The Equilibrium between Elementary Sulfur and Aqueous Polysulfide Solutions.

Teder, Ants; Christian, Sherril D.; Grundnes, Just; Roach, Stephen R.; Engebretsen, Jan E.; Ehrenberg, L.

doi:10.3891/acta.chem.scand.25-1722

Cited by 75 publications

(36 citation statements)

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“…Giggenbach [14] from spectroscopic studies, showed the optimum for S 4 S 2− at log B ˜ –7, for S 3 S 2− at log B ˜ –2, for S 2 S 2− at log B ˜ 2.5, and for SS 2− at log B ˜ 7, where log B = log P – log[S(0)]. Teder [34], using a potentiometric force titration procedure obtained different values and argued that if the activity of elementary sulfur (S 8 ) was 1, then B would be constant for all polysulfide solutions if in equilibrium with S(0) and independent of σ HS − [34]. He then determined an average polysulfide of S 4.4S 2− .…”

Section: Silver Inorganic Sulfur Chemistrymentioning

confidence: 99%

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

Bell

Kramer

1999

Enviro Toxic and Chemistry

123

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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Section: Silver Inorganic Sulfur Chemistrymentioning

confidence: 99%

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

Bell

Kramer

1999

Enviro Toxic and Chemistry

123

149

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“…The detailed reaction mechanisms of PS in the presence of carbohydrates and lignin are difficult to describe due to the high complexity of PS chemistry under alkaline conditions at elevated temperatures. The best approach was already described by Teder ' s group ( Teder 1965( Teder , 1968( Teder , 1969a( Teder , 1971Ahlgren and Teder 1967 ;Hartler et al 1967 ;Gustafsson and Teder 1969 ). Instability at elevated temperatures is one of the main disadvantages of PS.…”

Section: Introductionmentioning

confidence: 97%

Stabilization, degradation, and dissolution behavior of Scots pine polysaccharides during polysulfide (K-PS) and polysulfide anthraquinone (K-PSAQ) pulping

et al. 2015

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The behavior of Scots pine (Pinus sylvestris L.) polysaccharides was studied during modified kraft pulping processes of wood meal by polysulfide (K-PS) and polysulfide anthraquinone (K-PSAQ) at the hydroxide ion concentrations of 0.50 and 1.55 M [OH -] with a high liquorto-wood (L/W) ratio of 200. The high L/W ratio was selected for avoiding diffusion phenomena and to be able to focus on the chemistry of polysaccharides. A comparison with the kraft process reference at 160 ° C revealed a substantial increase in pulp yield (6 -7% in K-PS pulping and 7.5 -10.5% in K-PSAQ pulping) mainly attributed to galactoglucomannan (GGM) stabilization. Due to the rapid delignification rate at 1.55 M [OH -] concentration, the temperature could be lowered from 160 ° C to 130 ° C without a notable prolongation of cooking time. In K-PS pulping at 130 ° C, no additional GGM stability was observed compared to 160 ° C, whereas cellulose and arabinoxylan preservation was improved. In K-PSAQ pulping, GGM preservation was also significantly improved. At 130 ° C, pulp yield increase of approximately 8% in PS pulping and more than 11% in PSAQ pulping was observed. The amount of dissolved softwood hemicelluloses in black liquor was significantly increased at the higher [OH -] level and even further in the presence of PS and AQ. Simultaneously, the formation of hydroxy acids was decreased, indicating a significant stabilization of the dissolved polysaccharide fraction parallel to the pulp polysaccharides.

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“…While the oxidation of hydrogen sulfide (H 2 S (aq) ) and bisulfide (HS − ) can lead to polysulfide formation, polysulfides are usually thought to arise from the fast equilibrium (time scale of seconds to minutes) reactions between dissolved sulfide and colloidal elemental sulfur (Fossing and Jørgensen, 1990;Kamyshny et al, 2003b). This aqueous phase equilibrium distribution of sulfur and polysulfides have been extensively studied and discussed over the past fifty years (Maronny, 1959;Cloke, 1963;Wagman et al, 1968;Teder, 1971;Giggenbach, 1972;Giggenbach, 1974;Boulegue and Michard, 1978;Klimmek et al, 1991;Schauder and Müller, 1993;Amend and Shock, 2001;Kamyshny et al, 2004Kamyshny et al, , 2007Kamyshny et al, , 2009). Boulegue and Michard (1973) first predicted an equilibrium concentration of polysulfides in the presence of hydrogen sulfide and elemental sulfur under seawater conditions.…”

Section: Introductionmentioning

confidence: 98%

Dynamics of zero-valent sulfur species including polysulfides at seep sites on intertidal sand flats (Wadden Sea, North Sea)

Kamyshny

Ferdelman

2010

Marine Chemistry

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The Equilibrium between Elementary Sulfur and Aqueous Polysulfide Solutions.

Cited by 75 publications

References 0 publications

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

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

Stabilization, degradation, and dissolution behavior of Scots pine polysaccharides during polysulfide (K-PS) and polysulfide anthraquinone (K-PSAQ) pulping

Dynamics of zero-valent sulfur species including polysulfides at seep sites on intertidal sand flats (Wadden Sea, North Sea)

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