Lead Monoxide
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Lead(II) oxide, also called lead monoxide, is the
inorganic compound An inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds⁠that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemistry''. Inorgan ...
with the molecular formula Pb O. It occurs in two polymorphs:
litharge Litharge (from Greek , 'stone' + 'silver' ) is one of the natural mineral forms of lead(II) oxide, PbO. Litharge is a secondary mineral which forms from the oxidation of galena ores. It forms as coatings and encrustations with internal tetr ...
having a tetragonal crystal structure, and massicot having an orthorhombic crystal structure. Modern applications for PbO are mostly in
lead Lead () is a chemical element; it has Chemical symbol, symbol Pb (from Latin ) and atomic number 82. It is a Heavy metal (elements), heavy metal that is density, denser than most common materials. Lead is Mohs scale, soft and Ductility, malleabl ...
-based industrial
glass Glass is an amorphous (non-crystalline solid, non-crystalline) solid. Because it is often transparency and translucency, transparent and chemically inert, glass has found widespread practical, technological, and decorative use in window pane ...
and industrial ceramics, including computer components.


Types

Lead oxide exists in two polymorphs: * Red tetragonal (α-PbO), obtained at temperatures below * Yellow orthorhombic (β-PbO), obtained at temperatures above


Synthesis

PbO may be prepared by heating lead metal in air at approximately . At this temperature it is also the end product of decomposition of other oxides of lead in air: :PbO2->[] Pb12O19 ->[] Pb12O17 ->[] Pb3O4 ->[] PbO Thermal decomposition of lead(II) nitrate or lead carbonate, lead(II) carbonate also results in the formation of PbO: :2  → 2 PbO + 4  + : → PbO + PbO is produced on a large scale as an intermediate product in refining raw lead ores into metallic lead. The usual lead ore is
galena Galena, also called lead glance, is the natural mineral form of lead(II) sulfide (PbS). It is the most important ore of lead and an important source of silver. Galena is one of the most abundant and widely distributed sulfide minerals. It crysta ...
(
lead(II) sulfide Lead(II) sulfide (also spelled '' sulphide'') is an inorganic compound with the formula Pb S. Galena is the principal ore and the most important compound of lead. It is a semiconducting material with niche uses. Formation, basic properties, rel ...
). At a temperature of around in air, the sulfide converted to the oxide: :


From lead

Lead combusts at high temperature. According to the Barton pot method, refined molten lead droplets are oxidized under a forced air flow which carries them out to the separation system (e.g. cyclonic separators) for further processing. Oxides produced by this method are mostly a mixture of α-PbO and β-PbO. The overall reaction, which is conducted at 450 °C is: : Using a Ball mill, lead balls are oxidized in a cooled rotating drum. The oxidation is achieved by collisions of the balls. Just like in Barton pot method, the supply of air and separators may also be used.


Structure

As determined by
X-ray crystallography X-ray crystallography is the experimental science of determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to Diffraction, diffract in specific directions. By measuring th ...
, both polymorphs,
tetragonal In crystallography, the tetragonal crystal system is one of the 7 crystal systems. Tetragonal crystal lattices result from stretching a cubic lattice along one of its lattice vectors, so that the Cube (geometry), cube becomes a rectangular Pri ...
and
orthorhombic In crystallography, the orthorhombic crystal system is one of the 7 crystal systems. Orthorhombic Lattice (group), lattices result from stretching a cubic crystal system, cubic lattice along two of its orthogonal pairs by two different factors, res ...
feature a pyramidal four-coordinate lead center. In the tetragonal form the four lead–oxygen bonds have the same length, but in the orthorhombic two are shorter and two longer. The pyramidal nature indicates the presence of a stereochemically active
lone pair In chemistry, a lone pair refers to a pair of valence electrons that are not shared with another atom in a covalent bondIUPAC ''Gold Book'' definition''lone (electron) pair''/ref> and is sometimes called an unshared pair or non-bonding pair. Lone ...
of electrons. When PbO occurs in tetragonal lattice structure it is called
litharge Litharge (from Greek , 'stone' + 'silver' ) is one of the natural mineral forms of lead(II) oxide, PbO. Litharge is a secondary mineral which forms from the oxidation of galena ores. It forms as coatings and encrustations with internal tetr ...
; and when the PbO has orthorhombic lattice structure it is called massicot. The PbO can be changed from massicot to litharge or vice versa by controlled heating and cooling. The tetragonal form is usually red or orange color, while the orthorhombic is usually yellow or orange, but the color is not a very reliable indicator of the structure. The tetragonal and orthorhombic forms of PbO occur naturally as rare minerals.


