Lead sulfates

Lehman, T. A. Everett, W. W. Solubility of Lead Sulfate in Water and in Sodium Sulfate Solutions, /. Chem. Educ. 1982, 59, 797. 

By far the most common lead salt used for PVC stabilization is tribasic lead sulfate. It can be found either alone or combined with another lead salt in almost every lead-stabilized PVC formulation. Many of the combinations are actually coprecipitated hybrid products, ie, basic lead sulfophthalates. Dibasic lead stearate and lead stearate are generally used as costabilizers combined with other primary lead salts, particularly in rigid PVC formulations where they contribute lubrication properties dibasic lead stearate provides internal lubrication and lead stearate is a good external lubricant. Basic lead carbonate is slowly being replaced by tribasic lead sulfate in most appHcations due the relatively low heat stabiHty of the carbonate salt which releases CO2 at about 180°C during PVC processing. 

Rigid Applications. The use of the lead stabilizers is very limited in the United States but, they are stiU used in several rigid PVC appHcations in Europe and Asia. The highest use of lead stabilizers in rigid PVC is for pipe and conduit appHcations. Tribasic lead sulfate is the primary heat stabilizer with lead stearates included to provide lubrication. The lead products are typically fully formulated, usually including lubricants and pigments for pipe extmsion appHcations. These lead one-packs, when used at about 1.8—2.5 phr, provide all of the stabilizer and lubrication needed to process the polymer. A lead one-pack contains tribasic lead sulfate, dibasic lead stearate calcium stearate, polyethylene wax, paraffin wax, ester wax, and pigments. 

Acid Oxidation. Reactions of lead with acid and alkaUes are varied. Nitric acid, the best solvent for lead, forms lead nitrate acetic acid forms soluble lead acetate in the presence of oxygen sulfuric acid forms insoluble lead sulfate. Sulfuric acid is stored in containers with chemical or acid-grade lead. Lead dissolves slowly in HCl, but in the presence of aqueous alkaUes forms soluble plumbites and plumbates. 

A typical automobile battery weighs 16.4 kg and consists of 3.5 kg metallic lead, 2.6 kg lead oxides, 4.0 kg lead sulfate, 1.3 kg polypropylene, 1.1 kg PVC, mbber and other separators, and 3.9 kg electrolyte. Including acid and water, the lead-beating parts represent 61 wt %, ie, 21 wt % of lead alloy (2% Sb) and 40 wt % lead oxides and sulfate. Nonlead-beating parts constitute the remaining 39% the case (hard mbber or polypropylene) and separators (PVC) at 15 wt % and the electrolyte at 24 wt %. 

After acid removal, scrap batteries are fed to a hammer mill in which they are ground to <5 cm particles. The ground components are fed to a conveyor and passed by a magnet to remove undesirable contamination. The lead scrap is then classified on a wet screen through which fine particles of lead sulfate and lead oxide pass, and the large oversize soHd particles are passed on to a hydrodynamic separator. The fine particles are settled to a thick slurry and the clarified washwater recirculated to the wet screen. 

Copper-containing lead alloys undergo less corrosion in sulfuric acid or sulfate solutions than pure lead or other lead alloys. The uniformly dispersed copper particles give rise to local cells in which lead forms the anode and copper forms the cathode. Through this anodic corrosion of the lead, an insoluble film of lead sulfate forms on the surface of the lead, passivating it and preventing further corrosion. The film, if damaged, rapidly reforms. 

Lead shows excellent resistance to phosphoric and sulfuric acid in almost all concentrations and at elevated temperatures, as well as to sulfide, sulfite, and sulfate solutions. The corrosion film is insoluble lead sulfate which rapidly reforms if it is damaged. Lead is also resistant to chlorides, fluorides, and bromates at low concentrations and low temperatures. However, because lead is soluble in nitric and acetic acids, it is not resistant to these acids. 

