Diluted Sulfuric Acid

The reaction is carried out at low temperature in aqueous medium and then allowed to stand overnight (221). Ammonium thiocarbamate is prepared from a cold saturated solution of ammonium thiocyanate, which is gradually added to dilute sulfuric acid at 25°C. The liberated carbonyl sulfide is passed into a saturated solution of alcoholic ammonia at about 10°C (221). The fairly low yield indicates that the reaction has not been greatly developed. 

With cr-thiocyanatoacetophenones, 4-aryl-2-hydroxythiazoles can be obtained in 80 to 90% yields in an acetic acid solution with the addition of dilute sulfuric acid (87, 392, 416, 428, 484, 519). 

Halogenation (e.g., bromination) takes place in chloroform for the 2,4-dialkylthiazoles, and the majority of studies have been of 2,4-dimethylthiazole (227, 228). In other cases and in acetic or stronger acids, substitution occurs at the 5-position and is promoted by electronreleasing groups in the 2-position. When the releasing group is in the 4-(or 5-)-position, steric hindrance may decrease the yield of substitution at the 5- (or 4-) position. Nevertheless, the thiazole nucleus is not very reactive since 4-methylthiazole and 2.5-dimethylthiazole are inert in dilute sulfuric acid with bromine (229-231). 

According to Le Chatelier s principle, a system at equilibrium adjusts so as to mini mize any stress applied to it When the concentration of water is increased the system responds by consuming water This means that proportionally more alkene is converted to alcohol the position of equilibrium shifts to the right Thus when we wish to pre pare an alcohol from an alkene we employ a reaction medium m which the molar con centration of water is high—dilute sulfuric acid for example... 

Although 2 methylpropene undergoes acid catalyzed hydration m dilute sulfuric acid to form tert butyl alcohol (Section 6 10) a different reaction occurs m more concentrated solutions of sulfuric acid Rather than form the expected alkyl hydrogen sulfate (see Sec tion 6 9) 2 methylpropene is converted to a mixture of two isomeric C Hig alkenes... 

From cumene Almost all the phenol produced in the United States is prepared by this method Oxi dation of cumene takes place at the benzylic posi tion to give a hydroperoxide On treatment with dilute sulfuric acid this hydroperoxide is converted to phenol and acetone... 

The ratio of reactants had to be controlled very closely to suppress these impurities. Recovery of the acrylamide product from the acid process was the most expensive and difficult part of the process. Large scale production depended on two different methods. If soHd crystalline monomer was desired, the acrylamide sulfate was neutralized with ammonia to yield ammonium sulfate. The acrylamide crystallized on cooling, leaving ammonium sulfate, which had to be disposed of in some way. The second method of purification involved ion exclusion (68), which utilized a sulfonic acid ion-exchange resin and produced a dilute solution of acrylamide in water. A dilute sulfuric acid waste stream was again produced, and, in either case, the waste stream represented a... 

This process is currentiy used by Vista Chemical, successor to Continental Oil Company s chemical business, and by Condea. In the Ethyl Corporation process dilute sulfuric acid is used in place of water in the hydrolysis step producing alum rather than alumina. 

The second ceUulosic fiber process to be commercialized was invented by L. H. Despeissis (4) in 1890 and involved the direct dissolution of cotton fiber in ammoniacal copper oxide Uquor. This solvent had been developed by M. E. Schweizer in 1857 (5). The cuprammonium solution of ceUulose was spun into water, with dilute sulfuric acid being used to neutralize the ammonia and precipitate the ceUulose fibers. H. Pauly and co-workers (6) improved on the Despeissis patent, and a German company, Vereinigte Glanstoff Eabriken, was formed to exploit the technology. In 1901, Dr. Thiele at J. P. Bemberg developed an improved stretch-spinning system, the descendants of which survive today. 

