Carbon disulfide reactions atmosphere

Methane reacts with sulfur (an active nonmetal element of group 6A) at high temperatures to produce carbon disulfide. The reaction is endothermic, and an activation energy of approximately 160 KJ is required. Activated alumina or clay is used as the catalyst at approximately 675°C and 2 atmospheres. The process starts by vaporizing pure sulfur, mixing it with methane, and passing the mixture over the alumina catalyst. The reaction could be represented as ... 

The formato complex 0sH(K2-02CH)(C0)(P Pr3)2 has also been prepared by treatment of the hydride-chloro compound OsHCl(CO)(P Pr3)2 with NaOMe in benzene-methanol under carbon dioxide atmosphere. Under the same conditions, the reaction with carbon disulfide affords OsH(K2-S2COMe)(CO)(P Pr3)2.67... 

Contact of the reaction mixture with atmospheric oxygen is to be avoided, but the gas flow should be kept slow enough to minimize loss of carbon disulfide. A bubbler filled with water was placed between the gas cylinder and the gas-inlet tube. 

Benzoyl chloride, [98-88-4], C6HbCOC1, mp, — 1°C bp, 197.2°C at 101.3 kPa df, 1.2070 n], 1.55369. Benzoyl chloride is a colorless liquid that fumes upon exposure to the atmosphere, has a sharp odor, and in vapor form is a strong lachrimator. It is decomposed by water and alcohol, and is miscible with ether, benzene, carbon disulfide, and oils. Benzoyl chloride may be prepared in several ways, including the partial hydrolysis of benzotrichloride, the chlorination of benzaldehyde, and from benzoic acid and phosphorus pentachloride. The most common method is the reaction of benzoic acid and benzotrichloride [98-07-7]. Since benzoic acid may be easily obtained from benzotrichloride, the latter is used as the sole raw material for large-scale production of benzoyl chloride. 

The sodium amalgam is then drained out of the flask through the bottom stopcock. The mercury may be washed with ethanol and water and reused.5 Carbon disulfide (5 mL, 73 mmol) is added rapidly to the solution under a nitrogen atmosphere, and the mixture is stirred for 20-30 seconds. Methyl iodide (5 mL, 79 mmol) is then added immediately. The mixture is stirred for ca. 5 min under a nitrogen atmosphere. Longer reaction times reduce the yield. The operations beyond this point may be done in air. The reaction mixture is then decanted into a 1000-mL round-bottomed flask and evaporated to dryness on a rotary evaporator. 

Horclois et al.239 have suggested the use of NMA as a solvent for the reaction of thiosemicarbazide with carbon disulfide to produce 2-amino-5-mercapto-l,3,4-thiadiazole. The reaction proceeds at a lower pressure (atmospheric) and at a lower temperature than the comparable reaction in water. Campbell240 has described the polymerization of acrylonitrile by BF3 in amide solvents including NMA. 

Activity Tests with Atmospheric Residue. Activity tests with Arabian Heavy atmospheric residue were conducted for the fresh and aged catalysts in a fixed-bed reactor with 100 cm catalyst bed at a temperature of 360 °C, pressure of 12 MPa, and a LHSV of 1.0 Hr"l. Such a mild reaction condition was chosen to keep from further coke build-up during the test runs. The catalysts were presulfided with carbon disulfide in light gas oil up to 300 °C. A product sample was taken 18 hours after an operation condition was settled. 

A mixture of 30 g. (0.16 mole) of a-naphthoyl chloride (p. 209) [Org. Syntheses Coll. Vol. 2, 425 (1943)], 30 g. (0.19 mole) of 8-methylnaphthalene, and 100 g. of carbon disulfide is cooled in an ice bath and 30 g. (0.22 mole) of powdered aluminum chloride is added slowly in small portions. The reaction mixture is stirred for 3 hours while protected from atmospheric moisture with a calcium chloride tube. The carbon disulfide is decanted from the red-brown residue, and the residue is decomposed by the gradual addition of ice and hydrochloric acid. The resulting mixture plus the carbon disulfide layer is steam-distilled to remove unreacted -methylnaphthalene. The aqueous layer is decanted from the residue in the steam distillation vessel, and the residue is treated with dilute sodium hydroxide solution. The solid remaining is washed with water and dried. The yield of crude 2-methyl-l,T-dinaphthyl ketone is 90%. Pure ketone, m.p. 140-141°, may be obtained by several recrystallizations from ethanol including activated carbon treatment. 

