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PHYSICS
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SPECTROSCOPY
#1

GENERALSPECTROSCOPY
AND ITS APPLICATION
#2 DU

SPECTROPHOTOMETE
R
2

CONTENTS
1. Introduction
2. Physical Quantities measured
3. What Is Spectroscopy
4. Nature of light
5. The Electromagnetic Spectrum
6. General Types of Spectra
7. Continuous Spectra
8. Emission spectra
9. Absorption Spectra
10. Types of Spectroscopy
11. How Spectrometer work?
12. Types of Spectroscopy
13. Examples of Spectroscopy in Astronomy
14. Probing the Formation of Stars in Colliding
Galaxies in the universe.
15. Uncovering the mystery of quasar
16. Spectroscopy in Astronomy camp

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17. Stars like our own Sun


18. Bibliography
3

1. Introduction
Spectroscopy
(PIC: Extremely high resolution spectrum of the Sun showing
thousands of elemental absorption lines (fraunhofer lines))

Spectroscopy is the study of matter


and its properties by investigating
light, sound, or particles that are
emitted, absorbed or scattered by the
matter under investigation.
Spectroscopy may also be defined as
the study of the interaction between
lightand matter. Historically, spectroscopy
referred to a branch of science in
which visible light was used for theoretical
studies on the structure of matter and
for qualitative and quantitative analyses.
Recently, however, the definition has
broadened as new techniques have been
developed that utilize not only visible
light, but many other forms of
electromagnetic and non-electromagnetic
radiation: microwaves, radiowaves, x-rays,
electrons, phonons (sound waves)
and others. Impedance spectroscopy is a
study of frequency response in

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alternating current.
Spectroscopy is often used in physical and
analytical chemistry for the
identification of substances through the
spectrum emitted from them or absorbed
in them. A device for recording a spectrum
is a spectrometer. Spectroscopy can
be classified according to the physical
quantity which is measured or calculated
or the measurement process.
Spectroscopy is also heavily used in
astronomy and remote sensing. Most large
telescopeshave spectrographs, which are
used either to measure the chemical
composition and physical properties of
astronomical objects or to measure their
velocities from the Doppler shift of spectral
lines.
Physical Quantity Measured
The type of spectroscopy depends on the
physical quantity measured. Normally, the
quantity that is measured is an amount or
intensity of something.
The intensity of emitted electromagnetic
radiation and the amount of absorbed
electromagnetic radiation are studied by
electromagnetic spectroscopy (see also
cross section).

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The amplitude of macroscopic vibrations is


studied by acoustic spectroscopy and
dynamic mechanical spectroscopy.
Kinetic energy of particles is studied by
electron energy loss spectroscopy and
Auger electron spectroscopy (see also cross
section).
The mass-to-charge ratios of molecules
and atoms are studied in mass
spectrometry, sometimes called mass
spectroscopy. Mass spectrometry is more of
a
measuring technique (metric) than an
observation (scopic) technique but can
produce a spectrum of masses, a mass
spectrum, similar in appearance to other
spectroscopy techniques.
The number of molecules or atoms or quantummechanical states to which the
frequency or energy parameter applies. In this case the
spectrum is usually called
cross section.
What is Spectroscopy?
Spectroscopy pertains to the dispersion of
an object's light into its component
colors (i.e. energies). By performing this
dissection and analysis of an object's
light, astronomers can infer the physical
properties of that object (such as

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temperature, mass, luminosity and


composition).
But before we hurtle headlong into the wild
and woolly field of spectroscopy, we
need to try to answer some seemingly
simple questions, such as what is light?
And how does it behave? These questions
may seem simple to you, but they have
presented some of the most difficult
conceptual challenges in the long history of
physics. It has only been in this century,
with the creation of quantum mechanics
that we have gained a quantitative
understanding of how light and atoms work.
You see, the questions we pose are not
always easy, but to understand and solve
them will unlock a new way of looking at our
Universe.
The Nature of Light
To understand the processes in astronomy
that generate light, we must realize
first that light acts like a wave. Light has
particle-like properties too, so it's actually
quite a twisted beast (which is why it took
so many years to figure out). But right
now, let's just explore light as a wave.
Picture yourself wading around on an ocean
beach for a moment, and watch the

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many water waves sweeping past you.