Uranium ores are leached with dilute sulfuric acid or an alkaline carbonate [3812-32-6] solution. Hexavalent uranium forms anionic complexes, such as uranyl sulfate [56959-61-6], U02(S0 3, which are more selectively adsorbed by strong base anion exchangers than are other anions in the leach Hquors. Sulfate complexes are eluted with an acidified NaCl or ammonium nitrate [6484-52-2], NH NO, solution. Carbonate complexes are eluted with a neutral brine solution. Uranium is precipitated from the eluent and shipped to other locations for enrichment. Columnar recovery systems were popular in South Africa and Canada. Continuous resin-in-pulp (RIP) systems gained popularity in the United States since they eliminated a difficult and cosdy ore particle/leach hquor separation step. 

The reaction is especially useful because of the high emf (ca 2.2 V) of the Pb/Pb02 couple in dilute sulfuric acid (see Batteries, secondary). 

Mercurous Sulfate. Mercurous s Ai2LX.e[7783-36-0] Hg2S04, is a colodess-to-shghfly-yellowish compound, sensitive to light and slightly soluble ia water (0.05 g/100 g H2O). It is more soluble ia dilute acids. The compound is prepared by precipitation from acidified mercurous nitrate solution and dilute sulfuric acid. The precipitate is washed with dilute sulfuric acid until nitrate-free. Its most important use is as a component of Clark and Weston types of standard cells. 

Merthiolate/T4- )4-< 7 (3), sodium ethyLmercurithiosahcylate, known also as thimersol, is prepared from a 1 1 ratio of ethyhnercuric chloride/7(97-27-. and disodium thiosahcylate ia ethanol. After removal of the sodium chloride by filtration, the free acid is precipitated by acidification with dilute sulfuric acid. Purification is achieved by recrystallization from 95% ethanol, and the product, merthiolate, is obtained by neutralization with a stoichiometric amount of sodium hydroxide. 

Ma.nufa.cture. The preferred method for making nickel sulfate is adding nickel powder to hot dilute sulfuric acid. Adding sulfuric acid to nickel powder in hot water enhances the formation of H2S. Hydrogen sulfide always forms as a by-product upon reaction of metallic nickel and sulfuric acid. The hberated hydrogen is absorbed by the metal and then reduces the sulfate anion to H2S. 

Nickel sulfate also is made by the reaction of black nickel oxide and hot dilute sulfuric acid, or of dilute sulfuric acid and nickel carbonate. The reaction of nickel oxide and sulfuric acid has been studied and a reaction induction temperature of 49°C deterrnined (39). High purity nickel sulfate is made from the reaction of nickel carbonyl, sulfur dioxide, and oxygen in the gas phase at 100°C (40). Another method for the continuous manufacture of nickel sulfate is the gas-phase reaction of nickel carbonyl and nitric acid, recovering the soHd product in sulfuric acid, and continuously removing the soHd nickel sulfate from the acid mixture (41). In this last method, nickel carbonyl and sulfuric acid are fed into a closed-loop reactor. Nickel sulfate and carbon monoxide are produced the CO is thus recycled to form nickel carbonyl. 

The chemical production of aminophenols via the reduction of nitrobenzene occurs in two stages. Nitrobenzene [98-95-3] is first selectively reduced with hydrogen in the presence of Raney copper to phenylhydroxylamine in an organic solvent such as 2-propanol (37). With the addition of dilute sulfuric acid, nucleophilic attack by water on the aromatic ring of /V-phenylhydroxylamine [100-65-2] takes place to form 2- and 4-aminophenol. The by-product, 4,4 -diaminodiphenyl ether [13174-32-8] presumably arises in a similar manner from attack on the ring by a molecule of 4-aminophenol (38,39). Aniline [62-53-3] is produced via further reduction (40,41). 

In past years, metals in dilute sulfuric acid were used to produce the nascent hydrogen reductant (42). Today, the reducing agent is hydrogen in the presence of a catalyst. Nickel, preferably Raney nickel (34), chromium or molybdenum promoted nickel (43), or supported precious metals such as platinum or palladium (35,44) on activated carbon, or the oxides of these metals (36,45), are used as catalysts. Other catalysts have been suggested such as molybdenum and platinum sulfide (46,47), or a platinum—nithenium mixture (48). 

