Waters Symposium: Atomic Emission Spectroscopy
A Brief History of Atomic Emission Spectrochemical Analysis,
16661950
Richard F. Jarrell
173 Allen Ave., Waban, MA 02468-1734; rjarrell@thermo-optek.com
Emission spectrochemical analysis is the oldest technique
for performing a chemical analysis without the traditional
chemical procedure.
Foundations
Isaac Newton was the first person to discover the true
nature of white light. In 1666, Newton inserted a glass prism
in a beam of sunlight that was shining into his darkened room
through a hole in the shutter. This produced vivid and intense
colors on a wall in the same order as in a rainbow. Newton
used a mirror to reflect the colors back through the prism,
producing white light again. He deduced that white light
was made up of the spectral colors (1).
Newton found that the refrangibility increased from
red to violet. Newton believed that the light was transmitted
by minute corpuscles (particles) traveling at high speed (2).
Blue corpuscles were smaller than red and so were diverted
more by a prism.
In 1678 a Dutch physician, Christian Huygens, postulated
that light was composed of minute waves in the atmosphere.
Huygenss wave theory of light eventually triumphed over
Newtons particle theory (3).
Invention of the diffraction grating is ascribed to the
American astronomer David Rittenhouse. In 1786 Ritten-
house made a grating of parallel hairs laid across two fine
screws. When he looked through this at a small opening in the
window shutter of a darkened room, he saw three images of
approximately equal brightness and several others on either
side fainter and growing more faint, colored and indistinct,
the further they were from the main line. He noted that the
blue light was bent more than red light and ascribed these
effects to diffraction (4 ).
Between 1814 and 1824 a German optician, Joseph
Fraunhofer, built the first spectroscope by placing a prism
before the eyepiece of a telescope to study the dim light
of heavenly objects (5). Fraunhofer repeated Rittenhouses
experiments with fine wire gratings. He placed two very fine
wires on a framework of coarse wires. Next he carefully
a b
Figure 1. (a) Schematic of the KirchhoffBunsen, 1860, 20-cm quartz spectrometer. (b) Line drawing of the KirchhoffBunsen spectrometer
(reverse of schematic, reproduced in J. Chem. Educ. 1956, 33, 20, from an illustration provided by the Deutsches Museum, Munich).
JChemEd.chem.wisc.edu Vol. 77 No. 5 May 2000 Journal of Chemical Education
unwound one wire. When he placed this grating in a beam
of white light it produced a spectrum, with blue light dispersed
more than the red light (6 ).
Later Fraunhofer produced reflection gratings by ruling
grooves with a diamond point on a mirror surface. His fin-
est grating was only 12 mm wide and contained 9600 grooves,
but this enabled him to measure the wavelengths of light for
the first time. Fraunhofer explained the phenomenon of
diffracted orders and derived the grating equation (6 )
n = b(sin i sin r)
where n is the order number and is the wavelength, b is
the grating spacing in angstroms, and i and r are the angles
of incidence and reflection.
Spectrochemical Analysis
Emission spectrochemical analysis dates from the work of
the German physicist Gustav Kirchhoff and his collaborator, the
German chemist Robert Bunsen. In 1860, they demonstrated
to a group of geologists in Geneva, Switzerland, how they
could identify useful elements such as iron, copper, and lead,
or sodium and potassium, in potential ores, by the colors that
powdered specimens sprinkled into a Bunsen burner flame
produced. They could estimate concentrations by the intensi-
ties of the colors compared to those from chemically analyzed
standards to within about 4050%, enough to decide
whether a chemical analysis was worthwhile.
Later, Kirchhoff and Bunsen built a visual spectroscope
(Fig. 1) consisting of (a) an entrance slit of two narrow
jaws separated by 1 mm or less, (b) a glass collimating
lens to render the light parallel as it entered, (c) a glass prism,
60 60 60, to form a spectrum, (d) a camera lens to
focus the separated colors into spectral lines at (e) the focal
plane, and (f ) a movable eyepiece to examine the lines more
closely.
In 1859, Kirchhoff and Bunsen, after studying the emis-
sion spectrum of a sample, discovered spectral lines that did
not correspond to those of any known element. They postu-
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 Waters Symposium: Atomic Emission Spectroscopy
lated the existence of a new element, which they named ce-
sium. A year later they discovered another new element,
which they named rubidium. These discoveries were con-
firmed by older chemical techniques (7).
