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Chapter 25
Instruments for Optical Spectroscopy
Most spectroscopic instruments in the UV/visible
and IR regions are made up of five components,
(1) a stable source of radiant energy; (2) a
wavelength selector that isolates a limited region
of the spectrum for measurement; (3) one or more
sample containers; (4) a radiation detector, which
converts radiant energy to a measurable electrical
signal; (5) a signal processing and readout unit.
Optical Materials
The cells, windows, lenses, mirrors, and
wavelength selecting elements in an optical
spectroscopic instrument must transmit radiation in
the wavelength region being employed. Ordinary
silicate glass is completely adequate for the visible
region and has the considerable advantage of low
cost. In the UV region, at wavelengths shorter than
about 380 nm, glass begins to absorb and fused
silica or must be substituted. Also, glass, quartz,
and fused silica all absorb in the IR region at
wavelengths longer than about 2.5 m. Hence,
optical elements for IR spectrometry are typically
made from halide salts.
Spectroscopic Sources
To be suitable for spectroscopic studies, a source
must generate a beam of radiation that is
sufficiently powerful for easy detection and
measurement. In addition, its output power should
be stable for reasonable periods. Spectroscopic
sources are of two types: continuum sources,
which emit radiation that changes in intensity only
slowly as a function of wavelength, and line
sources, which emit a limited number of spectral
lines. Sources can also be classified as continuous
sources, which emit radiation continuously with
time, or pulsed sources, which emit radiation in
Continuum Sources in the UV/Visible Region
An ordinary tungsten filament lamp provides a
distribution of wavelengths from 320 to 2500 nm.
Generally, these lamps are operated at a temperature
of around 2900 K, which produces useful radiation
from about 350 to 2200 nm.
Tungsten/halogen lamps, also called quartz/halogen
lamps, contain a small amount of iodine within the
quartz envelope that houses the filament. Quartz
allows the filament to be operated at a temperature of
about 3500 K, which leads to higher intensities and
extends the range of the lamp well into the UV region.
The lifetime of a tungsten/halogen lamp is more than
double that of an ordinary tungsten lamp because the
life of the latter is limited by sublimation of tungsten
from the filament.
In the presence of iodine, the sublimed tungsten reacts to
give gaseous WI2 molecules, which then diffuse back to
the hot filament where they decompose and redeposit as W
Deuterium lamps are most often used to provide
continuum radiation in the UV region. A deuterium lamp
consists of a cylindrical tube, containing deuterium at low
pressure, with a quartz window from which the radiation
exits. Excitation is carried out by applying about 40 V
between a heated oxide-coated electrode and a metal
electrode. Excited deuterium dissociates in the resulting
plasma to give atomic species plus a UV photon. The
energy of the emitted radiation can vary in a continuous
manner. The result is a continuum spectrum from about
160 nm to about 350 to 400 nm.
Other UV/Visible Sources
Line sources can be used in the UV/visible region.
Low-pressure mercury arc lamps are very common
sources for use in liquid chromatography detectors.
The dominant line emitted by these sources is at
253.7 nm. Hollow cathode lamps are also common
line sources used specifically for atomic absorption
spectroscopy. Lasers have also been used in
molecular and atomic spectroscopy, both for single
wavelength and for scanning application. Tunable
dye laser can be scanned over wavelength ranges
of several hundred nanometers when more than
one dye is used.
Continuum Sources in the IR Region
The continuum sources for IR radiation are
normally heated inert solids. A Globar source
consists of a silicon carbide rod. Infrared
radiation is emitted when the Globar is heated to
about 1500 oC by the passage of electricity.
A Nernst Glower is a cylinder of zirconium and
yttrium oxides which emits IR radiation when
heated to a high temperature by an electric
current. Electrically heated spirals of nichrome
wire also serve as inexpensive IR sources.
Wavelength Selectors
Spectroscopic instruments in the UV and visible
regions are usually equipped with one or more
devices to restrict the radiation being measured to a
narrow band. Such devices greatly enhance both the
selectivity and the sensitivity of an instrument. In
addition, for absorption measurements, narrow bands
of radiation greatly diminish the chance for Beer’s
law deviations due to polychromatic radiation. Many
instruments employ a monochromator or filter to
isolate the desired wavelength band. Others use a
spectrograph to spread out the wavelengths and
detected with a multichannel detector.
Monochromator generally employ a diffraction grating
to disperse the radiation into its component
wavelengths. Older instruments used prisms for this
purpose. By rotating the grating, different wavelengths
can be made to pass through an exit slit. The output
wavelength of a monochromator is thus continuously
variable over a considerable spectral range. The
wavelength range passed by a monochromator, called
the spectral bandpass or effective bandwidth, can be
less than 1 nm for moderately expensive instruments to
grater than 20 nm for inexpensive systems.
Because of the ease with which the wavelength can be
changed with a monochromator-based instrument, these
system are widely used for spectral scanning applications
as well as for application requiring a fixed wavelength.
Filters use for absorption measurements are typically
interference filters. These filters transmit radiation over a
bandwidth of 5 to 20 nm. Radiation outside the transmitted
bandpass is removed by destructive interference. Filters
have the advantages of simplicity, reggedness, and low
cost. One filter, however, can only isolate one band of
wavelengths; a new filter must be used for a different
band. Therefore, interference filter instruments are used
only for measurements that are made at fixed or
infrequently changed wavelength.
Detecting and Measuring Radiant Energy
To obtain spectroscopic information, the radiant power
transmitted, fluoresced, or emitted must be detected in
some manner and converted into a measurable quantity.
A detector is a device that indicates the existence of
some physical phenomenon.
In modern instruments, the information of interest is
encoded and processed as an electrical signal. The term
transducer is used to indicate the type of detector that
converts quantities, such as light intensity, pH, mass, and
temperature, into such electrical signals that can be
subsequently amplified, manipulated, and finally
converted into numbers proportional to the magnitude of
the original quantity.
Properties of Radiation Transducers
The ideal transducer for electromagnetic
radiation responds rapidly to low levels of
radiant energy over a broad wavelength range. In
addition, it produces an electrical signal that is
easily amplifies and has a low electrical noise
level. Finally, the electrical signal produced by
the transducer be directly proportional to the
radiant power P of the beam
G = KP + K’
where G is the electrical response of the detector
in units of current, voltage, or charge.
The proportionality constant K measures the
sensitivity of the detector in terms of electrical
response per unit of radiant power input. A small
constant response K’, known as a dark current,
even when no radiation strikes their surfaces.
Instrument with detectors that have a significant
dark-current response are ordinarily capable of
compensation so that the dark current is
automatically subtracted.
G = KP
Types of Transducers
Two general types of transducers: one type
responds to photons, the other to heat. All photon
detectors are based on the interaction of radiation
with a reactive surface to produce electrons
(photoemission) or to promote electrons to energy
states in which they can conduct electricity
(photoconduction). Only UV, visible, and near-IR
radiation possess enough energy to cause
photoemission to occur; thus, photoemissive
detector are limited to wavelengths shorter than
about 2 m (2000 nm). Photoconductors can be
used in the near-, mid-, and far-IR regions of the
We detect IR radiation by measuring the
temperature rise of a blackened material located in
the path of the beam or by measuring the increase
in electrical conductivity of a photoconducting
material when it absorbs IR radiation.
Photon Detectors
Widely used types of photon detectors include
photodiodes, and photodiode arrays.