Introduction

The chemistry of artists' materials has its roots in ancient

and medieval technology and medicine. Among the earliest
"manufactured chemicals" were the synthetic pigments
Egyptian hlue, which was produced in the third milennium
B.C. ( 1, 2), and vermillion (HgS), a one-time staple of the
artist's palette (3). The technical literature of the Middle Ages
abounds with recipes for the synthesis of artists' pigments. A
dace of honor was accorded to synthetic hlue colorant be-
Mary Virginia Orna, O.S.U.
College of New Rochelle
New Rochelle. NY 10801
cause of the scarcity and prohibitive cost of natural blues ( 4) .
According to Eastlake (5). chemistry remained the professed
Chemistry and Artists' Colors
Part 1. Light and color
auxiliary of painting well intu the seventeenth century.
Althuugh, in later centuries, chemistry and art have gone
their srparate ways and rach discipline has develuped its own
specinlind vocal~ulary and methodology, there are still many
are:).; 01 hoth fields which areof mutual interest. Oneof these
areas of overlap is color. I t is a matter of history that Europe's
chemical industrv erew out of dve and ~i e me nt manufacture
(6). In 1978, the e"scmated glohz production of synthetic dyes
and pigments was close t o the two billion dollar mark. Al-
though a very small proportion of this output is actually used
bv practicing artists, the very magnitude of the husiness as-
s&& ongoing research which is constantly producing new
H
colorants with properties more desirable than many of the
0
traditional artists' pigments. For this reason, the artists'
0
palette has undergone a series of transformations over the past
century and a half. One notable example was the introduction
of titanium white, TiOz, in the early 1920's. Far superior to its
older counterparts, lead white and zinc white, in opacity,
c
stability, and adaptability to various media, Ti02 has almost
completely replaced them in artists' usage and has found use
in many new products as well.
E The historical and ongoing links between the chemical in-
M
dustry and artistic endeavor which are centered in their mu-
,
tual interest in colored materials, lead to a series of questions
which will form the basis of the topics covered in this feature.
S
(1) What is the nature of light and color? (2) How is light
T
modified by colored objects t o produce the sensation of color?
(3) What features of molecular or crystal structure must he
present for a compound t o he colored? (4) What physical
Y
properties of colorants make them desirable as artists' pig-
ments? (5) How are artists' colors synthesized? (6) How are
artists' colors classified?
The Nature of Llght and Color
Theories regarding the nature of light and the origin of color
go hack to the ancient Greeks. Aristotle himself is credited
with making the first important contribution to what is now
the modern theory of selective absorption (7). I t was Seneca,
a Roman philosopher of the first century, who first noted that
a prism reproduces the colors of the rainbow, hut it remained
for Isaac Newton in the seventeenth century t o formulate
modern color theory on the basis of experiment.
Light and Color
Newton allowed a narrow beam of sunlight to pass through
a prism in a darkened room, and he observed that the light
emerging from the other side w3s no longer white light, hut
exhibited a series of colors ranging from red, through orange,
yellow, green and blue t o violet (shown in Fig. 1 and in color
256 1 Journal of Chemical Education
Figure 1. Dispersing prism
on the front cover). Newton drew two conclusions from his
observations:
1) Sunlight must consist of a mixture of all the colors observed in
the prismatic spectrum.
2) The prism is capable of dispersing the white light into its con-
stituent colors. The various colors travel at various velocities
in the prism material, and therefore have different angles of
refraction ( Ri
The observed variation of angle of refraction with color is
due directly t o the wave nature of the incident lieht. Lieht is
energy of a special form known as electromagnetic rad~aiiun.
(The name results from the association of mcillntine elwtric
and magnetic fields with the radiation.) A characteristic
~ r o ~ e r t v of all electromaenetic radiation is the freauencv of
. .
ihe'field oscillation, u, wkch remains invariant as the wave
travels through anv medium. The freauencv is related to the
velocity of th; wave, c, and the wawle&h, X, by theequation
uA = r . It fullows from thi5 relationshio thar hoth Xand r must
vary as a wave of a given frequency tiavels through different
media. The frequency can also be related to the energy of the
wave through the Einstein-Planck relationship, E = hv, where
h is the Planck constant with units of energy times time. A
convenient value for h is 4.136 X 10-15 eV-sec. An electron volt
( ~ V I is defined as the energy an electron gains when moved
through a votential of one volt. If. for examole. each electron
"storeb" an ordinary 12-V automobile Lattery has a po-
tential energy of 12 eV, then this amount of energy is ex-
pended by each electron as the hattery discharges in use. The
energies of electromagnetic radiation vary from more than 3
X lo6 eV t o less than eV. The visible portion of this
spectrum, i.e., the energy response range of the human eve.