Initially, the eye and brain could distinguish only visible
light; that is, light between 4000 and 7000 angstroms. (An
angstrom, symbol , is 1010 meters and is named after the
Swedish astronomer Anders ngstrom, who measured the
wavelengths of many spectral lines.) All traditional wavelength
tables, including the M.I.T. Wavelength Tables and those
produced by National Institute of Standards and Technology
(NIST), utilize the angstrom because it provides a four-digit
number, the minimum essential to identify the spectral lines
of each individual element.
For example, it was found that sodium had two very
intense yellow lines close together. By the 1890s they were
designated as 5890 and 5896 . Potassium had a red
doublet, 7665 and 7699 . (Iron had a noted triplet at
3100.30 , 3100.67 , and 3100.90/97 in the ultraviolet,
as described later.)
In the 1870s and 1880s other spectrochemists in
England and Continental Europe introduced the concept of
the internal standard line, comparing the intensity of an ana-
lytical line to that of a nearby line of the major matrix ele-
ment. The analytical line could be much weaker than, weaker
than, equal to, more intense than, or much more intense than
the internal standard line in an unknown specimen. This could
be compared to the intensity ratio observed previously in a
set of chemically analyzed standards. This improved analyti-
cal accuracy to between 25% and 40%.
In 1882, H. A. Rowland built the first successful grating
ruling machine at Johns Hopkins University. In 1883, he
discovered that gratings ruled on concave aluminized spherical
surfaces yielded spectra excelling in sharpness. This impor-
tant discovery enabled wavelengths to be measured with an
accuracy not previously possible (8). (Gratings ruled at Johns
Hopkins became the standard used throughout the world
through World War II.)
Three developments in the 1890s made it easier to
explore the spectral lines in the ultraviolet range:
1. Using quartz prisms and lenses or gratings instead of
glass as a dispersant.
2. Using photographic plates as a recording mechanism.
3. Replacing Bunsen burners with dc arcs as source units.
(The dc arcs produced relatively intense spectral lines
on a weak background, making them useful for mea-
suring low concentrations)
Professors and their students in the physics and chemistry
departments at universities began building simple spectrographs
to study the ultraviolet lines, using natural quartz crystals for
prisms. But there was a problem because natural quartz occurs
in two forms, dextrorotatory and levorotatory, and a prism
of either produced close double images. So in the 1890s
Cornu developed a spectrograph using a 30 60 90
dextrorotatory natural crystalline quartz prism and a 30
60 90 levorotatory quartz prism, adhesed along their 90 a 60-cm focal length. It was developed to analyze the vacuum
sides. This combined 60 prism canceled the optical rotation
and yielded single, instead of the previous double, images at
the focal plane, and produced lines from 2300 to 7000 .
574 Journal of Chemical Education Vol. 77 No. 5 May 2000 JChemEd.chem.wisc.edu
R
2300
UV
4000
170 cm
Figure 2. 1910 Hilger Littrow quartz spectrograph.
Frank Twyman at Adam Hilger in London produced the
worlds first commercial spectrograph in 1900. It was built
in a mahogany housing for stability and had an adjustable-
width entrance slit, a 20-cm focal length quartz collimating
lens, a Cornu quartz prism, a 20-cm quartz camera lens,
and a plate holder for a 314 4-in. photographic plate. The
instrument was useful for analyzing nonferrous materials, but
the 20-cm focal length produced an unresolved continuum
with specimens containing heavy metals such as iron.
In 1906 Hilger produced a Cornu spectrograph with a
60-cm focal length. This spectrograph utilized a camera with
4 10-in. photographic plate. It was better, but still not good
for complex spectra.
In 1910 Hilger introduced a 170-cm focal length Littrow
quartz spectrograph to analyze powdered specimens in
graphite cups burned in dc arcs (Fig. 2). A Littrow mount
used a 30 60 90 natural quartz prism with the light
reflected back from the 90 side and a single quartz lens acting
as a collimator and objective. Littrow had demonstrated that
this arrangement:
1. Canceled the double images due to the two indices of
refraction.
2. Provided three times greater dispersion.
The 170-cm focal length provided sufficient dispersion in
the ultraviolet to resolve the spectral lines of iron and other
heavy metals. For specimens with useful wavelengths above
4000 , a glass prism and lens substituted for the quartz
system provided greater dispersion in the visible spectrum and
permitted analysis of nonferrous elements.
Until 1912 spectrographs were purchased by universities
to identify and measure spectral lines of newly discovered el-
ements. The first industrial application in the United States
is credited to W. H. Bassett at Anaconda Research Laboratories
in Waterbury, Connecticut (9). In 1912 Bassett used a 170-cm
Hilger Littrow spectrograph with a spark source to analyze
brass and other copper alloys and to control their composition.
Sparks produced an alternating discharge at 10,000 to 15,000 V.
