Lead dioxide

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Lead dioxide
Lead dioxide.jpg
Oxid olovicity.PNG
Names
IUPAC name
Lead(IV) oxide
Other names
Plumbic oxide
Plattnerite
Identifiers
ChemSpider
ECHA InfoCard 100.013.795 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 215-174-5
PubChem CID
RTECS number
  • OGO700000
UNII
UN number 1872
Properties
PbO2
Molar mass 239.1988 g/mol
Appearancedark-brown, black powder
Density 9.38 g/cm3
Melting point 290 °C (554 °F; 563 K) decomposes
insoluble
Solubility soluble in acetic acid
insoluble in alcohol
2.3
Structure
hexagonal
Hazards
GHS labelling:
GHS-pictogram-rondflam.svg GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Danger
H272, H302, H332, H360, H372, H373, H410
P201, P202, P210, P220, P221, P260, P261, P264, P270, P271, P273, P280, P281, P301+P312, P304+P312, P304+P340, P308+P313, P312, P314, P330, P370+P378, P391, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 0: Will not burn. E.g. waterInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazard OX: Oxidizer. E.g. potassium perchlorate
4
0
3
OX
Flash point Non-flammable
Safety data sheet (SDS) External MSDS
Related compounds
Other cations
Carbon dioxide
Silicon dioxide
Germanium dioxide
Tin dioxide
Related lead oxides
Lead(II) oxide
Lead(II,IV) oxide
Related compounds
Thallium(III) oxide
Bismuth(III) oxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Lead(IV) oxide, commonly known as lead dioxide, is an inorganic compound with the chemical formula PbO2. It is an oxide where lead is in an oxidation state of +4. [1] It is a dark-brown solid which is insoluble in water. [2] It exists in two crystalline forms. It has several important applications in electrochemistry, in particular as the positive plate of lead acid batteries.

Contents

Properties

Physical

Crystal structure of a-
PbO2 ScrutinyiteStructure.png
Crystal structure of α-PbO2
Crystal structure of b-
PbO2 PlattneriteStructure.png
Crystal structure of β-PbO2

Lead dioxide has two major polymorphs, alpha and beta, which occur naturally as rare minerals scrutinyite and plattnerite, respectively. Whereas the beta form had been identified in 1845, [3] α-PbO2 was first identified in 1946 and found as a naturally occurring mineral 1988. [4]

The alpha form has orthorhombic symmetry, space group Pbcn (No. 60), Pearson symbol oP12, lattice constants a = 0.497 nm, b = 0.596 nm, c = 0.544 nm, Z = 4 (four formula units per unit cell). [4] The lead atoms are six-coordinate.

The symmetry of the beta form is tetragonal, space group P42/mnm (No. 136), Pearson symbol tP6, lattice constants a = 0.491 nm, c = 0.3385 nm, Z = 2 [5] and related to the rutile structure and can be envisaged as containing columns of octahedra sharing opposite edges and joined to other chains by corners. This contrasts with the alpha form where the octahedra are linked by adjacent edges to give zigzag chains. [4]

Chemical

Lead dioxide decomposes upon heating in air as follows:

24 PbO2 → 2 Pb12O19 + 5 O2
Pb12O19 → Pb12O17 + O2
2 Pb12O17 → 8 Pb3O4 + O2
2 Pb3O4 → 6 PbO + O2

The stoichiometry of the end product can be controlled by changing the temperature – for example, in the above reaction, the first step occurs at 290 °C, second at 350 °C, third at 375 °C and fourth at 600 °C. In addition, Pb2O3 can be obtained by decomposing PbO2 at 580–620 °C under an oxygen pressure of 1,400 atm (140 MPa). Therefore, thermal decomposition of lead dioxide is a common way of producing various lead oxides. [6]

Lead dioxide is an amphoteric compound with prevalent acidic properties. It dissolves in strong bases to form the hydroxyplumbate ion, [Pb(OH)6]2−: [2]

PbO2 + 2 NaOH + 2 H2O → Na2[Pb(OH)6]

It also reacts with basic oxides in the melt, yielding orthoplumbates M4[PbO4].

