Lead dioxide

A review of the early literature reveals that a variety of functional group oxidations has been studied at Pb02 anodes [532-534]. Fichter and Grizard 

Recently, Fleszar and Ploszynska [546] re-examined the kinetics of electro-oxidation of benzene and phenol at Pb02 anodes. These authors concluded that the oxidation process does follow an E.C.E.-type mechanism, there not being enough evidence to indicate direct participation of Pb02 in the oxidation of these molecules. They observed a linear dependence between oxidation rate and the rate of water electrolysis. Fleszar and Ploszynska [546] advanced the hypothesis that hydroxyl radicals formed on the anode surface caused direct hydroxylation of the benzene and phenol compounds as shown in the following scheme. In a rationalization of this mechanism, the authors invoked semiconductor-based arguments, viz. 

The OH radicals either recombine into oxygen and water or react with adsorbed organic compounds. It may be noted that Levina et al. [547] have suggested that adsorbed OH radicals are responsible for phenol oxidation at platinum. Fleszar and Ploszynska s [546] results are somewhat at variance with those of Clarke et al. [537] in that the latter authors observed the highest efficiency for benzene oxidation at Pb02 anodes at potentials prior to the onset of oxygen evolution. 

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Lead dioxide is slightly soluble in concentrated nitric acid and concentrated sulphuric acid, and it dissolves in fused alkalis. It therefore has amphoteric properties, although these are not well characteri.sed since it is relatively inert. 

Hence sulphuric acid is used up and insoluble lead(II) sulphate deposited on both plates. This process maintains a potential difference between the two plates of about 2 V. If now a larger potential difference than this is applied externally to the cell (making the positive plate the anode) then the above overall reaction is reversed, so that lead dioxide is deposited on the anode, lead is deposited on the cathode, and sulphuric acid is re-formed. Hence in the electrolyte, we have ... 

If the charging process continues after all the lead sulphate has been used up, then the charging voltage rises. Hydrogen is liberated from the lead electrode, and oxygen is liberated from the lead dioxide electrode. The accumulator is then said to be gassing . 

Lead dioxide. A convenient method of preparation is to oxidi.se a plumbous salt in an alkaline medium with a hypochlorite solution ... 

This solution may also be employed in the test for bromine. If iodine has been found, add small amounts of sodium nitrite solution, warm shghtly and shake with fresh 1 ml. portions of carbon tetrachloride until the last extract is colourless boil the acid solution until no more nitrous fumes are evolved and cool. If iodine is absent, use 1 ml. of the fusion solution which has been strongly acidified with glacial acetic acid. Add a small amount of lead dioxide, place a strip of fluorescein paper across the mouth of the tube, and warm the solution. If bromine is present, it will colour the test paper rose-pink (eosin). 

Lead dioxide in acetic acid solution gives lead tetra acetate which oxidises hydrogen bromide (and also hydrogen iodide), but has practically no cflFect under the above experimental conditions upon hydrogen chloride. 

Manganese(II) can be titrated directly to Mn(III) using hexacyanoferrate(III) as the oxidant. Alternatively, Mn(III), prepared by oxidation of the Mn(II)-EDTA complex with lead dioxide, can be determined by titration with standard iron(II) sulfate. 

Hydroxylamine Barium oxide and peroxide, carbonyls, chlorine, copper(II) sulfate, dichromates, lead dioxide, phosphorus trichloride and pentachloride, permanganates, pyridine, sodium, zinc... 

Lead dioxide Aluminum carbide, hydrogen peroxide, hydrogen sulfide, hydroxylamine, ni-troalkanes, nitrogen compounds, nonmetal halides, peroxoformic acid, phosphorus, phosphorus trichloride, potassium, sulfur, sulfur dioxide, sulfides, tungsten, zirconium... 

Phosphorus trichloride Acetic acid, aluminum, chromyl dichloride, dimethylsulfoxide, hydroxylamine, lead dioxide, nitric acid, nitrous acid, organic matter, potassium, sodium water... 

