Lead(II,IV) oxide

Names
Preferred IUPAC name

Lead tetroxide [1]

Other names

Minium, red lead, triplumbic tetroxide

Identifiers

CAS Number

* 1314-41-6 Y

3D model (JSmol)

* Interactive image

ChemSpider |

* 21169908 Y

EC Number |

* 215-235-6

PubChem CID

* 16685188

UNII |

* A4G39L7HN2 Y

UN number | 1479

InChI

* InChI=1S/4O.3Pb Y

Key: XMFOQHDPRMAJNU-UHFFFAOYSA-N Y

SMILES

* O1[Pb]O[Pb]11O[Pb]O1

Properties

Chemical formula

| Pb

Molar mass | 685.6 g·mol−1
Appearance  | Vivid orange crystals
Density | 8.3 g/cm3
Melting point | 500 °C (decomposition)
Vapor pressure | 1.3 kPa (at 0 °C)
Structure

Crystal structure

| Tetragonal, tP28

Space group

| P42/mbc, No. 135
Hazards
GHS pictograms |
GHS Signal word | DANGER

GHS hazard statements

| H272, H302, H332, H360, H373, H410

GHS precautionary statements

| P201, P220, P273, P308+313, P501
NFPA 704 (fire diamond)  |

Related compounds

Related lead oxides

| Lead(II) oxide
Lead(IV) oxide

Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Y verify (what is YN ?)
Infobox references

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Lead(II,IV) oxide, also called red lead or minium, is the inorganic compound with the formula Pb

4. 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.[2]

## Contents

* 1 Structure
* 2 Preparation
* 3 Reactions
* 4 Use
* 5 Physiological effects
* 6 History
* 7 See also
* 8 References
* 9 External links

## Structure

Lead(II,IV) oxide may be thought of as lead(II) orthoplumbate(IV) [Pb2+]
2[PbO4−
4].[3] It has a tetragonal crystal structure at room temperature, which then transforms to an orthorhombic (Pearson symbol oP28, Space group Pbam, No. 55) form at temperature 170 K (−103 °C). This phase transition only changes the symmetry of the crystal and slightly modifies the interatomic distances and angles.[4]

* Unit cell of tetragonal Pb

(Key:  Pb O)

* Part of tetragonal red lead's crystal structure

## Preparation

Lead(II,IV) oxide is prepared by calcination of lead(II) oxide (PbO; also called litharge) in air at about 450–480 °C:[5]

6 PbO + O
2 → 2 Pb

The resulting material is contaminated with PbO. If a pure compound is desired, PbO can be removed by a potassium hydroxide solution:

PbO + KOH + H
2O → K[Pb(OH)

Another method of preparation relies on annealing of lead(II) carbonate (cerussite) in air:

6 PbCO
3 \+ O
2 → 2 Pb

4 \+ 6 CO

Yet another method is oxidative annealing of white lead:

3 Pb
2CO
3(OH)
2 \+ O
2 → 2 Pb

4 \+ 3 CO
2 \+ 3 H

In solution, lead(II,IV) oxide can be prepared by reaction of potassium plumbate with lead(II) acetate, yielding yellow insoluble lead(II,IV) oxide monohydrate Pb

4 * H2O, which can be turned into the anhydrous form by gentle heating:

2PbO
3 \+ 2 Pb(OCOCH

2 \+ H
2O → Pb

4 \+ 2 KOCOCH
3 \+ 2 CH
3COOH

Natural minium is uncommon, forming only in extreme oxidizing conditions of lead ore bodies. The best known natural specimens come from Broken Hill, New South Wales, Australia, where they formed as the result of a mine fire.[6]

## Reactions

Red lead is virtually insoluble in water and in ethanol. However, it is soluble in hydrochloric acid present in the stomach, and is therefore toxic when ingested. It also dissolves in glacial acetic acid and a diluted mixture of nitric acid and hydrogen peroxide.

When heated to 500 °C, it decomposes to lead(II) oxide and oxygen. At 580 °C, the reaction is complete.

2 Pb

4 → 6 PbO + O

Nitric acid dissolves the lead(II) oxide component, leaving behind the insoluble lead(IV) oxide:

4 \+ 4 HNO
3 → PbO
2 \+ 2 Pb(NO

2 \+ 2 H

With iron oxides and with elemental iron, lead(II,IV) oxide forms insoluble iron(II) and iron(III) plumbates, which is the basis of the anticorrosive properties of lead-based paints applied to iron objects.