.. .
&upies only the very small region betwien about 1.7 and i l
eV. An analysir of this visihle region relaiinc uther variables
.
t o color is given in Table 1.
Color, although arising from the presence of light, is fun-
damentally a subjective phenomenon. It is the result of a
stimulus received by the eye and interpreted by the brain. A
complete descri~tion of the color phenomenon must include
three factors: the light source, the ohject it illuminates, and
the eye-brain physiological-psychological mechanism which
receives and perceives the culur. For the purpuses oi thig
prtwntation, a short summary of these tigpics will suffice. A
more detailed rliscussion 01 these pl~unomena can he found
in the accurnpanying paper hy Thomas Rrill entitled ',Why
Objects Appear As They Do."
Color
Red
Orange
Yellow
Green
Blue
Violet
Table 1. The Vislble Spectrum
Wavelength Bandwidth Frequency Energy
(nm) (nm) (cm-') (eV1
647.0-700.0 53.0 15447-14277 1.77-1.92
585.0-647.0 62.0 17083-15447 1.92-2.12
575.0-585.0 10.0 17083-17380 2.12-2.16
491.2-575.0 83.8 17380-20343 2.16-2.52
420.0-491.2 71.2 20343-23810 2.52-2.95
400.0-420.0 20.0 23810-24983 2.95-3.10
3.1 Energy (eV) 1.7
400 Wavelength (nm) 700
Figure 2. Spectral energy distribution curve of typical daylighl
The Light Source
Every source of illumination emits a range of energies, the
intensities of which vary across the energy spectrumto yield
a spectral enerm distribution curve. A light source which emits
enkrgy with roughly constant intensity over the limited re-
sponse range of the eye, 1.7 t o 3.1 eV, or, in terms of wave-
length, 700-400 nanometers (1 nanometer, nm = 10-9 m), is
perceived by the eye as "white." Dispersion of this light by a
nrism or eratine vields the snectral colors raneine from red
at around-1.7 e c violet at around 3.1 eV. on;! way of illus-
tratine the enerev outnut of a lieht source is shown in Fieure
,.. .
2.l Thk source represented here is typical daylighr, and'the
relative intensitv of the liaht at each wavrlenath (or enermj
is plotted with respect to wavelength (and energy).
The Object
If the light described by the curve in Figure 2 were allowed
to fall on an object which absorbed some of the light, as shown
in Figure 3, the light reflected t o our eyes would no longer
consist of significant intensities of all the wavelengths of
visible light. The light in the shaded area, which is largely
green and blue light, has been absorbed to a great extent. Our
eyes then can be stimulated only by the unabsorbed light at
the red end of the spectrum, and so the ohject which yields this
reflectance curve is perceived by the eyes as "red." The shaded
area in the diagram is called an absorption band, and the
unshaded area is the resulting reflectance curve of this "red"
ohject. The color characteristics of most colored objects can
be described partially by reference to the shape, width, in-
tensitv and vosition of their resoective ahsorvtion hands. The
superimposition of the spectral energy distribution curve of
Figure 2 on the reflectance curve of Figure 3 yields a composite
curve called the "stimulus for color" curve, which stimulates
the eve-brain mechanism (9.10).
Color, however, is a very complex phenomenon. Objects can
modiiv lieht not onlv by reflectance and selertive absorntion.
. . . . .
but also by transmission, scattering, dispersion, interference,
and diffraction. It is the combination of all these uossihle in-
-
3.1 Energy ( eV) 1.7
400 Wavelength (nm) 700
Figure 3. Absorption spectrum of a red object.
Figure 4. 1931 CIE standard observer
teradions which ultimately determines the appearance of an
ohject.
