Chemical Education Today

NCW 2001: Celebrating Chemistry and Art

Chemistry, Color, and Art

by Mary Virginia Orna

and Randall J. Wildman

Photo by Jerrold J. Jacobsen
Sight is the primary sense and the
first to be mentioned in antiquity.
According to the Judeo-Christian
religious tradition, God did not say
“Let there be sound”, nor “Let there
be odors”, but “Let there be light.”
And so it was. The theme reappears
in the bow of color across the sky
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signifying a covenant between God

and humankind. As Michael Free-
mantle observed in his February 26,
2001, article in the Chemical and Figure 3. An array of modern pigments first manufactured and used in the 20th century. Art-
ists now use many synthetic pigments such as these because they are stable, have uniform
Downloaded via Mary Virginia Orna on April 15, 2020 at 17:41:40 (UTC).

Engineering News, “color is the most properties, and are widely available. Top row, from left: cobalt silicate blue; cobalt violet phos-
visual, pervasive example of the phate; zirconium vanadium blue zircon; cobalt titanate green spinel; titanium vanadium
importance of chemistry to our lives” antimony gray rutile. Bottom row, from left: nickel antimony titanium yellow rutile; zinc ferrite
(p 50). The purpose of this article is brown spinel; cadmium orange (CdS × CdSe); cadmium light red (CdS × CdSe); cadmium
to connect artists’ colors and all that dark red (CdS × CdSe).
their uses imply to this theme.
Pigments and artists’ colors came along quite a bit later in common use (1). From about the late 15th century up to
than the moment of creation. Palettes for grinding and mix- our own time, dozens more pigments were synthesized. The
ing face powders and eye painting unearthed from Egyp- dates when most of these pigments entered the artists’ pal-
tian tombs date back to only 6000 B.C.E. Egyptian Blue ette is well-known and documented (2), a fact that enables
(copper tetrasilicate, CaCuSi 4 O 10 ) and vermilion both scientist and historian to determine whether pigments
(mercury(II) sulfide) were among the earliest of the manu- present in certain works are historically correct or anoma-
factured pigments. In addition to these and the naturally lous. Some naturally-occurring coloring matter is also derived
occurring iron and manganese earth pigments, the Egyp- from plants and animals, although their use by artists has been
tians, by 3000 B.C.E., had succeeded in expanding the art- limited because of their instability. Two of the most famous
ists’ palette to red lead (Pb3O4), malachite (basic copper car- of these colorants are indigo and cochineal (Fig. 2). Since
bonate), orpiment (arsenic trisulfide), charcoal (carbon), and the development of modern chemical industry, hundreds
red madder (from the root of the perennial Rubia more pigments have become available for many industrial,
tinctorum). Figure 1 shows three important pigments from household, manufacturing, and artistic uses (Fig. 3).
times past: verdigris, a name used to designate several cop- Robert Feller (3) has listed four purposes for identifying
per compounds including the normal acetate, the dibasic by scientific examination the pigments that artists used: ob-
acetate, and several carbonates; vermilion, also called Chi- jective description of method, restoration, conservation, and
nese Vermilion; red iron oxide, called Venetian Red some authentication. Although most such work centers on the first
time after the 14th century, one of the earliest known and three objectives, it is the latter that has captured the imagi-
most widely used pigments. nation of the public.
As time went on, other pigments were added (see Table When I first entered the field of pigment identification,
1). By 1300, the list stood at about three dozen pigments it was in order to understand an artist’s method and, with a
Photo by Jerrold J. Jacobsen and

Randall J. Wildman
Photo by Jerrold J. Jacobsen and

Figure 2. A natural colorant,

cochineal, is derived from the
bodies of the female insect Coc-
cus cacti, shown here. This ma-
Randall J. Wildman

terial could be used either as a

pigment when applied with a
medium such as tempera or oil,
or as a dye. It is most famous as
the red dye used for 18th cen-
Figure 1. Artists’ Pigments Used in Ancient Times: Verdigris tury British military uniforms, the
[Cu(C2H3O2)2ⴢ2Cu(OH)2], Chinese Vermilion (HgS), and Venetian famous “Redcoats.” The chemi-
Red (red iron oxide, Fe2O3). All three are mentioned in Pliny the cal identity of the red color is car-
Elder’s 1st century work, Historia Naturalis. minic acid.

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 Chemical Education Today

NCW 2001: Celebrating Chemistry and Art

Figure 4. Portrait of St. Figure 5. El Arcángel Gabriel.