The photo-oxidation products of carbon disulfide in the laboratory were identified as carbon monoxide, carbonyl sulfide, sulfur dioxide, and a polymer that adhered to the sides of the reaction vessel (Heicklen et al. 1971). Although carbon disulfide absorbs light at wavelengths between 280 and 350 nm, dissociation does not occur under environmental conditions because of low molar absorptivity (Atkinson et al. 1978 Wood and Heicklen 1971) and direct photolysis of carbon disulfide in the atmosphere does not appear to be significant. EPA (1978a) stated that the information available indicated that carbon disulfide is relatively persistent in the atmosphere. For the atmospheric oxidation of carbon disulfide to sulfur dioxide, carbonyl sulfide, and carbon monoxide, the half-life was estimated to be about 12 days. 

The lifetime of carbon disulfide in the atmosphere has been estimated to be 12 days, too short a time to reach the stratosphere. Removal was suggested to occur by a hydroxyl radical reaction, or an oxygen atom reaction but not by dissociation (Khalil and Rasmussen 1984). 

The oily reaction products are weakly acidic. Electrometric titration of the product from 1-decene indicated about one acidic hydrogen for each two phosphorus atoms. Moreover, a barium salt is readily obtained, which is said to be a useful lubricating oil additive. The product appears to contain the tertiary phosphine structure, since treatment with carbon disulfide produces the red color characteristic of tertiary phosphines. The product is readily oxidized by the atmosphere, about three atoms of oxygen being absorbed for each two phosphorus atoms. Oxidation by nitric acid is said to give a crude mbcture of phosphonic and phosphinic acids, but only 7% of the phosphorus is oxidized to phosphoric acid, indicating that the remainder is bonded to carbon. Reactions of these materials with sulfur and with bromine have also been described (33). 

As discussed in Section 2.2, one of the major removal processes for most reduced sulfur compounds is gas phase oxidation initiated by reaction with OH or NO3 radicals. Carbon disulfide is unreactive towards NO3 [7,8] reaction with OH is the only significant chemical sink for atmospheric CS2. Early direct studies exploring the kinetics of the CS2 + OH reaction indicated CS2 was unreactive towards OH [9-12]. These experiments were conducted on millisecond timescales in the absence of O2. However, when O2 was added to the reaction mixture, a rapid reaction was observed and bimolecular rate coefficients on the order of 2 x 10 cm molec" s" were measured [13-16]. Jones etal. [14], were the first to propose a reaction mechanism involving formation of a CS2-OH adduct which could react with O2 in competition with adduct decomposition to reform reactants, reactions (1,-1) and (2) ... 

The insertion reaction of carbon disulfide is not limited to the amides of group V elements. Dialkylaminosilanes react with carbon disulfide at room temperature to give the silyldialkyldithiocarbamates 102, which can be distilled under vacuum without decomposition. However, at 100 °C and atmospheric pressure carbon disulfide is eliminated with regeneration of the starting material . 

Preparation by reaction of m-(trifluoromethyl) benzoyl fluoride with phenol in hydrofluoric acid at 100° for 6 h under 5 atmospheres (92%) [978]. - Preparation by reaction of m-(trifluoromethyl)benzoyl chloride with phenetole in the presence of aluminium chloride in carbon disulfide between 0° and 5°, then at r.t. for overnight (21%) [903]. m.p. 144-145° [903] Spectra (NA). 

Sulfides and disulfides can be produced by bacterial reactions in the marine environment. 2-Dimeth-ylthiopropionic acid is produced by algae and by the marsh grass Spartina alternifolia, and may then be metabolized in sediment slurries under anoxic conditions to dimethyl sulfide (Kiene and Taylor 1988), and by aerobic bacteria to methyl sulfide (Taylor and Gilchrist 1991). Further details are given in Chapter 11, Part 2. Methyl sulfide can also be produced by biological methylation of sulfide itself (HS ). Carbon radicals are not the initial atmospheric products from organic sulfides and disulfides, and the reactions also provide an example in which the rates of reaction with nitrate... 

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