Nitric Acid chemistry

H. Y. Wu et al.. Seed-mediated synthesis of high aspiect ratio gold nanorods with nitric acid. Chemistry of Materials, 17(25), 6447-6451 (2005). 

It is the nitronium ion which is responsible for nitrating actions in organic chemistry which are carried out in a mixture of nitric and sulphuric acids. When nitric acid is dissolved in water, its behaviour is that of a strong acid, i.e. ... 

Silver has little tendency to formally lose more than one electron its chemistry is therefore almost entirely restricted to the + 1 oxidation state. Silver itself is resistant to chemical attack, though aqueous cyanide ion slowly attacks it, as does sulphur or a sulphide (to give black Ag S). hence the tarnishing of silver by the atmosphere or other sulphur-containing materials. It dissolves in concentrated nitric acid to give a solution of silver(I) nitrate. AgNOj. 

Technetium is a silvery-gray metal that tarnishes slowly in moist air. The common oxidation states of technetium are +7, +5, and +4. Under oxidizing conditions technetium (Vll) will exist as the pertechnetate ion, TcOr-. The chemistry of technetium is said to be similar to that of rhenium. Technetium dissolves in nitric acid, aqua regia, and cone, sulfuric acid, but is not soluble in hydrochloric acid of any strength. The element is a remarkable corrosion inhibitor for steel. The metal is an excellent superconductor at IIK and below. 

Another aspect of my early research in Budapest was in nitration chemistry, specifically the preparation of nitronium tetrafluoroborate, a stable nitronium salt. 1 was able to prepare the salt in a simple and efficient way from nitric acid, hydrogen fluoride, and boron trifluoride. 

Acid—Base Chemistry. Acetic acid dissociates in water, pK = 4.76 at 25°C. It is a mild acid which can be used for analysis of bases too weak to detect in water (26). It readily neutralizes the ordinary hydroxides of the alkaU metals and the alkaline earths to form the corresponding acetates. When the cmde material pyroligneous acid is neutralized with limestone or magnesia the commercial acetate of lime or acetate of magnesia is obtained (7). Acetic acid accepts protons only from the strongest acids such as nitric acid and sulfuric acid. Other acids exhibit very powerful, superacid properties in acetic acid solutions and are thus useful catalysts for esterifications of olefins and alcohols (27). Nitrations conducted in acetic acid solvent are effected because of the formation of the nitronium ion, NO Hexamethylenetetramine [100-97-0] may be nitrated in acetic acid solvent to yield the explosive cycl o trim ethyl en etrin itram in e [121 -82-4] also known as cyclonit or RDX. 

Chemistry. Free-radical nitrations consist of rather compHcated nitration and oxidation reactions (31). When nitric acid is used in vapor-phase nitrations, the reaction of equation 5 is the main initiating step where NO2 is a free radical, either -N02 or -ON02. Temperatures of >ca 350° are required to obtain a significant amount of initiation, and equation 5 is the rate-controlling step for the overall reaction. Reactions 6 and 7 are chain-propagating steps. 

Nitric acid oxidation is used where carbohydrates, ethylene glycol, and propylene are the starting materials. The diaLkyl oxalate process is the newest, where diaLkyl oxalate is synthesized from carbon monoxide and alcohol, then hydrolyzed to oxahc acid. This process has been developed by UBE Industries in Japan as a CO coupling technology in the course of exploring C-1 chemistry. 

Peroxonitrite is beHeved to be present in the crystals of nitric acid trihydrate that form in the stratosphere and in Martian soil (see Extraterrestrial materials). Peroxonitrous acid may be present in mammalian blood and other biochemical systems. However, peroxonitric acid, HNO, is not known. Before the chemistry of peroxonitrous acid was understood, these two acids were sometimes confused. 

