Hydrogen sulfide mixtures

SolubiHty of carbon dioxide in ethanolamines is affected by temperature, amine solution strength, and carbon dioxide partial pressure. Information on the performance of amines is available in the Hterature and from amine manufacturers. Values for the solubiHty of carbon dioxide and hydrogen sulfide mixtures in monoethanolamine and for the solubiHty of carbon dioxide in diethanolamine are given (36,37). SolubiHty of carbon dioxide in monoethanolamine is provided (38). The effects of catalysts have been studied to improve the activity of amines and provide absorption data for carbon dioxide in both mono- and diethanolamine solutions with and without sodium arsenite as a catalyst (39). Absorption kinetics over a range of contact times for carbon dioxide in monoethanolamine have also been investigated (40). 

Figure 6.40 Methane + carbon dioxide + hydrogen sulfide mixture (Lyy-H-V) data.

Sobocinski, D.P. and F.Kurata. 1959. Heterogeneous phase equilibria of the hydrogen sulfide-carbon dioxide system. AlChE ). 5 545-551. Stouffer, C.E., Kellerman, S.J., Hall, K.R., Holste, J.C., Gammon, B.E., Marsh, K.N. 2001. Densities of carbon dioxide + hydrogen sulfide mixtures from 220 K to 450 K at pressures up to 25 MPa. /. of Chem. Eng. Data 46 1309-18. 

Hydrogen/hydrogen sulfide mixtures or sulfur vapor of a highly reducing nature... 

Nickel sulfide, NiS, can be prepared by the fusion of nickel powder with molten sulfur or by precipitation usiag hydrogen sulfide treatment of a buffered solution of a nickel(II) salt. The behavior of nickel sulfides ia the pure state and ia mixtures with other sulfides is of iaterest ia the recovery of nickel from ores, ia the high temperature sulfide corrosion of nickel alloys, and ia the behavior of nickel-containing catalysts. 

The hydrolysis of phosphoms sulfides has been studied quantitatively. A number of products are formed (Table 6). Whereas phosphoms(V) sulfide reacts slowly with cold water, the reaction is more rapid upon heating, producing mainly hydrogen sulfide and orthophosphoric acid, H2PO4. At high pH, P4S Q hydroly2es to a mixture of products containing thiophosphates and sulfides. 

Hydrogen Sulfide andMercaptans. Hydrogen sulfide and propylene oxide react to produce l-mercapto-2-propanol and bis(2-hydroxypropyl) sulfide (69,70). Reaction of the epoxide with mercaptans yields 1-aLkylthio- or l-arylthio-2-propanol when basic catalysis is used (71). Acid catalysts produce a mixture of primary and secondary hydroxy products, but ia low yield (72). Suitable catalysts iaclude sodium hydroxide, sodium salts of the mercaptan, tetraaLkylammonium hydroxide, acidic 2eohtes, and sodium salts of an alkoxylated alcohol or mercaptan (26,69,70,73,74). 

Fluorinated and Ghlorfluorinated Sulfonic Acids. The synthesis of chlorinated and fluorinated sulfonic acids has been extensively reviewed (91,92). The Hterature discusses the reaction of dialkyl sulfides and disulfides, sulfoxides and sulfones, alkanesulfonyl haHdes, alkanesulfonic acids and alkanethiols with oxygen, hydrogen chloride, hydrogen fluoride, and oxygen—chloride—hydrogen fluoride mixtures over metal haHde catalysts, such as... 

Certain of the above reactions are of practical importance. The oxidation of hydrogen sulfide in a flame is one means for producing the sulfur dioxide required for a sulfuric acid plant. Oxidation of hydrogen sulfide by sulfur dioxide is the basis of the Claus process for sulfur recovery. The Claus reaction can also take place under mil der conditions in the presence of water, which catalyzes the reaction. However, the oxidation of hydrogen sulfide by sulfur dioxide in water is a complex process leading to the formation of sulfur and polythionic acids, the mixture known as Wackenroeder s Hquid (105). 

Manufacture. Small cylinders of hydrogen sulfide are readily available for laboratory purposes, but the gas can also be easily synthesized by action of dilute sulfuric or hydrochloric acid on iron sulfide, calcium sulfide [20548-54-3], zinc sulfide [1314-98-3], or sodium hydrosulfide [16721 -80-5]. The reaction usually is mn in a Kipp generator, which regulates the addition of the acid to maintain a steady hydrogen sulfide pressure. Small laboratory quantities of hydrogen sulfide can be easily formed by heating at 280—320°C a mixture of sulfur and a hydrogen-rich, nonvolatile aUphatic substance, eg, paraffin. Gas evolution proceeds more smoothly if asbestos or diatomaceous earth is also present. 