Reactions

PbO is reduced to elemental lead when heated under
carbon monoxide Carbon monoxide (chemical formula CO) is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the si ...
at around : :PbO + CO → Pb + The red and yellow forms of this material are related by a small change in
enthalpy Enthalpy () is the sum of a thermodynamic system's internal energy and the product of its pressure and volume. It is a state function in thermodynamics used in many measurements in chemical, biological, and physical systems at a constant extern ...
: :PbO(red) → PbO(yellow) Δ''H'' = 1.6 kJ/mol PbO is amphoteric, which means that it reacts with both acids and with bases. With acids, it forms salts of via the intermediacy of oxo clusters such as . With strong bases, PbO dissolves to form plumbite (also called plumbate(II)) salts: :PbO + + →


Applications

PbO is used extensively in making glass. Depending on the glass, the benefit of using PbO in glass can be one or more of: * increasing the
refractive index In optics, the refractive index (or refraction index) of an optical medium is the ratio of the apparent speed of light in the air or vacuum to the speed in the medium. The refractive index determines how much the path of light is bent, or refrac ...
of the glass, * increasing the dispersion (i. e. reducing the
Abbe number In optics and lens design, the Abbe number, also known as the Vd-number or constringence of a Transparency (optics), transparent material, is an approximate measure of the material's dispersion (optics), dispersion (change of refractive index versu ...
) of the glass, * decreasing the
viscosity Viscosity is a measure of a fluid's rate-dependent drag (physics), resistance to a change in shape or to movement of its neighboring portions relative to one another. For liquids, it corresponds to the informal concept of ''thickness''; for e ...
of the glass, * increasing the electrical
resistivity Electrical resistivity (also called volume resistivity or specific electrical resistance) is a fundamental specific property of a material that measures its electrical resistance or how strongly it resists electric current. A low resistivity i ...
of the glass, * increasing the ability of the glass to absorb
X-rays An X-ray (also known in many languages as Röntgen radiation) is a form of high-energy electromagnetic radiation with a wavelength shorter than those of ultraviolet rays and longer than those of gamma rays. Roughly, X-rays have a wavelength ran ...
. Adding PbO to industrial
ceramics A ceramic is any of the various hard, brittle, heat-resistant, and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porce ...
(as well as glass) makes the materials more magnetically and electrically inert (by raising their
Curie temperature In physics and materials science, the Curie temperature (''T''C), or Curie point, is the temperature above which certain materials lose their permanent magnetic properties, which can (in most cases) be replaced by induced magnetism. The Curie ...
) and it is often used for this purpose. Historically PbO was also used extensively in
ceramic glaze Ceramic glaze, or simply glaze, is a glassy coating on ceramics. It is used for decoration, to ensure the item is impermeable to liquids and to minimize the adherence of pollutants. Glazing renders earthenware impermeable to water, sealing th ...
s for household ceramics, and it is still used, but not extensively any more. Other less dominant applications include the
vulcanization Vulcanization (British English: vulcanisation) is a range of processes for hardening rubbers. The term originally referred exclusively to the treatment of natural rubber with sulfur, which remains the most common practice. It has also grown to ...
of rubber and the production of certain pigments and paints. PbO is used in
cathode-ray tube A cathode-ray tube (CRT) is a vacuum tube containing one or more electron guns, which emit electron beams that are manipulated to display images on a phosphorescent screen. The images may represent electrical waveforms on an oscilloscope, a ...
glass to block
X-ray An X-ray (also known in many languages as Röntgen radiation) is a form of high-energy electromagnetic radiation with a wavelength shorter than those of ultraviolet rays and longer than those of gamma rays. Roughly, X-rays have a wavelength ran ...
emission, but mainly in the neck and funnel of the tube, because it can cause discoloration when used in the faceplate. Strontium oxide and
Barium oxide Barium oxide, also known as baria, is a white hygroscopic non-flammable chemical compound, compound with the formula BaO. It has a Cubic crystal system, cubic structure and is used in cathode-ray tubes, crown glass, and Catalysis, catalysts. It ...
are preferred for the faceplate. The consumption of lead, and hence the processing of PbO, correlates with the number of automobiles, because lead remains the key component of automotive lead–acid batteries.