The Eye-Brain Detector-Interpreter
After modification, the light must strike a detector in order
to he evaluated. The most imwrtant detector when discussine
-
color is the human eye, because perceived color is no more
than the suhiective versonal evaluation of the lieht reflected
or transmitted to thk eye. A complete description of the color
perception process must then involve the stimulus for color
curve superimposed on the proper response curve for the
human eye, which is slightly different for each human being.
In order to obviate this latter difficulty, in 1931 the Com-
mission Internationale de 1'Eclairage (CIE) defined the re-
sponse curve for a "standard observer." This curve, which is
illustrated in Fiaure 4 is actually three curves, one for each
response regionbf the spectrum, and it is based upon the
Young-Helmholtz theory. This theory postulates that since
the retina resnonds t o different colors in at least three dif-
ferent ways, t i ere must he three different kinds of receptors
present in the eye, each of which is sensitive to a particular
Differences i n Solar Spectra: Since our atmosphere creates
substantial loss of solar radiation due to absorption and scattering
throuehout the soectrum. a solar soeetral curve will deoend won the
pnth l r ngt h i d runlieht t hr uugh the atmusphere and tnrrelore, upm
t he position d the sun i n IIW sky. Thus, t he varying p z ~ t ~ o n of t he
sun from irszen~th give3 rke r u n fnm:lv of solnr spectral run,rs.
Volume 57, Number 4. April 1980 / 257
nortion of the snectrum (11). Modern research has shown that
there are indeek three different types of cones in the retina.
Each contains one of three lieht-sensitive oiements which
.
enable the eye t o respond to each of the primary colors-red,
green, and blue (12,13).
Liaht Modlfication to Produce Color
-
Chrmistry has traditionally been defined as the study of
matter and the changes that take place in matter. Therefore,
the chemistry of color could hp bn)adly defined as the study
of the chanres induced in matter as a result of its interaction
with visib~e~electroma~netic radiation. If impinging electro-
magnetic radiation of the visible region induces no color in the
chemical species under observation, then the object will simply
interact physically with the visible radiation. It could also, of
course, selectively absorb ultraviolet or infrared radiation. On
the other hand, if the species under ohservation is capable of
ahsorhine lieht between about 1.7 and 3.1 eV. then some
.. ..
\.isible rlectromagnetic radintion u,ill he absorbed and most
of the rest of it will be reflected or transn~itted. The iunda-
mental chemical questions therefore become:
1) What is the process which allows some materials to absorb
visible radiation?
2) Why can some materials undergo this process while others
cannot?
3) Why is this process different for different materials?
The answers t o these questions are not simple, and they in-
volve a reiteration of several important theories of atomic and
molecular structure.
The conceots of molecular structure develooed from the
theory of atomic structure provide us with a picture of vi-
brating nuclei linked bv electrons located in uermitted orbitals
of different energies. The consolidation of the quantum theory
by the successful interpretation of the energy distribution of
blackbody radiation, the line spectra of atoms, and the band
spectra of molecules, leads us to helieve in the existence of
permitted energy levels. Absorption of energy by these atoms,
molecules, and crystals serves to move the body from place to
place (translational energy), t o cause electrons in permitted
energy levels of the system t o enter higher energy levels
(electronic energy), to allow the atoms in the system to change
their distances with respect to one another (vibrational en-
erev). and t o allow naseous molecular systems t o rotate (ro-
ta&al energy). he energies of visihlelight are too great t o
he absorbed as rotational or vibrational energy, hut in many
instances, the energies of visihle light are sufficient to promote
electrons from the mound state to excited states. For example,
the energies necessary to promote hydrogen'ssingle electron
from thrgrounrl st i ~t e (n = 11 to~~xci redrr~rpsareal l ~reatcr
than the energies amesponding to visihle light (Lyman Se-
ricsj. Howe\w, the transitions invol\.ing the promorion of an
elerrnm from n = 2 to higher states fall within the visihle re-
pion (Ralmer Series). On the hasis of this single observation,
it is now oossible to begin to answer our fuudamentd chemical
In the firstplace, the process which allows some
species to absorb visible radiation is an electronic process
dherehy radiation is absorbed to promote the speciesinto the
excited states. In the second place, not all species can undergo
this process because their permitted energy leuel differences,
which are determined by the structure of each species, lie
outside the visible region. Thirdly, different mnterials exhibit
different colors, because the energy leuel spacings in their
molecules. atoms. and crvstals are different. However. all
. .
atoms, molecules, and crystals, whether colored or colorless,
exhibit absorption of electromagnetic radiation. Since there
is no difference in principle between electronic transitions
resulting from absorption from the visible or ultraviolet re-
gions, one can say that color is not connected with any one
special feature of molecular structure (14,15).
