Electrolytic, accelerated

It can be seen from Table 10 that the order of reactivity of the electrophilic reagent is BusHgBr < BusHgOAc < BusHgN03, and that the addition of various electrolytes accelerates both substitution by jec.-butylmercuric bromide and substitution by sec.-butylmercuric nitrate. All of this is evidence52 for mechanism SE2(open), and we may therefore write (XIX) as a general transition state for all the above substitutions, in solvent ethanol. 

Aniline and hydroquinone can be oxidised to quinone,1 and the addition of a manganese salt to the electrolyte accelerates the oxidation. 

The retarding effect of sodium sulphate in the application of mol larly-dispersed dyes has already been referred to. It must be emphas that the effect is only apparent when dyeing at low/>H values, and in nei solutions the presence of electrolytes accelerates adsorption. The expl tion which is usually accepted is that when the concentration of anioi the liquor is increased, there is more competition for the positive sit the fibre ... 

In some cases, particularly with iaactive metals, electrolytic cells are the primary method of manufacture of the fluoroborate solution. The manufacture of Sn, Pb, Cu, and Ni fluoroborates by electrolytic dissolution (87,88) is patented. A typical cell for continous production consists of a polyethylene-lined tank with tin anodes at the bottom and a mercury pool (ia a porous basket) cathode near the top (88). Pluoroboric acid is added to the cell and electrolysis is begun. As tin fluoroborate is generated, differences ia specific gravity cause the product to layer at the bottom of the cell. When the desired concentration is reached ia this layer, the heavy solution is drawn from the bottom and fresh HBP is added to the top of the cell continuously. The direct reaction of tin with HBP is slow but can be accelerated by passiag air or oxygen through the solution (89). The stannic fluoroborate is reduced by reaction with mossy tin under an iaert atmosphere. In earlier procedures, HBP reacted with hydrated stannous oxide. 

Electroless Electrolytic Plating. In electroless or autocatalytic plating, no external voltage/current source is required (21). The voltage/current is suppHed by the chemical reduction of an agent at the deposit surface. The reduction reaction must be catalyzed, and often boron or phosphoms is used as the catalyst. Materials that are commonly deposited by electroless plating (qv) are Ni, Cu, Au, Pd, Pt, Ag, Co, and Ni—Fe (permalloy). In order to initiate the electroless deposition process, a catalyst must be present on the surface. A common catalyst for electroless nickel is tin. Often an accelerator is needed to remove the protective coat on the catalysis and start the reaction. 

This reaction is accelerated by iacreased temperature, iacreased electrolyte concentration, and by the use of sodium hydroxide rather than potassium hydroxide ia the electrolyte. It is beheved that the presence of lithium and sulfur ia the electrode suppress this problem. Generally, if the cell temperature is held below 50°C, the oxidation and/or solubiUty of iron is not a problem under normal cell operating conditions. 

The intermediate HCIO2 is rapidly oxidized to chloric acid. Some chlorine dioxide may also be formed. Kinetic studies have shown that decomposition to O2 and chloric acid increase with concentration, temperature (88), and exposure to light (89—92), and are pH dependent (93). Decomposition to O2 is also accelerated by catalysts, and decomposition to chlorate is favored by the presence of other electrolytes, eg, sodium chloride (94—96). 

Insoluble corrosion prodiic ts may be completely impeivious to the corroding liquid and, therefore, completely protective or they may be quite permeable and allow local or general corrosion to proceed unhindered. Films that are nonuniform or discontinuous may tend to localize corrosion in particular areas or to induce accelerated corrosion at certain points by initiating electrolytic effects of the concentration-cell type. Films may tend to retain or absorb moisture and thus, by delaying the time of drying, increase the extent of corrosion resulting from exposure to the atmosphere or to corrosive vapors. 