In TBP extraction, the yeUowcake is dissolved ia nitric acid and extracted with tributyl phosphate ia a kerosene or hexane diluent. The uranyl ion forms the mixed complex U02(N02)2(TBP)2 which is extracted iato the diluent. The purified uranium is then back-extracted iato nitric acid or water, and concentrated. The uranyl nitrate solution is evaporated to uranyl nitrate hexahydrate [13520-83-7], U02(N02)2 6H20. The uranyl nitrate hexahydrate is dehydrated and denitrated duting a pyrolysis step to form uranium trioxide [1344-58-7], UO, as shown ia equation 10. The pyrolysis is most often carried out ia either a batch reactor (Fig. 2) or a fluidized-bed denitrator (Fig. 3). The UO is reduced with hydrogen to uranium dioxide [1344-57-6], UO2 (eq. 11), and converted to uranium tetrafluoride [10049-14-6], UF, with HF at elevated temperatures (eq. 12). The UF can be either reduced to uranium metal or fluotinated to uranium hexafluoride [7783-81-5], UF, for isotope enrichment. The chemistry and operating conditions of the TBP refining process, and conversion to UO, UO2, and ultimately UF have been discussed ia detail (40). 

Heterogeneous chemistry occurring on polar stratospheric cloud particles of ice and nitric acid trihydrate has been estabUshed as a dorninant factor in the aggravated seasonal depletion of o2one observed to occur over Antarctica. Preliminary attempts have been made to parameterize this chemistry and incorporate it in models to study ozone depletion over the poles (91) as well as the potential role of sulfate particles throughout the stratosphere (92). 

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 ... 

The solution chemistry of nitric acid is extremely varied. Redox data are summarized in Table 11.4 and Fig. 11.9 (pp. 434-8). In... 

The corrosion of tin by nitric acid and its inhibition by n-alkylamines has been reportedThe action of perchloric acid on tin has been studied " and sulphuric acid corrosion inhibition by aniline, pyridine and their derivatives as well as sulphones, sulphoxides and sulphides described. Attack of tin by oxalic, citric and tartaric acids was found to be under the anodic control of the Sn salts in solution in oxygen free conditions . In a study of tin contaminated by up to 1200 ppm Sb, it was demonstrated that the modified surface chemistry catalysed the hydrogen evolution reaction in deaerated citric acid solution. 

In aromatic compds, an amino group may be replaced by the nitro group by diazotization and reaction with nitric acid in the presence of cuprous salts (the Sandmeyer reaction). This method is used for lab work only and is described in standard textbooks on preparative organic chemistry... 

IndChem 23, 17—24 (1947) (Ammonia oxidation process and concentration of nitric acid) 37) O.A. Hougen K.M. Watson, Chemical Process Principles , J. Wiley, NY, Combined volume (1947), 224 (Heat capacities of nitric acid) 38) W.M. Latimer J.H. Hildebrand, Reference Book of Inorganic Chemistry , Macmillan, NY (1947), 202-207 39) S. 

Reference Book of Inorganic Chemistry , MacMillan, NY (1947), 195 202 4) Partington (1950), 569 5) F. Miles, Nitric Acid... 

Nitric acid is one of the most common, and cheaper, oxidants used in organic chemistry. It will oxidize sulphoxides to sulphones in good yields if heated under reflux for several... 

An overview is presented of plutonium process chemistry at Rocky Flats and of research in progress to improve plutonium processing operations or to develop new processes. Both pyrochemical and aqueous methods are used to process plutonium metal scrap, oxide, and other residues. The pyrochemical processes currently in production include electrorefining, fluorination, hydriding, molten salt extraction, calcination, and reduction operations. Aqueous processing and waste treatment methods involve nitric acid dissolution, ion exchange, solvent extraction, and precipitation techniques. 

Molten salt extraction residues are processed to recover plutonium by an aqueous precipitation process. The residues are dissolved in dilute HC1, the actinides are precipitated with potassium carbonate, and the precipitate redissolved in nitric acid (7M) to convert from a chloride to a nitrate system. The plutonium is then recovered from the 7M HNO3 by anion exchange and the effluent sent to waste or americium recovery. We are studying actinide (III) carbonate chemistry and looking at new... 

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