Quantitative 1H NMR analysis of alkaline polysulfide solutions

Dimitris S. Argyropoulos 1. , Yihua Hou 2. , Ramana Ganesaratnam 3. , David N. Harpp 4.  and Keiichi Koda 5.
  • 1. Department of Wood and Paper Science, North Carolina State University, Raleigh, NC 27695-8005, USA and Department of Chemistry, McGill University, Montreal, Quebec H3A 2A7, Canada
  • 2. Department of Chemistry, McGill University, Montreal, Quebec H3A 2A7, Canada
  • 3. Pulp and Paper Research Center, McGill University, Montreal, Quebec H3A 2A7, Canada
  • 4. Department of Chemistry, McGill University, Montreal, Quebec H3A 2A7, Canada
  • 5. Department of Wood and Paper Science, North Carolina State University, Raleigh, NC 27695-8005, USA and Graduate School of Agriculture, Hokkaido University, Sapporo, Hokkaido 060-8589, Japan

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.

  • Bittner, F., Hunrichs, W., Hovestadt, H., Lange, L., Splett, E. (1988) Manufacture of sodium polysulfides from the elements. German Patent DE3803243 C1 19880922.

  • 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.

    • Google Scholar
    • Export Citation
  • 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.

    • Google Scholar
    • Export Citation
  • Giggenbach, W. (1972) Optical spectra and equilibrium distribution of polysulfide ions in aqueous solution at 20 deg. Inorg. Chem. 11:1201–1207.

    • Google Scholar
    • Export Citation
  • Giggenbach, W.F. (1974) Equilibriums involving polysulfide ions in aqueous sulfide solutions up to 240 deg. Inorg. Chem. 13:1724–1730.

    • Google Scholar
    • Export Citation
  • 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.

    • Google Scholar
    • Export Citation
  • Ikeda, S., Satake, H., Segawa, H. (1985) Ion chromatography of sulfur species in polysulfide solution utilizing cyanolysis. Nippon Kagaku Kaishi 9:1704–1709.

    • Google Scholar
    • Export Citation
  • Lee, S.D. (1976) Synthesis and Chemical Investigations of Possible Singlet Diatomic Sulfur Precursors. PhD Dissertation. University of Arizona, Tucson, AZ, USA.

  • 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.

    • Google Scholar
    • Export Citation
  • Licht, S. (1989) Polysulfide battery. US Patent US4828942 A 19890509.

  • Licht, S., Davis, J. (1997) Disproportionation of aqueous sulfur and polysulfide: kinetics of polysulfide decomposition. J. Phys. Chem. B 101:2540–2545.

    • Google Scholar
    • Export Citation
  • 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.

    • Google Scholar
    • Export Citation
  • Minami, M., Ando, T. (1994) Analysis of polysulfide in sodium polysulfide. Japanese Kokai Tokkyo Koho Patent JP06027095 A2 19940204.

  • Moore, G.R. (1986) Two-stage process for hydrogen cyanide removal from gaseous stream. US Patent US4572826 A 19860225.

  • 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.

    • Google Scholar
    • Export Citation
  • 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.

  • 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.

  • Pickering, T.L., Saunders, K.J., Tobolsky, A.V. (1967) Disproportionation of polysulfides. J. Am. Chem. Soc. 89:2364–2367.

    • Google Scholar
    • Export Citation
  • 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.

  • 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.

    • Google Scholar
    • Export Citation
  • Schwarzenbach, G., Fischer, A. (1960) Acidity of sulfanes and the composition of aqueous polysulfide solutions. Helv. Chim. Acta 43:1365.

    • Google Scholar
    • Export Citation
  • Shen, G. (1999) Preparation of dimethyl sulfide. Huagong Shikan 13:20–22.

  • 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.

    • Google Scholar
    • Export Citation
  • 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.

    • Google Scholar
    • Export Citation
  • Steudel, R., Holdt, G., Goebel, T.J. (1989) Ion-pair chromatographic separation of inorganic sulfur anions including polysulfide. J. Chromatogr. 475:442–446.

    • Google Scholar
    • Export Citation
  • Vorlander, D., Mittag, E. (1914) Triphenylthiocarbinol. Bericht 46:3450–3460.

  • 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.

    • Google Scholar
    • Export Citation
  • Weddigen, G., Kleinschmager, H., Hoppe, S. (1978) Synthesis of sodium polysulfides. J. Chem. Res. Synop. 3:96.

    • Google Scholar
    • Export Citation
  • Williams, C.R., Britten, J.F., Harpp, D.N. (1994) Structure and chemistry of chloro(triphenylmethyl)sulfanes. J. Org. Chem. 59:806–812.

    • Google Scholar
    • Export Citation
Purchase article
Get instant unlimited access to the article.
$42.00
Log in
Already have access? Please log in.


or
Log in with your institution

Journal + Issues

Holzforschung is an international scholarly journal that publishes cutting-edge research on the biology, chemistry, physics and technology of wood and wood components. High quality papers about biotechnology and tree genetics are also welcome. Rated year after year as one of the top scientific journals in the category of Pulp and Paper (ISI Journal Citation Index), Holzforschung represents innovative, high quality basic and applied research.

Search