Sulfur and Sodium Polysulfides

Nicholson, N.D., Demott, D.S., and Hutchings, R. (1988) Proceedings of the International Power Sources Symposium, Paper 39. 

Coetzer, J. and Sudworth, ].L. (1996) Proceedings of the 13th International Electric Vehicle Symposium, Vol. I, p. 637. 

and Sudworth, J.L. (1993) Elektrische Strajienfahrzeuge im Stadtverkehr der Zukunfi, B163, 125. 

Sudworth, A.R. and Tilley, J.L. (eds) (1985) The Sodium Sulfur Battery, Chapman and Hall, London. 

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The main criteria for the selection of the current collector material in a central sulfur cell or for the cell case material in a central sodium cell are corrosion resistance to sulfur and sodium polysulfides, good electrical conductivity, and low costs. This cost argument has led to coated materials which have been compared with nickel—chromium alloys (Inconel 600). 

The manufacture of sulfur dyes involves sulfurisation processes, the chemistry of which remains rather mysterious and may arguably be considered still to be in the realms of alchemy The processes involve heating elemental sulfur or sodium polysulfide, or both, with aromatic amines, phenols or aminophenols. These reactions may be carried out either as a dry bake process at temperatures between 180 and 350 °C or in solvents such as water or aliphatic alcohols at reflux or at even higher temperatures under pressure. C. I. Sulphur Black 1, for example, is prepared by heating 2,4-dinitrophenol with sodium polysulfide. 

The phase Na2Sx is sodium polysulfide, a material with a sulfur content of between 3 and 5. The anode reaction takes place at the liquid sodium - (3"-alununa interface. Here sodium atoms lose an electron and the Na+ ions formed enter the conduction planes in the electrolyte. The cathode reaction, which occurs at the interface between the (3"-alumina and the liquid sulfur forms sodium polysulfides. Despite the desirable properties of the cell, technical and economic considerations have acted so as to curtail large-scale commercial production. 

Initially, sulfur dyes were water-insoluble, macromolecular, colored compounds formed by treating aromatic amines and aminophenols with sulfur and/or sodium polysulfide. R. Vidal developed these dyes in 1893 but they only became attractive for leather with the introduction of water-solubilizing groups. Today, the sulfur dyes can be divided into three classes conventional water-insoluble, leuco, and solubilized sulfur dyes. Most sulfur dyes are synthesized by condensation of aromatic amines with sulfur or sodium polysulfide in the so-called bake process, or else in water or under pressure as a solvent-reflux reaction. 

What makes the sodium-sulfur cell possible is a remarkable property of a compound called beta-alumina, which has the composition NaAlnOiy. Beta-alumina allows sodium ions to migrate through its structure very easily, but it blocks the passage of polysulfide ions. Therefore, it can function as a semipermeable medium like the membranes used in osmosis (see Section 11.5). Such an ion-conducting solid electrolyte is essential to prevent direct chemical reaction between sulfur and sodium. The lithium-sulfur battery operates on similar principles, and other solid electrolytes such as calcium fluoride, which permits ionic transport of fluoride ion, may find use in cells based on those elements. 

Thiokol A, Eihanite, Perdu ren. The first commercial poly-sulfide polymer, prepd from ethylene dichloride and sodium polysulfide. Sulfur content 84% d about 1.6. Mixes with natural rubber. Cured polymer retains unpleasant odor irritating fumes evolve during manuf. Stable to the usual organic solvents and dil mineral acids. Unstable to alkalies and oxidizing substances. Of low tensile strength and abrasion resistance. Not recommended where tropic or arctic climates prevail,... 

Thiokol FA Prepd from ethylene dichloride, dichlorodi-ethy] formal and sodium polysulfide Sulfur content 47% d ]. 34. No odor. Excellent solvent resistant characteristics but not as good as Thiokol A. Low temperature flexibility... 

It has been shown that modification of the distribution of species in aqueous polysulfide solution can be correlated to variations in transparency, conductivity, activity, and cadmium chalcogenide photoelectrochemistry. Specifically, the separate effects of hydroxide and pH modification [42], sulfur [43] and sulfide [44], and cation [45, 46] were investigated in terms of spedation and photoelectrochemical phenomena. Previously cadmium chalcogenide polysulfide PECs had generally employed electrolytes composed 1 molar in sodium sulfide, sulfur and sodium hydroxide and resulted in solar conversion efficiencies of approximately 7% [31-33]. However, added hydroxide is to be minimized in these cells, cesium is the... 

To produce viscose silk (rayon), the next stage is spinning under 3-5 bar pressure into what is known as a Muller bath, which consists of 7-12% H2SO4, 16-23% Na2S04, and 1-6% Zn-Mg-NH4-sulfate. Here, two events occur simultaneously coagulation of the cellulose xanthate and hydrolytic decomposition to cellulose with the reformation of CS2. As by-products, H2S and COS are found in the exhaust air and elementary sulfur (as sodium polysulfides) in the bath and on the fibers. Sodium sulfate should decrease dissociation and thus lessen the osmotic pressure drop of the bath with its high electrolyte content relative to the fiber gel, which is low in electrolytes. 

