The geologic role of polysulfides—Part II

Cloke, Paul

doi:10.1016/0016-7037(63)90051-6

Cited by 37 publications

(2 citation statements)

References 25 publications

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“…Much of the earlier published work on the geochemistry of the short chain ( n ≤ 5) polysulfides in low-temperature aqueous conditions uses free energy data for these species − that have considerable uncertainties . Kamyshny et al collected what appears to be a more accurate data set for the stability of polysulfides up to n ≤ 8 (Table ).…”

Section: 2 Polysulfide Chemistrymentioning

confidence: 99%

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Chemistry of Iron Sulfides

2007

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Section: 2 Polysulfide Chemistrymentioning

confidence: 99%

“…They used the Schwarzenbach and Fischer data set in combination with measured data to derive their stability constants. They employed a linear algorithm similar to that originally derived by Cloke, , Schoonen and Barnes, and Williamson and Rimstidt to determine protonation constants.…”

Section: 2 Polysulfide Chemistrymentioning

confidence: 99%

Chemistry of Iron Sulfides

2007

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Die Bedeutung des intermediär oxidierten Schwefels für die Genese hydrothermaler Sulfat‐Sulfid‐Lagerstätten

Oberste-Padtberg

1982

Ber Bunsenges Phys Chem

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What one observes in hydrothermal ore deposits and their wall rock are sulfates (baryte, anhydrite, alunite) and sulfides (pyrite, galena etc.). The nature of the ore forming solution has to be extrapolated. Many authors maintain that sulfur occurs in solution in the extreme oxidation states S6+ and S2− only. However, theoretical considerations and experiments show that intermediate oxidized sulfur species (IOSS) are more frequent than generally assumed. Under hydrothermal conditions (p, T, po2) sulfate will be reduced stepwise; IOSS are dominant. Oxidation, reduction and disproportionation lead to the formation of sulfides and/or sulfates. Sulfate‐acceptors resp. sulfide‐acceptors keep the disproportionation going. IOSS provide a new model to explain the transport of metals and sulfur in the same hydothermal solution and the simultaneous crystallization of sulfates and sulfides. A further advantage of this model is the fact that heavy metals and earth alkali metals are more soluble by orders of magnitude as IOSS than as sulfate and sulfide.

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Structural chemistry and geochemistry of silver‐sulfur compounds: Critical review

Bell

Kramer

1999

Enviro Toxic and Chemistry

125

149

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Silver(I) bindss srongly with sulfur(II –) in inorganic and organic species, resulting in picomolal aqueous dissolved concentrations. For sulfur species found in the environment, Ag(I)–S(II) bonding forms a linear di‐coordinate arrangement, – S–Ag–S–, which results in long zigzag chains in inorganic (minerals) and organic (thiolate) complexes. Silver(I) forms the neutral complex AgHS0 at low concentration of S(II –) and Ag(I). Polynuclear complexes form in solution above micromolal concentrations of S(II –). Silver(I) polysulfides may be significant at elevated S(II –). A number of organic mercaptans (thiols) are found in anoxic sediments in nanomolal to micromolal levels and these can act as ligands for Ag(I). The surprisingly limited, known properties of Ag(I) complexes (thiolates) of environmental mercaptans are reviewed. In these thiolate complexes in the solid phase, single crystal X‐ray diffraction shows that the –S(R)–Ag –S(R)– chains condense to form sheets that further link through silver–silver interactions to create a network, or slab of silver and sulfur atoms. From nuclear magnetic resonance spectroscopic evidence, zigzag chains also form in the solution phase and aggregate in a random manner to form colloids, which are the predominant form of Ag(I) in solution. The most crucial and important aspect of Ag(I) thiolate chemistry is the rapid exchange of Ag(I) among thiolates. This process is a mechanism whereby Ag(I) can transfer onto, or off, particulate materials or the cells of an organism. Silver(I) thiolates also react rapidly with H2S or HS− as ligands to form Ag2S, but the reverse process is poor because of the high aqueous insolubility and stability of A2Ss. This reaction represents a possible final fate for any Ag(I) thiolate formed in natural waters, as well as any Ag(I)–S(II –) species.

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The geologic role of polysulfides—Part II

Cited by 37 publications

References 25 publications

Chemistry of Iron Sulfides

Chemistry of Iron Sulfides

Die Bedeutung des intermediär oxidierten Schwefels für die Genese hydrothermaler Sulfat‐Sulfid‐Lagerstätten

Structural chemistry and geochemistry of silver‐sulfur compounds: Critical review

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