Mechanisms sulfide

Table 3.4 and Table 3.10 summarize quenching data of singlet-excited DBO by amines and sulfides. These quenchers are stronger electron donors than ethers or alcohols and therefore mainly involved in charge-transfer-induced mechanisms. Sulfides are somewhat weaker electron donors than amines, which is manifested in lower quenching rate constants, except where structural effects such as steric or stereoelectronic hindrance are involved (see below) [59],... 

Apparatus 5-1 round-bottomed, wide-necked flask with a mechanical stirrer for the preparation of CH3CEC-S-tert.C9H9 1-1 round-bottomed flask and a rubber stopper, perforated by a glass tube of 4-5 mm I.D., connected to a plastic tube, for the conversion into the allenic sulfide. The glass tube extended to 2 mm from the bottom of the flask. 

Total Sulfur and Sulfide Sulfur. Total sulfur is predominately in the form of metal sulfate, and because sulfates act as inerts, these materials have htde impact on the process. Sulfide sulfur compounds, on the other hand, react and leave the furnace as a sulfur vapor, which may deposit in the gas handling system. A possible mechanism for this is the partial reaction of SO2 to H2S, followed by... 

Retardation of the reaction rate by the addition of dimethyl sulfide is in accord with this mechanism. Borane—amine complexes and the dibromoborane—dimethyl sulfide complex react similarly (43). Dimeric diaLkylboranes initially dissociate (at rate to the monomers subsequentiy reacting with an olefin at rate (44). For highly reactive olefins > k - (recombination) and the reaction is first-order in the dimer. For slowly reacting olefins k - > and the reaction shows 0.5 order in the dimer. 

A typical example of a nonpolymeric chain-propagating radical reaction is the anti-Markovnikov addition of hydrogen sulfide to a terminal olefin. The mechanism involves alternating abstraction and addition reactions in the propagating steps ... 

The differences in the amino acid chemistry of the hide coUagen and the hair keratin are the basis of the lime-sulfide unhairing system. Hair contains the amino acid cystine. This sulfur-containing amino acid cross-links the polypeptide chains of mature hair proteins. In modem production of bovine leathers the quantity of sulfide, as Na2S or NaSH, is normally 2—4% based on the weight of the hides. The lime is essentially an unhmited supply of alkah buffered to pH 12—12.5. The sulfide breaks the polypeptide S—S cross-links by reduction. Unhairing without sulfide may take several days or weeks. The keratin can be easily hydrolyzed once there is a breakdown in the hair fiber stmcture and the hair can be removed mechanically. The coUagen hydrolysis is not affected by the presence of the sulfides (1—4,7). 

The treatments used to recover nickel from its sulfide and lateritic ores differ considerably because of the differing physical characteristics of the two ore types. The sulfide ores, in which the nickel, iron, and copper occur in a physical mixture as distinct minerals, are amenable to initial concentration by mechanical methods, eg, flotation (qv) and magnetic separation (see SEPARATION,MAGNETIC). The lateritic ores are not susceptible to these physical processes of beneficiation, and chemical means must be used to extract the nickel. The nickel concentration processes that have been developed are not as effective for the lateritic ores as for the sulfide ores (see also Metallurgy, extractive Minerals recovery and processing). 

Blends with good mechanical properties can be made from DMPPO and polymers with which DMPPO is incompatible if an appropriate additive, compatibilizing agent, or treatment is used to increase the dispersion of the two phases. Such blends include mixtures of DMPPO with nylon, polycarbonate, polyester, ABS, and poly(phenylene sulfide). 

The neat resin preparation for PPS is quite compHcated, despite the fact that the overall polymerization reaction appears to be simple. Several commercial PPS polymerization processes that feature some steps in common have been described (1,2). At least three different mechanisms have been pubUshed in an attempt to describe the basic reaction of a sodium sulfide equivalent and -dichlorobenzene these are S Ar (13,16,19), radical cation (20,21), and Buimett s (22) Sj l radical anion (23—25) mechanisms. The benzyne mechanism was ruled out (16) based on the observation that the para-substitution pattern of the monomer, -dichlorobenzene, is retained in the repeating unit of the polymer. Demonstration that the step-growth polymerization of sodium sulfide and /)-dichlorohenzene proceeds via the S Ar mechanism is fairly recent (1991) (26). Eurther complexity in the polymerization is the incorporation of comonomers that alter the polymer stmcture, thereby modifying the properties of the polymer. Additionally, post-polymerization treatments can be utilized, which modify the properties of the polymer. Preparation of the neat resin is an area of significant latitude and extreme importance for the end user. 

In general, steel having similar chemical compositions have similar mechanical and physical properties, no matter by which process they are made, unless the patterns of inclusions (oxides, siHcates, and sulfides) are very different. 

In the alcohol oxidations, the sulfonium intermediate (2, nucleophile = R2C(OH)) loses a proton and dimethyl sulfide to give the carbonyl compound (42). The most common mechanism for the decomposition of (2) is attack by a mild base to remove a proton from one of the methyl groups. Subsequent cycHc coUapse leads to the carbonyl compound and dimethyl sulfide (eq. 9) ... 

Health and Safety Factors. Carbonyl sulfide is dangerously poisonous, more so because it is practically odorless when pure. It is lethal to rats at 2900 ppm. Studies show an LD q (rat, ip) of 22.5 mg/kg. The mechanism of toxic action appears to iavolve breakdowa to hydrogea sulfide (36). It acts principally on the central nervous system with death resulting mainly from respiratory paralysis. Little is known regarding the health effects of subacute or chronic exposure to carbonyl sulfide a 400-p.g/m max level has been suggested until more data are available (37). Carbon oxysulfide has a reported inhalation toxicity in mice LD q (mouse) = 2900 ppm (37). 

NKK s Bio-SR process is another iron-based redox process which instead of chelates, uses Thiobacillusferroidans )2iQ. - 2i to regenerate the solution (9). This process absorbs hydrogen sulfide from a gas stream into a ferric sulfate solution. The solution reacts with the hydrogen sulfide to produce elemental sulfur and ferrous sulfate. The sulfur is separated via mechanical means, such as filtering. The solution is regenerated to the active ferric form by the bacteria. 

Many heavy metals are removed on activated carbon. A primary mechanism is sulfide precipitation on the carbon. 

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