Waves are disturbances, ripples on the
water, and they possess a certain height
(amplitude), with a certain number of
waves rushing past you every minute (the
frequency) and all moving at a
characteristic speed across the water (the
wave speed). Notice the distance
between successive waves? That's called
the wavelength.
Keeping this analogy in mind, let's leave the
ocean beach for a while and think
about light like a wave. The wave speed of a
light wave is simply the speed of
light, and different wavelengths of light
manifest themselves as different colors! The
energy of a light wave is inverselyproportional to its wavelength; in other
words, low-energy waves have long
wavelengths, and high-energy light waves
have short wavelengths.
The Electromagnetic Spectrum
Physicists classify light waves by their
energies (wavelengths). Labeled in
increasing energy, we might draw the entire
electromagnetic spectrum as shown
in the figure below:

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(The Electromagnetic Spectrum. Notice how


small the visible region of the spectrum is,
compared to the
entire range of wavelengths.)
Notice that radio, TV, and microwave signals
are all light waves, they simply lie
at wavelengths (energies) that your eye
doesn't respond to. On the other end of
the scale, beware the high energy UV, x-ray,
and gamma-ray photons! Each one
carries a lot of energy compared to their
visible- and radio-wave brethren.
They're the reasons you should wear
sunblock, for example.
When we look at the Universe in a different
"light", i.e. at "non-visible"
wavelengths, we probe different kinds of
physical conditions -- and we can see
new kinds of objects! For example, highenergy gamma-ray and X-ray telescopes
tend to see the most energetic dynamos in
the cosmos, such as active galaxies,
the remnants from massive dying stars,
accretion of matter around black holes,
and so forth. Visible light telescopes best
probe light produced by stars.
Longerwavelength
telescopes best probe dark, cool, obscured
structures in the Universe:

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dusty star-forming regions, dark cold


molecular clouds, the primordial radiation
emitted by the formation of the Universe
shortly after the Big Bang. Only
through studying astronomical objects at
many different wavelengths are
astronomers able to piece together a
coherent, comprehensive picture of how the
Universe works!
General Types of Spectra
Typically one can observe two distinctive
classes of spectra: continous and
discrete. For a continuous spectrum, the
light is composed of a wide, continuous
range of colors (energies). With discrete
spectra, one sees only bright or dark
lines at very distinct and sharply-defined
colors (energies). As we'll discover
shortly, discrete spectra with bright lines are
called emission spectra, those with
dark lines are termed absorption spectra.
Continuous Spectra
Continuous spectra arise from dense gases
or solid objects which radiate their
heat away through the production of light.
Such objects emit light over a broad
range of wavelengths, thus the apparent
spectrum seems smooth and

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continuous. Stars emit light in a


predominantly (but not completely!)
continuous
spectrum. Other examples of such objects
are incandescent light bulbs, electric
cooking stove burners, flames, cooling fire
embers and... you. Yes, you, right this
minute, are emitting a continuous spectrum
-- but the light waves you're
emitting are not visible -- they lie at infrared
wavelengths (i.e. lower energies,
and longer wavelengths than even red
light). If you had infrared-sensitive eyes,
you could see people by the continuous
radiation they emit!
Discrete Spectra
Discrete spectra are the observable result of
the physics of atoms. There are two
types of discrete spectra, emission (bright
line spectra) and absorption (dark line
spectra). Let's try to understand where
these two types of discrete spectra.
Emission Line Spectra
Unlike a continuous spectrum source, which
can have any energy it wants (all
you have to do is change the temperature),
the electron clouds surrounding the
nuclei of atoms can have only very specific
energies dictated by quantum

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mechanics. Each element on the periodic


table has its own set of possible energy
levels, and with few exceptions the levels
are distinct and identifiable.
Atoms will also tend to settle to the lowest
energy level (in spectroscopist's lingo,
this is called the ground state). This means
that an excited atom in a higher energy
level must `dump' some energy. The way an
atom `dumps' that energy is by
emitting a wave of light with that exact
energy.
In the diagram below, a hydrogen atom
drops from the 2nd energy level to the
1st, giving off a wave of light with an energy
equal to the difference of energy between
levels 2 and 1. This energy corresponds to a
specific color, or wavelength of light - and thus we see a bright line at that exact
wavelength! ...an emission spectrum is
born, as shown below:
An excited Hydrogen atom relaxes from
level 2 to level 1, yielding a photon. This
results in a
bright emission line.
Tiny changes of energy in an atom generate
photons with small energies and
long wavelengths, such as radio waves!
Similarly, large changes of energy in an

P a g e | 11

atom will mean that high-energy, shortwavelength photons (UV, x-ray, gammarays)
are emitted.
Absorption Line Spectra
On the other hand, what would happen if we
tried to reverse this process? That
is, what would happen if we fired this special
photon back into a ground state
atom? That's right, the atom could absorb
that `specially-energetic' photon and
would become excited, jumping from the
ground state to a higher energy level. If
a star with a `continuous' spectrum is
shining upon an atom, the wavelengths
corresponding to possible energy transitions
within that atom will be absorbed
and therefore an observer will not see them.
In this way, a dark-line absorption
spectrum is born, as shown below:
How does a spectrometer work?
Many people know how a telescope works,
but relatively few have
much experience with the innards of a
spectrometer. So let's take apart
the Astronomy Camp spectrometer to see
how it works! Keep in mind
that there are as many optical designs for
spectrometers as there are