## Use

Red lead has been used as a pigment for primer paints for iron objects. Due to its toxicity, its use is being limited. It finds limited use in some amateur pyrotechnics as a delay charge and was used in the past in the manufacture of dragon's egg pyrotechnic stars.

Red lead is used as a curing agent in some polychloroprene rubber compounds. It is used in place of magnesium oxide to provide better water resistance properties.

Red lead was used for engineer's scraping, before being supplanted by engineer's blue.

It is also used as an adulterating agent in turmeric powder.

## Physiological effects

Main article: Medicine:Lead poisoning

When inhaled, lead(II,IV) oxide irritates the lungs. In case of high dose, the victim experiences a metallic taste, chest pain, and abdominal pain. When ingested, it is dissolved in the gastric acid and absorbed, leading to lead poisoning. High concentrations can be absorbed through skin as well, and it is important to follow safety precautions when working with lead-based paint.

Long-term contact with lead(II,IV) oxide may lead to accumulation of lead compounds in organisms, with development of symptoms of acute lead poisoning. Chronic poisoning displays as agitation, irritability, vision disorders, hypertension, and a grayish facial hue.

Lead(II,IV) oxide was shown to be carcinogenic for laboratory animals. Its carcinogenicity for humans was not proven.

Minium from a mine fire at Broken Hill, Australia

## History

This compound's Latin name minium originates from the Minius, a river in northwest Iberia where it was first mined.

Lead(II,IV) oxide was used as a red pigment in ancient Rome, where it was prepared by calcination of white lead. In the ancient and medieval periods it was used as a pigment in the production of illuminated manuscripts, and gave its name to the minium or miniature, a style of picture painted with the colour.

Made into a paint with linseed oil, red lead was used as a durable paint to protect exterior ironwork. In 1504 the portcullis at Stirling Castle in Scotland was painted with red lead, as were cannons including Mons Meg.[7]

As a finely divided powder, it was also sprinkled on dielectric surfaces to study Lichtenberg figures.

In traditional Chinese medicine, red lead is used to treat ringworms and ulcerations, though the practice is limited due to its toxicity. Also, azarcón, a Mexican folk remedy for gastrointestinal disorders, contains up to 95% lead(II,IV) oxide.[8]

It was also used before the 18th century as medicine.[9]

## See also

* Lead paint
* Lead(II) oxide, PbO
* Lead(IV) oxide, PbO

* List of inorganic pigments
* Minium (mineral)
* Minium (pigment)

## References

1. ↑ "VOLUNTARY RISK ASSESSMENT REPORT ON LEAD AND SOME INORGANIC LEAD COMPOUNDS". http://echa.europa.eu/documents/10162/13630/vrar_annex8_hh_en.rtf.
2. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8.
3. ↑ Egon Wiberg; Nils Wiberg; Arnold Frederick Holleman (2001). Inorganic chemistry. Academic Press. p. 920. ISBN 0-12-352651-5.
4. ↑ Gavarri, J; Weigel, Dominique; Hewat, A. W. (1978). "Oxydes de plomb. IV. Évolution structurale de l'oxyde Pb3O4 entre 240 et 5 K et mécanisme de la transition". Journal of Solid State Chemistry 23 (3–4): 327. doi:10.1016/0022-4596(78)90081-6. Bibcode: 1978JSSCh..23..327G.
5. ↑ Carr, Dodd S.. "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a15_249.
6. ↑ Minium
7. ↑ James Balfour Paul, Accounts of the Treasurer of Scotland, vol. 2 (Edinburgh, 1900), p. 277.
8. ↑ Bose, A.; Vashistha, K; O'Loughlin, B. J. (1983). "Azarcón por empacho – another cause of lead toxicity". Pediatrics 72: 108–118. doi:10.1542/peds.72.1.106.
9. ↑ "The London Lancet: A Journal of British and Foreign Medicine, Physiology, Surgery, Chemistry, Criticism, Literature and News". 1853. https://books.google.com/books?id=3iQgAQAAMAAJ&q=minium+medicine&pg=PA124.

