Mercaptans compounds

Mercaptans Compounds containing sulfur which have an extremely offensive skunk-like odor. Also sometimes described as smelling like garlic or onions. Mesh count The number of threads in a linear inch of fabric/wire cloth. 

A drop in media pH may result in odor problems caused by the system s inability to treat organic sulfides and mercaptan compounds. 

The earlier entry into this new class of stabilizers was built upon a 6-aminouracil compoimd (7) formulated with some costabilizers, particularly the hydrotalcites (34,35) and lubricants. Shortly after this, another chemistry was introduced which relied on protected mercaptan compounds, called latent mer-captans of general structure (8). In this second type, a small amount of a metal kicker must be added to start the stabilizing activity of the latent mercaptan (36). The preferred metal kicker is reported to be zinc which could be used at as low as 0.04% in the PVC to be effective in the new stabilizer. Most of the stabilizer development has been for applications in soft PVC formulations however, the more recent work has focused on efficient stabilizer one-packs for rigid extrusion compoimds. 

Mercaptan Compounds resembling alcohols but having the oxygen of the hydroxyl group replaced by sulfur... 

Sometimes analyses are required for particular compounds such as sulfur, chlorine and lead, or for specific components such as mercaptans, hydrogen sulfide, ethers and alcohols. 

Of the general formula, R - S — H, where R represents an aliphatic or cyclic radical, the thiols —also known as mercaptans— are acidic in behavior owing to their S—H functional group they are corrosive and malodorous. Their concentration in crude oils is very low if not zero, but they are created from other sulfur compounds during refining operations and show up in the light cuts, as illustrated in Table 8.6. 

Mercaptans are naturally present in crude oil (Chapters 1 and 8), or they result from the decomposition of other sulfur compounds during thermai or catalytic cracking operations. 

Thio-p-cresol (p-tolyl mercaptan), p-CHjCjH SH. This compound may be similarly prepared from p-toluenesulphonyl chloride (Section IV,207). The thio-p-cresol crystallises in the steam distillate and is collected and dried m.p. 43°. The b.p. under normal pressure is 194r-195°. 

The following classes of sulphur compounds occur in Solubility Groups II, III and VII sulphonic acids and derivatives, ArSO,OR sulphinic acids and derivatives, ArSOOR mercaptans, RSH thiophenols, ArSH sulphides or thioethers, RSR disulphides, RSSR sulphoxides, RR S->0 ... 

Reactions with Alcohols, Mercaptans, and Phenols. Alcohols add readily to acetaldehyde in the presence of trace quantities of mineral acid to form acetals eg, ethanol and acetaldehyde form diethyl acetal [105-57-7] (65). Similarly, cycHc acetals are formed by reactions with glycols and other polyhydroxy compounds eg, ethylene glycol [107-21-1] and acetaldehyde give 2-methyl-1,3-dioxolane [497-26-7] (66) ... 

The physical properties of the principal constituents of natural gas are Hsted in Table 5. These gases are odorless, but for safety reasons, natural gas is odorized before distribution to provide a distinct odor to warn users of possible gas leaks in equipment. Sulfur-containing compounds such as organic mercaptans, aUphatic sulfides, and cycHc sulfur compounds are effective odorants at low concentrations and are added to natural gas at levels ranging from 4 to 24mg/m. ... 

Cost bilizers. In most cases the alkyl tin stabilizets ate particularly efficient heat stabilizers for PVC without the addition of costabilizers. Many of the traditional coadditives, such as antioxidants, epoxy compounds, and phosphites, used with the mixed metal stabilizer systems, afford only minimal benefits when used with the alkyl tin mercaptides. Mercaptans are quite effective costabilizets for some of the alkyl tin mercaptides, particularly those based on mercaptoethyl ester technology (23). Combinations of mercaptan and alkyl tin mercaptide ate currendy the most efficient stabilizers for PVC extmsion processes. The level of tin metal in the stabilizer composition can be reduced by up to 50% while maintaining equivalent performance. Figure 2 shows the two-roU mill performance of some methyl tin stabilizers in a PVC pipe formulation as a function of the tin content and the mercaptide groups at 200°C. 

