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Sulfate-Sensing Electrodes. The Lead- Amalgam/Lead-Sulfate Electrode (IUPAC Technical Report)

Published/Copyright: September 1, 2009
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Chemistry International -- Newsmagazine for IUPAC
From the journal Chemistry International -- Newsmagazine for IUPAC Volume 24 Issue 5

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Highlights from Pure and Applied Chemistry

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Sulfate-Sensing Electrodes. The Lead- Amalgam/Lead-Sulfate Electrode (IUPAC Technical Report)

by Patrizia R. Mussini and Torquato Mussini

Pure and Applied Chemistry, Vol. 74, No. 4, pp. 593-600 (2002)

It has long been recognized that sensitive and reproducible sulfate-reversible electrodes (e.g., the Pb|PbSO4 or Hg|Hg2SO4 electrode) are not as readily available as chloride-reversible electrodes (e.g., a widespread Hg|Hg2Cl2 or Ag|AgCl electrode). In this context, two major features are evident: the activity solubility products of PbSO4 and Hg2SO4 are larger than those of Hg2Cl2 and AgCl by several orders of magnitude, and in the case of the Pb|PbSO4 electrode, the preparative and operational procedure had not been assessed satisfactorily until recently, so that the electrode in both Pb|PbSO4 and Pb(Hg)|PbSO4 forms proved difficult to use and/or was unsatisfactorily reproducible.

In this report a new, simplified design and a convenient preparation procedure for the Pb(Hg)|PbSO4|SO42- electrode is proposed. This procedure ensures preparation of stable amalgams and reproducible electrode potentials, which make this electrode useful and attractive for both thermodynamic investigations and electroanalytical applications. For these purposes, the electrode prepared according to the proposed procedure has been exhaustively characterized both thermodynamically and as a sulfate-sensing electrode, in different sulfate solutions, including H2SO4.

The report also proposes a practical standardization procedure. The Pb(Hg)|PbSO4|SO42- electrode can be structured with a built-in concentrated Li2SO4 salt bridge for use as a sulfate-based reference electrode. Li2SO4 also has favorable properties as a salt bridge in some mixed aqueous-organic solvents, e.g., acetonitrile-water mixtures, and its combination with the lead-amalgam|lead-sulfate electrode in such solvents is an interesting perspective, for which further accumulation of data is awaited. This electrode can be operated as a reference electrode alternative to the conventional calomel or Ag|AgCl reference electrodes in electroanalytical practice.

www.iupac.org/publications/pac/2002/7404/7404x0593.html

Published Online: 2009-09-01
Published in Print: 2002-09

© 2014 by Walter de Gruyter GmbH & Co.

Articles in the same Issue

  1. Contents
  2. Balancing Sources and Uses
  3. A Glance Into the Future
  4. The Special Topics Project
  5. Accomplishments During the Past Decade and Relationships With Industry
  6. Candid Chemistry
  7. IUPAC Representative’s Report on the 34th Codex Committee Session
  8. Young Chemists to the 39th IUPAC Congress, Ottawa, August 2003
  9. Chemical Education International
  10. The “Orange Book” Online
  11. IUPAC–Empfehlungen
  12. Chemical Actinometry
  13. Conducting Polymer Colloids and Nanofilms
  14. Information Essential for Characterizing a Flow-Based Analytical System (IUPAC Technical Report)
  15. Sulfate-Sensing Electrodes. The Lead- Amalgam/Lead-Sulfate Electrode (IUPAC Technical Report)
  16. Future Requirements In the Characterization of Continuous Fiber Reinforced Polymeric Composites (IUPAC Technical Report)
  17. Nomenclature for the C60-Ih and C70-D5h(6) Fullerenes (IUPAC Recommendations 2002)
  18. Molecular Basis of Biodiversity, Conservation, and Sustained Innovative Utilization (IUPAC Technical Report)
  19. Naming of New Elements (IUPAC Recommendations 2002)
  20. “Heavy Metals”–A Meaningless Term? (IUPAC Technical Report)
  21. Phane Nomenclature. Part II. Modification of the Degree of Hydrogenation and Substitution Derivatives of Phane Parent Hydrides (IUPAC Recommendations 2002)
  22. Harmonized Guidelines for Single- Laboratory Validation of Methods of Analysis (IUPAC Technical Report)
  23. Polyaniline. Preparation of a Conducting Polymer (IUPAC Technical Report)
  24. Studies on Biodegradable Poly[hexano-6- lactone] Fibers. Part 3. Enzymatic Degradation in Vitro (IUPAC Technical Report)
  25. Free-Radical Polymerization: Kinetics and Mechanism
  26. C2+ Nitroalkanes With Water or Organic Solvents: Binary and Multicomponent Systems
  27. Advanced Organic Chemistry Part A: Structure and Mechanisms Part B: Reactions and Synthesis
  28. Modern Coordination Chemistry–The Legacy of Joseph Chatt
  29. Biodiversity
  30. Macromolecules and Materials Science
  31. Nuclear Analytical Techniques in the Life Sciences
  32. Prohibiting Chemical Weapons
  33. Rejuvenating the Learning and Teaching of Chemistry 30 November–4 December 2002, Melbourne, Australia
  34. 4th Florida Heterocyclic Conference 10–12 March 2003, Gainesville, Florida, USA
  35. 12th IUPAC International Symposium on Organo-Metallic Chemistry (OMCOS-12) 6–10 July 2003, Toronto, Canada
  36. Calendar of IUPAC Sponsored Conferences
https://doi.org/10.1515/ci.2002.24.5.21b

