Nitric acid early developments

The first nitration to be reported was that of beri2ene itself. Mitscher-lich in 1834 prepared nitrobenzene by treating benzene with fuming nitric acid. Not long afterwards the important method of effecting nitration with a mixture of nitric and sulphuric acids ( mixed acid ) was introduced, evidently in a patent by Mansfield the poor quality of early nitric acid was probably the reason why the method was developed. Since these beginnings, nitration has been the subject of continuous study. 

Although many variations of the cyclohexane oxidation step have been developed or evaluated, technology for conversion of the intermediate ketone—alcohol mixture to adipic acid is fundamentally the same as originally developed by Du Pont in the early 1940s (98,99). This step is accomplished by oxidation with 40—60% nitric acid in the presence of copper and vanadium catalysts. The reaction proceeds at high rate, and is quite exothermic. Yield of adipic acid is 92—96%, the major by-products being the shorter chain dicarboxytic acids, glutaric and succinic acids,and CO2. Nitric acid is reduced to a combination of NO2, NO, N2O, and N2. Since essentially all commercial adipic acid production arises from nitric acid oxidation, the trace impurities patterns ate similar in the products of most manufacturers. 

Odda A process for making a fertilizer by treating phosphate rock with nitric acid. Developed by Odda Smelteverk, Norway, in the early 1900s and still in use in 1988. Licensed by BASF and offered by Uhde. 

Since the early days of organic chemistry, nitration has been considered to be an important reaction and has been widely used. As early as 1825 Faraday discovered benzene and recorded its reaction with nitric acid. Shortly after, the use of nitric acid sulfuric acid mixtures to effect nitration was reported and was soon quoted in a patent. Nitration figured prominently in the development of ideas of theoretical organic chemistry in the early part of the twentieth century and, as the most widely applicable and most widely used example of electrophilic substitution, it played an important role in the consideration of aromatic stability and reactivity. In 1910 the first report of orientation and deactivation in aromatic electrophilic substitution was published (10MI1). 

Researchers returned to the oxidation of ammonia in air, (recorded as early as 1798) in an effort to improve production economics. In 1901 Wilhelm Ostwald had first achieved the catalytic oxidation of ammonia over a platinum catalyst. The gaseous nitrogen oxides produced could be easily cooled and dissolved in water to produce a solution of nitric acid. This achievement began the search for an economic process route. By 1908 the first commercial facility for production of nitric acid, using this new catalytic oxidation process, was commissioned near Bochum in Germany. The Haber-Bosch ammonia synthesis process came into operation in 1913, leading to the continued development and assured future of the ammonia oxidation process for the production of nitric acid. 

Ammonium nitrate (AN) was first prepared in the sixteenth century. Its early industrial development was primarily for use in explosives. However, about 1940 its use as a fertilizer developed rapidly. Ammonium nitrate is produced mainly by the reaction of gaseous ammonia with aqueous nitric acid ... 

The benzene derivatives presented an enigma to structural chemists in that although the benzene rings had three double bonds, they underwent substitution rather than addition when treated with reagents such as bromine and nitric acid. No adequate explanation for their behavior was presented prior to the development of quantum mechanics. In the early 1930 s, two explanations were presented. One was by Pauling making use of valence bond theory,2 and the other was by E. Huckel making use of molecular orbital theory.3... 

Inorganic chemistry as a field of study was extremely important during the early years of the exploration and development of mineral resources. Qualitative analysis methods were developed to help identify minerals and, combined with quantitative methods, to assess their purity and value. As the industrial revolution progressed, so did the chemical industry. By the early 20th century, plants for the production of ammonia, nitric acid, sulfuric acid, sodium hydroxide, and many other inorganic chemicals produced on a large scale were common. 

The method of manufacture of nitroform from acetylene found as early as 1900 by Baschieri (Voi. I, p. 587) was described by Orton and McKie [141]. It became possible to convert one of the carbons of acetylene to nitroform through a mercury catalysed oxidation-nitration process with nitric acid. Nitroform is an intermediate product of nitration and yields tetranitromethane under the action of excess nitric acid (Vol. I, p. S94). The method was developed during World War II by Schultheiss I42] and Schimmelschmidt 143 on a large laboratory scale with the atm of producing tetranitromethane. l ater the industrial scale method for the manufacture of nitroform was created by Wctter-holm [I44 (and is described below). 

Another kind of early slurry was that developed by Gehrig of Atlas Chemical Industries [85]. It consisted of a saturated solution of ammonium nitrate in nitric acid of 60-70% IINO3 and some organic substances which are not attacked by nitric acid, for example, vinyl polymers. However handling of the solution with nitric acid is difficult and can be dangerous. A fire occurred in a factory in Rourkela (India) in 1972 througli spilling nitric acid slurry on wooden boards [86]. 

The precise mechanism resppnsible for the passivity conferred on metals by anodic inhibitors, such as chromate, is not known. While some early workers thought that a protective salt film (e.g., chromate) was formed, this view is not generally applicable, since passivity can occur in a system where the salt film would be freely soluble (e.g., iron in nitric acid). It is, however, generally accepted that passivity is associated with the formation of a protective film, and current views ascribe the action of anodic inhibitors either to adsorption at anodic sites or to continuous repair of the protective film. The former view has received attention in recent publications by Cartledge ), while the latter is favored by Evans (2). However, work on aluminum has suggested that true passivity is associated with the crystal structure of the film, which in turn determines its stability. This principle has recently been introduced by one of the authors (3) and is developed below into a general theory of passivity. 

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