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optical designs for telescopes, and that this


is but one example.
Nevertheless, it points out the salient
features of most optical
spectrometers.
It all starts with the telescope
light beam entering the
spectrometer. The focal point
of the telescope beam is
brought to the slit of the
spectrometer. This slit is
what is ultimately imaged on
the detector. In the case of the
Camp spectrometer, the slit is
arranged at an angle and the
slit surroundings are silvered
so that the portion of the
telescope beam not passing
through the slit can be routed
instead to an eyepiece for
easy telescope guiding.
The light passing through the
slit then is reflected off a
collimating mirror, which
parallelizes the beam of light,
before sending it off...
... to the diffraction grating!
This optical element disperses
the parallel beams of light

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into their component


colors/wavelengths/energies.
Each different wavelength
comes off of the grating at a
slightly different angle. So
now, we have an image of the
slit that is spread out like a
rainbow by color.
This new color-dispersed
beam of light is then focused
and imaged on the detector
by the camera lens. A 35 mm
camera is the detector in this
diagram, but at Camp, we
typically use an eyepiece or a
CCD array.
So, now let's put all of this together to make
a spectrometer!
There is something interesting to note here
-- in spectroscopy, we are
not looking at ALL of the light from an
object, just a certain "band" of
wavelengths or colors. Furthermore, even
that band is dispersed
("smeared out") over the entire detector.
This means that the effective
brightness, or surface brightness of an
object on the detector is much

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lower than when simply taking images of an


object. This means that it
takes a bigger telescope and/or more
integration time to get a good
spectrum of a given object than an image.
The broader you disperse the light and the
narrower you make the slit, the better
your spectral resolution; you can see finer
and more subtle features in the
spectrum. However, there is a stiff price to
pay: the emergent spectrum becomes
much dimmer and more diffuse. High
resolution spectroscopy therefore requires
large telescopes and fairly bright objects.
For very faint objects, some spectral
resolution often must be compromised to
even SEE the object.
TYPES OF SPECTROSCOPY
In general there are three main types of
spectroscopy. They are as listed
below:
1. Absorption Spectroscopy
2. Emission Spectroscopy
3. Scattering Spectroscopy
Absorption spectroscopy uses the range of
electromagnetic spectra in which a
substance absorbs. In atomic absorption
spectroscopy, the sample is atomized

P a g e | 15

and then light of a particular frequency is


passed through the vapour. After
calibration, the amount of absorption can be
related to the concentrations of
various metal ions through the Beer-Lambert
law. The method can be automated
and is widely used to measure
concentrations of ions such as sodium and
calcium in blood. Other types of
spectroscopy may not require sample
atomization. For example, ultraviolet/visible
(UV/ Vis) absorption spectroscopy
is most often performed on liquid samples to
detect molecular content and
infrared (IR) spectroscopy is most often
performed on liquid, semi-liquid (paste
or grease), dried, or solid samples to
determine molecular information, including
structural information.
Emission spectroscopy uses the range of
electromagnetic spectra in which a
substance radiates. The substance first
absorbs energy and then radiates this
energy as light. This energy can be from a
variety of sources, including collision
(either due to high temperatures or
otherwise), and chemical reactions.
Scattering spectroscopy measures certain
physical properties by measuring the

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amount of light that a substance scatters at


certain wavelengths, incident angles,
and polarization angles. Scattering
spectroscopy differs from emission
spectroscopy due to the fact that the
scattering process is much faster than the
absorption/emission process. One of the
most useful applications of light
scattering spectroscopy is Raman
spectroscopy.
iCBSE.com
12
NMR SPECTROSCOPY
Nuclear Magnetic Resonance spectroscopy
is a powerful and theoretically
complex analytical tool. On this page, we
will cover the basic theory behind the
technique. It is important to remember that,
with NMR, we are performing
experiments on the nuclei of atoms, not the
electrons. The chemical environment
of specific nuclei is deduced from
information obtained about the nuclei.
Examples of Spectroscopy in
Astronomy
Spectroscopy is a powerful tool in astronomy
-- from it, we can often get
information about the temperature, density,
composition, and

P a g e | 17

important physical processes of an


astronomical object. This
information can help us answer the
questions:
What is it?
What is it like?
What is it made out of?
How did it get there? What will happen to
it?
Does it give us clues as to how WE got
here?
A few examples of astronomical spectra are
highlighted here. Some cool
Astronomy Camp spectra also live in these
pages.
Molecular Spectroscopy and Comets
Comets consist of almost pristine material
from the early formation of
our solar system, unprocessed by harsh
solar sunlight. Studying the
chemistry of these "dirty snowballs" gives us
a clue as to the
composition and nature of our solar system
in its infancy and constrains
theories of how life may have formed on
Earth.
Probing the Formation of Stars in Colliding
Galaxies

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Billions of years ago, when our galaxy took


form, it is thought that there
must have been an epoch of rapid starforming activity that has since
subsided. We can get clues to how this may
have looked by observing
galaxies currently exhibiting violent,
extreme star-formation. Such
"starburst" galaxies are studied best in the
infrared and at radio
wavelengths, since star-forming galaxies
often harbor so much dust and
gas that visible light cannot penetrate to the
centers where the majority
of the star formation is taking place. Below
is an infrared (2.0 - 2.5
microns wavelength, or 20,000 - 25,000
Angstroms) spectrum of two
such starburst galaxies. Most of the features
you see are from molecular
hydrogen, H2, the stuff from which stars are
made! These molecular
hydrogen emission lines tell us that the
molecular gas we see is very
warm; in the top galaxy, the gas is excited
by shock-heated gas. The
bottom galaxy has molecular hydrogen
excited by ultraviolet light

