White lead is the basic lead carbonate 2PbCO
3·Pb(OH)
2.
It is a complex salt, containing both carbonate and hydroxide ions. White lead occurs naturally as a mineral, in which context it is known as hydrocerussite,
a
hydrate
In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
of
cerussite
Cerussite (also known as lead carbonate or white lead ore) is a mineral consisting of lead carbonate (PbCO3), and is an important ore of lead. The name is from the Latin ''cerussa'', white lead. ''Cerussa nativa'' was mentioned by Conrad Gessner ...
. It was formerly used as an ingredient for
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 ...
and a cosmetic called
Venetian ceruse
Venetian ceruse, also known as ''blanc de ceruse de Venise'' and Spirits of Saturn, was a 16th-century cosmetic used as a skin whitener. It was in great demand and considered the best available at the time, supposedly containing the best quality ...
, because of its
opacity and the satiny smooth mixture it made with dryable oils. However, it tended to cause
lead poisoning
Lead poisoning, also known as plumbism and saturnism, is a type of metal poisoning caused by lead in the body. The brain is the most sensitive. Symptoms may include abdominal pain, constipation, headaches, irritability, memory problems, inferti ...
, and its use has been banned in most countries.
White lead compounds known as
lead soap were also used as additive for lubricants for
bearings and in machine shops. Lead soap was also used as an
oil drying agent An oil drying agent, also known as siccative, is a coordination compound that accelerates ( catalyzes) the hardening of drying oils, often as they are used in oil-based paints. This so-called "drying" (actually a chemical reaction that produces an ...
for paints made with
drying oil
A drying oil is an oil that hardens to a tough, solid film after a period of exposure to air, at room temperature. The oil hardens through a chemical reaction in which the components crosslink (and hence, polymerize) by the action of oxygen (not ...
or air drying paints made with
alkyd resin
An alkyd is a polyester resin modified by the addition of fatty acids and other components. Alkyds are derived from polyols and organic acids including dicarboxylic acids or carboxylic acid anhydride and triglyceride oils. The term ''alkyd'' is a m ...
s. Lead is often used with cobalt driers. Lead free substitutes have been developed to replace this use of lead in paint.
History
What is commonly known today as the "Dutch method" for the preparation of white lead was described as early as
Theophrastus of Eresos (ca. 300 BC), in his brief work on rocks or minerals,
''On Stones'' or ''History of Stones.'' His directions for the process were repeated throughout history by many authors of chemical and
alchemical
Alchemy (from Arabic: ''al-kīmiyā''; from Ancient Greek: χυμεία, ''khumeía'') is an ancient branch of natural philosophy, a philosophical and protoscientific tradition that was historically practiced in China, India, the Muslim world, ...
literature. The uses of cerussa were described as an external medication and pigment.
Clifford Dyer Holley quotes from Theophrastus' ''History of Stones'' as follows, in his book ''The Lead and Zinc Pigments''.
Lead is placed in earthen vessels over sharp vinegar, and after it has acquired some thickness of a sort of rust, which it commonly does in about ten days, they open the vessels and scrape it off, as it were, in a sort of foulness; they then place the lead over vinegar again, repeating over and over again the same method of scraping it till it has wholly dissolved. What has been scraped off they then beat to powder and boil for a long time, and what at last subsides to the bottom of the vessel is ceruse.
Later descriptions of the Dutch process involved casting metallic
lead
Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
as thin buckles and corroded with
acetic acid
Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main component ...
in the presence of
carbon dioxide
Carbon dioxide (chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is transpar ...
. This was done by placing them over pots with a little
vinegar
Vinegar is an aqueous solution of acetic acid and trace compounds that may include flavorings. Vinegar typically contains 5–8% acetic acid by volume. Usually, the acetic acid is produced by a double fermentation, converting simple sugars to et ...
(which contains acetic acid). These were stacked up and covered with a mixture of decaying dung and spent
tanner's bark, which supplied the CO
2, and left for six to fourteen weeks, by which time the blue-grey lead had corroded to white lead. The pots were then taken to a separating table where scraping and pounding removed the white lead from the buckles. The powder was then dried and packed for shipment or shipped as a paste. One benefit of the process was that it was not necessary to dry the paste of white lead, removing its water. All that needed was to mill the paste with
linseed oil
Linseed oil, also known as flaxseed oil or flax oil (in its edible form), is a colourless 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 the white lead would take up the oil and reject the residual water, to give white lead in oil.
