3(aq) complex dominates over the MCln (2-n)+ species. The lower stability of the different complexes of ZnII compared with those of CuII, PbII, and CdII is also illustrated by the percentage of uncomplexed M2+ in seawater, which is ca. 55, 3, 2, and 3.3% of [MII]T, respectively.

Original languageEnglish
Pages (from-to)2249-2311
Number of pages63
JournalPure and Applied Chemistry
Volume85
Issue number12
DOIs
Publication statusPublished - 2013

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Chemical speciation
Seawater
Metals
Ligands
Ions
Ionic strength
Enthalpy
Thermodynamics
Water
hydroxide ion

Keywords

  • Chemical speciation
  • Environmental chemistry
  • Inorganic ligands
  • IUPAC Analytical Chemistry Division
  • Stability constants
  • Zinc

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Chemical speciation of environmentally significant metals with inorganic ligands. Part 5 : The Zn2+ + OH-, Cl-, CO3 2-, SO4 2-, and PO4 3-systems (IUPAC Technical Report). / Powell, Kipton J.; Brown, Paul L.; Byrne, Robert H.; Gajda, T.; Hefter, Glenn; Leuz, Ann Kathrin; Sjöberg, Staffan; Wanner, Hans.

In: Pure and Applied Chemistry, Vol. 85, No. 12, 2013, p. 2249-2311.

Research output: Contribution to journalArticle

Powell, Kipton J. ; Brown, Paul L. ; Byrne, Robert H. ; Gajda, T. ; Hefter, Glenn ; Leuz, Ann Kathrin ; Sjöberg, Staffan ; Wanner, Hans. / Chemical speciation of environmentally significant metals with inorganic ligands. Part 5 : The Zn2+ + OH-, Cl-, CO3 2-, SO4 2-, and PO4 3-systems (IUPAC Technical Report). In: Pure and Applied Chemistry. 2013 ; Vol. 85, No. 12. pp. 2249-2311.
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abstract = "The numerical modeling of ZnII speciation amongst the environmental inorganic ligands Cl-, OH-, CO3 2-, SO4 2-, and PO4 3-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 at Im = 0 mol·kg-1 and 25 °C (298.15 K), and reports the empirical reaction ion interaction coefficients, Δ∈required to calculate log10βp,q,r values at higher ionic strengths using the Br{\o}nsted-Guggenheim-Scatchard specific ion interaction theory (SIT). Values for the corresponding reaction enthalpies, ΔrH, are reported where available. There is scope for additional high-quality measurements for the Zn2+ + H+ + CO3 2-system and for the Zn2+ + OH-and Zn2+ + SO4 2-systems at I > 0. In acidic and weakly alkaline fresh water systems (pH II speciation is dominated by Zn2+(aq). In this respect, ZnII contrasts with CuII and PbII (the subjects of earlier reviews in this series) for which carbonato-and hydroxido-complex formation become important at pH > 7. The speciation of ZnII is dominated by ZnCO3(aq) only at pH > 8.4. In seawater systems, the speciation at pH = 8.2 is dominated by Zn2+(aq) with ZnCl+, Zn(Cl)2(aq), ZnCO3(aq), and ZnSO4(aq) as minor species. This behaviour contrasts with that for CuII and PbII for which at the pH of seawater in equilibrium with the atmosphere at 25 °C (log10 {[H+]/c°} ≈ 8.2) the MCO3(aq) complex dominates over the MCln (2-n)+ species. The lower stability of the different complexes of ZnII compared with those of CuII, PbII, and CdII is also illustrated by the percentage of uncomplexed M2+ in seawater, which is ca. 55, 3, 2, and 3.3{\%} of [MII]T, respectively.",
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