P a g e | 19

emitted from recently-formed young, hot


stars.
Uncovering the mystery of Quasars
The distant nature of quasars were
discovered in the early 1960's, when
spectral lines were noted to be substantiallyshifted redder than they
should normally be. This redshift can be
attributed to the recession
(speeding away) of quasars from us. In the
standard Big Bang model of
cosmology (the faster it's speeding away
from you, the more distant it
is), this rapid motion implies that quasars
are the most distant objects
known. Below is a typical spectrum of a
quasar. The wavelength scale
has been rescaled to the "appropriate" rest
wavelengths for the spectral
lines. The most noticeable feature is the
broad emission line at 1216
Angstroms due to hydrogen atoms making
the transition from the first
excited state to the ground state. Although
1216 Angstroms lies deep in
the ultraviolet, where the Earth's
atmosphere is opaque, many quasars
are receding from us so fast, this line is
redshifted into the visible part of

P a g e | 20

the spectrum (4000-7000 Angstroms).


Spectroscopy at Astronomy Camp!
Spectroscopy at Astronomy Camp is done
with a spectrograph from
Optomechanics Research Inc, coupled with
the Mount Lemmon 40" or 60"
telescopes and the Camp's SBIG ST6 CCD
detector array. With relatively short
exposure times, good quality spectra can be
taken of most catalogued stars and
high surface-brightness deep-sky objects. A
few examples of Astronomy
Campers' handiwork are shown below.
Planetary Nebulae, Or 'Why Light Pollution
Filters Work'!
Here's an image of M57 (a.k.a. the Ring
Nebula), with a crude representation of the
spectrometer slit superimposed. This image
is a 180 second exposure using the Camp's
ST6 CCD on a 10" Meade SchmidtCassagrain telescope. Astronomy Camp's
spectrograph was mounted on the Mount
Lemmon 60" telescope with the same ST6
CCD. The slit length is about 8 arcminutes
long and 1 arcsecond wide; the
representation of the slit width in the
diagram is exaggerated.
We combined four 5-minute exposures on
the Ring Nebula using the 60" and the

P a g e | 21

ST6 camera. We subtracted an appropriate 5


minute dark frame from each image
and then combined the images using IRAF.
The resulting ST6 image follows: the
dispersion (wavelength) axis is horizontal,
and the spatial axis (along the Ring
Nebula) is vertical. The central lines are
M57, the upper and lower spikes are the
calibration lamp spectra (Hg+He).
We make a 1-D spectrum from the 2-D
image by summing over the aperture of
the slit covering M57. Using the wellcharacterized wavelengths of the
calibration lamps, we can use IRAF to
register our spectrum to provide a nice
wavelength scale. Here's what our spectrum
looks like once plotted as intensity
versus wavelength.
The emission line at 4861 Angstroms comes
from hot, excited atomic hydrogen.
Highlyexcited
hydrogen atoms in M57's gaseous
shell, starting in energy level 4, may
eventually de-excite to level 2, giving up the
energy difference in waves of light at that
particular energy (and... they have a
wavelength of 4861 Angstroms!).
The brightest two lines at 4959 and 5007
Angstroms come from twice-ionized

P a g e | 22

oxygen (labeled O++, or O III in


spectroscopic notation). This means that
two of
oxygen's eight electrons have been ripped
away. This is a also clue that
conditions in this nebula must be harsh. In
fact, these lines can only be excited to
emit light in temperatures of several
thousand Kelvins and rather thin densities
of 1-100 atoms per cubic centimeter. There
is no continuous spectrum here -- this
points out the important fact that planetary
nebulae are hot rarified gases -- you
see a LINE spectrum. This also points out
how astronomers can get valuable
information about the physical conditions
and important processes in distant
astronomical objects.
This spectrum also demonstrates why you
can use light-pollution filters (like
those made by Lumicon or Orion) to get
great contrast from reflection/emission
nebulae! These filters pass light waves that
lie at wavelengths covered by these
three lines, but block light at all other
wavelengths. For nebulae, this is very
beneficial since they only emit visible light
in this wavelength range. You can

P a g e | 23

remove all that ugly skyglow and light


pollution without reducing the brighness
of the nebula you're looking for.
Would such a narrow-band filter be good for
looking at stars or galaxies? Hmm?
Stellar Spectroscopy
A look at Sirius
Now, onto stellar spectroscopy. This 1/2
second exposure of Sirius is centered
near 4000 Angstroms (blue, near-ultraviolet)
and clearly shows a series of deep
absorption lines. These lines are due to the
hydrogen atom. Let's explore how.
In the cooler outer "atmosphere" around
Sirius, mildly excited hydrogen atoms
in the 2nd energy level (the 1st excited
state) are 'zapped' by photons (light
waves) with just the right energy to send
them to even higher excited states. In
this figure, we match the dark absorption
line that results from each transition
upward in the hydrogen atom. Notice that
the higher-energy transitions on the
left result in higher energy absorption lines
out in the ultraviolet. This series of
lines, starting from level 2, is called the
Balmer series after their discoverer.
Stars are classified by their temperatures,
which can be determined by the star's