Table 2. Colors of Absorbed LlgMand Corresponding
Complementary Colors
Wavelength
(nm)
400-420
420-450
445-490
490-510
510-530
530-545
545-580
580-630
-
630-720
Energy
lev)
3.10-2.95
2.95-2.76
2.76-2.53
2.53-2.43
2.43-2.34
2.34-2.28
2.28-2.14
2.14-1.97
1.97-1.72
Color of
Absorbed
Light
Violet
Violet-Blue
Blue
Cyan
Green
Green-Yellow
Yellow
Orange
Red
Color Seen
Green-Yellow
Yellow
Orange
Red
Magenta
Violet
Violet-Blus
Blue
Cyan
Because vibrational and rotational energy levels are su-
~erimoosed on the electronic levels in a molecule. a numher
bf wavelengths on both sides of the principal absorption hand
are alsoabsorbed, giving rise to broad bands which are char-
acteristic of ultraviolet and visible absorption spectra. When
these broad bands correspond to eachof several different re-
gions of the visible spect;um, they are capable of inducing a
mental color response interpreted as a single color. For ex-
ample, if red, green, and blue lights are mixed in the proper
proportions, the mental color response of the human eye is
"white!'If hlue light is subtracted from this mixture, and only
the red-green combination remains, the human eye interprets
this combination as "yellow." Together, hlue and yellow
"complete" the visible spectrum; thus they are termed com-
plementary colors. When a chemical compound absorbs the
wavelengths of hlue light from a "white2'light source, the re-
maining waveleneths will he reflected t o the eve and inter-
preted & the color yellow. Newton himself first recognized
these relationships and organized the spectral colors into a
color circle. when two colo& directly opposite one another in
the circle were mixed in equal proportions, the result was
white (considered to be at the center of the circle). This view
leads to an infinite numher of complementary colors, and a
numher of variations on Newton's original color circle are in
use today (16,17). Table 2 is a rough rendition of Newton's
color circle in tabular form. Brill's paper (p. 259) contains a
color circle diagram.
Literature Clted
. .
~ " l ~ mb ~ ~ , Ohio, 1956. p. 203.
8 Oma. M. V., Low, M. J. D., and Beer N. S., "Synthetic Blue Pigments: IX-XVI
Centuries. I: Literature." Studies in Conssruafion. 25, WO (February, 1980).
Eastlake, C.L., " Me t hd~a nd Materials of Painting of thecleat Schoolsand Masfem,
Val.I."Daver.NawYork,1960.p.11.
O'Sullivan. Dennot A., "Outlmk Clouds for Color Chemicals Businpas." Chemical and
Engineering Neus, 57.16 Web. 26.1979).
Arislotle, YOn Sense and the Sensible." ( ~awl ot oc B-. J. E.1 The Clarendan P-,
Oxford. 1908. sect. 2 & 3.
Newton. I.. "Optickr," in "Great Books of the Wasfern Wodd. vol. 34." (Editor
Hutchin* R. M.), Encyclapedia Britsnniee, New York, 1952, pp. 386412.
Billmeyer. F. W.. .lr. and Saltrman, Mar. "Principles of Color Technology." Wiley-
Interscience. New York, 1966, pp. %12.
Oma, M. V.,"The Chemical Originaaf Color," J. CHEM.EDUC.,55.478 (1978).
MacNichal. E. F., Jr., "Three-Pigment Color Vinion," Scientific Amerreon, 221.48
(Deeembr 1964).
Wsld. G., "The Rempton of Human Color Vision," Sliance. 145. lW7 (September
19611.
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258 1 Journal of Chemical Education