A spectroscope or optical spectrometer is a device that measures different properties of light

over a specific range in the spectrum used for the analysis of various objects. The property
measured is mostly the intensity of light, although polarization of light is also measured under
some conditions.

Spectroscopes are commonly used in studies regarding astronomy and chemistry for the analysis
of various samples. Traditionally, prisms were used as spectroscopes, however, nowadays,
diffraction gratings, mobile slit, and photodetectors are used.

These are mostly used to deduce the chemical composition of objects based on the radiation
produced by different objects.

Emission spectra

The electrons surrounding the atomic nucleus are arranged in a series of levels of increasing
energy. Each element has a unique number of electrons in a unique configuration therefore each
element has its own distinct set of energy levels. This arrangement of energy levels serves as the
atom's unique fingerprint.

When an electron in an atom falls from a higher energy level to a lower energy level, it emits a
photon to carry off the extra energy. This photon's energy is equal to the energy difference
between the two energy levels
The frequency of a photon is related to its energy through the equation E=hfE=hf. Since a
specific photon frequency (or wavelength) gives us a specific colour, we can see how each
coloured line is associated with a specific transition.

Absorption spectra
Atoms do not only emit photons; they also absorb photons. If a photon hits an atom and the
energy of the photon is the same as the gap between two electron energy levels in the atom, then
the electron in the lower energy level can absorb the photon and jump up to the higher energy
level. If the photon energy does not correspond to the difference between two energy levels then
the photon will not be absorbed (it can still be scattered).
 When an atom or molecule in an excited state returns to a lower energy state, the excess
energy often is released as a photon, a process we call emission. There are several ways in
which an atom or molecule may end up in an excited state, including thermal energy, absorption
of a photon, or by a chemical reaction. Emission following the absorption of a photon is also
called photoluminescence, and that following a chemical reaction is called chemiluminescence.

 If the object emitting the light is moving towards us, then the wavelength of the light
appears shorter (called blueshifted). If the object is moving away from us, then the wavelength
of its light appears stretched out (called redshifted).
 The Doppler effect affects the spectra of objects in space depending on their motion
relative to us on the earth. For example, the light from a distant galaxy that is moving away from
us at some velocity will appear redshifted. This means that the emission and absorption lines in
the galaxy's spectrum will be shifted to a longer wavelength (lower frequency).

Absorption spectroscopy
Absorption spectroscopy is a spectroscopic technique that measures the frequency of wavelength
of absorbed light as a result of the interaction between the light and a sample.

Principle of Absorption spectroscopy

 Absorption spectroscopy is based on the principle that materials have an absorption
spectrum which is a range of radiation absorbed by the material at different frequencies.
 The absorption spectrum of materials depends on the atomic and molecular composition
of that material.
 The frequency of light radiation absorbed by a material is dependent on the energy
difference between the two energy states of the molecules.
 The absorption results in the formation of an absorption line, which, together with other
lines, form an absorption spectrum.
 Thus, when a photon with sufficient energy reaches an object, the energy is absorbed by
the electrons causing them to bump into a higher energy state.
 The amount of photon (radiation) absorbed results in an absorption spectrum which can
then be measured in terms of absorbance.
 The absorbance of a sample is dependent on the number of excited electrons which in
turn is dependent on the concentration of molecules in the sample.

Steps of Absorption spectroscopy

 Solvent liquid and the sample solution are taken in two transport vessels, also termed as
cuvettes.
 The vessel with solvent liquid is then placed in the spectrometer to determine the light
loss due to scattering and absorbance by the solvent. Any absorbance observed in this process is
to be subtracted from the absorbance of the sample.
 The cuvette with the sample solution is then placed in the spectrometer.
 The absorbance of the sample is noted in different frequencies which usually ranges from
200-800 nm.
 A similar spectrum is formed from a different concentration of the samples.
 A graph of the absorbance measured against the concentration of the sample is plotted,
which can then be used for the determination of the unknown concentration of the sample.
Basic Components of Spectroscopic Instruments

All forms of spectroscopy require a source of energy. In absorption and scattering spectroscopy
this energy is supplied by photons. Emission and photoluminescence spectroscopy use thermal,
radiant (photon), or chemical energy to promote the analyte to a suitable excited state.

Sources of Electromagnetic Radiation. A source of electromagnetic radiation must provide an

output that is both intense and stable. Sources of electromagnetic radiation are classified as
either continuum or line sources. A continuum source emits radiation over a broad range of
wavelengths, with a relatively smooth variation in intensity. A line source, on the other hand,
emits radiation at selected wavelengths

Sources of Thermal Energy. The most common sources of thermal energy are flames and
plasmas. Flames sources use the combustion of a fuel and an oxidant to achieve temperatures of
2000–3400 K. Plasmas, which are hot, ionized gases, provide temperatures of 6000–10 000 K.
Chemical Sources of Energy. Exothermic reactions also may serve as a source of energy. In
chemiluminescence the analyte is raised to a higher-energy state by means of a chemical
reaction, emitting characteristic radiation when it returns to a lower-energy state. When the
chemical reaction results from a biological or enzymatic reaction, the emission of radiation is
called bioluminescence. Commercially available ―light sticks‖ and the flash of light from a
firefly are examples of chemiluminescence and bioluminescence.

