Hydrolysis of carbon disulfide

Commercial-scale processes have been developed for the production of hydrogen sulfide from heavy fuel oils and sulfur as well as from methane, water vapor, and sulfur. The latter process can be carried out in two steps reaction of methane with sulfur to form carbon disulfide and hydrogen sulfide followed by hydrolysis of carbon disulfide (116). 

Elliott S. (1989) The effect of hydrogen peroxide on the alkaline hydrolysis of carbon disulfide. Environ. Sci. Technol. 24, 264-267. 

Microbial degradation of large amounts of carbon disulfide in soil would not be expected to be significant since this compound is a soil disinfectant and toxic to bacteria. Hydrolysis of carbon disulfide on wet soil surfaces is also unlikely (EPA 1986b). Oxidation of carbon disulfide by a Thiobacillus species isolated from soil has been observed (Plas et al. 1993). 

During the combustion of the hydrogen sulfide some of the sulfur reacts with hydrocarbons normally present to form carbon disulfide and methyl mercaptan. Carbonyl sulfide is also formed either by the partial hydrolysis of carbon disulfide and/or by the reaction of carbon dioxide and hydrogen sulfide. Some hydrogen and carbon monoxide are also formed in the Claus combustion step. 

In practice, a degree of substitution of 0.5-0.6 xanthate groups per glucose unit is sufficient to yield a soluble xanthate. Hydrolysis of carbon disulfide by alkali is an unavoidable side reaction which consumes 20-30 per cent of the carbon disulfide charged. 

Equilibrium constants for the hydrolysis of carbon disulfide according to equation 13-5 have been determined experimentally by Tetres and Wesemann (1932). Since the reaction takes place in two steps, the equilibrium constants for the two intermediate reaction.s— shown in equations 13-9 and 13-10—were determined, and the constant for the overall reaction was obtained by simple multiplication ... 

Adewuyi, Y.G. and Carmichael, G.R. Kinetics of hydrolysis and oxidation of carbon disulfide by hydrogen peroxide in alkaline medium and application to carbonyl sulfide, Environ. Sci. Technol, 21(2) 170-177, 1987. 

In a 5-1. three-necked flask mounted on a steam bath in the hood and equipped with a mechanical stirrer (Note 1) and a wide-bore condenser (Note 1) is placed 1.4 kg. (I.l I.) of carbon disulfide. Through the open neck of the flask 202 g. (1.5 moles) of acetanilide and 300 g. (2.66 moles) of chloroacetyl chloride (Note 2) are introduced. The mixture is vigorously stirred while 600 g. (4.5 moles) of aluminum chloride is added in 25-50-g. portions over a period of 20-30 minutes the neck of the flask is stoppered between additions (Note 3). After the addition of the last portion of aluminum chloride, the mixture is heated at reflux temperature for 30 minutes while stirring is continued. Heating and stirring are discontinued and the mixture is allowed to stand for 3 hours, during which time it separates into layers. The upper layer (carbon disulfide) is decanted, and the viscous red-brown louder layer is poured cautiously with stirring into about 1 kg. of finely crushed ice to which 100 ml. of concentrated hydrochloric acid has been added. After the hydrolysis of the aluminum chloride, the product crystallizes as a white solid, which is collected on a Buchner funnel and washed well with water. It is then trans-... 

The distribution of free carbon disulfide and bound carbon disulfide liberated by acid hydrolysis was investigated in the tissues of white rats after a large, single subcutaneous dose (approximately 361 mg/kg) of carbon disulfide (Bartonicek 1957, 1959). Results of these studies indicate that following absorption, free carbon disulfide is rapidly removed from the blood and tissues. Negligible blood levels were present 11 hours after the dose was administered (Bartonicek 1957, 1959). Initially, free carbon disulfide accumulated in the blood, adrenals, and brain, but levels in the organs rapidly decreased, and only very small amounts were present after 10-16 hours. 

The primary disposition of carbon disulfide in the environment is related to its use as an industrial solvent and chemical intermediate. Releases from industrial processes are almost exclusively to the atmosphere. Releases of the compound to surface waters and soils are expected to partition rapidly to the atmosphere through volatilization. Hydrolysis and biodegradation do not appear to be important processes in determining the environmental fate of carbon disulfide. It has been detected at generally low levels in ambient air, surface water, groundwater, drinking water, food products, and human milk. Concentrations in environmental media are greatest near source areas (e g., industrial point sources, oceans and marshes, volcanoes). 

