Sulfide stabilization

In the search for substitutes, other considerations than just sulfide stability have to be considered. These include the possible interference of the newly introduced element with other steel porperties, the plasticity of the new sulfides, the physical alloyability of the additive and, of course, the cost effectiveness of the additive. Zirconium and titanium interfere with other properties of the steel because of the excessive stability of their nitrides. Figure 9, and carbides. Figure 10. Although considerable usage of these two elements has played a part in sulfide substitution — over 500 metric tons of nuclear zircalloy scrap were used in — it appears that their role will progressively fade away primarily because of poor low temperature impact properties of steels treated with Zr and Ti. 

To gain an insight into the sulfide stabilization, examine the solubility product constants for the sulfides and phosphates of hazardous metals listed in Table 16.4. In this table, except for barium sulfide, other sulfides as well as phosphates have very high pK p, indicating that their aqueous solubility is almost negligible. In particular, the pA sp of HgS and Ag2S is very high, and these two sulfides are insoluble in water. Therefore, when a waste stream contains one of these two, sulfide pretreatment followed by phosphate ceramic formation is an ideal way to treat the waste stream. 

Polyphenylene Sulfide Stability and Long-Term Behavior... 

Further works are required to elucidate the possible mechanism of hydrogenation over sulfided or non-sulfided stabilized Y-zeolites. 

Addition of organocuprates to cr Dimethyl sulfide stabilizes the cuprai reaction medium. ... 

Addition of organocuprates to cross-conjugated enynones leads to the dienones. Dimethyl sulfide stabilizes the cuprate adduct intermediates when it is employed as a reaction medium. ... 

The mechanism of this process has been investigated [9]. The reaction exhibits the features of electrophilic substitution electron-releasing substituents in the aromatic nucleus accelerate the metalation. Usually a-aryl complexes of palladium(ll) are not stable and cannot be isolated. However, dialkyl sulfides stabilize the complexes which can be isolated as yellow crystals [10] ... 

We now have sufficient information to provide answers to the question posed earlier in the chapter about sulfide stability in the presence of nitrate. 

Observed stability constants of metal ion-acetato complexes Calculated constant of metal ion complexes with NH3 Enthalpy of formation of sulfides Stability constant of metal ion complexes with sulfate Average molar metal concentration in soil at 10% moisture Medians of elemental composition of soils Calculated mean of the elemental content in land plants Intrinsic (van der Waals) molecular volume... 

New in this chapter are a number of mixed tellurides. The new tellurides are less sensitive towards hydrolysis than selenides which in turn are more resistant than sulfides. Stability also increases going from germanium to the higher homologues. All alkali metal derivatives are very sensitive to air and moisture. The compounds are listed in Table 6k. Methods of preparation are summarized in the following scheme. 

Samarium has a bright silver luster and is reasonably stable in air. Three crystal modifications of the metal exist, with transformations at 734 and 922oC. The metal ignites in air at about ISOoC. The sulfide has excellent high-temperature stability and good thermoelectric efficiencies up to llOOoC. 

The stability of the various cumulenic anions depends to a large extent upon the nature of the groups linked to the cumulenic system. Whereas solutions of lithiated allenic ethers and sulfides in diethyl ether or THF can be kept for a limited period at about O C, the lithiated hydrocarbons LiCH=C=CH-R are transformed into the isomeric lithium acetylides at temperatures above about -20 C, probably via HC C-C(Li )R R Lithiated 1,2,4-trienes, LiCH=C=C-C=C-, are... 

The high degree of crystallization and the thermal stability of the bond between the benzene ring and sulfur are the two properties responsible for the polymer s high melting point, thermal stability, inherent flame retardance, and good chemical resistance. There are no known solvents of poIy(phenyIene sulfide) that can function below 205°C. 

Medicine and Nutrition. A stabilized buffered suspension of selenium sulfide has been marketed for many years as Selsun Blue (Abbott Laboratories) for control of seborrheic dermatitis of the scalp. A similar sulfur or selenium sulfide shampoo containing a metallic cation complex has been prepared (122). Topical appHcation of selenium sulfide controls dermatitis, pmritis, and mange iu dogs (see Cosmetics Veterinarydrugs). 