P a g e | 24

spectral features. The hottest stars are


termed O-stars, the next cooler are B stars,
then A, F, G, K, and finally M-stars. Sirius is a
relatively hot A-type star at about
10,000 degrees Kelvin. Such stars have the
strongest hydrogen-features (simply
due to temperature -- cooler stars can't 'zap'
the hydrogen atoms as effectively,
and hotter stars will destroy/ionize the
hydrogen atoms that create the spectral
lines!).
Molecules in Cool Stars!
On the other end of the scale -- here is Delta
Virgo; a cool M3-type giant star at
about 3,500 K and viewed at about 6000
Angstroms (in red light). Note a bright
continuum at far left, which suddenly dims
into a series of striations (bands).
These don't look like the sharp absorption
lines of the hydrogen atom, do they?
In fact, these bands are due to MOLECULES
that can live in the atmospheres of
these cool stars!
This particular molecule is TiO (titanium
oxide). Molecules have a dizzying
number of lines because they not only have
the electron energy levels like atoms,
but also have energy sublevels due to the
rotation and vibration of the molecule!

P a g e | 25

At the modest resolution of our


spectrometer, these hundreds of lines are
blended into absorption bands like what we
see here.
STARS LIKE OUR SUN
Somewhere between hotter A-type stars and
cool M-class stars are stars like our
sun, around 5500 degrees Kelvin. Here's
Beta-Bootes, a G8 giant star (roughly
what our sun will be when it begins dying in
about 5 billion years). The first
spectrum is at 5500 Angstroms (yellow
light), just like the M-star spectrum
above. Notice that molecules don't form
here (it's too hot for molecules to readily
form without being quickly destroyed), but
there are still an awful lot of lines
around. Most of these features are due to
heavy elements -- things like carbon (in
several ionization stages), iron, oxygen,
magnesium, calcium etc.
This is a spectrum of the same star, but now
taken at 4000 Angstroms (deep blueviolet
light). The deep absorption lines at left are
due to the ion Calcium II (the
difference between this and normal, neutral
calcium is that one electron has been
stripped off here). The small dip in the
middle is due to a blend of metallic

P a g e | 26

features and hydrogen. Notice that the


hydrogen lines are very weak here -nothing at all like Sirius (a hotter A-class
star).

DU spectrophotometer

P a g e | 27

DU spectrophotometer

DU Spectrophotometer,
National Technical
Laboratories, 1947
measuring ultraviolet light
absorbed
Inventor(s Arnold Orville
)
Beckman
Develope National
d
Technical
Laboratories
External video
"The
Instrument
that Made the
Ultraviolet
Spectrum

P a g e | 28

Visible to
Scientists
Everywhere",
Chemical
Heritage
Foundation
The DU spectrophotometer or Beckman DU was
the first commercially viable scientific
instrument for measuring the amount
of ultraviolet light absorbed by a substance. This
model of spectrophotometer enabled scientists to
easily examine and identify a given substance
based on its absorption spectrum, the pattern of
light absorbed at different wavelengths.
[1]:148
National Technical
Laboratories (later Beckman Instruments)
developed three in-house prototype models (A, B,
C) and one limited distribution model (D) before
moving to full production with the DU. Introduced
in 1941, approximately 30,000 DU
spectrophotometers were manufactured and sold
between 1941 and 1976.[2][3]
Measuring both the visible and ultraviolet
spectra,[4] the model DU spectrophotometer
yielded more accurate results, and substantially
reduced the time needed to accurately determine
the chemical composition of a complex substance
from weeks or hours to minutes.[5] The Beckman

P a g e | 29

Ultraviolet-Visible (UV-Vis) DU spectrophotometer


was essential to several critical secret research
projects during World War II.[6][7] Schmidt credits it
with having "brought about a breakthrough in
optical spectroscopy".[2] It has been identified as
one of the "most essential instruments" of
postwar science,[8] and "probably the most
important instrument ever developed towards
the advancement of bioscience".[9]

Development[edit]
The DU was developed at National Technical
Laboratories (later Beckman Instruments) under
the direction of Arnold Orville Beckman, an
American chemist and inventor.[1][10][11]
[12]
Beckman's research team was led by Howard
Cary, who went on to co-found Applied Physics
Corporation (later Cary Instruments) and become
one of Beckman's strongest competitors. Other
scientists included Roland Hawes and Kenyon
George.[13]
Spectroscopic methods for observing absorption
in the visible spectrum were used as early as the
1860s.[14] In 1940, the equipment needed to
measure light energy in the visible spectrum
could cost a laboratory as much as $3,000, a
huge amount.[1]:149 Complicated equipment had to

