Sulfuric acid production chemistry

It is hard to overemphasize the importance of sulfuric acid in chemistry and in the economy. As far as chemicals are concerned, its impact on the economy is second to none. Without sulfuric acid utilization on a large scale, many of the products in general use would not exist, and our very way of life would be altered. The next section presents some of the essential chemistry of H2S04 to show why it so important. 

Table 10 shows that special shortages occurred in basic chemistry. Sulfuric acid production, which was underrepresented in the SBZ, fell still farther behind. The sole gypsum-based sulfuric acid facility in the Wolfen plant was completely dismantled. Complete dismantling occurred also in Doberitz (37,800 tons), Leuna (20,000 tons) and Magdeburg (53,800 tons). A total of 231,600 tons were taken out of production. This dismantling affected the textile industry especially. 

TATP does not decompose by action of diluted bases and its decomposition by diluted, but strong, inorganic acids proceeds to completion only at higher temperatures. Concentrated hydroiodic acid causes it to decompose violently without flames [18, 52] however in contact with concentrated sulfuric acid it ignites. TATP also slowly decomposes by the action of concentrated hydrochloric acid and 35 % sulfuric acid. The chemistry of decomposition by the action of these acids has been studied by Armitt et al. [53]. TATP decomposes both on exposure to acid vapors and suspended in liquid acid. Acetone, DADP, chloroacetone, and 1,1-dichloroacetone are the major products of decomposition by hydrochloric acid in the vapor phase. As the decomposition progresses, DADP decomposes and other poly-chlorinated acetones form (as far as hexachloroacetone). When the decomposition took place in liquid hydrochloric acid the main product was 1,1-dichloroacetone and poly-chlorinated acetones were only minor products. Sulfuric acid causes TATP to decompose to DADP and acetone, and DADP... 

Herman arrived in Philadelphia at the home of his imcle in August 1868. As diseussed previously, Philadelphia was the heart of the early American chemical industry and was the center of sulfuric acid production. The yoimg Frasch, though, did not join one of the major chemical firms, but worked in the pharmacy business. Then, pharmacies were more than dispensers of medicines. They were a place to obtain practical training in chemistry outside of imiversity and provided chemical consulting services. 

Alkylation of 2-methylaminothiazole (204) with ROH in 85% sulfuric acid gives 2-methylimino-3-alkyl-4-thiazoIine (54). 2-Amino-4-rnethyl-thiazoie alkylated with an excess of isopropanol, however, gives 95% of 2-isopropylamino-4-methyl-5-isopropylthiazole (56). The same result is obtained with cyclohexanol (242). These results and those reported in Sections III.l.C and IV.l.E offer interesting new synthetic possibilities in thiazole chemistry. The reactive species in these alkylations is the conjugate acid of 2-aminothiazole. and the diversity of the products obtained suggests that three nucleophilic centers may be operative in this species. 

Normally, a slight excess of sulfuric acid is used to bring the reaction to completion. There are, of course, many side reactions involving siHca and other impurity minerals in the rock. Fluorine—silica reactions are especially important as these affect the nature of the calcium sulfate by-product and of fluorine recovery methods. Thermodynamic and kinetic details of the chemistry have been described (34). 

Again, irrespective of the hardware the chemistry is consistent. The partially regenerated fiber from the spinning machine is contaminated with sulfuric acid, 2inc sulfate, sodium sulfate, carbon disulfide, and the numerous incompletely decomposed by-products of the xanthation reactions. The washing and drying systems must yield a pure cellulose fiber, suitably lubricated for the end use, and dried to a moisture level of around 10%. 

Nitric oxide is the simplest thermally stable odd-electron molecule known and, accordingly, its electronic structure and reaction chemistry have been very extensively studied. The compound is an intermediate in the production of nitric acid and is prepared industrially by the catalytic oxidation of ammonia (p. 466). On the laboratory scale it can be synthesized from aqueous solution by the mild reduction of acidified nitrites with iodide or ferrocyanide or by the disproportionation of nitrous acid in the presence of dilute sulfuric acid ... 

