Sulfur dioxide chemistry

The application of the solvent system concept to liquid sulfur dioxide chemistry stimulated the elucidation of reactions such as those of aluminum sulfite. However, there is no direct evidence at all for the formation of S02+ in solutions of thionyl halides. In fact, there is evidence to the contrary. When solutions of thionyl bromide or thionyl chloride are prepared in 3JS-labeled (S ) sulfur dioxide, almost no exchange takes place. The half-life for the exchange is about two years or more. If ionization took place ... 

A clumsy, Stone-Age chemist would have discovered this reaction by accidentally dropping sulfur into a fire. The surprising result was that this yellow dirt burned with an alluring blue flame, producing a pungent odor (sulfur dioxide). Chemistry is the accidental science, as there are many more fortuitous discoveries as compared to other sciences. The most famous chemists are often the luckiest ones. 

Modem chrome-tanning methods are weU controUed and employ an extensive knowledge of the chemistry of the system. The most common chromium-tanning material used is basic chromium sulfate [12336-95-7] Cr(0H)S04, made by the reduction of sodium bichromate with sulfur dioxide or by sulfuric acid and a sugar. 

Sulfochlorination of Paraffins. The sulfonation of paraffins using a mixture of sulfur dioxide and chlorine in the presence of light has been around since the 1930s and is known as the Reed reaction (123). This process is made possible by the use of free-radical chemistry and has had limited use in the United States. Other countries have had active research into process optimization (124,125). 

Chemica.1 Properties. Reviews of carbonyl sulfide chemistry are available (18,23,24). Carbonyl sulfide is a stable compound and can be stored under pressure ia steel cylinders as compressed gas ia equiUbrium with Hquid. At ca 600°C carbonyl sulfide disproportionates to carbon dioxide and carbon disulfide at ca 900°C it dissociates to carbon monoxide and sulfur. It bums with a blue flame to carbon dioxide and sulfur dioxide. Carbonyl sulfide reacts... 

Chemical Properties. The chemistry of the sulfur chlorides has been reviewed (141,142). Sulfur monochloride is stable at ambient temperature but undergoes exchange with dissolved sulfur at 100°C, indicating reversible dissociation. When distilled at its atmospheric boiling point, it undergoes some decomposition to the dichloride, but decomposition is avoided with distillation at ca 6.7 kPa (50 mm Hg). At above 300°C, substantial dissociation to S2 and CI2 occurs. Sulfur monochloride is noncombustible at ambient temperature, but at elevated temperatures it decomposes to chlorine and sulfur (137). The sulfur then is capable of burning to sulfur dioxide and a small proportion of sulfur trioxide. 

Chemical Properties. Thionyl chloride chemistry has been reviewed (169—173). Significant inorganic reactions of thionyl chloride include its reactions with sulfur trioxide to form pyrosulfuryl chloride and with hydrogen bromide to form thionyl bromide [507-16-4]. With many metal oxides it forms the corresponding metal chloride plus sulfur dioxide and therefore affords a convenient means for preparing anhydrous metal chlorides. 

Chemical Properties. The chemistry of sulfuryl chloride has been reviewed (170,172,195). It is stable at room temperature but readily dissociates to sulfur dioxide and chlorine when heated. The equiUbrium constant has the following values (194) ... 

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). 

The absorption of sulfur dioxide in alkaline (even weakly alkaline) aqueous solutions affords sulfites, bisulfites, and metabisulfites. The chemistry of the interaction of sulfur dioxide with alkaline substances, either in solution, slurry, or soHd form, is also of great technological importance in connection with air pollution control and sulfur recovery (25,227,235—241). Even weak bases such as 2inc oxide absorb sulfur dioxide. A slurry of 2inc oxide in a smelter can be used to remove sulfur dioxide and the resultant product can be recycled to the roaster (242). 