Commercial Stabilizers. The performance of the antimony stabilizers is significantly enhanced by adding polyhydroxybenzene compounds, eg, catechol, to the PVC (36). In commercial practice, about 5—10% catechol is formulated with the antimony mercaptide stabilizer products. The antimony mercaptides are normally prepared by heating antimony oxide with the appropriate mercaptan, normally isooctyl thioglycolate, under conditions to remove water. 

The biochemical basis for the toxicity of mercury and mercury compounds results from its ability to form covalent bonds readily with sulfur. Prior to reaction with sulfur, however, the mercury must be metabolized to the divalent cation. When the sulfur is in the form of a sulfhydryl (— SH) group, divalent mercury replaces the hydrogen atom to form mercaptides, X—Hg— SR and Hg(SR)2, where X is an electronegative radical and R is protein (36). Sulfhydryl compounds are called mercaptans because of their ability to capture mercury. Even in low concentrations divalent mercury is capable of inactivating sulfhydryl enzymes and thus causes interference with cellular metaboHsm and function (31—34). Mercury also combines with other ligands of physiological importance such as phosphoryl, carboxyl, amide, and amine groups. It is unclear whether these latter interactions contribute to its toxicity (31,36). 

Apparently the alkoxy radical, R O , abstracts a hydrogen from the substrate, H, and the resulting radical, R" , is oxidized by Cu " (one-electron transfer) to form a carbonium ion that reacts with the carboxylate ion, RCO - The overall process is a chain reaction in which copper ion cycles between + 1 and +2 oxidation states. Suitable substrates include olefins, alcohols, mercaptans, ethers, dienes, sulfides, amines, amides, and various active methylene compounds (44). This reaction can also be used with tert-huty peroxycarbamates to introduce carbamoyloxy groups to these substrates (243). 

Since the original cmde oils contain some sulfur compounds, the resulting products and gasolines also contain sulfur compounds, including hydrogen sulfide, mercaptans, sulfides, disulfides, and thiophenes. The processes used to sweeten, ie, desulfurize, the products depend on the type and amount of the sulfur compounds present and the specifications of the finished gasoline or other stocks. 

Cross-country gas pipelines generally must odorize the normally odorless, colorless, and tasteless gas ia urban and suburban areas, as is required of gas distribution companies. Organosulfur compounds, such as mercaptans, are usually used for this purpose, and code requires that the odor must be strong enough for someone with a normal sense of smell to detect a gas leak iato air at one-fifth the lower explosive limit of gas—air mixtures. The latter is about 5%, so the odorant concentration should be about 1%, but most companies odorize more heavily than this as a safety precaution. 

The compound R X is a chain-transfer agent, with X usually H or Cl. The net effect of chain transfer is to kill a growing chain and start a new one in its place, thus shortening the chains. Mercaptan chain-transfer agents ate often used to limit molecular weight, but under appropriate conditions, almost anything in the reaction mass (solvent, dead polymer, initiator) can act as a chain-transfer agent to a certain extent. 

The close electrochemical relationship of the simple quinones, (2) and (3), with hydroquinone (1,4-benzenediol) (4) and catechol (1,2-benzenediol) (5), respectively, has proven useful in ways extending beyond their offering an attractive synthetic route. Photographic developers and dye syntheses often involve (4) or its derivatives (10). Biochemists have found much interest in the interaction of mercaptans and amino acids with various compounds related to (3). The reversible redox couple formed in many such examples and the frequendy observed quinonoid chemistry make it difficult to avoid a discussion of the aromatic reduction products of quinones (see Hydroquinone, resorcinol, and catechol). 

Sulfurization of unsaturated compounds ia the presence of hydrogen sulfide also affords polysulfides (9). It is postulated that this reaction forms the mercaptan in situ which then further reacts to form the polysulfide (see Sulfurcompounds). 

Sulfurization of unsaturated compounds and meicaptans is normally carried out at atmospheric pressure, in a mild or stainless steel, batch-reaction vessel equipped with an overhead condenser, nitrogen atmosphere, an agitator, heating media capable of 120—215°C temperatures and a scmbber (typically caustic bleach or diethanolamine) capable of handling hydrogen sulfide. If the reaction iavolves the use of H2S as a reactant or the olefin or mercaptan is a low boiling material, a stainless steel pressurized vessel is recommended. 

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