Quantitative 1H NMR analysis of alkaline polysulfide solutions
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Dimitris S. Argyropoulos
Abstract
A novel analytical protocol for the absolute determination of the various polysulfide species present in alkaline aqueous media was developed. The method is comprised of alkylating polysulfide ions with dimethyl sulfate, followed by quantitative proton NMR spectroscopy using 1,3,5-tributyl benzene as the internal standard. In order to arrive at a quantitative acquisition protocol, a number of variables were examined in detail for their effect on the alkylation reaction, including the presence of oxygen, the amount of dimethyl sulfate and sodium hydroxide, and the various modes of adding the alkylating reagent to the reaction mixture. Most of these variables were found to play a role in determining the quantitative reliability of the procedure. Consequently, a method is described that can be used for the efficient and reliable quantitative detection of polysulfide ions. The protocol developed could be particularly useful in promoting our understanding of the intricate and delicate chemistry of polysulfide equilibria in aqueous alkaline media.
References
Bittner, F., Hunrichs, W., Hovestadt, H., Lange, L., Splett, E. (1988) Manufacture of sodium polysulfides from the elements. German Patent DE3803243 C1 19880922.Suche in Google Scholar
Brown, A.P., Battles, J.E. (1984) The direct synthesis of sodium polysulfides from sodium and sulfur. Synth. React. Inorg. Met.-Org. Chem.14:945–951.10.1080/00945718408058275Suche in Google Scholar
Deryagina, E.N., Kozlov, I.A., Vershal, V.V., Babkin, V.A. (1996) Highly effective solvents and reagents for elemental sulfur. Zh. Obshch. Khim.66:1279–1282.Suche in Google Scholar
Giggenbach, W. (1972) Optical spectra and equilibrium distribution of polysulfide ions in aqueous solution at 20 deg. Inorg. Chem.11:1201–1207.10.1021/ic50112a009Suche in Google Scholar
Giggenbach, W.F. (1974) Equilibriums involving polysulfide ions in aqueous sulfide solutions up to 240 deg. Inorg. Chem.13:1724–1730.10.1021/ic50137a038Suche in Google Scholar
Hou, Y., Abu-Yousef, I.A., Harpp, D.N. (2000) Three sulfur atom insertion into the S−S bond, pentasulfide preparation. Tetrahedron Lett.41:7809–7812.10.1016/S0040-4039(00)01357-5Suche in Google Scholar
Ikeda, S., Satake, H., Segawa, H. (1985) Ion chromatography of sulfur species in polysulfide solution utilizing cyanolysis. Nippon Kagaku Kaishi9:1704–1709.10.1246/nikkashi.1985.1704Suche in Google Scholar
Lee, S.D. (1976) Synthesis and Chemical Investigations of Possible Singlet Diatomic Sulfur Precursors. PhD Dissertation. University of Arizona, Tucson, AZ, USA.Suche in Google Scholar
Li, J., McLeod, M., Berry, R. (1998) Improving extended delignification technology for kraft pulping. Part III. Pulp yield improvement from two-stage kraft cooking with initial polysulfide treatment. Pulp. Conf.1:407–418.Suche in Google Scholar
Licht, S. (1989) Polysulfide battery. US Patent US4828942 A 19890509.Suche in Google Scholar
Licht, S., Davis, J. (1997) Disproportionation of aqueous sulfur and polysulfide: kinetics of polysulfide decomposition. J. Phys. Chem. B101:2540–2545.10.1021/jp962661hSuche in Google Scholar
Licht, S., Hodes, G., Manassen, J. (1986) Numeral analysis of aqueous polysulfide solutions and its application to cadmium chalcogenide/polysulfide photoelectric solar cells. Inorg. Chem.25:2486–2489.10.1021/ic00235a003Suche in Google Scholar
Minami, M., Ando, T. (1994) Analysis of polysulfide in sodium polysulfide. Japanese Kokai Tokkyo Koho Patent JP06027095 A2 19940204.Suche in Google Scholar
Moore, G.R. (1986) Two-stage process for hydrogen cyanide removal from gaseous stream. US Patent US4572826 A 19860225.Suche in Google Scholar
Mott, A.W., Barany, G. (1984) The reaction of methoxycarbonyl disulfanes and trisulfanes with hydrogen sulfide: a new preparation of some symmetrical alkyl pentasulfanes. Sulfur Lett.2:137–142.Suche in Google Scholar
Munro, F., Uloth, V., Tench, L., MacLeod, M., Dorris, G. (2001) Mill scale implementation of Paprican's process for polysulfide liquor production in kraft mill causticizers. Part 2: results of pulp mill production trials. In: 87th PAPTAC Annual Meeting Book C. pp. C187–C193.Suche in Google Scholar
Pickering, T.L., Tobolsky, A.V. (1972) Inorganic and organicpolysulfides. In: Sulfur in Organic and Inorganic Chemistry,Vol. 3. Ed. Senning, A. Dekker, New York. pp. 19–38.Suche in Google Scholar
Pickering, T.L., Saunders, K.J., Tobolsky, A.V. (1967) Disproportionation of polysulfides. J. Am. Chem. Soc.89:2364–2367.10.1021/ja00986a021Suche in Google Scholar
Pickering, T.L., Saunders, K.J., Tobolsky, A.V. (1968) Cleavage and disproportionation reactions in organic polysulfides. In: The Chemistry of Sulfides. Ed. Tobolsky, A.V. Interscience, New York. pp. 61–72.Suche in Google Scholar