Orga.nic Chemistry. The organic chemistry of sulfur dioxide, particularly as it relates to food appHcations, has been discussed (246). Although no reaction takes place with saturated hydrocarbons at moderate temperatures, the simultaneous passage of sulfur dioxide and oxygen into an alkane in the presence of a free-radical initiator or ultraviolet light affords a sulfonic acid such as hexanesulfonic acid [13595-73-8]. This is the so-called sulfoxidation reaction (247) ... 

Sodium sulfite undergoes addition of sulfur to form sodium thiosulfate. At acidic pH, the chemistry of sodium sulfite is that of bisulfite, metabisulfite, and sulfur dioxide. 

Chemical Properties. Anhydrous sodium dithionite is combustible and can decompose exothermically if subjected to moisture. Sulfur dioxide is given off violentiy if the dry salt is heated above 190°C. At room temperature, in the absence of oxygen, alkaline (pH 9—12) aqueous solutions of dithionite decompose slowly over a matter of days. Increased temperature dramatically increases the decomposition rate. A representation of the decomposition chemistry is as follows ... 

Snia Viscosa. Catalytic air oxidation of toluene gives benzoic acid (qv) in ca 90% yield. The benzoic acid is hydrogenated over a palladium catalyst to cyclohexanecarboxyhc acid [98-89-5]. This is converted directiy to cmde caprolactam by nitrosation with nitrosylsulfuric acid, which is produced by conventional absorption of NO in oleum. Normally, the reaction mass is neutralized with ammonia to form 4 kg ammonium sulfate per kilogram of caprolactam (16). In a no-sulfate version of the process, the reaction mass is diluted with water and is extracted with an alkylphenol solvent. The aqueous phase is decomposed by thermal means for recovery of sulfur dioxide, which is recycled (17). The basic process chemistry is as follows ... 

Fluidized beds are ideal for the combustion of high sulfur coals since the sulfur dioxide produced by combustion reacts with the introduced calcined limestone to produce calcium sulfate. The chemistry involved can be simplified and reduced to two steps, calcination and sulfation. 

This process is used to treat gas streams containing high concentrations of H2S. The chemistry of the units involves partial oxidation of hydrogen sulfide to sulfur dioxide and the catalytically promoted reaction of hh.S and SO2 to produce elemental sulfur. The reactions are staged and arc. is lollows ... 

U. IL F. Sander, H. Fischer, U. Rcthe and R. Kola, (Engl. edn. prepared by A. I. More), Sulfur, Sulfur Dioxide, Su unc Acid Induslrkd Chemistry a>id Technology, Brili.sh Sulfur Corporation, London, 1984, 428 pp. 

Sulfur forms several oxides that in atmospheric chemistry are referred to collectively as SOx (read sox ). The most important oxides and oxoacids of sulfur are the dioxide and trioxide and the corresponding sulfurous and sulfuric acids. Sulfur burns in air to form sulfur dioxide, S02 (11), a colorless, choking, poisonous gas (recall Fig. C.1). About 7 X 1010 kg of sulfur dioxide is produced annually from the decomposition of vegetation and from volcanic emissions. In addition, approximately 1 X 1011 kg of naturally occurring hydrogen sulfide is oxidized each year to the dioxide by atmospheric oxygen ... 

Another key feature of sulfur chemistry is the Lewis acidity of sulfur dioxide. Sulfur dioxide is a common atmospheric pollutant that results from burning coal to produce electricity. Most coal reserves in North America include significant amounts of sulfur-containing impurities. When coal is burned, sulfur combines with O2 to form SO2, a hard Lewis acid. 

Intramolecular cyclization of sulfonyl radicals is almost absent from literature. The fact that free radical cyclization has been the subject of a large number of studies and applications in the last decade in organic chemistry s and that sulfonyl radicals add quickly to multiple bonds vide infra) makes cyclization of sulfonyl radicals a rather attractive area. Recently, Johnson and Derenne S studied the reaction of 6-methylhept-5-en-2-ylcobaloxime(III) with sulfur dioxide and, based on the product analysis, they suggested reaction 15 to be an intermediate step. 