Wavelength Selection

If two components in the sample absorbs different wavelengths of light, then a quantitative
analysis using Nessler’s original method becomes impossible. Ideally we want to select a
wavelength that only the analyte absorbs. Unfortunately, we cannot isolate a single wavelength
of radiation from a continuum source. A wavelength selector passes a narrow band of radiation
characterized by a nominal wavelength, an effective bandwidth and a maximum throughput of
radiation. The effective bandwidth is defined as the width of the radiation at half of its maximum
throughput.

The ideal wavelength selector has a high throughput of radiation and a narrow effective
bandwidth. A high throughput is desirable because more photons pass through the wavelength
selector, giving a stronger signal with less background noise. A narrow effective bandwidth
provides a higher resolution, with spectral features separated by more than twice the effective
bandwidth being resolved. Conditions favoring a higher throughput of radiation usually provide
less resolution. Decreasing the effective bandwidth improves resolution, but at the cost of a
noisier signal. For a qualitative analysis, resolution is usually more important than noise, and a
smaller effective bandwidth is desirable. In a quantitative analysis less noise is usually desirable.
Wavelength Selection Using Filters. The simplest method for isolating a narrow band of
radiation is to use an absorption or interference filter. Absorption filters work by selectively
absorbing radiation from a narrow region of the electromagnetic spectrum. Interference filters
use constructive and destructive interference to isolate a narrow range of wavelengths. A simple
example of an absorption filter is a piece of colored glass. A purple filter, for example, removes
the complementary color green from 500–560 nm. Commercially available absorption filters
provide effective bandwidths of 30–250 nm, although the throughput may be only 10% of the
source’s emission intensity at the low end of this range. Interference filters are more expensive
than absorption filters, but have narrower effective bandwidths, typically 10–20 nm, with
maximum throughputs of at least 40%.

Wavelength Selection Using Monochromators. A filter has one significant limitation—because

a filter has a fixed nominal wavelength, if you need to make measurements at two different
wavelengths, then you need to use two different filters. A monochromator is an alternative
method for selecting a narrow band of radiation that also allows us to continuously adjust the
band’s nominal wavelength.

Radiation from the source enters the monochromator through an entrance slit. The radiation is
collected by a collimating mirror, which reflects a parallel beam of radiation to a diffraction
grating. The diffraction grating is an optically reflecting surface with a large number of parallel
grooves. The diffraction grating disperses the radiation and a second mirror focuses the radiation
onto a planar surface containing an exit slit. In some monochromators a prism is used in place of
the diffraction grating.

Radiation exits the monochromator and passes to the detector. A monochromator converts
a polychromatic source of radiation at the entrance slit to a monochromatic source of finite
effective bandwidth at the exit slit. The choice of which wavelength exits the monochromator is
determined by rotating the diffraction grating. A narrower exit slit provides a smaller effective
bandwidth and better resolution, but allows a smaller throughput of radiation.

Monochromators are classified as either fixed-wavelength or scanning. In a fixed-wavelength

monochromator we select the wavelength by manually rotating the grating. Normally a fixed-
wavelength monochromator is used for a quantitative analysis where measurements are made at
one or two wavelengths. A scanning monochromator includes a drive mechanism that
continuously rotates the grating, allowing successive wavelengths to exit from the
monochromator. Scanning monochromators are used to acquire spectra, and, when operated in a
fixed-wavelength mode, for a quantitative analysis.

Interferometers. An interferometer provides an alternative approach for wavelength selection.

Instead of filtering or dispersing the electromagnetic radiation, an interferometer allows source
radiation of all wavelengths to reach the detector simultaneously. Radiation from the source is
focused on a beam splitter that reflects half of the radiation to a fixed mirror and transmits the
other half to a movable mirror. The radiation recombines at the beam splitter, where constructive
and destructive interference determines, for each wavelength, the intensity of light reaching the
detector. As the moving mirror changes position, the wavelengths of light experiencing
maximum constructive interference and maximum destructive interference also changes. The
signal at the detector shows intensity as a function of the moving mirror’s position, expressed in
units of distance or time. The result is called an interferogram, or a time domain spectrum. The
time domain spectrum is converted mathematically, by a process called a Fourier transform, to a
spectrum (also called a frequency domain spectrum) showing intensity as a function of the
radiation’s energy.