P a g e | 30

be assembled, and test samples were run


through awkward and time-consuming processes
to separate them into analyzable components.
[11]
Further, the spectrum of visible light was not
broad enough to enable scientists to examine
substances such as vitamin A.[15]
Beckman had already developed a successful pH
meter for measuring acidity of solutions.
Coleman Instruments had recently coupled a pH
meter with an optical phototube unit to examine
the visual spectrum (the Coleman Model DM).
Rather than depending on a human observer's
visual ability, or the development of a
photographic plate, to detect wavelengths,
phototubes could be used to register and report
specific wavelengths. Beckman made it a goal to
create an easy-to-use instrument extending into
the ultraviolet range.[1]:149151
Model A[edit]
The first prototype Beckman spectrophotometer,
the Model A, was created at National
Technologies Laboratories in 1940. It used
a tungsten light source with a glass Fery prism as
a monochromator. An external amplifier from the
Beckman pH meter and a vacuum tube photocell
were used to detect wavelengths.[11]
Model B[edit]

P a g e | 31

Optical quality quartz crystals


It was quickly realized that the glass prism was
not suitable for use with the ultraviolet spectrum,
and a quartz prism was substituted instead,
resulting in the Model B. In the model B, a
tangent bar mechanism was used to adjust the
monochromator. The mechanism was highly
sensitive and required a skilled operator.[11]
Model C[edit]
Three Model C instruments were then built,
improving the instrument's wavelength
resolution. The Model B's rotary cell compartment
was replaced with a linear sample chamber. The
tangent bar mechanism was replaced by a scroll
drive mechanism,[11] which could be more
precisely controlled to reset the quartz prism and

P a g e | 32

select the desired wavelength.[16] With this new


mechanism, results could be more easily and
reliably obtained, without requiring a highly
skilled operator. This set the pattern for all of
Beckman's later quartz prism instruments.[11]
Model D[edit]
The A, B, and C models all coupled an external
Beckman pH meter to the optical component to
obtain readouts. In developing the Model D,
Beckman took the DC amplifier circuit from the
pH meter and combined the optical and
electronic components in a single housing,
making it more economical.[16] The model D also
used a hydrogen lamp as a light source rather
than tungsten.[11]
Moving from a prototype to production of the
Model D involved challenges. Beckman originally
approached Bausch and Lomb about making
quartz prisms for the spectrophotometer. When
they turned down the opportunity, National
Technical Laboratories designed its own optical
system, including both a control mechanism and
a quartz prism. Large, high optical quality quartz
suitable for creating prisms was difficult to
obtain. It came from Brazil, and was in demand
for wartime radio oscillators. Beckman had to
obtain a wartime priority listing for the

P a g e | 33

spectrophotometer to get access to suitable


quartz supplies.[11]
The company designed its own hydrogen lamp
for the Model D, enclosing an anode in a thin
blown-glass window. The instrument's design also
required a more sensitive phototube than was
commercially available at that time. Beckman
was able to obtain small batches of an
experimental phototube from RCA for the first
Model D instruments. The Model D
spectrophotometer, using the experimental RCA
phototube, was shown at MIT's Summer
Conference on Spectroscopy in July 1941. It was
the first model to enter actual production, and
only a small number of Model D instruments were
sold before it was superseded by the DU.[11]
Model DU[edit]
When RCA could not meet Beckman's demand for
experimental phototubes, National Technical
Laboratories again had to design its own
components in-house. With the incorporation of
Beckman's own newly developed UV-sensitive
phototubes, the Model D became the Model DU
UV-Vis spectrophotometer.[11] As he had done with
the pH meter, Beckman had replaced an array of
complicated equipment with a single, easy-to-use
instrument. One of the first "black boxes" used in

P a g e | 34

modern chemical laboratories,[17] it sold for $723


in 1941.[9]
Design[edit]
From 1941 until 1976, when it was discontinued,
the Model DU spectrophotometer was built upon
what was essentially the same design.[9] It was a
single beam instrument.[13]:11 The DU
spectrophotometers used a quartz prism to
separate light into its absorption spectrum and a
phototube to electrically measure the light
energy across the spectrum. This allowed the
user to plot the light absorption spectrum of a
substance to obtain a standardized "fingerprint"
characteristic of a compound.[1]:151 [18] All modern
UV-Vis spectrometers are built on the same basic
principles as the DU spectrophotometer.[4]
Use[edit]

Beckman DU spectrophotometer in use


The model D and DU spectrophotometer was the
first easy-to-use single instrument containing
both the optical and electronic components