Because of the instability of its Pb4+ cation, lead dioxide reacts with hot acids, converting to the more stable Pb2+ state and liberating oxygen: [6]

2 PbO2 + 2 H2SO4 → 2 PbSO4 + 2 H2O + O2
2 PbO2 + 4 HNO3 → 2 Pb(NO3)2 + 2 H2O + O2
PbO2 + 4 HClPbCl2 + 2 H2O + Cl2

However these reactions are slow.

Lead dioxide is well known for being a good oxidizing agent, with an example reactions listed below: [7]

2 MnSO4 + 5 PbO2 + 6 HNO3 → 2 HMnO4 + 2 PbSO4 + 3 Pb(NO3)2 + 2 H2O
2 Cr(OH)3 + 10 KOH + 3 PbO2 → 2 K2CrO4 + 3 K2 PbO2 + 8 H2O

Electrochemical

Although the formula of lead dioxide is nominally given as PbO2, the actual oxygen to lead ratio varies between 1.90 and 1.98 depending on the preparation method. Deficiency of oxygen (or excess of lead) results in the characteristic metallic conductivity of lead dioxide, with a resistivity as low as 10−4 Ω·cm and which is exploited in various electrochemical applications. Like metals, lead dioxide has a characteristic electrode potential, and in electrolytes it can be polarized both anodically and cathodically. Lead dioxide electrodes have a dual action, that is both the lead and oxygen ions take part in the electrochemical reactions. [8]

Production

Chemical processes

Lead dioxide is produced commercially by several methods, which include oxidation of red lead (Pb3O4) in alkaline slurry in a chlorine atmosphere, [6] reaction of lead(II) acetate with "chloride of lime" (calcium hypochlorite), [9] [10] The reaction of Pb3O4 with nitric acid also affords the dioxide: [2] [11]

Pb3O4 + 4 HNO3 → PbO2 + 2 Pb(NO3)2 + 2 H2O

PbO2 reacts with sodium hydroxide to form the hexahydroxoplumbate(IV) ion [Pb(OH)6]2−, soluble in water.

Electrolysis

An alternative synthesis method is electrochemical: lead dioxide forms on pure lead, in dilute sulfuric acid, when polarized anodically at electrode potential about +1.5 V at room temperature. This procedure is used for large-scale industrial production of PbO2 anodes. Lead and copper electrodes are immersed in sulfuric acid flowing at a rate of 5–10 L/min. The electrodeposition is carried out galvanostatically, by applying a current of about 100 A/m2 for about 30 minutes.

The drawback of this method for the production of lead dioxide anodes is its softness, especially compared to the hard and brittle PbO2 which has a Mohs hardness of 5.5. [12] This mismatch in mechanical properties results in peeling of the coating which is preferred for bulk PbO2 production. Therefore, an alternative method is to use harder substrates, such as titanium, niobium, tantalum or graphite and deposit PbO2 onto them from lead(II) nitrate in static or flowing nitric acid. The substrate is usually sand-blasted before the deposition to remove surface oxide and contamination and to increase the surface roughness and adhesion of the coating. [13]

Applications

Lead dioxide is used in the production of matches, pyrotechnics, dyes and the curing of sulfide polymers. It is also used in the construction of high-voltage lightning arresters. [6]

Lead dioxide is used as an anode material in electrochemistry. β-PbO2 is more attractive for this purpose than the α form because it has relatively low resistivity, good corrosion resistance even in low-pH medium, and a high overvoltage for the evolution of oxygen in sulfuric- and nitric-acid-based electrolytes. Lead dioxide can also withstand chlorine evolution in hydrochloric acid. Lead dioxide anodes are inexpensive and were once used instead of conventional platinum and graphite electrodes for regenerating potassium dichromate. They were also applied as oxygen anodes for electroplating copper and zinc in sulfate baths. In organic synthesis, lead dioxide anodes were applied for the production of glyoxylic acid from oxalic acid in a sulfuric acid electrolyte. [13]

Lead acid battery

The most important use of lead dioxide is as the cathode of lead acid batteries. Its utility arises from the anomalous metallic conductivity of PbO2. The lead acid battery stores and releases energy by shifting the equilibrium (a comproportionation) between metallic lead, lead dioxide, and lead(II) salts in sulfuric acid.