Sulfuryl dichloride Alkalis, diethyl ether, dimethylsulfoxide, dinitrogen tetroxide, lead dioxide, phosphorus... 

Oxidative Fluorination of Aromatic Hydrocarbons. The economically attractive oxidative fluorination of side chains in aromatic hydrocarbons with lead dioxide or nickel dioxide in Hquid HF stops at the ben2al fluoride stage (67% yield) (124). 

Anodes. Lead—antimony (6—10 wt %) alloys containing 0.5—1.0 wt % arsenic have been used widely as anodes in copper, nickel, and chromium electrowinning and metal plating processes. Lead—antimony anodes have high strength and develop a corrosion-resistant protective layer of lead dioxide during use. Lead—antimony anodes are resistant to passivation when the current is frequendy intermpted. 

Lea.dAnodes. A principal use for lead—calcium—tin alloys is lead anodes for electrowinning. The lead—calcium anodes form a hard, adherent lead dioxide layer during use, resist corrosion, and gready reduce lead contamination of the cathode. Anodes produced from cast lead—calcium (0.03—0.09 wt %) alloys have a tendency to warp owing to low mechanical strength and casting defects. 

Silver reduces the oxygen evolution potential at the anode, which reduces the rate of corrosion and decreases lead contamination of the cathode. Lead—antimony—silver alloy anodes are used for the production of thin copper foil for use in electronics. Lead—silver (2 wt %), lead—silver (1 wt %)—tin (1 wt %), and lead—antimony (6 wt %)—silver (1—2 wt %) alloys ate used as anodes in cathodic protection of steel pipes and stmctures in fresh, brackish, or seawater. The lead dioxide layer is not only conductive, but also resists decomposition in chloride environments. Silver-free alloys rapidly become passivated and scale badly in seawater. Silver is also added to the positive grids of lead—acid batteries in small amounts (0.005—0.05 wt %) to reduce the rate of corrosion. 

The excellent corrosion-resistant lead dioxide, Pb02, film formed on anodes and lead—acid battery positive grids in sulfuric acid has enabled lead insoluble anodes and lead—acid batteries to maintain the dominant positions in their respective fields. 

Tetravalent lead is obtained when the metal is subjected to strong oxidizing action, such as in the electrolytic oxidation of lead anodes to lead dioxide, Pb02 when bivalent lead compounds are subjected to powerful oxidizing conditions, as in the calcination of lead monoxide to lead tetroxide, Pb O or by wet oxidation of bivalent lead ions to lead dioxide by chlorine water. The inorganic compounds of tetravalent lead are relatively unstable eg, in the presence of water they hydrolyze to give lead dioxide. 

Lead Dioxide. Lead dioxide (lead peroxide, plattnerite), Pb02, is a brownish black crystalline powder consisting of fine crystalline flakes ia... 

Lead dioxide is electrically conductive and is formed ia place as the active material of the positive plates of lead-acid storage batteries. Because it is a vigorous oxidizing agent when heated, it is used ia the manufacture of dyes, chemicals, matches (qv), pyrotechnics (qv), and Hquid polysulfide polymers (42) (see Polypous containing sulfur). 

Lead Sesquioxide. Lead sesquioxide (lead trioxide), Pb202, is an amorphous, orange-yeUow powder soluble ia cold water. It decomposes ia hot water and ia acids to lead salts plus Pb02. Lead sesquioxide can be prepared from lead dioxide by hydrothermal dissociation (43). 

Several more traditional materials have found specific though limited commercial apphcation as metal anodes. Examples are lead [7439-92-1] and ziac [7440-66-6] ia the electrogalvaniziag practice. Lead dioxide [1309-60-0] and manganese dioxide [1313-13-9] anode technologies have also been pursued. Two iadustrial electrolytic iadustries, aluminum [7429-90-5] and electric arc steel, stiU use graphite anodes. Heavy investment has been devoted to research and development to bring the advantages of DSA to these operations, but commercialization has not been achieved. 