Releases of carbon disulfide to the environment as a result of industrial activity are expected to be primarily to the atmosphere. Any carbon disulfide released to surface waters in effluent streams is expected to partition rapidly to the atmosphere as a result of the high ratio of vapor pressure to the solubility (Henry s law constant = 1.01 x 10"2 atm m3/mol) of the compound. Hydrolysis is not a significant removal mechanism since the evaporation half-life from a saturated solution is estimated to be 11 minutes (EPA 1978a). 

Examples of the reaction of carbon disulfide with lithium dimethylhydrazone anions derived from ketones were reported by Oliva and Delgado. In these reactions, the initial lithium dimethylhydrazono-alkanedithioate (56) was not isolated but was instead alkylated to yield an alkyl dithiolate (57 equation 26). High yields of products were obtained using various alkyl iodides. Hydrolysis of the product hydra-zone was not described. 

The finished xanthate, colored a strong red-orange by the trithiocarbonate by-product, is dissolved in dilute caustic to.form viscose (ts ically, 6-9 per cent cellulose and 5-8 per cent sodium hydroxide plus by-products of carbon disulfide hydrolysis, of viscosity 30-50 poises at 20°C). Viscose, in turn, yields regenerated cellulose fibers or film when extruded into an acid coagulating and regenerating bath. The instability of the xanthate halfester under acid conditions makes rapid regeneration possible. 

The mechanism for formation of 101 was assumed to begin by addition of the amino group to carbon disulfide to give 106, followed by nucleophilic attack of the thiolate anion at C-3 and rearrangement via 107 to 108. Hydrolysis gives the jS-oxothione 109, which reacts with a second molecule of carbon disulfide to give 110, and oxidation completes the synthesis. Scheme 29 (90H1). 

Alternative means for removal of carbonyl sulfide for gas streams iavolve hydrogenation. For example, the Beavon process for removal of sulfur compounds remaining ia Claus unit tail gases iavolves hydrolysis and hydrogenation over cobalt molybdate catalyst resulting ia the conversion of carbonyl sulfide, carbon disulfide, and other sulfur compounds to hydrogen sulfide (25). 

Further hydrolysis of the carbon disulfide and the trithiocarbonate produces hydrogen sulfide, etc (33). In another study of the decomposition of sodium ethyl xanthate [140-90-9] in flotation solutions, eleven components of breakdown were studied. The dependence of concentration of those components vs time was examined by solving a set of differential equations (34). 

The most suitable routine analytical method for the determination of alkylenebis-(dithiocarbamate) residues in fruits and vegetables is hot acid hydrolysis with stannnous chloride and concentrated hydrochloric acid, followed by determination of the evolved carbon disulfide by spectrophotometry or GC. 

The genus Thiobacillus, especially the species T. denitrificans catalyzed the oxidation reactions of hydrogen sulfide yielding soluble hydrosulfide compounds, elemental sulfur, and sulfuric acid. Carbonyl sulfide and carbon disulfide are converted to hydrogen sulfide by hydrolysis. Additionally, they are oxidized to SOx and sulfates via microbial action. The reported oxidation reactions of thiosulfate using nitrate as electron acceptor are ... 

Titanium(IV) iodide is extremely hygroscopic. It dissolves in water with decomposition, and it fumes in air owing to hydrolysis. It forms 2 1 adducts with ammonia,7 pyridine,33 and ethyl acetate.34 With excess ammonia it undergoes ammo-nolysis to give ammonobasic titanium(IV) iodides.7 Analogous aminolysis reactions occur when titanium(IV) iodide is treated with an excess of primary or secondary amine.36 Titanium(IV) iodide is sparingly soluble in petroleum ether, moderately soluble in benzene, and even more soluble in chlorinated hydrocarbons and carbon disulfide. At elevated temperatures it... 

Fundamentally, O-esters of N-hydroxy-2-thiopyridone are photo-lyzed in the presence of an excess of white phosphorus in a methylene chloride/carbon disulfide medium. On solvent removal, hydrolysis, and oxidation with hydrogen peroxide, good yields of phosphonic acids (Figure 2.10) bearing the carbon functionality of the parent acid are isolated. 

It also is obtained by the reaction of methane with sulfur vapor to produce carbon disulfide which on hydrolysis yields H2S ... 

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. 

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