## External links

* National Pollutant Inventory - Lead and Lead Compounds Fact Sheet
* Minium mineral data

* v
* t
* e

Lead compounds

Pb(II)|

* PbBr2
* Pb(C5H5)2
* Pb(C2H3O2)2
* PbCl2
* PbCO3
* PbCrO4
* PbF2
* PbHAsO4
* PbI2
* Pb(NO3)2
* Pb(N3)2
* PbO
* Pb(OH)2
* Pb3(PO4)2
* PbS
* Pb(SCN)2
* PbSe
* PbSO4
* PbTe
* PbTiO3
* plumbite
* PbC2 (hypothetical)

Pb(II,IV)|

* Pb3O4

Pb(IV)|

* Pb(C2H3O2)4
* PbCl4
* PbF4
* PbH4
* PbO2
* PbS2
* plumbate
* Pb(OH)4 (hypothetical)

* v
* t
* e

Oxides

Mixed oxidation states|

* Antimony tetroxide (Sb2O4)
* Cobalt(II,III) oxide (Co3O4)
* Europium(II,III) oxide (Eu3O4)
* Iron(II,III) oxide (Fe<sub>3O4)
* Lead(II,IV) oxide (Pb3O4)
* Manganese(II,III) oxide (Mn3O4)
* Silver(I,III) oxide (Ag2O2)
* Triuranium octoxide (U3O8)
* Carbon suboxide (C3O2)
* Mellitic anhydride (C12O9)
* [[Chemistry:Praseodymium(III,IV) Praseodymium(III,IV) oxide]] (Pr6O11)
* Terbium(III,IV) oxide (Tb4O7)

+1 oxidation state|

* Copper(I) oxide (Cu<sub>2O)
* Caesium oxide (Cs2O)
* Dicarbon monoxide (C2O)
* Dichlorine monoxide (Cl2O)
* Gallium(I) oxide (Ga2O)
* Lithium oxide (Li2O)
* Potassium oxide (K2O)
* Rubidium oxide (Rb2O)
* Silver oxide (Ag2O)
* Thallium(I) oxide (Tl2O)
* Sodium oxide (Na2O)
* Water (hydrogen oxide) (H2O)

+2 oxidation state|

* Aluminium(II) oxide (AlO)
* Barium oxide (BaO)
* Beryllium oxide (BeO)
* Cadmium oxide (CdO)
* Calcium oxide (CaO)
* Carbon monoxide (CO)
* Chromium(II) oxide (CrO)
* Cobalt(II) oxide (CoO)
* Copper(II) oxide (CuO)
* Europium(II) oxide (EuO)
* Germanium monoxide (GeO))
* Iron(II) oxide (FeO)
* Lead(II) oxide (PbO)
* Magnesium oxide (MgO)
* Manganese(II) oxide (MnO)
* Mercury(II) oxide (HgO)
* Nickel(II) oxide (NiO)
* Nitric oxide (NO)
* Palladium(II) oxide (PdO)
* Silicon monoxide (SiO)
* Strontium oxide (SrO)
* Sulfur monoxide (SO)
* Disulfur dioxide (S2O2)
* Thorium monoxide (ThO)
* Tin(II) oxide (SnO)
* Titanium(II) oxide (TiO)
* Vanadium(II) oxide (VO)
* Zinc oxide (ZnO)

+3 oxidation state|

* Aluminium oxide (Al<sub>2O3)
* Antimony trioxide (Sb2O3)
* Arsenic trioxide (As2O3)
* Bismuth(III) oxide (Bi2O3)
* Boron trioxide (B2O3)
* Cerium(III) oxide (Ce2O3)
* Dibromine trioxide (Br2O3)
* Chromium(III) oxide (Cr2O3)
* Dinitrogen trioxide (N2O3)
* Dysprosium(III) oxide (Dy2O3)
* Erbium(III) oxide (Er2O3)
* Europium(III) oxide (Eu2O3)
* Gadolinium(III) oxide (Gd2O3)
* Gallium(III) oxide (Ga2O3)
* Holmium(III) oxide (Ho2O3)
* Indium(III) oxide (In<sub>2O3)
* Iron(III) oxide (Fe2O3)
* Lanthanum oxide (La2O3)
* Lutetium(III) oxide (Lu2O3)
* Manganese(III) oxide (Mn2O3)
* Neodymium(III) oxide (Nd2O3)
* Nickel(III) oxide (Ni2O3)
* Phosphorus trioxide (P4O6)
* Praseodymium(III) oxide (Pr2O3)
* Promethium(III) oxide (Pm2O3)
* Rhodium(III) oxide (Rh2O3)
* [[Chemistry:Samarium(III) Samarium(III) oxide]] (Sm2O3)
* Scandium oxide (Sc2O3)
* Terbium(III) oxide (Tb2O3)
* Thallium(III) oxide (Tl2O3)
* Thulium(III) oxide (Tm2O3)
* Titanium(III) oxide (Ti2O3)
* Tungsten(III) oxide (W2O3)
* Vanadium(III) oxide (V2O3)
* Ytterbium(III) oxide (Yb2O3)
* Yttrium(III) oxide (Y2O3)