The carbonates, sulfates, nitrates, and haUdes of lead (except the yeUow iodide) are colodess. Bivalent lead forms a soluble nitrate, chlorate, and acetate a slightly soluble chloride and an insoluble sulfate, carbonate, chromate, phosphate, molybdate, and sulfide. Highly crystalline basic lead salts of both anhydrous and hydrated types are readily formed. Tetrabasic lead sulfate [52732-72-6] 4PbO PbSO, and the hydrated tribasic salt [12397-06-7] ... 

PbO PbO H2O, for example, may be formed by boiling suspensions of lead oxide and lead sulfate in water. In addition, complex mixed salts, such as white lead, 2PbC02 Pb(OH)2, are readily formed. 

Lead forms a normal and an acid sulfate and several basic sulfates. Basic and normal lead sulfates ate fundamental components in the operation of lead-sulfuric acid storage batteries. Basic lead sulfates also ate used as pigments and heat stabilizers (qv) in vinyl and certain other plastics. 

Dibasic Lead Sulfate. Dibasic lead sulfate [12036-76-9] 2PbOPbSO, is a white powder, mol wt 749.70, mp 961°C. The dibasic compound can be prepared by fusion of the two components. It has been sold as a PVC stabilizer in Japan and is sold in Europe in combination with dibasic lead phosphite. 

Tribasic Lead Sulfate. Tribasic lead sulfate [12202-17 ] 3PbO PbSO 2 hue white powder, mol wt 890.93, sp gr 6.9, refractive... 

Tetrabasic Lead Sulfate. Tetrabasic lead sulfate [12065-90-6] 4PbO PbSO, mol wt 1196.12, sp gr 8.15, is made by fusion of stoichiometric quantities of Htharge (PbO) and lead sulfate (PbSO heat of formation, Ai/ = — 1814 kJ/mol (—434.1 kcal/mol). Alternatively, tetrabasic lead sulfate may be prepared by boiling the components in aqueous suspensions. At about 70°C, tribasic hydrate reacts with lead oxide to form tetrabasic sulfate. At 80°C, this transformation is complete in - 20 hours. Tetrabasic lead sulfate is used in limited quantities in Europe as a PVC stabilizer. However, in the United States, lead-acid batteries have been developed by BeU Telephone Laboratories, which contain tetrabasic lead sulfate. Such batteries are used for emergency power at telephone switchboard stations and have an anticipated service life of over 50 years. 

Metals less noble than copper, such as iron, nickel, and lead, dissolve from the anode. The lead precipitates as lead sulfate in the slimes. Other impurities such as arsenic, antimony, and bismuth remain partiy as insoluble compounds in the slimes and partiy as soluble complexes in the electrolyte. Precious metals, such as gold and silver, remain as metals in the anode slimes. The bulk of the slimes consist of particles of copper falling from the anode, and insoluble sulfides, selenides, or teUurides. These slimes are processed further for the recovery of the various constituents. Metals less noble than copper do not deposit but accumulate in solution. This requires periodic purification of the electrolyte to remove nickel sulfate, arsenic, and other impurities. 

The metal salts of MSA are highly soluble in water as well as in some organic solvents, making MSA usefijl in electroplating operations. For example, lead sulfate is insoluble in water, whereas lead methanesulfonate (lead mesylate) is water soluble. 

Stabilizers. Lead stabilizers, particularly tribasic lead sulfate, is commonly used in plasticized wire and cable compounds because of its good nonconducting electrical properties (122). 

Leaded Zinc Oxide. Oxides containing more than 5 wt % basic lead sulfate are classified as leaded and are made ia the American process from high lead materials, usually lead sulfide mineral, or by blending ziac oxide and basic lead sulfate. There is only one manufacturer ia the United States and the product contains 20—28 wt % basic lead sulfate. Leaded oxides are used only ia mbber ia the United States. 

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. 

PIa.tes, Plates are the part of the cell that ultimately become the battery electrodes. The plates consist of an electrically conductive grid pasted with a lead oxide—lead sulfate paste which is the precursor to the electrode active materials which participate in the electrochemical charge—discharge reactions. 

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