The sulfate ester hydrolysate is stripped to give a mixture of isopropyl alcohol, isopropyl ether, and water overhead, and dilute sulfuric acid bottoms. The overhead is neutralized using sodium hydroxide and refined in a two-column distillation system. Diisopropyl ether is taken overhead in the first, ie, ether, column. This stream is generally recycled to the reactors to produce additional isopropyl alcohol by the following equiUbrium reaction ... 

The bottoms from the stripper (40—60 wt % acid) are sent to an acid reconcentration unit for upgrading to the proper acid strength and recycling to the reactor. Because of the associated high energy requirements, reconcentration of the diluted sulfuric acid is a cosdy operation. However, a propylene gas stripping process, which utilizes only a small amount of added water for hydrolysis, has been described (63). In this modification, the equiUbrium quantity of isopropyl alcohol is stripped so that acid is recycled without reconcentration. Kquilibrium is attained rapidly at 50°C and isopropyl alcohol is removed from the hydrolysis mixture. Similarly, the weak sulfuric acid process minimizes the reconcentration of the acid and its associated corrosion and pollution problems. 

Nitrogen oxide sampling is simpler. This gas is drawn into an evacuated sample flask containing dilute sulfuric acid and hydrogen peroxide. The flask is shaken and allowed to stand for 16 h before the flask pressure is measured. Then the solution is made alkaline, and the nitrogen oxides are deterrnined by the phenoldisulfonic colorimetric test. 

Silver Chloride. Silver chloride, AgCl, is a white precipitate that forms when chloride ion is added to a silver nitrate solution. The order of solubility of the three silver halides is Cl" > Br" > I. Because of the formation of complexes, silver chloride is soluble in solutions containing excess chloride and in solutions of cyanide, thiosulfate, and ammonia. Silver chloride is insoluble in nitric and dilute sulfuric acid. Treatment with concentrated sulfuric acid gives silver sulfate. 

By-Products and Waste Disposal. A by-product of sulfamic acid manufacturing is fuming sulfuric acid or dilute sulfuric acid. The amount of sulfuric acid (as 100% H2SO is 1—1.5 times as much by weight as the sulfamic acid product. This by-product also contains ammonium salts and is therefore normally used as raw material for fertilizer (see Fertilizers). 

Until the 1970s, the main production countries of sulfamic acid were the United States, several European countries, and Japan. The large amounts of dilute sulfuric acid by-product generated led to the difficult situation of by-product acid disposal. Concomitandy, the start of chemical production in developing Asian countries caused successional sulfamic acid production withdrawal in the 1980s. As of the mid-1990s production countries are Japan, Taiwan, Indonesia, India, and China. The 1995 wodd production capacity was ca 96,000 metric tons. 

The principal direct raw materials used to make sulfuric acid are elemental sulfur, spent (contaminated and diluted) sulfuric acid, and hydrogen sulfide. Elemental sulfur is by far the most widely used. In the past, iron pyrites or related compounds were often used but as of the mid-1990s this type of raw material is not common except in southern Africa, China, Ka2akhstan, Spain, Russia, and Ukraine (96). A large amount of sulfuric acid is also produced as a by-product of nonferrous metal smelting, ie, roasting sulfide ores of copper, lead, molybdenum, nickel, 2inc, or others. 

Sulfuric Acid Concentrators. Concentrators for increasing the strength of dilute sulfuric acid by removing water have been used since the early days of the industry. A two-volume text on this subject was pubHshed ia 1924 (135) more recent discussions of the subject are also available (32,136-141). 

Sulfates. ThaHous sulfate is a commercial product produced by reaction of the metal with sulfuric acid and concentration of the solution until crystallization begins (9). It reacts with thalHc sulfate, yielding T1 T1 (S0 2 [37475-01-7] and with SO, forming the pyrosulfate, TI2S2O2 [82391-11-5]. ThaHic sulfate is extremely unstable and therefore caimot be isolated. Reaction of thaHic oxide with dilute sulfuric acid results in HT1(S0 2 [15478-75-8] or T1(0H)S04 [37205-71 -3] depending on the concentration of sulfuric acid used. 

If a solution of the acid sulfate ia dilute sulfuric acid is evaporated at 200°C, greea crystals of the anhydrous neutral salt form. The anhydrous salt is... 

---