Rosen, E., Tegman, R. (1971) Preparative and X-ray powder diffraction study of the polysulfides Na2S2, Na2S4 and Na2S5. Acta Chem. Scan.25:3329–3336.10.3891/acta.chem.scand.25-3329Suche in Google Scholar
Schwarzenbach, G., Fischer, A. (1960) Acidity of sulfanes and the composition of aqueous polysulfide solutions. Helv. Chim. Acta43:1365.Suche in Google Scholar
Shen, G. (1999) Preparation of dimethyl sulfide. Huagong Shikan13:20–22.Suche in Google Scholar
Steudel, R. (1996) Mechanism for the formation of elementalsulfur from aqueous sulfide in chemical and microbiological desulfurization processes. Ind. Eng. Chem. Res.35:1417–1423.10.1021/ie950558tSuche in Google Scholar
Steudel, R., Holdt, G., Nagorka, R. (1986) Sulfur compounds. 104. On the autooxidation of aqueous sodium polysulfide. Z. Naturforsch. B Anorg. Org. Chem.41B:1519–1522.Suche in Google Scholar
Steudel, R., Holdt, G., Goebel, T.J. (1989) Ion-pair chromatographic separation of inorganic sulfur anions including polysulfide. J. Chromatogr.475:442–446.10.1016/S0021-9673(01)89701-6Suche in Google Scholar
Vorlander, D., Mittag, E. (1914) Triphenylthiocarbinol. Bericht46:3450–3460.Suche in Google Scholar
Wajon, J.E., Alexander, R., Kegi, R.I. (1985) Determination of trace levels of dimethyl polysulfides by capillary gas chromatography. J. Chromatogr.319:187–194.10.1016/S0021-9673(01)90553-9Suche in Google Scholar
Weddigen, G., Kleinschmager, H., Hoppe, S. (1978) Synthesis of sodium polysulfides. J. Chem. Res. Synop.3:96.Suche in Google Scholar
Williams, C.R., Britten, J.F., Harpp, D.N. (1994) Structure and chemistry of chloro(triphenylmethyl)sulfanes. J. Org. Chem.59:806–812.10.1021/jo00083a022Suche in Google Scholar
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Artikel in diesem Heft
- Obituary
- The role of non-phenolic lignin in chlorate-forming reactions during chlorine dioxide bleaching of softwood kraft pulp
- Study of the oxygen effect on mechanical pulp lignin using an improved lignin isolation method
- Quantitative 1H NMR analysis of alkaline polysulfide solutions
- A comparative study on the degradation of cotton linters induced by carbonate and hydroxyl radicals generated from peroxynitrite
- The carbonate radical as one-electron oxidant of carbohydrates in alkaline media
- Leaf-fiber lignins of Phormium varieties compared bysolid-state 13C NMR spectroscopy
- Antifungal activity of iridoid glycosides from the heartwood of Gmelina arborea
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Artikel in diesem Heft
- Obituary
- The role of non-phenolic lignin in chlorate-forming reactions during chlorine dioxide bleaching of softwood kraft pulp
- Study of the oxygen effect on mechanical pulp lignin using an improved lignin isolation method
- Quantitative 1H NMR analysis of alkaline polysulfide solutions
- A comparative study on the degradation of cotton linters induced by carbonate and hydroxyl radicals generated from peroxynitrite
- The carbonate radical as one-electron oxidant of carbohydrates in alkaline media
- Leaf-fiber lignins of Phormium varieties compared bysolid-state 13C NMR spectroscopy
- Antifungal activity of iridoid glycosides from the heartwood of Gmelina arborea
- Antioxidant activity of different components of pine species
- Dislocations in Norway spruce fibres and their effect on properties of pulp and paper
- Isolation and identification of antifungal compounds from Amboyna wood
- Biomechanical pulping of spruce wood chips with Streptomyces cyaneus CECT 3335 and handsheet characterization
- Three-dimensional visualisation of bacterial decay in individual tracheids of Pinus sylvestris
- Mass loss and moisture dynamics of Scots pine (Pinus sylvestris L.) exposed outdoors above ground in Sweden
- The influence of cation and anion structure of new quaternary ammonium salts on adsorption and leaching
- Speciation of arsenic and chromium in the leachate from chromated copper arsenate (CCA) type C treated southern pine (Pinus spp.)
- Metal chelation studies relevant to wood preservation.1. Complexation of propyl gallate with Fe2+
- Comparison of UV and confocal Raman microscopy to measure the melamine–formaldehyde resin content within cell walls of impregnated spruce wood
- Comparison of Pinus taeda L. wood property calibrations based on NIR spectra from the radial-longitudinal and radial-transverse faces of wooden strips
- Detection of failures of adhesively bonded joints using the acoustic emission method
- Effect of cross-sectional change of a board specimen on stress wave velocity determination
- Comments on the experimental methodology for determination of the hygro-mechanical properties of wood
- Properties of chemically and mechanically isolated fibres of spruce (Picea abies [L.] Karst.). Part 1: Structural and chemical characterisation
- Properties of chemically and mechanically isolated fibres of spruce (Picea abies[L.] Karst.). Part 2: Twisting phenomena
