Sulfuric acid oleum

Sulfation and Sulfonation. a-Olefin reactions involving the introduction of sulfur-containing functional groups have commercial importance. As with many derivatives of olefins, several of these products have appHcations in the area of surfactants (qv) and detergents. Typical sulfur reagents utilized in these processes include sulfuric acid, oleum, chlorosulfonic acid, sulfur trioxide, and sodium bisulfite. 

Table 5. Composition of Sulfuric Acid, Oleum, and Liquid SO Sulfonating Reagents...

Oleum Ma.nufa.cture, To produce fuming sulfuric acid (oleum), SO is absorbed in one or more special absorption towers irrigated by recirculated oleum. Because of oleum vapor pressure limitations the amount of SO absorbed from the process gas is typically limited to less than 70%. Because absorption of SO is incomplete, gas leaving the oleum tower must be processed in a nonfuming absorption tower. 

Sulfonation. Benzene is converted iato benzenesulfonic acid [98-11-3] C H SO, upon reaction with fuming sulfuric acid (oleum) or chlorosulfonic acid. y -Benzenedisulfonic acid [98-48-6] CgHgS20, is prepared by reaction of benzene-sulfonic acid with oleum for 8 h at 85°C. Often under these conditions, appreciable quantities ofT -benzenedisulfonic acid [31375-02-7] are produced. 1,3,5-Benzenetrisulfonic acid [617-99-2] C H S Og, is produced by heating the disulfonic acid with oleum at 230°C (21). 

Perfluoro-y-butyrolactone can be prepared from 1,4 diiodoperfluorobutane by reaction with turning sulfuric acid (oleum) [7S] (equation 19) The yield depends on the concentration of sulfur trioxide One of the by-products, 4-iodoperfluo-robutyryl fluoride, can be recycled to increase the overall yield of the lactone Pure sulfur trioxide generates only perfluorotetrahydrofuran, the lodo acyl fluoride, and perfluorosuccmyl fluoride... 

Preparation of 2-nitro-2-methyl-1 -propanol-nitrate. 50g of the 2-nitro-2-methyl-1-propanol purified as above were sifted into a mixt of 58.5g of 90.5% nitric acid.and 241,5g of 103.1% sulfuric acid (oleum) while the well-agitated mixt was maintained close to 15°. Stirring was continued for 1 hour and the mixt allowed to stand for hour. No separation of the nitration product occurred and the mixt was poured over cracked ice. An oily layer separated. The mixt was transferred to a separatory funnel, washed with water, Na bicarbonate, and twice with water to neutrality. The separated diluted spent acid together with the washings were thoroughly extracted with ether, the ether extract washed to neutrality and added to the main product. 

The sulfonation of LAB can be carried out with concentrated sulfuric acid, oleum, or sulfur trioxide (S03). With the first two sulfonation reagents large quantities of waste sulfuric acid are obtained, which must be disposed of or processed further. Therefore the use of S03 is preferred. Special reactions were developed for sulfonation using S03 (Table 13). For sulfonation in batch pro-... 

The structures and stabilities of several 8 dications are well established. Red, yellow or blue solutions are obtained if sulfur is added to 803-contain-ing sulfuric acid (oleum). Gillespie et al. have suggested that the colours are due to the nonadecasulfur dication 819, octasulfur dication 8g, and tetra-... 

Nowadays, ultramarine-type pigments are produced synthetically. Inside the zeolite structure the highly reactive sulfur radical anions are well protected which explains the stability of the blue color over thousands of years in air. However, the species responsible for the blue color should not be confused with the sulfur radical cations responsible for the blue color of sulfur solutions in fuming sulfuric acid (oleum) and similar oxidizing mixtures... 

Dilution of cone, sulfuric acid by water is vigorously exothermic and must be effected by adding acid to water to avoid local boiling. Mixtures of sulfuric acid and excess snow form powerful freezing mixtures. Fuming sulfuric acid (oleum, containing sulfur trioxide) reacts violently with water. 

Solutions of sulfur trioxide in cone, sulfuric acid (oleum) are available with various proportions of dissolved sulfur trioxide, and the 3 entries in Handling Chemicals Safely 1980 deal with the properties and hazards of solutions with 65, 30 and 20% of sulfur trioxide, respectively. As expected, the reactivity and oxidising power increase with the content of sulfur trioxide. 

With this last point in mind, the synthesis of mono-, bis- and tra-sulfonated triphenylphosphine will be described, but the same methodology can be applied to the preparation of other sulfonated arylphosphines. In general, these phosphines are made by direct sulfonation using fuming sulfuric acid (oleum) [21], The extent of sulfonation is determined by the SO3 strength, as well as factors such as the temperature and time of the reaction. The monosulfonated phosphine (tppms) is prepared using oleum of 20% SO3 strength, with typically 30% SO3 used... 

Fuming sulfuric acid (oleum) of 20% SO3 strength is suitable for preparation of monosulfonated products [1-3] while for multiple sulfonation 30% (or more) SO3 is required [4-10], The phosphine is dissolved in cold oleum with protonation of the phosphoms atom therefore in cases when the phenyl rings are directly attached to the phosphoms (e.g. triphenylphosphine or the bis(diphenylphosphino)alkanes) sulfonation takes place in the 3-position. 

Hydroxylamine-O-sulfonic acid can also be prepared from hy-droxylamine sulfate and 30% fuming sulfuric acid (oleum).3 The present procedure is essentially that of F. Sommer et al.4... 

In case of fuming sulfuric acid (oleum) not contg any other acids, total acidity is higher than 100 5 and w content will be expressed as a negative value, such as -5.50%. It is customary with such acids to express their acidity in terms of 30, as,... 

Caution. Fuming sulfuric acid (oleum) is corrosive, a strong oxidant, and toxic. Protective clothing should be worn when handling oleum. The material should be used in an efficient fume hood. 

Sulfonic acids are prepared on a commercial scale by the sulfonalion of organic substrates using a variety of sulfonating agents, including sulfur trioxidc (diluted in air), sulfur trioxide (in sulfur dioxide), sulfuric acid, oleum (fuming sulfuric acid), chlorosulfuric acid, sulfamic add, trialkylamine-sulfur trioxide complexes, and sulfite ions. Other methods of sulfonic acid production, practiced on an industrial scale, include the oxidation of thiols, sulfide, disulfides, sulfoxides, sulfones, and sulfinic acids. See also Sulfonalion and Sulfation. 

While the dinitration mixture is stirred actively at a temperature of about 90°, 145 grams of fuming sulfuric acid (oleum containing 15 per... 

Sulfuric acid Sulfur trioxide mixed with oxygen and nitrogen Sulfur trioxide Sulfuric acid, oleum Sulfuric acid manufacture Stripping not practiced... 

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