Mark, p 188, Glajor Gos- 18th centur y Ecuador bulto.
pel Book, UCLA Special Col- Stapleton Collection, National Mu-
lections. Used with permis- seum of American Histor y,
sion of Department of Spe- Smithsonian Institution. Photograph
cial Collections, Charles E. by Donald Hurlbert, Smithsonian
Young Research Library, Institution Office of Imaging, Print-
UCLA. (Image not available ing and Photographic Services.
for electronic version.) Used with permission.

little bit of luck, to be able to distinguish among the hands While such analysis provides an objective description of
of several artists by noting possible differences in their the work, the knowledge gained can also lead to conserva-
palettes. My work on the Glajor Gospel Book (4) involved tion and/or restoration. For example, analysis of numerous
sampling of microscopic particles taken from the spectrum manuscripts of Armenian and Byzantine origin that date be-
of hues used by each of the five artists known to have con- tween the 10th and 13th centuries revealed the fact that the
tributed to this massive 14th century work. The results of Armenian palette, with one exception, consisted of mineral
the X-ray diffraction analysis and chemical microscopy in- pigments, while the Byzantine palette consisted largely of pig-
dicated a distinct difference in the palettes used by the two ments of plant and animal origin (6). (The exception is mad-
different workshops to which the five artists belonged. For der, a red pigment composed mainly of alizarin and extracted
example, the individual we called the Evangelist Painter used from the root of the madder plant, Rubia tinctorum.) Since
azurite, 2CuCO3ⴢCu(OH)2, a commonly used blue pigment, organic pigments are not lightfast, knowledge of the respec-
in the portrait shown in Figure 4, whereas his assistant, whose tive palettes dictated immediately how these manuscripts were
work faces Figure 4 in the original manuscript, typically used to be conserved with respect to display and exposure to light.
good quality ultramarine as the blue pigment. Members of Chemical analysis can also lead to restoration of a work
the second workshop consistently used poorer quality ultra- of art so that it can be viewed as the artist had originally
marine in their work (5). intended. An example is the restoration of “St. Sebastian”

Table 1. Common Artists’ Pigments Used from Early Times

Common Name Chemical Identity Starting Date Comments
Charcoal Elemental Carbon Before 1300 Also called carbon black. Produced by dry
distillation of wood in a closed vessel.
Cochineal Carminic acid, a glucopyranose First described in 1549, but Made from the bodies of the female cactus
derivative of alizarin possibly used at least from insect, Coccus cacti
the conquest of Mexico in 1523
Egyptian Blue Calcium copper tetrasilicate, IV Egyptian Dynasty, Crystalline compound containing some glass
CaCuSi4O10 or before impurity
Indigo Indigotin, C16H10N2O2 From prehistoric times; probably Derived from different plants of the genus
the oldest colorant known Indigofera
Iron oxide, red Fe2O3 From prehistoric times In continuous use in all geographic regions
and time periods.
Madder Alizarin; From prehistoric times Extracted from the ground root of the madder
1,2-dihydroxyanthraquinone plant, Rubia tinctorum
Malachite Basic copper carbonate, From prehistoric times Oldest known bright green pigment
CuCO3ⴢCu(OH)2
Orpiment Arsenic trisulfide, As2S3 From prehistoric times Derives its name from a corruption of
auripigmentum, meaning gold color
Red Lead Lead tetroxide, Pb3O4 From antiquity Bright scarlet pigment with good hiding power;
also known as minium
Verdigris Dibasic acetate of copper From antiquity Other copper compounds, including
Cu(C2H3O2)2ⴢ2Cu(OH)2 carbonates, are also called verdigris
Vermilion Cinnabar, HgS From antiquity One of the oldest synthetic pigments known

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 Chemical Education Today

NCW 2001: Celebrating Chemistry and Art

Figure 6. Workshop of Figure 7. “San Rafael,”

Daniel Miguel Sánchez. José bulto. José Armijo, Española,
Luis Valentín, 1996, Puerto New Mexico, 1999. Collec-
Rico bulto from the collection tion of Taylor Museum, Colo-
of Nitza and Paco Toste. rado Springs Fine Arts Cen-
Photograph by Donald ter, Colorado Springs, CO.
Hurlbert, Smithsonian Institu- Used with permission.
tion Office of Imaging, Print-
ing and Photographic Ser-
vices. Used with permission.

