Lead(II,IV) oxide

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Lead(II,IV) oxide
Sample of pulverised lead(II,IV) oxide
Identifiers
CAS number 1314-41-6 YesY
PubChem 16685188
ChemSpider 21169908 YesY
EC number 215-235-6
UN number 1479
Jmol-3D images Image 1
Properties
Molecular formula Pb
3
O
4
Molar mass 685.6 g mol-1
Appearance Vivid orange crystals
Density 8.3 g cm-3
Melting point 500 °C (932 °F; 773 K)
Vapor pressure 1.3 kPa (at 0 °C)
Structure
Crystal structure Tetragonal, tP28
Space group P42/mbc, No. 135
Hazards
GHS pictograms The exclamation-mark pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS) The health hazard pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS) The environment pictogram in the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)
GHS signal word DANGER
GHS hazard statements H272, H302, H332, H360, H373, H410
GHS precautionary statements P201, P220, P273, P308+313, P501
EU classification Toxic T Dangerous for the Environment (Nature) N
R-phrases R61, R20/22, R33, R50/53, R62
S-phrases S53, S45, S60, S61
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Lead(II,IV) oxide, also called minium, red lead or triplumbic tetroxide, is a bright red or orange crystalline or amorphous pigment. Chemically, red lead is Pb3O4, or 2 PbO·PbO2. Lead(II,IV) oxide is used in the manufacture of batteries, lead glass and rust-proof primer paints.

Structure[edit]

Lead(II,IV) oxide has a tetragonal crystal structure at room temperature, which transforms to an orthorhombic (Pearson symbol oP28, Space group = Pbam, No 55) form at temperature 170 K. This phase transition only changes the symmetry of the crystal and slightly modifies the interatomic distances and angles.[2]

Preparation[edit]

Lead(II,IV) oxide is prepared by calcination of lead(II) oxide (also called litharge) in air at about 450 to 480 °C:

6 PbO + O2 → 2 Pb3O4

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

PbO + KOH + H2O → K[Pb(OH)3] (aq)

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

6 PbCO3 + O2 → 2 Pb3O4 + 6 CO2

Yet another method is oxidative annealing of white lead:

3 Pb2CO3(OH)2 + O2 → 2 Pb3O4 + 3 CO2 + 3 H2O

In solution, lead(II,IV) oxide can be prepared e.g. by reaction of potassium plumbate with lead acetate, yielding yellow insoluble lead(II,IV) oxide monohydrate, Pb3O4·H2O, which can be turned into the anhydrous form by gentle heating:

K2PbO3 + 2 Pb(OCOCH3)2 + H2O → Pb3O4 + 2 KOCOCH3 + 2 CH3COOH

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.[3]

Reactions[edit]

Red lead is virtually insoluble in water and in alcohol. 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 Pb3O4 → 6 PbO + O2

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

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

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 anti-corrosive properties of lead-based paints applied to iron objects.

Use[edit]

Lead tetraoxide is most often used as a pigment for primer paints for iron objects. Due to its toxicity, its use is being limited. In the past, it was used in combination with linseed oil as a thick, long-lasting anti-corrosive paint. The combination of minium and linen fibres was also used for plumbing, now replaced with PTFE tape. Currently it is mostly used for manufacture of glass, especially lead glass (crystal glass). It finds limited use in some amateur pyrotechnics as a delay charge.

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 also used for engineer's scraping, before being supplanted by Engineer's blue. In traditional Chinese medicine, red lead is used to treat ringworms and ulcerations, though the practice is limited due to its toxicity. Also, azarcon, a Mexican folk remedy for gastrointestinal disorders contains up to 95% lead(II,IV) oxide.[4] It is also used for worshipping Hindu deities.

Physiological effects[edit]

Main article: Lead poisoning

When inhaled, lead(II,IV) oxide irritates 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 also 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[edit]

This compound's Latin name minium originates from the Minius River in northwest Spain 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. As a finely divided powder, it was also sprinkled on dielectric surfaces to study Lichtenberg figures.

See also[edit]

References[edit]

  1. ^ "VOLUNTARY RISK ASSESSMENT REPORT ON LEAD AND SOME INORGANIC LEAD COMPOUNDS". Retrieved 2012-12-25. 
  2. ^ Gavarri, J; Weigel, Dominique; Hewat, A.W. (1978). "Oxydes de plomb. IV. Evolution 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. 
  3. ^ Minium
  4. ^ Bose A, Vashistha K, O'Loughlin BJ. Azarcon por empacho--another cause of lead toxicity. Pediatrics 1983; 72: 108-18.

External links[edit]