Lead tetroxide
From Wikipedia, the free encyclopedia
| Lead tetroxide | |
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| IUPAC name | Lead(II,IV) oxide |
| Identifiers | |
| CAS number | [1314.41-6] |
| Properties | |
| Molecular formula | Pb3O4 |
| Molar mass | 685.598 g/mol |
| Appearance | orange red powder |
| Density | 8.3 g/cm3 |
| Melting point |
500°C |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references |
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Red lead, also called minium, lead tetroxide or triplumbic tetroxide, is a bright red or orange crystalline or amorphous pigment. Its Latin name minium originates from the Minius River in northwest Spain where it was first mined. Natural minium is uncommon, forming only in extreme oxidizing conditions of lead ore bodies. The best specimens known come from Broken Hill, New South Wales, Australia, where they formed as the result of a mine fire [1]. A map and list of known occurrences is available here.
The melting point of lead tetroxide is 500 °C, at which it decomposes to lead(II) oxide and oxygen.
Chemically red lead is lead tetroxide, Pb3O4, or 2PbO.PbO2. It is used in the manufacture of batteries, lead glass and rust-proof paint.
Red lead is virtually insoluble in water. However, it is soluble in hydrochloric acid present in the stomach, and therefore it is toxic when ingested. It is also insoluble in alcohol. It dissolves in hydrochloric acid, glacial acetic acid, and diluted mixture of nitric acid and hydrogen peroxide.
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[edit] Preparation
Lead tetroxide 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 lead white:
- 3 Pb2CO3(OH)2 + O2 → 2 Pb3O4 + 3 CO2 + 3 H2O
In solution, lead tetroxide can be prepared eg. by reaction of potassium plumbate with lead acetate:
- K2PbO3 + 2 Pb(OCOCH3)2 + H2O → Pb3O4 + 2 KOCOCH3 + 2 CH3COOH
yielding yellow insoluble lead tetroxide monohydrate, Pb3O4.H2O, which can be turned into the anhydrous form by gentle heating.
[edit] Chemical properties
With iron oxides and with elementary iron, lead tetroxide 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.
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
[edit] Use
Lead tetroxide is most often used as a pigment for undercoat paints for iron objects. Due to its toxicity its use is being limited. In past it was used in combination with linseed oil as a thick, long-protecting anticorrosive paint. Also combination of minium and linen fibres was used for plumbing, now replaced with PTFE tape. Currently it is mostly used for manufacture of glass, especially lead glass. It finds limited use in some amateur pyrotechnics as a relatively potent oxidizer. Minium mixed with fine aluminium powder, tightly wrapped with round rocks in plastic foil with adhesive tape could serve as improvised weak flashbang impact grenade.
[edit] Physiological effects
When breathed in, lead tetroxide irritates lungs. In case of high dose, the victim feels metallic taste in mouth, chest pain, and abdominal pain. When ingested, it gets dissolved in the gastric acid and gets absorbed, leading to lead poisoning. High concentrations can be absorbed through skin as well; therefore it is important to keep the safety precautions when working with lead-based paint.
Long-term contact with lead tetroxide may lead to accumulation of lead compounds in organism, with development of symptoms of acute lead poisoning. Chronic poisoning displays as agitation, irritability, vision disorders, hypertension, and usually also by grayish hue of face.
Lead tetroxide was shown to be carcinogenic for laboratory animals. Its carcinogenicity for humans was not proven.
[edit] History
Lead tetroxide was used as a red pigment in ancient Rome, where it was prepared by calcination of lead white. 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.