P a g e | 35

needed for ultraviolet-absorption


spectrophotometry.[1]:153 The user could insert a
sample, dial up the desired wavelength of light,
and read the amount of absorption of that
frequency from a simple meter. A series of
readings at different wavelengths could be taken
without disturbing the sample. Working in both
the ultraviolet and the visible regions of the
spectrum, the model D produced accurate
absorption spectra which could be obtained with
relative ease and accurately replicated.
[19]
The National Bureau of Standards ran tests to
certify that the DU's results were accurate and
repeatable and recommended its use.[1]:156
The DU spectrophotometer's manual scanning
method was extremely fast, reducing analysis
times from weeks or hours to minutes. It was
accurate in both the visible and ultraviolet
spectrums.[4] Advantages included its higher
resolution and the minimization of stray light in
the ultraviolet region.[9] Although it was not
cheap, its price point made it available to most
scientists.[8]
Impact[edit]

P a g e | 36

World War II poster encouraged researchers to


"Give this job Everything You've got"
Beckman's DU spectrophotometer has been
referred to as the "Model T" of scientific
instruments. It enabled researchers to perform
easier analysis of mixtures of chemicals by
quickly taking measurements at more than one
wavelength to produce an absorption spectrum
describing the complete substance. "This device
forever simplified and streamlined chemical
analysis, by allowing researchers to perform a
99.9% accurate quantitative measurement of a
substance within minutes, as opposed to the
weeks required previously for results of only 25%
accuracy."[20] Theodore L. Brown notes that it
"revolutionized the measurement of light signals
from samples".[21]:2 Nobel laureate Bruce
Merrifield is quoted as calling the DU
spectrophotometer "probably the most important

P a g e | 37

instrument ever developed towards the


advancement of bioscience."[9]
Vitamins[edit]
Development of the spectrophotometer had
direct relevance to World War II and the American
war effort. The role of vitamins in health was of
significant concern, as scientists wanted to
identify Vitamin A-rich foods to keep soldiers
healthy. Previous methods of assessing Vitamin A
levels involved feeding rats a food for several
weeks and then performing a biopsy to estimate
ingested Vitamin A levels. In contrast, examining
a food sample with a DU spectrophotometer
yielded better results in a matter of minutes.
[22]
The DU spectrophotometer could be used to
study both vitamin A and its
precursor carotenoids,[23] and rapidly became the
preferred method of spectrophotometric analysis.
[15][24][25]

Penicillin[edit]
The DU spectrophotometer was also an important
tool for scientists studying and producing the
new wonder drug penicillin.[16] The development
of penicillin was a secret national mission,
involving 17 drug companies, with the goal of
providing penicillin to all U.S. Forces engaged in
World War II.[7][26] It was known that penicillin was

P a g e | 38

more effective than sulfa drugs,[26] and that its


use reduced mortality, severity of long-term
wound trauma, and recovery time.[1]:158 However,
its structure was not understood, isolation
procedures used to create pure cultures were
primitive, and production using known surface
culture techniques was slow.[26]
At Northern Regional Research
Laboratory in Peoria, Illinois, researchers
collected and examined more than 2,000
specimens of molds (as well as
other microorganisms).[27] An extensive research
team included Dr.RobertCoghill, Dr. Norman
Heatley, Dr. Andrew Moyer, lab
bacteriologist Mary Hunt,[28][29][30] Frank H.
Stodola and Morris E. Friedkin. Friedkin recalls
that an early model of the Beckman DU
spectrophotometer was used by the penicillin
researchers in Peoria.[26] The Peoria lab was
successful in isolating and commercially
producing superior strains of the mold, which
were 200 times more effective than the original
forms discovered by Alexander Fleming.[28] By the
end of the war, American pharmaceutical
companies were producing 650 billion units of
penicillin each month.[28] Much of the work done
in this area during World War II was kept secret
until after the war.[1]:158[7]

P a g e | 39

Hydrocarbons[edit]
The DU spectrophotometer was also used for
critical analysis of hydrocarbons in crude oil. A
number of hydrocarbons were of interest to the
war effort. Toluene, a hydrocarbon in crude oil,
was used in production ofTNT for military use.
[1]:158159[11]
Benzene and butadienes were used in
the production of synthetic rubber.[31] Rubber,
used in tires for jeeps, airplanes and tanks, was
in critically short supply because the United
States was cut off from foreign supplies of natural
rubber.[1]:158159[32] The Office of Rubber Reserve
organized researchers at universities and in
industry to secretly work on the problem.[6] The
demand for synthetic rubber caused Beckman
Instruments to develop infrared
spectrophotometers, which were better suited to
measuring wavelengths of hydrocarbons.[1]:159[14]
Enzyme assays and DNA research[edit]
Gerty Cori and her husband Carl Ferdinand
Cori won the Nobel Prize in Physiology or
Medicine in 1947 in recognition of their work
on enzymes. They made several discoveries
critical to understanding carbohydrate
metabolism, including the isolation and discovery
of the Cori ester, glucose-1 phosphate, and the
understanding of the Cori cycle. They determined