In comparison to a monochromator, an interferometer has two significant advantages. The first

advantage, which is termed Jacquinot’s advantage, is the higher throughput of source radiation.
Because an interferometer does not use slits and has fewer optical components from which
radiation can be scattered and lost, the throughput of radiation reaching the detector is 80–200×
greater than that for a monochromator. The result is less noise. The second advantage, which is
called Fellgett’s advantage, is a savings in the time needed to obtain a spectrum. Because the
detector monitors all frequencies simultaneously, an entire spectrum takes approximately one
second to record, as compared to 10–15 minutes with a scanning monochromator.

Detectors
In Nessler’s original method for determining ammonia the analyst’s eye serves as the detector,
matching the sample’s color to that of a standard. Modern detectors use a sensitive transducer to
convert a signal consisting of photons into an easily measured electrical signal. Ideally the
detector’s signal, S, is a linear function of the electromagnetic radiation’s power, P,

S=kP+D(10.1.10)(10.1.10)S=kP+D

where k is the detector’s sensitivity, and D is the detector’s dark current, or the background
current when we prevent the source’s radiation from reaching the detector.
Transducer is a general term that refers to any device that converts a chemical or physical
property into an easily measured electrical signal. The retina in your eye, for example, is a
transducer that converts photons into an electrical nerve impulse. There are two broad classes of
spectroscopic transducers: thermal transducers and photon transducers.

Photon Transducers. Phototubes and photomultipliers contain a photosensitive surface that

absorbs radiation in the ultraviolet, visible, or near IR, producing an electrical current
proportional to the number of photons reaching the transducer. Other photon detectors use a
semiconductor as the photosensitive surface. When the semiconductor absorbs photons, valence
electrons move to the semiconductor’s conduction band, producing a measurable current. One
advantage of the Si photodiode is that it is easy to miniaturize. Groups of photodiodes may be
gathered together in a linear array containing from 64–4096 individual photodiodes. By placing
a photodiode array along the monochromator’s focal plane, it is possible to monitor
simultaneously an entire range of wavelengths.

Thermal Transducers. Infrared photons do not have enough energy to produce a measurable
current with a photon transducer. A thermal transducer, therefore, is used for infrared
spectroscopy. The absorption of infrared photons by a thermal transducer increases its
temperature, changing one or more of its characteristic properties. A pneumatic transducer, for
example, is a small tube of xenon gas with an IR transparent window at one end and a flexible
membrane at the other end. Photons enter the tube and are absorbed by a blackened surface,
increasing the temperature of the gas. As the temperature inside the tube fluctuates, the gas
expands and contracts and the flexible membrane moves in and out. Monitoring the membrane’s
displacement produces an electrical signal.
Signal Processors
A transducer’s electrical signal is sent to a signal processor where it is displayed in a form that
is more convenient for the analyst. Examples of signal processors include analog or digital
meters, recorders, and computers equipped with digital acquisition boards. A signal processor
also is used to calibrate the detector’s response, to amplify the transducer’s signal, to remove
noise by filtering, or to mathematically transform the signal.

Uses of Absorption spectroscopy

 Absorption spectroscopy is used to determine the presence of a particular substance in a
sample and then to quantify the present substance.
 This technique has been applied in remote sensing, which allows the determination of the
concentration of hazardous substances without the direct interaction of the instrument and the
sample.
 Absorption spectroscopy is also used for the determination of the atomic and molecular
structure of various substances.

Atomic absorption spectroscopy

Atomic absorption is an analytical technique utilizing the principle of spectroscopy for the
quantitative determination of chemical elements.
Principle of Atomic absorption spectroscopy
 Atomic absorption spectroscopy utilizes the principle that free electrons generated in an
atomizer absorb radiation of different wavelengths.
 The free electrons absorb UV or visible light, causing the electrons to transfer to higher
energy orbits.
 During this process, the absorption spectrum is released, which is detected by the
photodetectors.
 The absorption spectrum formed allows the quantification of free electrons in the gaseous
state of the matter.
 The amount of photon (radiation) absorbed results in an absorption spectrum which can
then be measured in terms of absorbance.
 The absorbance of a sample is dependent on the concentration of molecules in the
sample.
Steps of Atomic absorption spectroscopy
 The liquid sample is mixed with a particular volume of spirit which is added to a flask
which is then vaporized into a gas by a fuel-rich acetylene-nitrous oxide flame.
 A lamp is set with the necessary wavelength as a light source.
 The gas formed from the liquid sample is then passed through a detector that detects the
absorbance of the atoms in the gas.
 A similar process is performed for the detection of absorbance of solvent bank and
standard solution.
 A graph is plotted for the absorbance against the concentration of the molecules in the
sample.
Uses of Atomic absorption spectroscopy
 Atomic absorption spectroscopy can be used for the quantitative and qualitative
determination of metallic elements in biological systems.
 This also helps in the detection of metals as an impurity in alloys and other mixtures.
 Atomic absorption spectroscopy has been utilized for the purification of environmental
samples like water and soil.
 Detection of metals in pharmaceutical products and oil products can also be done by this
method.