+4 oxidation state|

* Americium dioxide (AmO2)
* Carbon dioxide (CO2)
* Carbon trioxide (CO3)
* Cerium(IV) oxide (CeO2)
* Chlorine dioxide (ClO2)
* Chromium(IV) oxide (CrO<sub>2)
* Dinitrogen tetroxide (N2O4)
* Germanium dioxide (GeO<sub>2)
* [[Chemistry:Hafnium(IV) Hafnium(IV) oxide]] (HfO2)
* Lead dioxide (PbO2)
* Manganese dioxide (MnO2)
* Neptunium(IV) oxide (NpO2)
* Nitrogen dioxide (NO2)
* Osmium dioxide (OsO2)
* Plutonium(IV) oxide (PuO2)
* Praseodymium(IV) oxide (PrO2)
* Protactinium(IV) oxide (PaO2)
* Rhodium(IV) oxide (RhO2)
* Ruthenium(IV) oxide (RuO<sub>2)
* Selenium dioxide (SeO2)
* Silicon dioxide (SiO2)
* Sulfur dioxide (SO2)
* Tellurium dioxide (TeO<sub>2)
* [[Chemistry:Terbium(IV) Terbium(IV) oxide]] (TbO2)
* Thorium dioxide (ThO2)
* Tin dioxide (SnO2)
* Titanium dioxide (TiO<sub>2)
* Tungsten(IV) oxide (WO2)
* Uranium dioxide (UO2)
* Vanadium(IV) oxide (VO2)
* Zirconium dioxide (ZrO2)

+5 oxidation state|

* Antimony pentoxide (Sb2O5)
* Arsenic pentoxide (As2O5)
* Dinitrogen pentoxide (N2O5)
* Niobium pentoxide (Nb2O5)
* Phosphorus pentoxide (P2O5)
* Protactinium(V) oxide (Pa2O5)
* Tantalum pentoxide (Ta2O5)
* Vanadium(V) oxide (V2O5)

+6 oxidation state|

* Chromium trioxide (CrO3)
* Molybdenum trioxide (MoO3)
* Rhenium trioxide (ReO3)
* Selenium trioxide (SeO3)
* Sulfur trioxide (SO3)
* Tellurium trioxide (TeO3)
* Tungsten trioxide (WO3)
* Uranium trioxide (UO3)
* Xenon trioxide (XeO3)
* Iridium trioxide (IrO3)

+7 oxidation state|

* Dichlorine heptoxide (Cl2O7)
* Manganese heptoxide (Mn2O7)
* [[Chemistry:Rhenium(VII) Rhenium(VII) oxide]] (Re2O7)
* Technetium(VII) oxide (Tc2O7)

+8 oxidation state|

* Osmium tetroxide (OsO4)
* Ruthenium tetroxide (RuO4)
* Xenon tetroxide (XeO4)
* Iridium tetroxide (IrO4)
* Hassium tetroxide (HsO4)

Related|

* Oxocarbon
* Suboxide
* Oxyanion
* Ozonide
* Peroxide
* Superoxide

Oxides are sorted by oxidation state. Category:Oxides

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*[CID]: Compound ID
*[H272]: May intensify fire: oxidizer
*[H302]: Harmful if swallowed
*[H332]: Harmful if inhaled
*[H360]: May damage fertility or the unborn child
*[H373]: May cause damage to organs through prolonged or repeated exposure
*[H410]: Very toxic to aquatic life with long lasting effects
*[P201]: Obtain special instructions before use
*[P220]: Keep/Store away from clothing/…/combustible materials
*[P273]: Avoid release to the environment
*[P308+313]: IF exposed or concerned: Get medical advice/attention
*[P501]: Dispose of contents/container to …
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