P a g e | 40

that the enzyme phosphorylase catalyzes


formation of glucose 1-phosphate, which is the
beginning and ending step in the conversions of
glycogen into glucose and blood glucose to
glycogen. Gerty Cori was also the first to show
that a defect in an enzyme can be the cause of a
human genetic disease.[33] The Beckman DU
spectrophotometer was used in the Cori
laboratory to calculate enzyme concentrations,
including phosphorylase.[34]
Arthur Kornberg worked with Severo Ochoa,
learning the process of enzyme purification of
aconitase, and then spent six months in 1947 at
the Cori laboratory, "the most vibrant place in
biochemistry at that time", before returning to
the National Institutes of Health (NIH) in 1948. He
too used the DU spectrophotometer.[35]
"The enzyme could be assayed in a few minutes
by coupling it to isocitrate dehydrogenase and in
measuring the NADH formed using the Beckman
DU spectrophotometer, an instrument that
transformed biochemistry."[36]
Kornberg and Bernard L. Horecker used the
Beckman DU spectrophotometer for enzyme
assays measuring NADH and NADPH. They
determined their extinction coefficients,
establishing a basis for quantitative

P a g e | 41

measurements in reactions involving nucleotides.


This work became one of the most cited papers
in biochemistry.[36]:115 Kornberg went on to study
nucleotides in DNA synthesis, isolating the first
DNA polymerizing enzyme (DNA polymerase I) in
1956 and receiving the Nobel Prize in Physiology
or Medicine with Severo Ochoa in 1959.[37]
The bases of DNA absorbed ultraviolet light near
260 nm.[16] Inspired by the work of Oswald
Avery[38] on DNA, Erwin Chargaff used a DU
spectrophotometer in the 1940s in measuring the
relative concentrations of bases in DNA.[39]:260, 290
302
Based on this research, he
formulated Chargaff's rules.[40] In the first
complete quantitative analysis of DNA, he
reported the near-equal correspondence of pairs
of bases in DNA, with the number
of guanine units equaling the number
of cytosine units, and the number
of adenine units equaling the number
of thymine units. He further demonstrated that
the relative amounts of guanine, cytosine,
adenine and thymine varied between species. In
1952, Chargaff met Francis Crick and James D.
Watson, discussing his findings with them.
Watson and Crick built upon his ideas in their
determination of the structure of DNA.[40]
Biotechnology[edit]

P a g e | 42

Ultraviolet spectroscopy has wide applicability


in molecular biology, particularly the study
of photosynthesis.[41] It has been used to study a
wide variety of flowering plants and ferns[42] by
researchers in departments of biology, biology,
plant physiology and agriculture science as well
as molecular genetics.[43]
Particularly useful in detecting conjugated double
bonds, the new technology made it possible for
researchers like Ralph Holman and George O.
Burr to study dietary fats, work with significant
implications for human diet.[44] The DU
spectrophotometer was also used in the study
of steroids[23][45] by researchers like Alejandro
Zaffaroni,[46] who helped to develop the birth
control pill, the nicotine patch,
and corticosteroids.[47]
Later models[edit]

Beckman Model DK1 Ultraviolet


Spectrophotometer
The Beckman team eventually developed
additional models, as well as a number of
accessories or attachments which could be used

P a g e | 43

to modify the DU for different types of work. One


of the first accessories was a flame attachment
with a more powerful photo multiplier to enable
the user to examine flames such
as potassium, sodium and cesium(1947).[13]:11[48]
In the 1950s, Beckman Industries developed the
DR and the DK, both of which were double-beam
ultraviolet spectrophotometers. The DK was
named for Wilbur I. Kaye, who developed it by
modifying the DU to expand its range into the
near-infrared.[13] He did the initial work while at
Tennessee Eastman Kodak, and later was hired
by Beckman Instruments.[49] The DKs introduced
an automatic recording feature. The DK-1 used a
non-linear scroll, and the DK-2 used a linear scroll
to automatically record the spectra.[49]:21
The DR incorporated a "robot operator" which
would reset the knobs on the DU to complete a
sequence of measurements at different
wavelengths, just like a human operator would to
generate results for a full spectrum. It used a
linear shuttle with four positions, and a
superstructure to change the knobs. It had a
moving chart recorder to plot results, with red,
green and black dots.[13] The cost of recording
spectrophotometers was substantially higher
than non-recording machines.[23]

P a g e | 44

The DK was ten times faster than the DR, but not
quite as accurate.[13] It used a photomultiplier,
which had introduced a source of error.[49]:21 The
DK's speed made it preferred to the DR.[13] Kaye
eventually developed the DKU, combining
infrared and ultraviolet features in one
instrument, but it was more expensive than other
models.[49]
The last DU spectrophotometer was produced on
July 6, 1976.[50]

This project is made using the analytical


data provided by the following
reference books and websites:
1. SchaumsOutlines Organic Chemistry,
Third Edition, Chapter
Spectroscopy, Page number 230-244.

P a g e | 45

2. The Science of Spectroscopy - supported by NASA,


includes Open Spectrum, a
Wiki-based learning tool.
3. Wikipedia (Encyclopedia)
4. Professors Lectures University of Arizona (Semester
II)

ABHISHEK M.
STD XI SCI
ROLL NO. = 4

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