They are useful for measuring higher concentrations because
they are more repeatable, but the continuous background is
higher so detection limits are poor.
Between 1912 and 1920 other companies began manu-
facturing spectrographs with quartz prismsLeitz and Zeiss
in Germany, Bausch & Lomb and Gaertner in the United
States, and Shimadzu in Japan.
In 1920, Hilger produced the first evacuated spectro-
graph. This spectrograph utilized a Cornu-quartz prism and
ultraviolet lines of sulfur 1807 and phosphorous 1782 ,
important trace elements that must be held at low levels in
steels.
 Waters Symposium: Atomic Emission Spectroscopy
By the 1920s and 1930s the wavelengths of spectra of most
common elements had been exactly measured and classified
into atom and singly ionized lines. Their energy levels had been
identified and evaluated (10). Determining relative intensities
was less satisfactory because most measurements were based
on a visual estimate of the relative blackness of the photo-
graphed spectra (spectral lines in the red range were much
blacker than lines in the ultraviolet range).
In 1930, there was a major development in spectro-
chemical analysis when Kipp and Zonen, in Holland, produced
a recording microphotometer capable of measuring repeatably
the transmissions of narrow spectral lines on a photographic
plate or film. The instrument scanned the plate slowly and
recorded the output on a strip chart recorder. In 1932, Hilger
introduced a less expensive and faster nonrecording micro-
photometer. Microphotometers improved analytical accuracy
but increased the time required for analysis. Analysis required
the following steps (11):
1. Measuring on each plate or film for each wavelength
range the transmissions of the steps of an iron calibra-
tion line in an exposure, through a stepped sector disk
or a stepped neutral filter. The disk was preferred
because the relative transmissions were known and
were the same at all wavelengths. The transmissions
of the filter had to be measured at each significantly
different wavelength.
2. Plotting the measured transmission of each step against
the known relative intensity to produce a character-
istic curve for each wavelength region. The longer
wavelengths have steeper gammas.
3. Converting the measured transmissions of the line of
the element to be determined and a nearby internal
standard line of the matrix element and its relative
intensities, using the characteristic curve.
4. Plotting Ia/Is against concentrations in chemically ana-
lyzed standards to produce a calibration or analytical
curve for each element.
5. Analyzing an unknown sample by measuring the rela-
tive intensities in step 3 and converting these into
concentrations from the analytical curves obtained in
step 4.
The procedure improved accuracy to 23%, but the
process took a single operator about 3045 minutes for an
analysis of 1020 elements. It was expensive to hold a furnace
of steel or cast iron for 3045 minutes while a routine spec-
trographic analysis was being conducted to control the
composition of cast irons.
Sawyer and Vincent, at the University of Michigan,
developed the following assembly-line approach for the Ford
Motor Company in 1939, utilizing a Bausch and Lomb
Littrow Quartz Spectrograph with its plate holder mounted
in the darkroom and a four-person team (12).
Team member 1: received the specimen by pneumatic
tube from the melt foreman, ground it, mounted it on the
Petrey Stand, sparked it, and notified member 2 that the ex-
posure was complete. Then he cleaned the stand for the next
specimen.
JChemEd.chem.wisc.edu Vol. 77 No. 5 May 2000 Journal of Chemical Education
Team member 2: in the darkroom, developed, fixed,
washed and dried the photographic plate and delivered it back
through the wall to team member 3. Then he loaded the plate
holder for the next sample.
Team member 3: measured the transmissions of the
stepped filter exposures at several wavelengths and reported
these to member 4. Then he measured the transmissions of
the analytical lines and their internal standards, and reported
these to member 4.
Team member 4: used a calculating board to prepare
characteristics curves at the required wavelengths, then used
these to determine intensity ratios; then from the appropriate
calibration curves, reported the corresponding elemental
concentration back to the melt foreman.
This procedure reduced analytical times to 1018 min
for a cast iron sample.
By 1932, Medium and Littrow quartz spectrographs were
being manufactured in the United States by Bausch and Lomb
Optical Company and by Gaertner Scientific Company. They
were protected from lower-cost European instruments by a
60% duty.
In the late 1930s, U.S. manufacturers began producing
spectrographs using gratings instead of prisms as a dispers-
ing element. In 1937, Maurice Hasler at Applied Research
Laboratories produced the first grating spectrograph (1.5 m,
7 /mm) for the Geological Survey of California. In 1938,
Baird produced its first Eagle 3-m grating spectrograph having
15,000 grooves per inch and Jarrell Ash delivered its first 21-
foot Wadsworth grating spectrograph to the General Electric
Companys River Works in Lynn, Massachusetts, for quality
control in the production of aircraft engines.