Hydrogen sulfide can react with S2CI2 to produce, depending on conditions, a mixture of sulfanes ( 28 where a > 1) or dichlorosulfanes (S Cl2 where x > 2). These compounds tend to be unstable at ambient temperatures. 

The equiHbrium constant is 0.013 at 18°C. Sulfur dichloride reacts violently with water, forming hydrogen chloride, sulfur dioxide, hydrogen sulfide, sulfur, and a mixture of thionic acids. 

When the Claus reaction is carried out in aqueous solution, the chemistry is complex and involves polythionic acid intermediates (105,211). A modification of the Claus process (by Shell) uses hydrogen or a mixture of hydrogen and carbon monoxide to reduce sulfur dioxide, carbonyl sulfide, carbon disulfide, and sulfur mixtures that occur in Claus process off-gases to hydrogen sulfide over a cobalt molybdate catalyst at ca 300°C (230). 

Chemical Properties. Ammonium thiocyanate rearranges upon heating to an equiHbrium mixture with thiourea 30.3 wt % thiourea at 150°C, 25.3 wt % thiourea at 180°C (373,375). At 190—200°C, dry ammonium thiocyanate decomposes to hydrogen sulfide, ammonia, and carbon disulfide, leaving guanidine thiocyanate [56960-89-5] as a residue. Aqueous solutions of ammonium thiocyanate are weakly acidic a 5 wt % solution has a pH of 4—6. 

In a typical batch operation, carbon disulfide is added to four molar equivalents of 25—30 wt % aqueous ammonia in a stirred vessel, which is kept closed for the first one to two hours. The reaction is moderately exothermic and requires cooling. After two to three hours, when substantially all of the disulfide has reacted, the reaction mixture is heated to decompose dithiocarbamate and trithiocarbonate and vented to an absorption system to collect ammonia, hydrogen sulfide, and any unreacted carbon disulfide. 

Benzamidomethyl-A -methylcysteine has been prepared as a crystalline derivative (H0CH2NHC0C6H 5, anhydr. CF3CO2H, 25°, 45 min, 88% yield as the tri-fluoroacetate salt) and cleaved (100% yield) by treatment with mercury(II) acetate (pH 4, 25°, 1 h) followed by hydrogen sulfide. Attempted preparation of S-acetamidomethyl-N-methylcysteine resulted in noncrystalline material, shown by TLC to be a mixture. ... 

In a copper or iron kettle of 4-I. capacity is placed a solution of 200 g. of d-tartaric acid and 700 g. of sodium hydroxide in 1400 cc. of water. A 12-I. flask through which cold water is run is placed in the mouth of the kettle in order to prevent loss of water vapor, and the mixture is boiled gently over an open flame for four hours. The solution is now transferred to a 12-I. flask or crock and partially neutralized with 1400 cc. of commercial hydrochloric acid (density 1.19). To the still alkaline solution is now added just enough sodium sulfide to precipitate all the iron or copper which has been dissolved from the kettle (Note i). The filtered solution is then just acidified with hydrochloric acid, boiled to expel all hydrogen sulfide, and made very faintly alkaline to phenolphthalein with sodium hydroxide solution. To the hot solution is then added a concentrated solution of 300 g. of anhydrous calcium chloride which causes an immediate precipitation of calcium tff-tartrate and mesotartrate. 

B. Aminolhymol.—The crude, wet nitrosothymol so obtained is worked up with a mixture of 900 cc. of 28 per cent ammonia water (sp. g. 0.90) and 1600 cc. of water the brown solution is filtered free of a little resinous matter, and hydrogen sulfide is passed into it. The brown color disappears and a white precipitate of aminothymol forms. The passage of hydrogen sulfide is continued for thirty minutes longer (Note 3), when the base is filtered and washed well with cold water, contact with air being avoided as far as possible (Note 4). 

For example, carbon dioxide from air or ethene nitrogen oxides from nitrogen methanol from diethyl ether. In general, carbon dioxide, carbon monoxide, ammonia, hydrogen sulfide, mercaptans, ethane, ethene, acetylene (ethyne), propane and propylene are readily removed at 25°. In mixtures of gases, the more polar ones are preferentially adsorbed). 

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