Carothers claimed that he kept going only because he finally received one of Illinois few scholarships, 750 embellished with esteem. But he must also have persevered because he loved chemistry. As he admitted, even the smell of his laboratory coat, saturated with the inexpressibly pungent and complicated odors of lab no. 219 [filled him] with a nostalgia to return to the atmosphere of sweetly blended sulfur dioxide, bromine, chlorine, ammonia, hydrogen chloride, phosgene, chloroacetone, etc., etc., etc. ... 

The chemistry involved in this explosively unstable system is reviewed [1]. The mechanism of the trigger reactions that initiate the exothermic decomposition of chlorate-sulfur mixtures has been studied. Mixtures containing 1-30% of sulfur can decompose well below the m.p. of sulfur, and addition of sulfur dioxide, the suspected chemical trigger, causes immediate onset of the reaction [2], Autoignition of stoichiometric mixtures can be as low as 115°C, with frictional sensitivity at 5N, the lowest load the test apparatus permitted. Both were dependent upon the history of the sulphur used [3],... 

The thiophene ring system can be utilized as a synthetic scaffold for the preparation of nonthiophene materials as the sulfur moiety can be removed by reduction (desulfurization) or extrusion (loss of SO2). The extrusion of sulfur dioxide from 3-sulfolenes (2,5-dihydrothiophene 1,1-dioxides) give dienes (butadienes or o-quinodimethanes) that can be utilized to prepare six-membered rings by cycloaddition chemistry. For example, thermolysis of 3-sulfolene 120 provided tricyclic pyrazole 122 via an intramolecular cycloaddition of the o-quinodimethane 121 that results by extrusion of sulfur dioxide <00JOC5760>. Syntheses of 3-sulfolenes 123 and 124 <00S507> have recently been reported. 

It is roughly estimated that there are more than 1,200,000 water bodies in eastern North America that are currently affected by acid deposition. A subset of these lakes has been sampled since early 1980s in order to monitor the changes in lake water chemistry induced by the declining sulfur dioxide emissions and wet sulfate deposition... 

Sulfur has four unique characteristics related to its occurrence and chemistry in soil. As sulfate, it is one of the principle counterions that keep the soil electrically neutral. Soil receives constant additions of sulfur through volcanic activity around the world and industrial pollution, usually in the form of acid rain. This means that soils usually have sufficient sulfur for plant growth. Lastly, plants can take and use sulfur dioxide from the air as a source of sulfur for growth [22,38],... 

Another class of "chain scission" positive resists is the poly(olefin sulfones). These polymers are alternating copolymers of an olefin and sulfur dioxide. The relatively weak C-S bond is readily cleaved upon irradiation and several sensitive resists have been developed based on this chemistry (49,50). One of these materials, poly(butene-l sulfone) (PBS) has been made commercially available for mask making. PBS exhibits an e-beam sensitivity of 1.6 pC cm-2 at 20 kV and 0.25 pm resolution. 

That propargylic starting materials are often employed in modern allene hydrocarbon chemistry is not surprising and the following examples are just a small selection from a much larger synthetic effort. Thus, the sulfones 61 are first cleaved in an aluminum amalgam-mediated reduction to the intermediates 62, which lose sulfur dioxide under the reaction conditions and furnish the trisubstituted allenes 63 in good to excellent yields (75-95%) (Scheme 5.7) [18]. 

Because of its relevance in environmental chemistry the reaction of photochemically excited sulfur dioxide with hydrocarbons in the gas phase has received considerable attention in recent years. In this reaction the principal path for formation of sulfinic acids is believed (Sherwell and Tedder, 1978) to be that shown in Scheme 2. Sherwell and Tedder do not think that abstraction of a hydrogen atom from RH by RS02-, i.e., RS02 + RH - RS02H + R-, occurs to any significant extent in such systems, although a summary of earlier studies of this reaction (Horowitz and Rajbenbach, 1975) shows that such a reaction has been proposed on occasion in the past. 

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