Surface activation nitric acid

Radioactivity of uranium can be measured by alpha counters. The metal is digested in nitric acid. Alpha activity is measured by a counting instrument, such as an alpha scintillation counter or gas-flow proportional counter. Uranium may be separated from the other radioactive substances by radiochemical methods. The metal or its compound(s) is first dissolved. Uranium is coprecipitated with ferric hydroxide. Precipitate is dissolved in an acid and the solution passed through an anion exchange column. Uranium is eluted with dilute hydrochloric acid. The solution is evaporated to near dryness. Uranium is converted to its nitrate and alpha activity is counted. Alternatively, uranium is separated and electrodeposited onto a stainless steel disk and alpha particles counted by alpha pulse height analysis using a silicon surface barrier detector, a semiconductor particle-type detector. 

Catalytic gas-phase reactions play an important role in many bulk chemical processes, such as in the production of methanol, ammonia, sulfuric acid, and nitric acid. In most processes, the effective area of the catalyst is critically important. Since these reactions take place at surfaces through processes of adsorption and desorption, any alteration of surface area naturally causes a change in the rate of reaction. Industrial catalysts are usually supported on porous materials, since this results in a much larger active area per unit of reactor volume. 

Uranium tarnishes readily in the atmosphere at room temperature. Electropolishing inhibits the process whilst etching in nitric acid activates the surface. Uranium dioxide and hydrated UO3 are the principal solid products. 

With materials like the stainless steels, which may be either active or passive in a test environment, it is common practice to produce a particular initial level of passivity or activity by some special chemical treatment prior to exposure. With stainless steels this objective may be subsidiary to eliminating surface contamination, such as iron from processing tools, by treatment in a nitric acid solution which might also be expected to achieve substantial passivity incidental to the cleaning action (ASTM A380 1988). 

A 3.5 ml portion in a 4 ml polyethylene vial was irradiated for 5 min. Another portion, 3.0 ml in a 3.5 ml silica vial, was irradiated for 3 d. After the short irradiation, 3 ml of the irradiated solution were transferred into an activity-free vial and submitted to y-ray spectrometry with a Ge(Ii) detector coupled to a 4000-channel analyser. After the long irradiation, the sample was allowed to cool for 3 d, then the surface of the silica ampoule was cleaned with dilute nitric acid and the sealed ampoule was placed in the counter (the background activity of the ampoule was negligible). Gamma-ray energy and the areas under peaks were calculated by computer. To determine the half-fives of the nuclides produced, the counting was repeated at appropriate intervals. 

In mixtures containing nitric acid various fuels may be employed. Fuels used for hypergolic ones, i.e. those which autoignite on mixing, differ essentially from those used in other mixtures. In hypergolic mixtures, fuels are used which reac. violently with nitric acid, e.g. aliphatic or aromatic amines, furfuryl alcohol, mercapt tans, hydrazine etc. It is also advisable to add surface-active substances to the mixture-... 

Several formal and informal intercomparisons of nitric acid measurement techniques have been carried out (43-46) these intercomparisons involve a multitude of techniques. The in situ measurement of this species has proven difficult because it very rapidly absorbs on any inlet surfaces and because it is involved in reversible solid-vapor equilibria with aerosol nitrate species. These equilibria can be disturbed by the sampling process these disturbances lead to negative or positive errors in the determination of the ambient vapor-phase concentration. The intercomparisons found differences of the order of a factor of 2 generally, and up to at least a factor of 5 at levels below 0.2 ppbv. These studies clearly indicate that the intercompared techniques do not allow the unequivocal determination of nitric acid in the atmosphere. A laser-photolysis, fragment-fluorescence method (47) and an active chemical ionization, mass spectrometric technique (48) were recently reported for this species. These approaches may provide more definite specificity for HN03. Challenges clearly remain in the measurement of this species. 

Specific surface area is crucial for air purifying materials, because unlike usual catalytic reactions the reaction products (nitric acid or nitrate) remain on the surface to cover active sites. This has been demonstrated by the fact that photocatalytic performance is very much improved by using finer Ti02 particles, increasing Ti02 content and making porous structures. 

Other studies were directed toward the activation of inert pyro-lusite. Metallic copper was dissolved in dilute nitric acid, in the presence of an excess of pyrolusite that had been previously washed in nitric acid. A slight excess of ammonia was then added and the suspension was aerated for 24 hours. The thoroughly washed and dried product was completely active at — 20°C. Similar activity was exhibited by the product obtained by etching the surface of the granules of pyrolusite by a mixture of nitric acid and cobalt, the amount of nitric oxide liberated being just sufficient to dissolve one-tenth of a given amount of pyrolusite. The mixed oxides were redeposited upon the etched surface by ammoniacal aeration. 

The importance of catalysts in our energy and pollution conscious age is growing. Many catalysts depend for their activity on low levels of rather exotic metals, while even trace surface levels of elements such as lead may impair their activity. Thus there is plenty of scope for atomic absorption spectrometry. Many homogeneous catalysts are deposited on an alumina base, thus obtaining dissolution is not always easy and some interference in the air/acetylene flame may be encountered. A leaching procedure (e.g. with nitric acid) to dissolve adsorbed trace metals may be used to circumvent these problems. 

For many catalysts, the major component is the active material. Examples of such unsupported catalysts are the aluminosilicates and zeolites used for cracking petroleum fractions. One of the most widely used unsupported metal catalysts is the precious metal gauze as used, for example, in the oxidation of ammonia to nitric oxide in nitric acid plants. A very fast rate is needed to obtain the necessary selectivity to nitric oxide, so a low metal surface area and a short contact time are used. These gauze s are woven from fine wires (0.075 mm in diameter) of platinum alloy, usually platinum-rhodium. Several layers of these gauze s, which may be up to 3 m in diameter, are used. The methanol oxidation to formaldehyde is another process in which an unsupported metal catalyst is used, but here metallic silver is used in the form of a bed of granules. 

The purer forms of iron (wrought iron and steel) appear to be much more susceptible to this kind of reaction than cast iron.3 If the attacking acid is readily reducible by hydrogen, many secondary reactions may take place. Thus with nitric acid, oxides of nitrogen and ammonia may be evolved, whilst with selenic acid a deposit of elementary selenium is obtained (see below). When iron is exposed to the action of acids that are also powerful oxidisers—such as, for example, fairly concentrated solutions of nitric and chromic acids,—it is frequently rendered inert or passive.4 Its surface may remain perfectly bright, but the metal does not show any appreciable solution in the acid, and if removed and immersed in dilute solutions of such salts as copper and silver sulphates, no reaction takes place, although ordinary active iron would cause an immediate precipitation of the more electronegative metal. 

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