Polysulfide solution

The dinuclear ion Mo2(S2) g (F - prepared from the reaction of molybdate and polysulfide solution (13) is a usehil starting material for the preparation of dinuclear sulfur complexes. These disulfide ligands are reactive toward replacement or reduction to give complexes containing the Mo2S " 4 core (Fig. 3f). 

The polysulfanes were at one time made by fusing cmde Na2S.9H20 with various amounts of sulfur and pouring the resulting polysulfide solution into an excess of dilute hydrochloric acid at — 10°C. The resulting cmde yellow oil is a mixture mainly of H2S (n = 4-7). Polysulfanes can now also be readily prepared by a variety of other reactions, e.g. ... 

Add polysulfide solution to neutralize the cyanide. Air can be injected into the main column overhead to make polysulfide. 

Monitor Ammonia Chloride in the Overhead Water, keep Ammonia Sulfide <5,000 ppm Use Steam Condensate as Water Wash at a Rate of 1-2 gpm/1000 bbl of Fresh Feed Use Ammonium Polysulfide Solution (especially if HCN > 25 ppm) to 10-20 ppm Residual HCN Make sure the Wash Water is injected uniformly into the Gas Stream Use Feed Forward Water Wash Scheme instead of Reverse Cascade ... 

In polysulfide solutions there exist chainlike dianions with practically arbitrary chain lengths n. Berghof, 8ommerfeld, and Cederbaum have investigated the onset of stabihty in the 8 (n=2-8) series of dianions based on 8CF calculations with the DZPD basis set [89]. The isolated chainlike 8 isomers were found to exhibit twisted structures, and the onset of electronic stabihty (with respect to electron auto detachment) was predicted to occur at 71=7. Branched isomers were found to be electronically more stable than the... 

Since the chain-lengths of the molecules present in crude sulfane oil is different from the chain-length of the anions in the original sodium polysulfide solution one has to conclude that in addition to the reaction at Eq. (4) the reactions at Eqs. (5) and (6) also take place during the preparation by protonation of the polysulfide anions. 

Hamilton critically reviewed the literature on aqueous polysulfide solutions and proposed a speciation model of his own [13]. 

If Sg is dissolved in a polysulfide solution the reactions according to Eqs. (24) and (25) are faster than the reactions at Eqs. (22) and (23) since disulfide (and also trisulfide) anions are evidently stronger nucleophiles than HS ... 

Consequently, sulfur dissolves in polysulfide solutions much faster than in equimolar monosulfide solutions [73]. In this context it is of interest that the analogous decaselenium dianion Scio has been prepared and structurally characterized in solid [PPN]2Seio [74]. This anion is however bi-cyclic. 

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. 

Hamilton [13] assumed the presence of all ions with n ranging from 1 to 8 in aqueous polysulfide solutions which is by far the most acceptable model but since there is insufficient experimental data available this model cannot be worked out quantitatively without additional assumptions. The general idea is that those species are most abundant which are close to the average composition of the particular solution, e.g., 84 and 85 for a solution of composition Na284.5, and that the larger and smaller ions are symmetrically less abundant. Equilibrium constants for the various reactions... 

The chemistry of elemental sulfur and sulfur-rich molecules including polysulfides in liquid ammonia [82] and in primary as well as secondary amines [83] is complex because of the possible formation of sulfur-nitrogen compounds. Therefore, polysulfide solutions in these solvents will not be discussed here. Inert solvents which have often been used are dimethylfor-mamide (DMF) [84-86], tetrahydrofuran (THF) [87], dimethylsulfoxide (DMSO) [87], and hexamethylphosphoric triamide (HMPA) [86, 88]. 

However, some interconversion reactions take place simultaneously and therefore the composition of the sulfane mixtime is not a mirror image of the composition of the polysulfide solution [103]. The sulfane mixture forms a yellow oily hydrophobic liquid which precipitates from the aqueous phase. At 20 °C it decomposes more or less rapidly to H2S and Sg. 

Aqueous polysulfide solutions are thermodynamically unstable with respect to thiosulfate and sulfide. Therefore, on heating to 150-240 °C under anaerobic conditions polysulfide ions disproportionate reversibly [72, 80, 104], e.g. ... 

The red tetrasulfide radical anion 84 has been proposed as a constituent of sulfur-doped alkali hahdes, of alkah polysulfide solutions in DMF [84, 86], HMPA [89] and acetone [136] and as a product of the electrochemical reduction of 8s in DM80 or DMF [12]. However, in all these cases no convincing proof for the molecular composition of the species observed by either E8R, Raman, infrared or UV-Vis spectroscopy has been provided. The problem is that the red species is formed only in sulfur-rich solutions where long-chain polysulfide dianions are present also and these are of orange to red color, too (for a description of this dilemma, see [89]). Furthermore, the presence of the orange radical anion 8e (see below) cannot be excluded in such systems. 

More recently, 84 may have been identified by ESR spectroscopy of solutions of Li2S ( >6) in DMF at 303 K. The lithium polysulfide was prepared from the elements in liquid ammonia. These polysulfide solutions also contain the trisulfide radical anion ( 2.0290) but at high sulfur contents a second radical at g=2.031 (Lorentzian lineshape) was formed which was assumed to be 84 generated by dissociation of octasulfide dianions see Eq. (32) [137],... 

Licht et al. [17] developed a method of numerical analysis to describe the above-quoted equilibria of the 11 participating species (including alkali metal cations) in aqueous polysulfide solution, upon simple input to the algorithm of the temperature and initial concentration of sulfur, alkali metal hydroxide, and alkali metal hydrosulfide in solution. The equilibria constants were evaluated by compensation of the polysulfide absorption spectrum for the effects of H8 absorption and by computer analysis of the resultant spectra. Results from these calculations were used to demonstrate that the electrolyte is unstable, and that gradual degradation of polysulfide-based PECs (in the long term) can be attributed to this factor (Chap. 5). 

Differences in behavior between polycrystalline and single-crystal CdSe electrodes in polysulfide PEC involving the short- and long-term changes in photovoltage and photocurrents have been discussed by Cahen et al. [88], on the basis of XPS studies, which verified the occurrence of S/Se substitution in these electrodes when immersed in polysulfide solution, especially under illumination. The presence of a thin (several nanometers) layer of CdS on top of the CdSe was shown to influence... 

Fig. 5.5 SEM surface view and cross section of an electrodeposited, ca. 1 p.m thick, CdSe/li film subjected to accelerated photocorrosion by the apphcation of -0.1 V vs. Pt bias in polysulfide solution under a focused, high-power (1 W cm ) solar illumination for 30 min. The coherence of the as-deposited film morphology is evident. The authors emphasize that, even in this situation, the liquid junction nature prevents the flow of high leakage currents during the process (as it might be the case with a solid junction). (Reprinted from [99], Copyright 2009, with permission from Elsevier)...

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