Übergangsmetallchalkogenverbindungen. Bildung und Zerfall von Chalkogenoanionen der Übergangsmetalle in wäßriger Lösung

Müller, Achim; Glemser, Oskar; Diemann, E.; Hofmeister, Helmut

doi:10.1002/zaac.19693710109

Cited by 16 publications

(3 citation statements)

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“…Wildervanck and Jellinek described the immediate formation of MoS 3 precipitates in acidified thiomolybdate solutions for pH values of <4. Müller et al determined increasing decomposition rates of tetrathiomolybdate with decreasing pH, and Quagraine et al observed the formation of polynuclear thiomolybdates in tetrathiomolybdate solutions acidified to pH 2–3. In our case, the formation of polynuclear thiomolybdates would also result in a loss of detectable Mo species.…”

Section: Resultsmentioning

confidence: 99%

“…This can be attributed to environmentally low Mo concentrations in the nanomolar range and the lack of an analytical method, which is sensitive enough to detect nanomolar concentrations of thiomolybdates. Thiomolybdates can be determined by ultraviolet–visible (UV-Vis) spectroscopy. − However, impurities in synthesized thiomolybdate standards and overlapping spectra constitute problems for quantification. Moreover, a low sensitivity and possible interferences by other trace elements or matrix components make UV–Vis spectroscopy unsuitable for the determination of thiomolybdates in natural samples.…”

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confidence: 99%

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Ion-Pair Chromatography Coupled to Inductively Coupled Plasma–Mass Spectrometry (IPC-ICP-MS) as a Method for Thiomolybdate Speciation in Natural Waters

et al. 2015

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Molybdenum precipitates preferentially under reducing conditions; therefore, its occurrence in sediment records is used as an indicator of paleoredox conditions. Although thiomolybdates (MoO4-xSx(2-) with x = 1-4) supposedly are necessary intermediates in the process of molybdenum precipitation under anoxic conditions, there is no information about their abundance in natural environments, because of a lack of element-specific methods with sufficiently low detection limits. Here, we optimized ion-pair chromatographic separation for coupling to an inductively coupled plasma-mass spectrometry detector (IPC-ICP-MS). 2-Propanol (10%-25% gradient) replaced the previously used acetonitrile (25%-75%) as the solvent, to reduce the carbon load into the plasma. In synthetic solutions, formation of thiomolybdates was found to occur spontaneously in the presence of excess sulfide and the degree of thiolation was highest at pH 7. Excess hydroxyl led to a transformation of thiomolybdates to molybdate. Under acidic to neutral conditions, precipitation of molybdenum and hydrolysis of tetrathiomolybdate were observed. Flash-freezing was found to be suitable to stabilize tetrathiomolybdate, with <4% transformation over more than two months. High ionic strengths matrices (>2 mM) negatively affected the detection of molybdate, which eluted mainly in the dead volume, but had no negative effect on higher thiolated molybdates. Detection limits were ∼10 nM. With the newly developed IPC-ICP-MS method, thiomolybdates were found to form spontaneously in euxinic marine waters after adding a molybdate spike and occur naturally in sulfidic geothermal waters.

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Ion-Pair Chromatography Coupled to Inductively Coupled Plasma–Mass Spectrometry (IPC-ICP-MS) as a Method for Thiomolybdate Speciation in Natural Waters

et al. 2015

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“…Although the hydrolysis of tetrathiometalates has been studied previously, this report examines the effects of changes in the metal ion, pH, and cation [77][78][79][80]. The absorption of MoS 2À 4 was followed at 469 nm and the absorption of WS 2À 4 was followed at 394 nm.…”

Section: Hydrolytic Stabilitymentioning

confidence: 99%

Reversible precipitation of bovine serum albumin by metal ions and synthesis, structure and reactivity of new tetrathiometallate chelating agents

Lee

Schulman

Stiefel

et al. 2007

Journal of Inorganic Biochemistry

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Directed Syntheses of New Quaternary Niobium Oxysulfides: Crystal Structures and Properties of K4Nb2S10O and Rb4Nb2S10O Compared to K4Nb2S11

Krause

Dürichen

Näther

et al. 1999

Eur. J. Inorg. Chem.

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Übergangsmetallchalkogenverbindungen. Bildung und Zerfall von Chalkogenoanionen der Übergangsmetalle in wäßriger Lösung

Abstract: Die Stabilität von Thio‐ und Selenoanionen von Übergangsmetallen wird mit Hilfe von kinetischen Messungen an einigen Beispielen untersucht. Die Abhängigkeit der Bildung und des Zerfalls solcher Ionen vom pH‐Wert wird in einem qualitativen Schema angegeben.

Cited by 16 publications

References 17 publications

Ion-Pair Chromatography Coupled to Inductively Coupled Plasma–Mass Spectrometry (IPC-ICP-MS) as a Method for Thiomolybdate Speciation in Natural Waters

Ion-Pair Chromatography Coupled to Inductively Coupled Plasma–Mass Spectrometry (IPC-ICP-MS) as a Method for Thiomolybdate Speciation in Natural Waters

Reversible precipitation of bovine serum albumin by metal ions and synthesis, structure and reactivity of new tetrathiometallate chelating agents

Directed Syntheses of New Quaternary Niobium Oxysulfides: Crystal Structures and Properties of K4Nb2S10O and Rb4Nb2S10O Compared to K4Nb2S11

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