Mercaptans, detection

Sulfur (detection of H2S and mercaptans) ( Doctor Test ) NF M 07-029 ASTM D 325 Sodium plumbite test (coloration of interface)... 

At one time thiols were named mercaptans Thus CH3CH2SH was called ethyl mercaptan according to this system This nomenclature was abandoned beginning with the 1965 revision of the lUPAC rules but is still sometimes encountered When one encounters a thiol for the first time especially a low molecular weight thiol its most obvious property is its foul odor Ethanethiol is added to natural gas so that leaks can be detected without special equipment—your nose is so sensitive that it can detect less than one part of ethanethiol m 10 000 000 000 parts of arr The odor of thiols weakens... 

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. 

LPG is considered to be non-toxic witli no chronic effects, but the vapour is slightly anaesthetic. In sufficiently high concentrations, resulting in oxygen deficiency, it will result in physical asphyxiation. The gases are colourless and odourless but an odorant or stenching agent (e.g. methyl mercaptan or dimethyl sulphide) is normally added to facilitate detection by smell down to approximately 0.4% by volume in air, i.e. one-fifth of the lower flammable limit. The odorant is not added for specific applications, e.g. cosmetic aerosol propellant. 

The water (moisture) content can rapidly and accurately be determined in polymers such as PBT, PA6, PA4.6 and PC via coulometric titration, with detection limits of some 20 ppm. Water produced during heating of PET was determined by Karl Fischer titration [536]. The method can be used for determining very small quantities of water (10p,g-15mg). Certified water standards are available. Karl Fischer titrations are not universal. The method is not applicable in the presence of H2S, mercaptans, sulfides or appreciable amounts of hydroperoxides, and to any compound or mixture which partially reacts under the conditions of the test, to produce water [31]. Compounds that consume or release iodine under the analysis conditions interfere with the determination. 

Odorization. Natural gas is odorized so that leaks can be detected, whereas gasoline is normally smelly. Odorization of natural gas is a prudent although not entirely effective safety measure. Hydrogen as an industrial gas or fuel cell vehicle fuel is not odorized because sulfur-containing substances (mercaptans) contaminate the catalysts of a fuel cell. 

Leek and Bagander [221] determined reduced sulfide compounds (hydrogen sulfide, methyl mercaptan, carbon disulfide, dimethyl sulfide, and dimeth-yldisulfide) in water by gas chromatography using flame detection. Detection limits ranged from 0.2 ng/1 for carbon disulfide to 0.6 ng/1 for methyl mercaptan. Hydrogen sulfide was determined at the 1 ng/1 level. 

Leek and Baagander [311] determined reduced sulfide compounds in seawater by gas chromatography using a flame ionisation detector. Substances determined include methyl mercaptan, dimethyl sulfide, hydrogen sulfide and carbon disulfide. Detection limits range from 0.2ng/l (carbon disulfide) to 0.6 ng/1 (methyl mercapton). 

In a method described by Bates and Carpenter [8] for the characterization of organosulphur compounds in the lipophilic extracts of marine sediments these workers showed that the main interference is elemental sulphur (S8). Techniques for its elimination are discussed. Saponification of the initial extract is shown to create organosulphur compounds. Activated copper removes S8 from an extract and appears neither to create nor to alter organosulphur compounds. However, mercaptans and most disulphides are removed by the copper column. The extraction efficiency of several other classes of sulphur compounds is 80-90%. Extracts are analyzed with a glass capillary gas chromatograph equipped with a flame photometric detector. Detection limit is lg S and precision 10%. 

Present formula gasolines contain approximately 300 ppm. No. 2 fuel oil contains 2,200 to 2,600 ppm by weight of sulfur. Even pipeline gas contains sulfur-containing odorants (mercaptans, disulfides, or commercial odorants) for leak detection. Metal catalysts in the fuel reformer can be susceptible to sulfur poisoning and it is very important that sulfur in the fuel reformate be removed. Some researchers have advised limiting the sulfur content of the fuel in a stream reformer to less than 0.1 ppm, but noted the limit may be higher in an autothermal... 

N2. Sulfur containing odorants (mercaptans, disulfides, or commercial odorants) are added for leak detection. Because neither fuel cells nor commercial reformer catalysts are sulfur tolerant, the sulfur must be removed. This is usually accomplished with a zinc oxide sulfur polisher and the possible use of a hydrodesulfurizer, if required. The zinc oxide polisher is able to remove the mercaptans and disulfides. However, some commercial odorants, such as Pennwalf s Pennodorant 1013 or 1063, contain THT (tetrahydrothiophene), more commonly known as thiophane, and require the addition of a hydrodesulfurizer before the zinc oxide catalyst bed. 

Isoamyl ether and -amyl ether formed In preparation of amyl alcohols from amyl chloride very slightly soluble In water used mainly as a solvent. am-al e-thar) amyl mercaptan org chem C5H11SH A colorless to light yellow liquid with a boiling range of 104-130°C soluble In alcohol used In odorant for detecting gas line leaks. am-ol mor kapitan ... 

Colorless to white granular crystals or amber-colored oil with a mercaptan-like odor. The average least detectable odor threshold concentration in water at 60 °C was 12 pg/L (Alexander et al, 1982). 

Humans are extremely sensitive to hydrogen sulfide, most likely as a danger signal. The recognition threshold lies at 0.00047 ppm (vol) (cited in Cain, 1978). Only 40 molecules of methyl mercaptan, distributed over several receptors, sufficed for detection (cited in Harborne, 1993). 

Example 2-8 Suppose the room you are in now actually contains 9.5% CH4. [You could not detect the presence of CH4 in air unless the natural gas contained a mercaptan odorizer.] If someone turned on the light switch and created a spark, what would be the temperature and pressure in the room before the windows and walls burst ... 

Butadiene is available commercially as a liquefied gas underpressure. The polymerization grade has a minimum purity of 99%, with acetylene as an impurity in the parts-per-million (ppm) range. Isobutene, 1-butene, butane and cis-l- and Zrc//7.s-2-butcnc have been detected in pure-grade butadiene (Miller, 1978). Typical specifications for butadiene are purity, > 99.5% inhibitor (/c/V-butylcatecliol). 50-150 ppm impurities (ppm max.) 1,2-butadiene, 20 propadiene, 10 total acetylenes, 20 dimers, 500 isoprene, 10 other C5 compounds, 500 sulfur, 5 peroxides (as H2O2), 5 ammonia, 5 water, 300 carbonyls, 10 nonvolatile residues, 0.05 wt% max. and oxygen in the gas phase, 0.10 vol% max. (Sun Wristers, 1992). Butadiene has been stabilized with hydroquinone, catechol and aliphatic mercaptans (lARC, 1986, 1992). 

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