Nitric acid electrolyte

The largest group of elements comprises those isolated from solution in the elemental form as a result of reduction, usually electrochemical. In acid solution, the electrolytic deposition of metal on a solid cathode is limited to noble and semi-noble metals. Trace analysis of copper and its compounds may serve as an example [100]. An anodic dissolution technique may be applied for the isolation of macroscopic amounts of copper. A sample in the form of a bar, plate, or wire is the anode in the electrolytic system. When current is passed through the electrolyte (nitric acid + persulphate), Cu is deposited on the graphite cathode, while most trace elements accumulate in the solution. In the trace analysis of platinum, the matrix has been also separated on a cathode [101]. 

Nitrous add, HNOg, is a weak electrolyte. Nitric acid, HNO3, is a strong electrolyte. Write equations to represent the ionization of each in water. Include the hydronium ion, and show the appropriate kind of arrow in each equation. 

Hydroxylamine is derived from ammonia by replacing one hydrogen atom by a hydroxyl group. It is prepared by the electrolytic reduction of nitric acid, using a lead cathode ... 

Eor the negative electrolyte, cadmium nitrate solution (density 1.8 g/mL) is used in the procedure described above. Because a small (3 —4 g/L) amount of free nitric acid is desirable in the impregnation solution, the addition of a corrosion inhibitor prevents excessive contamination of the solution with nickel from the sintered mass (see Corrosion and corrosion inhibitorsCorrosion and corrosion control). In most appHcations for sintered nickel electrodes the optimum positive electrode performance is achieved when one-third to one-half of the pore volume is filled with active material. The negative electrode optimum has one-half of its pore volume filled with active material. 

Oxidative surface treatment processes can be gaseous, ie, air, carbon dioxide, and ozone Hquid, ie, sodium hypochlorite, and nitric acid or electrolytic with the fiber serving as the anode within an electrolytic bath containing sodium carbonate, nitric acid, ammonium nitrate, ammonium sulfate, or other electrolyte. Examples of electrolytic processes are described in the patent Hterature (39,40)... 

Standard two-compartment H cell. The catholyte consisted of 3.25 M nitric acid and was separated by a medium-porosity sintered glass frit. Experiments were also carried out to determine if surface oxidation of hydrocarbon polymers could be obtained in an electrolyte consisting only of nitric acid. 

Alternatively, hydroxylammonium salts can be made either (a) by the electrolytic reduction of aqueous nitric acid between amalgamated lead electrodes in the presence of H2SO4/HCI, or (b) by the hydrogenation of nitric oxide in acid solutions over a Pl/charcoal catalyst ... 

Resistance to corrosion Most authors who compare resistance to corrosion of electroless nickel with that of electrodeposited nickel conclude that the electroless deposit is the superior material when assessed by salt spray testing, seaside exposure or subjection to nitric acid. Also, resistance to corrosion of electroless nickel is said to increase with increasing phosphorus level. However, unpublished results from International Nickel s Birmingham research laboratory showed that electroless nickel-phosphorus and electrolytic nickel deposits were not significantly different on roof exposure or when compared by polarisation data. 

Electrolyte-sulphuric acid (5% wt.%) plus an inhibitor (0-5kgm ) such as diorthotolyl thiourea, quinoline ethiodide or /3-naphthol quinoline. The temperature should be 75°C, the cathode current density 2000 Am and the time of cathodic polarisation 3 min. The anode should be carbon or lead. If lead anodes are used, lead may deposit on the specimens and cause an error in the weight loss. If the specimen is resistant to nitric acid the lead may be removed by a flash dip in 1 1 nitric acid. Except for this possible source of error, lead is preferred as an anode, as it gives more efficient corrosion product removal. 

The action is rapid, and the acidity of the electrolyte is unaffected. The error due to nitrous acid is increased by the presence of a large amount of iron iron is reduced by the current to the iron(II) state, whereupon the nitric acid is reduced. This error may be minimised by the proper regulation of the pH and by the addition of ammonium nitrate instead of nitric acid, or, best, by the removal of the iron prior to the electrolysis, or by complexation with phosphate or fluoride. 

Some interesting results have been obtained by Akand and Wyatt56 for the effect of added non-electrolytes upon the rates of nitration of benzenesulphonic acid and benzoic acid (as benzoic acidium ion in this medium) by nitric acid in sulphuric acid. Division of the rate coefficients obtained in the presence of nonelectrolyte by the concentration of benzenesulphonic acid gave rate coefficients which were, however, dependent upon the sulphonic acid concentration e.g. k2 was 0.183 at 0.075 molal, 0.078 at 0.25 molal and 0.166 at 0.75 molal (at 25 °C). With a constant concentration of non-electrolyte (sulphonic acid +, for example, 2, 4, 6-trinitrotoluene) the rate coefficients were then independent of the initial concentration of sulphonic acid and only dependent upon the total concentration of non-electrolyte. For nitration of benzoic acid a very much smaller effect was observed nitromethane and sulphuryl chloride had a similar effect upon the rate of nitration of benzenesulphonic acid. No explanation was offered for the phenomenon. 

Takahashi et al. [220] first reported the formation of Bi-Te alloy films with varying chemical composition by means of cathodic electrodeposition from aqueous nitric acid solutions (pH 1.0-0.7) containing Bi(N03)3 and Te02. The electrodeposition took place on Ti sheets at room temperature under diffusion-limited conditions for both components. In a subsequent work [221], it was noted that the use of the Bi-EDTA complex in the electrolyte would improve the results, since Bi " is easily converted into the hydrolysis product, Bi(OH)3, a hydrous polymer, thus impairing the reproducibility of electrodeposition. The as-produced films were found to consist of mixtures of Te and several Bi-Te alloy compounds, such as Bi2Tc3, Bi2+xTe3 x, Bi Tee, and BiTe. Preparation of both n- and p-type Bi2Te3 was reported in this and related works [222]. 

The electrolyte volume of the STM cells is usually very small (ofthe order of a 100 pi in the above-described case) and evaporation of the solution can create problems in long-term experiments. Miniature reference electrodes, mostly saturated calomel electrodes (SCE), have been described in the literature [25], although they are hardly used anymore in our laboratory for practical reasons Cleaning the glassware in caroic acid becomes cumbersome. For most studies, a simple Pt wire, immersed directly into solution, is a convenient, low-noise quasireference electrode. The Pt wire is readily cleaned by holding it into a Bunsen flame, and it provides a fairly constant reference potential of fcj>i — + 0.55 0.05 V versus SCE for 0.1 M sulfuric or perchloric acid solutions (+ 0.67 0.05 V for 0.1 M nitric acid), which has to be checked from time to time and for different solutions. 

Moebius An electrolytic process for removing gold and platinum from silver. The crude metal, known as Dore, is used as the anode. The cathodes are of silver or stainless steel. The electrolyte is a diluted solution of silver nitrate and nitric acid. Gold and other metals collect as anode slimes. Invented in Mexico by B. Moebius, first operated there in 1884, and subsequently widely operated in Germany and the United States. See also Balbach, Thum, Wohlwill. 

Silver II An electrolytic oxidation process for destroying traces of organic substances in water. The oxidizing agent is the silver ion in a nitric acid environment. Developed by AEA Technology, Oxford, and used for destroying war gases. 

Nitrotoluene may be oxidized by means of strong nitric acid,2 chromic acid mixture,3 or permanganates.4 Electrolytic oxidation 5 has also been proposed. The procedure given above involves the use of chromic acid mixture, but, owing to a change in the concentration of sulfuric acid, the time of reaction is greatly shortened and the preparation is thus considerably improved. 

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