A solventless synthesis of pyrazoles, a green chemistry approach, has been described where an equimolar amount of the diketone and the hydrazine are mixed in a mortar with a drop of sulfuric acid and ground up. After an appropriate length of time ( 1 h) the product is purified to provide clean products. Even acyl pyrazoles 42 were obtained under the solvent-less reaction conditions in good yields. 

Despite more than 200 years of sulfur research the chemistry of elemental sulfur and sulfur-rich compounds is still full of white spots which have to be filled in with solid knowledge and reliable data. This situation is particularly regrettable since elemental sulfur is one of the most important raw materials of the chemical industry produced in record-breaking quantities of ca. 35 million tons annually worldwide and mainly used for the production of sulfuric acid. 

The atom economy for this process is 86.5% (100 X 116/134), which is reasonable. To calculate the E-factor and EMY further information is needed. From published literature (Vogel s Practical Organic Chemistry ), a standard procedure is to mix butanol (37 g) with glacial acetic acid (60 g), and a small amount of sulfuric acid catalyst (ignored in all calculations). Following completion of the reaction the mixture is added to water (250 g). The crude ester is washed further with water (100 g), then saturated sodium bicarbonate solution (25 g) and finally water (25 g). After drying over 5 g of anhydrous sodium sulfate the crude ester is distilled to give product (40 g) in a yield of 69%. 

Sulfur displays rich and varied chemical behavior, but from the commercial standpoint, sulfuric acid dominates the chemistry of this element. Sulfuric acid is used in every major chemical-related industry fertilizers (60% of annual production), chemical manufacture (6%), petroleum refining (5%), metallurgy (5%), detergents, plastics,... 

Chemists are not the only ones who make use of acid-base chemistry. In fact, most of the chemical manufacturing that goes on in the world is related to the production of four simple, but very useful, products—sulfuric acid, phosphoric acid, sodium hydroxide, and sodium chloride. 

Direct production of benzoquinone (BQ) from benzene is one of the targets in industrial chemistry. Considerable efforts have been made to develop the electrochemical oxidation of benzene to p-benzoquinone to the industrial scale thus forming a basis for a new hydroquinone process [40]. Benzene in aqueous emulsions containing sulfuric acid (1 1 mixture of benzene and 10% aqueous H2S04) forms, at the anode, p-benzoquinone which can be reduced cathodically to yield hydroquinone in a paired synthesis. A divided cell with Pb02 anodes is used. 

Acetaldehyde is the product of the Wacker process. At the end of the fifties oxidation of ethene to ethanal replaced the addition of water to acetylene, because the acetylene/coal-based chemistry became obsolete, and the ethene/petrochemistry entered the commercial organic chemicals scene. The acetylene route involved one of the oldest organometallics-mediated catalytic routes started up in the 1920s the catalyst system comprised mercury in sulfuric acid. Coordination of acetylene to mercury(II) activates it toward nucleophilic attack of water, but the reaction is slow and large reactor volumes of this toxic catalyst were needed. An equally slow related catalytic process, the zinc catalysed addition of carboxylic acids to acetylene, is still in use in paint manufacture. 

When the metals were studied, the release of gases and vapors was observed. For example, Paracelsus reported that when iron was dissolved in sulfuric acid air comes out like a wind. The differentiation of these kinds of air took more than two centuries. Research on the analysis of gases was extremely productive in developing the basic methods to handle and study gases and even paved the way to design techniques for elementary analysis of the constituents of organisms. Thus the study of gases became the second epoch of analytical chemistry it is called the pneumatic age. ... 

Both the nitrosoenamine II and the nitrosamino acetate III demonstrated some unusual chemistry which led us to the study of nitrosamine fragmentation reactions which will be discussed below. Treatment of the nitrosoenamine II with dilute sulfuric acid led to the formation of benzyl phenyl ketone as anticipated, but the major product from this reaction was benzoin, as is illustrated in equation 2 (3). While this transformation and the proper-... 

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