by Tanzio da Varallo that was accomplished by conservation used not only wood from native trees but also recycled wood
chemist Barbara H. Berrie at the National Gallery of Art (7). from various sources, including shipping crates (from the 17th
Berrie’s analysis showed that two layers of overpainting ap- century, when the santos began to be created, until the present
plied much later to this early 17th century work could be time), whereas New Mexican artists working during this same
safely removed to reveal “a pulsating yellow color [and] the period tended to confine themselves to the use of local woods.
sensuous folds of…drapery as Tanzio originally painted it.” Pigment analysis showed that the Puerto Rican artists tended
Closer to home, a recent exhibit, “Santos: Substance and to use conventional oil paints, but New Mexican artists made
Soul,” mounted by the Smithsonian Center for Materials their own paints from locally available materials. Figure 6 is
Research and Education, (8) focuses on the scientific study a modern work showing a Puerto Rican santero in his work-
of the techniques and materials used by artists steeped in the shop, possibly using colorants imported for his use. Figure
tradition of santo-making throughout the Hispanic Ameri- 7, on the other hand, is a work by José Armijo, a practicing
cas from the 17th through the 20th centuries. Figure 5 de- santero from Española, New Mexico, whose practice bears out
picts a typical santo, an 18th century bulto, or sculpture, from the analytical conclusions of the Smithsonian Institution. In
Ecuador. The exhibit documents how analysis of these works recent correspondence, Armijo indicated that with few ex-
of art by a wide variety of instrumentation familiar to most ceptions he uses local materials listed in Table 2. Figure 7
chemists—X-ray diffraction, X-ray fluorescence, ultraviolet, shows a work created from the local New Mexican materials
visible, infrared, and mass spectroscopy, chromatographic used by Armijo.
methods, and scanning electron microscopy—has provided Rarely does one have the opportunity to verify by analysis
information about the evolution of this art form in separate the materials that an artist deliberately chooses, but even so,
areas where local traditions of materials usage developed. For some of the materials that Armijo uses almost defy analysis.
example, wood analysis showed how artists in Puerto Rico While there is a limited number of possible chemical identi-

Table 2. Sources of Colors Used by New Mexican Santero, José Armijo

Color Source Processing

Yellow Chamisal bush Boil the leaves

Yellow Yellow ocher from stone
Green Clay from Placitas, NM Grind smooth with a glass muller on a marble slab
and strain through cheesecloth
Red Clay from Questa, NM Processed like the green clay
Blue Azurite purchased locally Processed like the clays
Blue Indigo purchased from a pigment Processed like the clays
supply house
Purple Cochineal beetles obtained locally Processed like the clays
Brown Black walnuts gathered locally Boil hulls for hours; strain through cheesecloth
Black Chimney soot gathered locally
White Rabbit skin glue plus gypsum
Varnish 1 part piñon sap; 5 parts ethanol Must remain in contact for one week
Flesh Colors 1 part marble dust; 1 part yellow
ocher; 1 part red clay
Woods Pine, aspen, cottonwood root, jelutong wood

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 Chemical Education Today

NCW 2001: Celebrating Chemistry and Art

Figure 8. The miniature results of the santos featured in the Smithsonian exhibit, please
shown is from the Archaic visit the Web site (8), http://www.si.edu/scmre/santos.
Mark, a purported 12th Robert Feller’s fourth stated purpose for the scientific
century Byzantine Gospel examination of works of art is authentication. I like to think
of Mark that was written in
of this activity as “de-authentication” since one is more likely
an archaic form of Greek.
Analysis of the blue pig-
to be able to prove that a certain object is a fake rather than
ment in this manuscript in- genuine. Two examples illustrate how an analytical tool can
dicated that it belonged to work in favor of the insurance agent. In the first instance, I
a more modern period, pos- was involved with a project some years ago that eventually
sibly even the 20th century. showed that a purported 12th century Byzantine manu-
Used with permission of the script, the “Archaic Mark,” shown in Figure 8, was more
Department of Special Col- than likely a modern forgery. This work housed in the Spe-
lections, University of Chi- cial Collections at the University of Chicago was found by
cago Library. chemical microscopy to contain large amounts of Prussian
blue, a pigment that was first synthesized in the 18th cen-
tury (6, 9).
Another method, among many, that has entrapped
would-be forgers of ceramic pieces is thermoluminescence
dating. All clay materials contain radioactive materials that
ties to red clay, which normally contains a high percentage emit energy as they decay and some of this energy gets
of iron oxide, green clay can present problems. One might trapped in the clay body. When the clay is fired, the en-
guess that a close relative would be terre-verte, a complex mix- ergy is released and the clock is reset, so to speak, so that
ture of the minerals glauconite and celadonite. At least Table the age of the piece can be measured from the time of fir-
2 can point the analyst in the right direction—ultimately with ing by its thermoluminescent output. This method was first
the triple goal of objective description of method, restora- applied successfully (10) to the identification of numerous
tion, and conservation. For a more complete account of the forgeries found among the 6th millennium B.C.E. Haçilar
pottery pieces from southeastern Turkey (Fig. 9). Many other
methods have been applied to famous and not-so-famous
works of art to determine their authenticity and origin and
some of their stories have appeared in this Journal (11).
Attention is so often focused on how chemistry can ex-
amine a work of art that we seldom allude to the fact that
chemistry itself has been the subject of artists from at least
the time of the later alchemists (15th century). Figures 10
and 11 are two delightful paintings from the Fisher Col-
lection depicting alchemists in their laboratories. Now
housed at the Chemical Heritage Foundation in Philadel-
phia, these works portray alchemists working as metallur-
gists, physicians, dentists, and pharmacists. Plans are now
underway to study these paintings comprehensively from the
outside in and from the inside out. From the outside in, they
will be examined for the materials they contain and the meth-
ods by which they were produced with a view to maximiz-
ing their conservation and preservation; they will be exam-
ined from the inside out, that is, by their subject matter, by
Lawrence Principe of The Johns Hopkins University so that
we can learn more about the chemistry that went on at the
time of the paintings’ origins.
This short paper has given a quick overview of some of
chemistry’s relationships to the practice of art. For more in-
formation please see several articles from this Journal on
artist’s colors (12) and the delightfully informative book re-
cently published by Heinrich Zollinger, a renowned Swiss
dye chemist, who deals with color in all of its aspects and
especially as it touches the world of art (13).