Paints
White lead has been the principal white pigment of classical European
oil painting
Oil painting is the process of painting with pigments with a medium of drying oil as the binder. It has been the most common technique for artistic painting on wood panel or canvas for several centuries, spreading from Europe to the rest of ...
.
[ Commercial supplier, offering original pigments to the conservation and reproduction markets] There have been claims that it is partly responsible for darkening of old paintings over time, reacting with trace amounts of
hydrogen sulfide
Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The unde ...
in the air to produce black
lead sulfide Lead sulfide refers to two compounds containing lead and sulfur:
*Lead(II) sulfide
Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is s ...
. Other authorities dispute this; the most traditional view is that impermanent pigments and dirty varnish (which is often cleanable) are more likely responsible for darkening.
Paintings and the role of varnish, which might protect the white lead yet itself darken, aside—according to Michelle Facini, a paper conservator at the National Gallery of Art, conversion of lead carbonate to lead sulfide is indeed what happens to some lead chalks/paints in drawings and watercolors and other works done on paper and unvarnished. Varnish is meant to be removable from an oil painting, to strip off when it dirties or cracks; but on paper it soaks through and becomes inseparable from the paper fibers, ruinous as it ages. This is why works on paper are never, or should never be, varnished.
In any event, white lead has been mostly supplanted in artistic use by
titanium white
Titanium dioxide, also known as titanium(IV) oxide or titania , is the inorganic compound with the chemical formula . When used as a pigment, it is called titanium white, Pigment White 6 (PW6), or CI 77891. It is a white solid that is insolubl ...
, which has much higher tinting strength than white lead. Critics argue that substitutes like zinc oxide and titanium dioxide are more reactive, become brittle, and can flake off.
[ The Smithsonian's Museum Conservation Institute exposes long-term problems with zinc white] White lead is less used by today's painters, not because of its toxicity directly; but simply because its toxicity in other contexts has led to trade restrictions that make white lead difficult for artists to obtain in sufficient quantities.
Winsor & Newton
Winsor & Newton (also abbreviated W&N) is an English manufacturing company based in London that produces a wide variety of fine art products, including acrylics, oils, watercolour, gouache, brushes, canvases, papers, inks, graphite and coloured ...
, the English paint company, was restricted in 2014 from selling its flake white in tubes and now must sell exclusively in tins.
In the eighteenth century, white lead paints were routinely used to repaint the hulls and floors of
Royal Navy
The Royal Navy (RN) is the United Kingdom's naval warfare force. Although warships were used by English and Scottish kings from the early medieval period, the first major maritime engagements were fought in the Hundred Years' War against F ...
vessels, to waterproof the timbers and limit infestation by
shipworm
The shipworms are marine bivalve molluscs in the family Teredinidae: a group of saltwater clams with long, soft, naked bodies. They are notorious for boring into (and commonly eventually destroying) wood that is immersed in sea water, including ...
.
Other synonyms (as an art pigment)
Among the synonyms for white lead are Berlin white, Cremnitz white, Dutch white lead, flake white, Flemish white, Krems white, London white, Pigment White 1, Roman white, silver white, slate white and Vienna white.
See also
*
List of inorganic pigments
The following list includes commercially or artistically important inorganic pigments of natural and synthetic origin..
Purple pigments
Aluminum pigments
* Ultramarine violet: (PV15) - a synthetic or naturally occurring sulfur containing silicat ...
*
Venetian ceruse
Venetian ceruse, also known as ''blanc de ceruse de Venise'' and Spirits of Saturn, was a 16th-century cosmetic used as a skin whitener. It was in great demand and considered the best available at the time, supposedly containing the best quality ...
*
White Lead (Painting) Convention, 1921
White Lead (Painting) Convention, 1921 is an International Labour Organization Convention established in 1921 to advance the prohibition of using white lead in paint.
As of 2017 many leading global nations, including the United States, the Unit ...
References
Further reading
* Gettens, R.J., Kühn, H. and Chase, W.T. "Lead White", in Roy, A., (Ed), ''Artists' Pigments'', Vol 2, Oxford University Press, 1993, pp. 67–81
External links
Lead white Colourlex
{{Authority control
Lead(II) compounds
Inorganic pigments
Environmental impact of paint