Pb + PbO2 + 2 HSO4 + 2 H+ → 2 PbSO4 + 2 H2O E° = +2.05 V

Safety

Lead compounds are poisons. [14] Lead dioxide is a strong oxidizer, so any contact of skin, eyes with either lead dioxide or its vapours may cause severe injury in the form of burns which can even lead to death.

PbO2 is not combustible, but it enhances flammability of other substances and the intensity of the fire. In case of a fire it gives off irritating and toxic fumes. [15]

Lead dioxide and other lead compound pose a huge environmental hazard when they are not disposed of properly. it is especially poisonous to aquatic life. [16]

Related Research Articles

<span class="mw-page-title-main">Electrochemistry</span> Branch of chemistry

Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference and identifiable chemical change. These reactions involve electrons moving via an electronically-conducting phase between electrodes separated by an ionically conducting and electronically insulating electrolyte.

<span class="mw-page-title-main">Nitric acid</span> Highly corrosive mineral acid

Nitric acid is the inorganic compound with the formula HNO3. It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into oxides of nitrogen. Most commercially available nitric acid has a concentration of 68% in water. When the solution contains more than 86% HNO3, it is referred to as fuming nitric acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86%, or white fuming nitric acid at concentrations above 95%.

In chemistry, a half reaction is either the oxidation or reduction reaction component of a redox reaction. A half reaction is obtained by considering the change in oxidation states of individual substances involved in the redox reaction. Often, the concept of half reactions is used to describe what occurs in an electrochemical cell, such as a Galvanic cell battery. Half reactions can be written to describe both the metal undergoing oxidation and the metal undergoing reduction.

<span class="mw-page-title-main">Redox</span> Chemical reaction in which oxidation states of atoms are changed

Redox is a type of chemical reaction in which the oxidation states of a reactant change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a decrease in the oxidation state.

<span class="mw-page-title-main">Oxidizing agent</span> Chemical compound used to oxidize another substance in a chemical reaction

An oxidizing agent is a substance in a redox chemical reaction that gains or "accepts"/"receives" an electron from a reducing agent. In other words, an oxidizer is any substance that oxidizes another substance. The oxidation state, which describes the degree of loss of electrons, of the oxidizer decreases while that of the reductant increases; this is expressed by saying that oxidizers "undergo reduction" and "are reduced" while reducers "undergo oxidation" and "are oxidized". Common oxidizing agents are oxygen, hydrogen peroxide, and the halogens.

<span class="mw-page-title-main">Lead(II) nitrate</span> Chemical compound

Lead(II) nitrate is an inorganic compound with the chemical formula Pb(NO3)2. It commonly occurs as a colourless crystal or white powder and, unlike most other lead(II) salts, is soluble in water.

<span class="mw-page-title-main">Lead(II) sulfate</span> Chemical compound

Lead(II) sulfate (PbSO4) is a white solid, which appears white in microcrystalline form. It is also known as fast white, milk white, sulfuric acid lead salt or anglesite.

<span class="mw-page-title-main">Copper(II) oxide</span> Chemical compound – an oxide of copper with formula CuO

Copper(II) oxide or cupric oxide is an inorganic compound with the formula CuO. A black solid, it is one of the two stable oxides of copper, the other being Cu2O or copper(I) oxide (cuprous oxide). As a mineral, it is known as tenorite. It is a product of copper mining and the precursor to many other copper-containing products and chemical compounds.

The lead chamber process was an industrial method used to produce sulfuric acid in large quantities. It has been largely supplanted by the contact process.

<span class="mw-page-title-main">Permanganate</span> Chemical compound

A permanganate is a chemical compound with the manganate(VII) ion, MnO
4
, the conjugate base of permanganic acid. Because the manganese atom has a +7 oxidation state, the permanganate(VII) ion is a strong oxidising agent. The ion is a transition metal ion with a tetrahedral structure. Permanganate solutions are purple in colour and are stable in neutral or slightly alkaline media. The exact chemical reaction depends on the carbon-containing reactants present and the oxidant used. For example, trichloroethane (C2H3Cl3) is oxidised by permanganate ions to form carbon dioxide (CO2), manganese dioxide (MnO2), hydrogen ions (H+), and chloride ions (Cl).