As metal ion concentration increases in the crevice, a net positive charge accumulates in the crevice electrolyte. This attracts negatively charged ions dissolved in the water. Chloride, sulfate, and other anions spontaneously concentrate in the crevice (Figs. 2.4 and 2.5). Hydrolysis produces acids in the crevice, accelerating attack (Reactions 2.5 and 2.6). Studies have shown that the crevice pH can decrease to 2 or less in salt solutions having a neutral pH. 

Figure 4.9 Smooth acceleration through liquid electrolyte starters...

This type of switching provides very smooth acceleration. This is an advantage of electrolyte switchings over other conventional types of switchings. It exerts no kicks and calls for no special coupling arrangement to transmit the power smoothly to the drive if the requirement of the drive is to be precise and to have a smoother acceleration. 

Enantioresolution in capillary electrophoresis (CE) is typically achieved with the help of chiral additives dissolved in the background electrolyte. A number of low as well as high molecular weight compounds such as proteins, antibiotics, crown ethers, and cyclodextrins have already been tested and optimized. Since the mechanism of retention and resolution remains ambiguous, the selection of an additive best suited for the specific separation relies on the one-at-a-time testing of each individual compound, a tedious process at best. Obviously, the use of a mixed library of chiral additives combined with an efficient deconvolution strategy has the potential to accelerate this selection. 

C. The corrosion of the metal considered may be markedly increased by the contact metal. (Acceleration is likely to occur only when the metal becomes wet hy moisture containing an electrolyte, e.g, salt, acid, combustion products. In ships, acceleration may be expected to occur under in-board conditions, since salinity and condensation are frequently present. Under less severe conditions the acceleration may be slight or negligible.)... 

There is an accelerating trend away from the use of lead-containing solders in contact with potable water. The effects of galvanic corrosion of one of the substitute alloys (Sn3%Ag) in contact with a number of other metals including copper have therefore been studied . The corrosion of tin/Iead alloys in different electrolytes including nitrates, nitric and acetic acids, and citric acid over the pH range 2-6 were reported. The specific alloy Pb/15%Sn was studied in contact with aqueous solutions in the pH range... 

Zinc in contact with wood Zinc is not generally affected by contact with seasoned wood, but oak and, more particularly, western red cedar can prove corrosive, and waters from these timbers should not drain onto zinc surfaces. Exudations from knots in unseasoned soft woods can also affect zinc while the timber is drying out. Care should be exercised when using zinc or galvanised steel in contact with preservative or fire-retardant-treated timber. Solvent-based preservatives are normally not corrosive to zinc but water-based preservatives, such as salt formulated copper-chrome-arsenic (CCA), can accelerate the rate of corrosion of zinc under moist conditions. Such preservatives are formulated from copper sulphate and sodium dichromate and when the copper chromium and arsenic are absorbed into the timber sodium sulphate remains free and under moist conditions provides an electrolyte for corrosion of the zinc. Flame retardants are frequently based on halogens which are hygroscopic and can be aggressive to zinc (see also Section 18.10). 

In view of the electrochemical nature of corrosion, it has seemed reasonable to many investigators to assume that suitable accelerated corrosion tests could be made by observing the response to electrolytic stimulation of the corrosion processes, or by attaching particular significance to the results of quickly made electrode potential and current measurements. 

Acceleration of corrosion by electrolytic stimulation has sometimes been found to distort normal corrosion reactions to such an extent that the results bear no consistent relationship to ordinary corrosion and are, therefore, quite inconsistent and unreliable. This was shown, for example, by a series... 

Some investigatorshave advocated a type of accelerated test in which the specimens are coupled in turn to a noble metal such as platinum in the corrosive environment and the currents generated in these galvanic couples are used as a measure of the relative corrosion resistance of the metals studied. This method has the defects of other electrolytic means of stimulating anodic corrosion, and, in addition, there is a further distortion of the normal corrosion reactions and processes by reason of the differences between the cathodic polarisation characteristics of the noble metal used as an artificial cathode and those of the cathodic surfaces of the metal in question when it is corroding normally. 

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