Niche or declining uses

A mixture of PbO with
glycerine Glycerol () is a simple triol compound. It is a colorless, odorless, sweet-tasting, viscous liquid. The glycerol backbone is found in lipids known as glycerides. It is also widely used as a sweetener in the food industry and as a humectant in ...
sets to a hard, waterproof
cement A cement is a binder, a chemical substance used for construction that sets, hardens, and adheres to other materials to bind them together. Cement is seldom used on its own, but rather to bind sand and gravel ( aggregate) together. Cement mi ...
that has been used to join the flat glass sides and bottoms of
aquarium An aquarium (: aquariums or aquaria) is a vivarium of any size having at least one transparent side in which aquatic plants or animals are kept and displayed. fishkeeping, Fishkeepers use aquaria to keep fish, invertebrates, amphibians, aquati ...
s, and was also once used to seal glass panels in window frames. It is a component of
lead paint Lead paint or lead-based paint is paint containing lead. As pigment, lead(II) chromate (, "chrome yellow"), lead(II,IV) oxide, (, "red lead"), and lead(II) carbonate (, "white lead") are the most common forms.. Lead is added to paint to acceler ...
s. PbO was one of the raw materials for century eggs, a type of Chinese preserved
egg An egg is an organic vessel grown by an animal to carry a possibly fertilized egg cell (a zygote) and to incubate from it an embryo within the egg until the embryo has become an animal fetus that can survive on its own, at which point the ...
. but it has been gradually replaced due to health problems. It was an unscrupulous practice in some small factories but it became rampant in
China China, officially the People's Republic of China (PRC), is a country in East Asia. With population of China, a population exceeding 1.4 billion, it is the list of countries by population (United Nations), second-most populous country after ...
and forced many honest manufacturers to label their boxes "lead-free" after the scandal went mainstream in 2013. In powdered tetragonal litharge form, it can be mixed with
linseed oil Linseed oil, also known as flaxseed oil or flax oil (in its edible form), is a colorless to yellowish oil obtained from the dried, ripened seeds of the flax plant (''Linum usitatissimum''). The oil is obtained by pressing, sometimes followed by ...
and then boiled to create a weather-resistant
sizing Sizing or size is a substance that is applied to, or incorporated into, other materials—especially papers and textiles—to act as a protective filler or glaze. Sizing is used in papermaking and textile manufacturing to change the absorption ...
used in
gilding Gilding is a decorative technique for applying a very thin coating of gold over solid surfaces such as metal (most common), wood, porcelain, or stone. A gilded object is also described as "gilt". Where metal is gilded, the metal below was tradi ...
. The litharge would give the sizing a dark red color that made the gold leaf appear warm and lustrous, while the linseed oil would impart adhesion and a flat durable binding surface. PbO is used in certain
condensation reaction In organic chemistry, a condensation reaction is a type of chemical reaction in which two molecules are combined to form a single molecule, usually with the loss of a small molecule such as water. If water is lost, the reaction is also known as a ...
s in
organic synthesis Organic synthesis is a branch of chemical synthesis concerned with the construction of organic compounds. Organic compounds are molecules consisting of combinations of covalently-linked hydrogen, carbon, oxygen, and nitrogen atoms. Within the gen ...
. PbO is the input photoconductor in a video camera tube called the
Plumbicon Video camera tubes are devices based on the cathode-ray tube that were used in television cameras to capture television images, prior to the introduction of charge-coupled device (CCD) image sensors in the 1980s. Several different types of tubes ...
.


Health issues

Lead oxide is toxic and irritate to skin, eyes, and respiratory tract. It affects gum tissue, the central nervous system, the kidneys, the blood, and the reproductive system. It can bioaccumulate in plants and in mammals.


References


External links


Case Studies in Environmental Medicine - Lead Toxicity
* ttp://www.webelements.com/compounds/lead/lead_oxide.html Webelements PbO {{Oxides Amphoteric compounds Lead(II) compounds Oxides