1310 Journal of Chemical Education • Vol. 78 No. 10 October 2001 • JChemEd.chem.wisc.edu

 Chemical Education Today

Figure 10 (above). The Alchemist. Mattheus van

Hellemont (1623–1674). Photo by Will Brown,
Fisher Collection, Chemical Heritage Founda-
Figure 9. Counterclockwise from right. tion, Philadelphia, PA. Used with permission.
Genuine anthropomorphic vessel, 6th mil-
lennium B.C.E,; fake “Haçilar” double- Figure 11 (at right). The Medical Alchemist.
headed vessel; fake “Haçilar” figurine; Franz Christoph Janneck (1703–1761). Photo
fake “Haçilar” snake. © Copyright The by Will Brown, Fisher Collection, Chemical Heri-
British Museum. ((Image not available for tage Foundation, Philadelphia, PA. Used with
electronic version.) permission.

Literature Cited
1. Orna, M. V.; Goodstein. M. Chemistry and Artists’ Colors;
Union Press: Wallingford, CT, 1998; p 283.
2. Gettens, R. J.; Stout, G. L. Painting Materials: A Short Ency-
clopedia; Dover Publications: New York, 1966.
3. Feller, R. L., Ed.; Artists’ Pigments: A Handbook of their His-
tory and Characteristics, Vol. I (of three); National Gallery of
Art: Washington, DC, 1986.
4. Mathews, T. F.; Sanjian, A. K. Armenian Gospel Iconography:
The Tradition of the Glajor Gospel; Dumbarton Oaks Research
Library and Collection: Washington, DC, 1991; pp 48–51
and 227–230.
5. Orna, M. V.; Mathews, T. F. Studies in Conservation 26, 1981,
57–72.
6. Orna, M. V.; Lang, P. L.; Katon, J. E.; Mathews, T. F.;
Nelson, R. S. Applications of Infrared Microspectroscopy to
Art Historical Questions about Medieval Manuscripts. In Ar-
chaeological Chemistry–IV; Allen, R. O., Ed.; American Chemi-
cal Society Advances in Chemistry Series 220, American
Chemical Society: Washington, DC; pp 265–288.
7. Ember, L. Science in the Service of Art. Chemical and Engi-
neering News (April 16, 2001), p 9.
8. Santos: Substance and Soul, Smithsonian Center for Mate-
rials Research and Education. http://www.si.edu/scmre/santos/
mainmenu.asp (accessed Aug 2001).
9. Orna, M. V. J. Chem. Educ. 1997, 74, 373–376.
10. Jones, Mark, Ed. Fake? The Art of Deception; The University
of California Press: Berkeley and Los Angeles, 1990; p 286.
11. See for example the papers by Rogers, F. E. J. Chem. Educ.
1965, 42, 619 and J. Chem. Educ. 1972, 49, 418.
12. Orna, M. V. Chemistry and Artist’s Colors, Parts I, II, III. J.
Chem. Educ. 1980, 57, 256–267.
13. Zollinger, H. Color: A Multidisciplinary Approach; Wiley-VCH:
New York, 1999.

Mary Virginia Orna is a member of the Department of

Chemistry, College of New Rochelle, New Rochelle, NY, 10805;
mvorna@cnr.edu.

JChemEd.chem.wisc.edu • Vol. 78 No. 10 October 2001 • Journal of Chemical Education 1311