The standard potential for the anodic reaction is 1.19 V, close to that of 1.228 V for water oxidation. In order to minimize the oxygen production from water oxidation, the cell is operated at a high potential that requires either platinum-coated or lead dioxide anodes. Various mechanisms have been proposed for the formation of perchlorates at the anode, including the discharge of chlorate ion to chlorate radical (87—89), the formation of active oxygen and subsequent formation of perchlorate (90), and the mass-transfer-controUed reaction of chlorate with adsorbed oxygen at the anode (91—93). Sodium dichromate is added to the electrolyte ia platinum anode cells to inhibit the reduction of perchlorates at the cathode. Sodium fluoride is used in the lead dioxide anode cells to improve current efficiency. 

The preparation of triaryknethane dyes proceeds through several stages formation of the colorless leuco base in acid media, conversion to the colorless carbinol base by using an oxidising agent, eg, lead dioxide, manganese dioxide, or alkah dichromates, and formation of the dye by treatment with acid (Fig. 1). The oxidation of the leuco base can also be accompHshed with atmospheric oxygen in the presence of catalysts. 

The central carbon atom is derived from an aromatic aldehyde or a substance capable of generating an aldehyde during the course of the condensation. Malachite green is prepared by heating benzaldehyde under reflux with a slight excess of dimethyl aniline in aqueous acid (Fig. 2). The reaction mass is made alkaline and the excess dimethylaniline is removed by steam distillation. The resulting leuco base is oxidized with freshly prepared lead dioxide to the carbinol base, and the lead is removed by precipitation as the sulfate. Subsequent treatment of the carbinol base with acid produces the dye, which can be isolated as the chloride, the oxalate [2437-29-8] or the zinc chloride double salt [79118-82-4]. 

Diphenylmethane Base Method. In this method, the central carbon atom is derived from formaldehyde, which condenses with two moles of an arylamine to give a substituted diphenylmethane derivative. The methane base is oxidized with lead dioxide or manganese dioxide to the benzhydrol derivative. The reactive hydrols condense fairly easily with arylamines, sulfonated arylamines, and sulfonated naphthalenes. The resulting leuco base is oxidized in the presence of acid (Fig. 4). 

The most suitable oxidizing agent is potassium ferricyanide, but ferric chloride, hydrogen peroxide ia the presence of ferrous salts, ammonium persulfate, lead dioxide, lead tetraacetate or chromate, or silver and cupric salts may be useful. Water mixed, eg, with methanol, dimethylformamide, or glycol ethers, is employed as reaction medium. 

Fig. 1. Schematic representation of a battery system also known as an electrochemical transducer where the anode, also known as electron state 1, may be comprised of lithium, magnesium, zinc, cadmium, lead, or hydrogen, and the cathode, or electron state 11, depending on the composition of the anode, may be lead dioxide, manganese dioxide, nickel oxide, iron disulfide, oxygen, silver oxide, or iodine.

At the cathode, or positive electrode, lead dioxide [1309-60-0] Pb02, reacts with sulfuric acid to form lead sulfate [7446-14-2] PbSO, and water in the discharging reaction... 

The mercurous sulfate [7783-36-OJ, Hg2S04, mercury reference electrode, (Pt)H2 H2S04(y ) Hg2S04(Hg), is used to accurately measure the half-ceU potentials of the lead—acid battery. The standard potential of the mercury reference electrode is 0.6125 V (14). The potentials of the lead dioxide, lead sulfate, and mercurous sulfate, mercury electrodes versus a hydrogen electrode have been measured (24,25). These data may be used to calculate accurate half-ceU potentials for the lead dioxide, lead sulfate positive electrode from temperatures of 0 to 55°C and acid concentrations of from 0.1 to Sm. 

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