The Jarrell Ash Wadsworth stigmatic spectrograph
combined high resolution and dispersion (5.4 /mm with a wide
wavelength range on two 4 10-in. photographic plates).
This instrument was the largest grating spectrograph produced.
It was designed to perform exacting measurements on a
nickel, chromium, and iron super alloy for aircraft engines
(13 ). It was necessary to keep volatile elements such as bismuth,
cadmium, and arsenic at a parts-per-million level to prevent
corrosion and failure of the engines. The high dispersion and
wide wavelength range of a Wadsworth spectrograph permitted
this kind of quality control (14 ).
Spectrographs also played an important role during
World War II. For example, Jarrell Ash spectrographs were
used by International Nickel to ensure the quality of the
nickel being shipped to GE for aircraft engines, and by the
National Bureau of Standards, Union Carbide, and Velmer
Fassels laboratory at Iowa State to analyze uranium for harm-
ful trace elements. The NBS spectrograph was later used for
most of the experimental work that was published as Tables
of Spectral-line Intensities, Arranged by Elements (15 ).
After World War II, universities that had supplied gratings
were unable to keep up with demand, so manufacturers built
their own ruling machines. Jarrell Ash built a machine that
lasted for three decades before it was modernized. In 1950,
Jarrell Ash produced its first replica grating (16 ).
In the 1940s, professors and students at various univer-
sities experimented with replacing photographic plates in
spectrographs with exit slits and photomultipliers. These ex-
periments led to the development of three different types of
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 Waters Symposium: Atomic Emission Spectroscopy
direct readers (17). Applied Research Laboratories produced
the first commercial direct reader in 1947. The direct reader
still had to be standardized frequently, but a single operator
could report a complete analysis for an unknown in a few
minutes with an accuracy to 13%. Baird and Jarrell Ash
introduced other types of direct readers.
Literature Cited
1. Richtmyer, F. K. Introduction to Modern Physics; McGraw-Hill:
New York, 1934; pp 3640.
2. Wood, R. W. Physical Optics, 3rd ed.; MacMillan: New York,
1934; p 1.
3. Richtmyer, F. K. Op. cit., p 49.
4. Hutley, M. C. Diffraction Gratings; Academic: London, 1982;
p 3.
5. Asimov, I. The History of Physics; Walker: New York, 1984; p
298.
6. Hutley, M. C. Op. cit.; p 4.
7. Asimov, I. Op. cit.; pp 298299.
8. Wood, R. W. Op. cit.; p 260.
9. ASTM E-2 Committee. Five Decades of Optical Emission Spec-
trochemical Instrumentation; American Society for Testing and
Materials: Conshohocken, PA, 1982; p 2.
10. Ibid.; p 3.
11. Ibid.; p 7.
12. Jarrell, R. F. A Brief History of the Development of Optical Emis-
sion Spectrochemical Analysis; Thermo Jarrell Ash, 1993; pp 4a5.
576 Journal of Chemical Education Vol. 77 No. 5 May 2000 JChemEd.chem.wisc.edu
13. Gustafson, M. Good Company: A History of Thermo Jarrell Ash
and Spectroscopist Richard F. Jarrell; Thermo Jarrell Ash, 1998;
p 7.
14. Ibid.; p 9.
15. Ibid.; pp 910.
16. Ibid.; pp 1314.
17. Jarrell, R. F. Op. cit.; p 5.
Further Reading
Asimov, I. The History of Physics; Walker: New York, 1984.
ASTM E-2 Committee. Five Decades of Optical Emission Spectrochemical
Instrumentation; American Society for Testing and Materials:
Conshohocken, PA, 1982.
Gustafson, M. Good Company: A History of Thermo Jarrell Ash and
Spectroscopist Richard F. Jarrell; Thermo Jarrell Ash, 1998.
Hutley, M. C. Diffraction Gratings; Academic: London, 1982.
Jarrell, R. F. A Brief History of the Development of Optical Emission
Spectrochemical Analysis; Thermo Jarrell Ash, 1993.
Jenkins, F; White, H. Fundamentals of Physical Optics; McGraw-
Hill: New York, 1937.
Richtmyer, F. K. Introduction to Modern Physics; McGraw-Hill: New
York, 1934.
Robertson, J. K. Introduction to Physical Optics, 2nd ed.; Van
Nostrand: New York, 1935.
Slickers, K. Automatic Emission Spectroscopy, English Transl.; Ap-
plied Research Laboratories: Lausanne, 1980.
Wood, R. W. Physical Optics, 3rd ed.; MacMillan: New York, 1934.