Sulfur dioxide, properties

A polysulfone is characterized by the presence of the sulfone group as part of its repeating unit. Polysulfones may be aUphatic or aromatic. AUphatic polysulfones (R and are alkyl groups) were synthesized by radical-induced copolymerization of olefins and sulfur dioxide and characterized many years ago. However, they never demonstrated significant practical utiUty due to their relatively unattractive physical properties, not withstanding the low cost of their raw materials (1,2). The polysulfones discussed in this article are those based on an aromatic backbone stmcture. The term polysulfones is used almost exclusively to denote aromatic polysulfones. 

Rhenium oxides have been studied as catalyst materials in oxidation reactions of sulfur dioxide to sulfur trioxide, sulfite to sulfate, and nitrite to nitrate. There has been no commercial development in this area. These compounds have also been used as catalysts for reductions, but appear not to have exceptional properties. Rhenium sulfide catalysts have been used for hydrogenations of organic compounds, including benzene and styrene, and for dehydrogenation of alcohols to give aldehydes (qv) and ketones (qv). The significant property of these catalyst systems is that they are not poisoned by sulfur compounds. 

Silver sulfate decomposes above 1085°C into silver, sulfur dioxide, and oxygen. This property is utilized ia the separation of silver from sulfide ores by direct oxidation. Silver sulfate is reduced to silver metal by hydrogen, carbon, carbon monoxide, zinc, and copper. 

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. 

Physical Properties. Sulfuryl chloride [7791-25-5] SO2CI2, is a colorless to light yellow Hquid with a pungent odor. Physical and thermodynamic properties are Hsted ia Table 7. Sulfuryl chloride dissolves sulfur dioxide, bromine, iodine, and ferric chloride. Various quaternary alkyl ammonium salts dissolve ia sulfuryl chloride to produce highly conductive solutions. Sulfuryl chloride is miscible with acetic acid and ether but not with hexane (193,194). 

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) ... 

Physical Properties. Sulfur dioxide [7446-09-5] SO2, is a colorless gas with a characteristic pungent, choking odor. Its physical and thermodynamic properties ate Hsted in Table 8. Heat capacity, vapor pressure, heat of vaporization, density, surface tension, viscosity, thermal conductivity, heat of formation, and free energy of formation as functions of temperature ate available (213), as is a detailed discussion of the sulfur dioxide—water system (215). 

Table 8. Physical and Thermodynamic Properties of Sulfur Dioxide...

Chemical Properties. Anhydrous sodium sulfite is stable in dry air at ambient temperatures or at 100°C, but in moist air it undergoes rapid oxidation to sodium sulfate [7757-82-6]. On heating to 600°C, sodium sulfite disproportionates to sodium sulfate and sodium sulfide [1313-82-2]. Above 900°C, the decomposition products are sodium oxide and sulfur dioxide. At 600°C, it forms sodium sulfide upon reduction with carbon (332). 

Physical Properties. Sodium metabisulfite (sodium pyrosulfite, sodium bisulfite (a misnomer)), Na2S20, is a white granular or powdered salt (specific gravity 1.48) and is storable when kept dry and protected from air. In the presence of traces of water it develops an odor of sulfur dioxide and in moist air it decomposes with loss of part of its SO2 content and by oxidation to sodium sulfate. Dry sodium metabisulfite is more stable to oxidation than dry sodium sulfite. At low temperatures, sodium metabisulfite forms hydrates with 6 and 7 moles of water. The solubiHty of sodium metabisulfite in water is 39.5 wt % at 20°C, 41.6 wt % at 40°C, and 44.6 wt % at 60°C (340). Sodium metabisulfite is fairly soluble in glycerol and slightly soluble in alcohol. 

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 ... 

Physical Properties. Ammonium thiocyanate [1762-95-4] NH SCN, is a hygroscopic crystalline soHd which deHquesces at high humidities (375,376). It melts at 149°C with partial isomerization to thiourea. It is soluble in water to the extent of 65 wt % at 25°C and 77 wt % at 60°C. It is also soluble to 35 wt % in methanol and 20 wt % in ethanol at 25°C. It is highly soluble in Hquid ammonia and Hquid sulfur dioxide, and moderately soluble in acetonitrile. 

The thermodynamic properties of sulfur trioxide, and of the oxidation reaction of sulfur dioxide are summarized in Tables 3 and 4, respectively. Thermodynamic data from Reference 49 are beheved to be more accurate than those of Reference 48 at temperatures below about 435°C. 

Further heating to 440—500°C gives sodium sulfide and sulfur dioxide (33). Table 1. Physical Properties of Sodium Thiosulfate Pentahydrate... 

Addition of up to 200 ppm sulfur dioxide to grape musts is customary. Strains of S. cerevisiae and S. bayanus grown in the presence of sulfite, become tolerant of fairly high concentrations of SO2. Cultures propagated in the winery are added in Hquid suspension, usually at 1—2% of the must volume. Many strains are available in pure culture. Factors such as flocculence, lack of foaming, fast fermentation, lack of H2S and SO2 formation, resistance to sulfur dioxide and other inhibitors, and flavor production will affect strain choice. No strain possesses all the desired properties. 

Catalysis. Catalytic properties of the activated carbon surface are useful in both inorganic and organic synthesis. For example, the fumigant sulfuryl fluoride is made by reaction of sulfur dioxide with hydrogen fluoride and fluorine over activated carbon (114). Activated carbon also catalyzes the addition of halogens across a carbon—carbon double bond in the production of a variety of organic haUdes (85) and is used in the production of phosgene... 

Metals and alloys, the principal industrial metalhc catalysts, are found in periodic group TII, which are transition elements with almost-completed 3d, 4d, and 5d electronic orbits. According to theory, electrons from adsorbed molecules can fill the vacancies in the incomplete shells and thus make a chemical bond. What happens subsequently depends on the operating conditions. Platinum, palladium, and nickel form both hydrides and oxides they are effective in hydrogenation (vegetable oils) and oxidation (ammonia or sulfur dioxide). Alloys do not always have catalytic properties intermediate between those of the component metals, since the surface condition may be different from the bulk and catalysis is a function of the surface condition. Addition of some rhenium to Pt/AlgO permits the use of lower temperatures and slows the deactivation rate. The mechanism of catalysis by alloys is still controversial in many instances. 

When a liquid or solid substance is emitted to the air as particulate matter, its properties and effects may be changed. As a substance is broken up into smaller and smaller particles, more of its surface area is exposed to the air. Under these circumstances, the substance, whatever its chemical composition, tends to combine physically or chemically with other particles or gases in the atmosphere. The resulting combinations are frequently unpredictable. Very small aerosol particles (from 0.001 to 0.1 Im) can act as condensation nuclei to facilitate the condensation of water vapor, thus promoting the formation of fog and ground mist. Particles less than 2 or 3 [Lm in size (about half by weight of the particles suspended in urban air) can penetrate the mucous membrane and attract and convey harmful chemicals such as sulfur dioxide. In order to address the special concerns related to the effects of very fine, iuhalable particulates, EPA replaced its ambient air standards for total suspended particulates (TSP) with standards for particlute matter less than 10 [Lm in size (PM, ). 

TABLE 8.6.1 Physical Properties of Sulfur Dioxide (SO2) CAS Registry Number 7446-09-5... 

N. 1. Sa., ed.. Sulfur Dioxide, Dangerous Properties of Industrial Materials Report, Vol. 1, No. 3, Januaiy -February, New York, 1981. Material Safety Data Sheet, Liquid Air Corporation, Alphagaz Division, Walnut Creek, CA, October 1985. 

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