Both the m- and -phenylenediamines are used to manufacture sulfur dyes, either by refluxing in aqueous sodium polysulfide, or heating with elementary sulfur at 330°C to give the leuco form of the dye. These dyes are polymeric, high molecular weight compounds, and soluble in base. The color is developed by oxidation on the fabric. 2,4-Toluenediamine and sulfur give Sulfur Orange 1 (14). 

The decomposition of dithionite in aqueous solution is accelerated by thiosulfate, polysulfide, and acids. The addition of mineral acid to a dithionite solution produces first a red color which turns yellow on standing subsequentiy, sulfur precipitates and evolution of sulfur dioxide takes place (346). Sodium dithionite is stabilized by sodium polyphosphate, sodium carbonate, and sodium salts of organic acids (347). 

The process of sulfurization is usually carried out by a sulfur bake, in which the dry organic starting material is heated with sulfur between 160 and 320°C a polysulfide bake, which includes sodium sulfide a polysulfide melt, in which aqueous sodium polysulfide and the organic starting material are heated under reflux or under pressure in a closed vessel or a solvent melt, in which butanol, CeUosolve, or dioxitol are used alone or together with water. 

Sodium thiosulfate is a by-product of the manufacture of Sulfur Black and other sulfur dyes (qv), where organic nitro compounds are treated with a solution of sodium polysulfide to give thiosulfate. The dyes ate insoluble and ate recovered by fUtration. The fUtrate is treated with activated carbon and filteted to obtain a sodium thiosulfate solution. After concentration and crystallization, the final product assays ca 96% Na2S202 5H20 (34) (see Dyes AND... 

Both batch and continuous processes employ excess sulfur and operate at 85—110°C. Trace amounts of polysulftdes produce a yellow color which iadicates that all the ammonium sulfite has been consumed. Ammonium bisulfite is added to convert the last polysulfide to thiosulfate and the excess ammonia to ammonium sulfite. Concentrations of at least 70% (NH 2S2 3 obtained without evaporation. Excess sulfur is removed by filtration and color is improved with activated carbon treatment or sodium siUcate (66). Upon cooling the aqueous concentrated solution, ammonium thiosulfate crystallines. 

Both sodium sulfide and the bisulfide are used in the flotation process for copper minerals and as a depilatory for animal liides (see Copper Copper ALLOYS Leather). Also, sodium polysulfide can be produced from Na2S, and elemental sulfur can be produced if H2S is generated as an intemiediate. 

In the sodium—sulfur storage battery above 300°C, the overall chemical reaction occurs between molten sodium metal and sulfur to form sodium polysulfide. The cell voltage is related to the activity of the sodium ( Aia) sulfide relative to its activity in the metal. 

Sulfur dyes are used for dyeing ceUulosic fibers. They are insoluble in water and are reduced to the water-soluble leuco form for appHcation to the substrate by using sodium sulfide solution. The sulfur dye proper is then formed within the fiber pores by atmospheric oxidation (5). Sulfur dyes constitute an important class of dye for producing cost-effective tertiary shades, especially black, on ceUulosic fibers. One of the most important dyes is Cl Sulfur Black 1 [1326-82-5] (Cl 53185), prepared by heating 2,4-dinitrophenol with sodium polysulfide. 

In the Na/S system the sulfur can react with sodium yielding various reaction products, i.e. sodium polysulfides with a composition ranging from Na2S to Na2S5. Because of the violent chemical reaction between sodium and sulfur, the two reactants have to be separated by a solid electrolyte which must be a sodium-ion conductor. / " -Alumina is used at present as the electrolyte material because of its high sodium-ion conductivity. 

Polysulfides are the key reactants in the high-density sodium-sulfur and Hthium-sulfur batteries [4] which are based on the following reversible redox reaction taking place in the polysulfide melt ... 

The composition of sodium polysulfide solutions saturated with sulfur of zero oxidation number (S°) has also been studied at 25 and 80 °C (solutions in contact with elemental sulfur) [76]. In this case the ratio 8° 8 per polysulfide ion increases with increasing alkahnity. The maximum average number of sulfur atoms per polysulfide molecule was obtained as 5.4 at 25 °C and 6.0 at 80 °C and pH values of >12. Equilibrium constants for reactions as in Eqs. (26) and (27) have been derived assuming various models with differing numbers of polysulfide ions present. 

Ionic polysulfides dissolve in DMF, DMSO, and HMPA to give air-sensitive colored solutions. Chivers and Drummond [88] were the first to identify the blue 83 radical anion as the species responsible for the characteristic absorption at 620 nm of solutions of alkali polysulfides in HMPA and similar systems while numerous previous authors had proposed other anions or even neutral sulfur molecules (for a survey of these publications, see [88]). The blue radical anion is evidently formed by reactions according to Eqs. (5)-(8) since the composition of the dissolved sodium polysulfide could be varied between Na2S3 and NaaS with little impact on the visible absorption spectrum. On cooling the color of these solutions changes via green to yellow due to dimerization of the radicals which have been detected by magnetic measurements, ESR, UV-Vis, infrared and resonance Raman spectra [84, 86, 88, 89] see later. 

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