Articles in the same Issue

  1. Contents
  2. Balancing Sources and Uses
  3. A Glance Into the Future
  4. The Special Topics Project
  5. Accomplishments During the Past Decade and Relationships With Industry
  6. Candid Chemistry
  7. IUPAC Representative’s Report on the 34th Codex Committee Session
  8. Young Chemists to the 39th IUPAC Congress, Ottawa, August 2003
  9. Chemical Education International
  10. The “Orange Book” Online
  11. IUPAC–Empfehlungen
  12. Chemical Actinometry
  13. Conducting Polymer Colloids and Nanofilms
  14. Information Essential for Characterizing a Flow-Based Analytical System (IUPAC Technical Report)
  15. Sulfate-Sensing Electrodes. The Lead- Amalgam/Lead-Sulfate Electrode (IUPAC Technical Report)
  16. Future Requirements In the Characterization of Continuous Fiber Reinforced Polymeric Composites (IUPAC Technical Report)
  17. Nomenclature for the C60-Ih and C70-D5h(6) Fullerenes (IUPAC Recommendations 2002)
  18. Molecular Basis of Biodiversity, Conservation, and Sustained Innovative Utilization (IUPAC Technical Report)
  19. Naming of New Elements (IUPAC Recommendations 2002)
  20. “Heavy Metals”–A Meaningless Term? (IUPAC Technical Report)
  21. Phane Nomenclature. Part II. Modification of the Degree of Hydrogenation and Substitution Derivatives of Phane Parent Hydrides (IUPAC Recommendations 2002)
  22. Harmonized Guidelines for Single- Laboratory Validation of Methods of Analysis (IUPAC Technical Report)
  23. Polyaniline. Preparation of a Conducting Polymer (IUPAC Technical Report)
  24. Studies on Biodegradable Poly[hexano-6- lactone] Fibers. Part 3. Enzymatic Degradation in Vitro (IUPAC Technical Report)
  25. Free-Radical Polymerization: Kinetics and Mechanism
  26. C2+ Nitroalkanes With Water or Organic Solvents: Binary and Multicomponent Systems
  27. Advanced Organic Chemistry Part A: Structure and Mechanisms Part B: Reactions and Synthesis
  28. Modern Coordination Chemistry–The Legacy of Joseph Chatt
  29. Biodiversity
  30. Macromolecules and Materials Science
  31. Nuclear Analytical Techniques in the Life Sciences
  32. Prohibiting Chemical Weapons
  33. Rejuvenating the Learning and Teaching of Chemistry 30 November–4 December 2002, Melbourne, Australia
  34. 4th Florida Heterocyclic Conference 10–12 March 2003, Gainesville, Florida, USA
  35. 12th IUPAC International Symposium on Organo-Metallic Chemistry (OMCOS-12) 6–10 July 2003, Toronto, Canada
  36. Calendar of IUPAC Sponsored Conferences
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