In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. The reverse of disproportionation, such as when a compound in an intermediate oxidation state is formed from precursors of lower and higher oxidation states, is called comproportionation, also known as synproportionation.

<span class="mw-page-title-main">Lead(II,IV) oxide</span> Chemical compound

Lead(II,IV) oxide, also called red lead or minium, is the inorganic compound with the formula Pb3O4. A bright red or orange solid, it is used as pigment, in the manufacture of batteries, and rustproof primer paints. It is an example of a mixed valence compound, being composed of both Pb(II) and Pb(IV) in the ratio of two to one.

<span class="mw-page-title-main">Sodium periodate</span> Chemical compound

Sodium periodate is an inorganic salt, composed of a sodium cation and the periodate anion. It may also be regarded as the sodium salt of periodic acid. Like many periodates, it can exist in two different forms: sodium metaperiodate (formula‍ NaIO4) and sodium orthoperiodate (normally Na2H3IO6, but sometimes the fully reacted salt Na5IO6). Both salts are useful oxidising agents.

<span class="mw-page-title-main">Uranium trioxide</span> Chemical compound

Uranium trioxide (UO3), also called uranyl oxide, uranium(VI) oxide, and uranic oxide, is the hexavalent oxide of uranium. The solid may be obtained by heating uranyl nitrate to 400 °C. Its most commonly encountered polymorph, γ-UO3, is a yellow-orange powder.

<span class="mw-page-title-main">Selenium compounds</span> Chemical compounds containing selenium

Selenium compounds are compounds containing the element selenium (Se). Among these compounds, selenium has various oxidation states, the most common ones being −2, +4, and +6. Selenium compounds exist in nature in the form of various minerals, such as clausthalite, guanajuatite, tiemannite, crookesite etc., and can also coexist with sulfide minerals such as pyrite and chalcopyrite. For many mammals, selenium compounds are essential. For example, selenomethionine and selenocysteine are selenium-containing amino acids present in the human body. Selenomethionine participates in the synthesis of selenoproteins. The reduction potential and pKa (5.47) of selenocysteine are lower than those of cysteine, making some proteins have antioxidant activity. Selenium compounds have important applications in semiconductors, glass and ceramic industries, medicine, metallurgy and other fields.

<span class="mw-page-title-main">Birkeland–Eyde process</span> Nitrogen fixation process using electrical arcs

The Birkeland–Eyde process was one of the competing industrial processes in the beginning of nitrogen-based fertilizer production. It is a multi-step nitrogen fixation reaction that uses electrical arcs to react atmospheric nitrogen (N2) with oxygen (O2), ultimately producing nitric acid (HNO3) with water. The resultant nitric acid was then used as a source of nitrate (NO3) in the reaction which may take place in the presence of water or another proton acceptor.

<span class="mw-page-title-main">Lead compounds</span> Type of compound

Compounds of lead exist with lead in two main oxidation states: +2 and +4. The former is more common. Inorganic lead(IV) compounds are typically strong oxidants or exist only in highly acidic solutions.

<span class="mw-page-title-main">Polonium dioxide</span> Chemical compound

Polonium dioxide (also known as polonium(IV) oxide) is a chemical compound with the formula PoO2. It is one of three oxides of polonium, the other two being polonium monoxide (PoO) and polonium trioxide (PoO3). It is a pale yellow crystalline solid at room temperature. Under lowered pressure (such as a vacuum), it decomposes into elemental polonium and oxygen at 500 °C. It is the most stable oxide of polonium and is an interchalcogen.

<span class="mw-page-title-main">Technetium(IV) oxide</span> Chemical compound

Technetium(IV) oxide, also known as technetium dioxide, is a chemical compound with the formula TcO2 which forms the dihydrate, TcO2·2H2O, which is also known as technetium(IV) hydroxide. It is a radioactive black solid which slowly oxidizes in air.

References

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