Thermal Stability. Dimethyl sulfoxide decomposes slowly at 189°C to a mixture of products that includes methanethiol, formaldehyde, water, bis(methylthio)methane, dimethyl disulfide, dimethyl sulfone, and dimethyl sulfide. The decomposition is accelerated by acids, glycols, or amides (30). This product mixture suggests a sequence in which DMSO initially undergoes a Pummerer reaction to give (methylthio)methano1, which is labile and reacts according to equations 1—3. Disproportionation (eq. 4) also occurs to a small extent ... 

Unlike other stabilizers, tin mercaptide, or the mercaptan that is formed after the HCl reacts with the mercaptide, can react with the allyhc chlorine to produce a sulfide (47), thus eliminating the labile chlorine groups and stopping the unzipping. 

Aqueous sodium thiosulfate solutions ate neutral. Under neutral or slightly acidic conditions, decomposition produces sulfite and sulfur. In the presence of air, alkaline solutions decompose to sulfate and sulfide. Dilute solutions can be stabilized by small amounts of sodium sulfite, sodium carbonate, or caustic, and by storage at low temperatures away from air and light. Oxidation is inhibited by Hgl2 (10 Ppm) amyl alcohol (1%), chloroform (0.1%), borax (0.05%), or sodium benzoate (0.1%). 

Antimony tris(isooctylthioglycolate) has found use in pipe formulations at low levels. Its disadvantage is that it cross-stains with sulfide-based tin stabilizers (122). Barium—zinc stabilizers have found use in plasticized compounds, replacing barium—cadmium stabilizers. These are used in mol dings, profiles, and wire coatings. Cadmium use has decreased because of environmental concerns surrounding certain heavy metals. 

Ethers, esters, amides and imidazolidines containing an epithio group are said to be effective in enhancing the antiwear and extreme pressure peiformance of lubricants. Other uses of thiiranes are as follows fuel gas odorant (2-methylthiirane), improvement of antistatic and wetting properties of fibers and films [poly(ethyleneglycol) ethers of 2-hydroxymethyl thiirane], inhibition of alkene metathesis (2-methylthiirane), stabilizers for poly(thiirane) (halogen adducts of thiiranes), enhancement of respiration of tobacco leaves (thiirane), tobacco additives to reduce nicotine and to reduce phenol levels in smoke [2-(methoxymethyl)thiirane], stabilizers for trichloroethylene and 1,1,1-trichloroethane (2-methylthiirane, 2-hydroxymethylthiirane) and stabilizers for organic compounds (0,0-dialkyldithiophosphate esters of 2-mercaptomethylthiirane). The product of the reaction of aniline with thiirane is reported to be useful in the flotation of zinc sulfide. 

Chemically stabilized steels, such as Type 304L have been successfully used in a sulfidic corrodent environment but actual installation tests have not been consistent. 

The influence of Zn-deposition on Cu(lll) surfaces on methanol synthesis by hydrogenation of CO2 shows that Zn creates sites stabilizing the formate intermediate and thus promotes the hydrogenation process [2.44]. Further publications deal with methane oxidation by various layered rock-salt-type oxides [2.45], poisoning of vana-dia in VOx/Ti02 by K2O, leading to lower reduction capability of the vanadia, because of the formation of [2.46], and interaction of SO2 with Cu, CU2O, and CuO to show the temperature-dependence of SO2 absorption or sulfide formation [2.47]. 

Applicability Most hazardous waste slurried in water can be mixed directly with cement, and the suspended solids will be incorporated into the rigid matrices of the hardened concrete. This process is especially effective for waste with high levels of toxic metals since at the pH of the cement mixture, most multivalent cations are converted into insoluble hydroxides or carbonates. Metal ions also may be incorporated into the crystalline structure of the cement minerals that form. Materials in the waste (such as sulfides, asbestos, latex and solid plastic wastes) may actually increase the strength and stability of the waste concrete. It is also effective for high-volume, low-toxic, radioactive wastes. 

Chemical Reactivity - Reactivity with Water. Reacts with liquid water or atmospheric moisture to liberate toxic hydrogen sulfide gas Reactivity with Common Materials No reaction Stability During Transport Can be ignited by friction Neutralizing Agents for Acids and Caustics Not pertinent Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

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