Analytical Instrumentation

Topics:
 Monochromators
 Filters
 Diffraction gratings
 Flame emission photometry
 Absorption spectroscopy
 1. Monochromators
A monochromator is an optical system that transmits a specific band of the
electromagnetic spectrum.
The device is based on the separating capability of refraction (prism) or
diffraction (diffraction grating). Typical applications are isolation of a narrow
band of radiation from a continuum light source for absorption measurements,
or analysis of the emission from excited atoms or molecules.

Monochromator Types:
 Prism monochromator
 Diffraction grating monochromator

Prism Monochromator

Based on refraction of light and fact that different wavelengths of

radiation have different values of refractive index in a medium.

Entrance slit allows source radiation to illuminate the first lens which
collimates the light spreading it across the face of the prism. Prism
disperses radiation into component wavelengths and the second lens
focuses the spectrum at the focal plane. An exit slit selects the band of
radiation to reach the detector. Dispersing element can be a prism or a
diffraction grating. Focusing elements can be lenses or mirrors.
• Desired wavelength can be selected by rotating the prism.
• In visible region – can use glass down to 350 nm
• In the UV region – quartz is material of choice
• In the IR region – NaCl, KBr, etc.
Kinds of Prisms Littrow Prism & Mounting – compact design

Problem with quartz prisms is that quartz is optically active (optically

anisotropic). With the Littrow prism or any reflecting prism, the light
travels essentially the same path in both directions and this effect is
eliminated.
 Gratings

Based on diffraction & interference Transmission Gratings & Reflection

Gratings consist of a series of grooves in glass or quartz or a mirror (usual
kind).

Reflection Grating: most commonly used Grating Monochromator: based on

diffraction of light (constructive and deconstructive interference) - grooved
surface with reflective coating (Al, Au, Pt).

Now, spacing of slits (d) is distance from one groove to next. Typically have
300-2000 grooves/mm.

Constructive and deconstructive interference occurs because light travels

different distances when reflected from each grating
– Increase size of either prism or grating will give better dispersion.
– Stray light can be removed with filters.
– Glass absorbs light l ≤ 350 nm.

Function of Monochromator:
If you wanted to perform quantitative analysis, monochromatic light would
need to be passed through the sample otherwise Beer’s Law would not hold
true. Alternatively, if you needed to scan a sample to produce a spectrum,
monochromatic light at every wavelength to be scanned would also be
required.

In effect, a monochromator produces monochromatic light by removing

unwanted wavelengths from the source light beam.
The function of the monochromator is to isolate a single atomic resonance line
from the spectrum of lines emitted by the hollow cathode lamp. Essentially it is
an adjustable filter that selects a specific, narrow region of the spectrum for
transmission to the detector and excludes all wavelengths outside this region.

A monochromator comprises an entrance slit, a dispersion device and an exit slit.

 The entrance slit selects a defined beam of (polychromatic) light from the
source.
 The dispersion device causes the different wavelengths of light in the
source beam to be dispersed at different angles.
 2. Filters
Essential building blocks of any Electronic and Communication Systems
that alter the amplitude and/or phase characteristics of a signal with
respect to frequency. Filter is basically linear circuit that helps to remove
unwanted components such as Noise, Interference and Distortion from the
input signal. Ideally Filter alters the relative amplitudes of the various
frequency components and the phase characteristics and its ‘Gain’
depends entirely on the signal frequency.
Classification of Filters
Filter is mainly classified into two types:
 Active Filter
 Passive Filter

Active Filters
Filter Circuit which consists of active components like Transistors and
Op-amps in addition to Resistors and Capacitors is called as Active
Filter.

Passive Filters
Filter circuit which consists of passive components such as Resistors,
Capacitors and Inductors is called as Passive Filter. The operating
frequency range of the filter banks on the components used to build the
circuit. Hence the filter can be further categorized based on the operating
frequency of a particular circuit. They are:
 Low Pass Filter
 High Pass Filter
 Band Pass Filter
 Band Stop Filter
 All Pass Filter
Low Pass Filters
It is a type of Filter which attenuates all the frequencies above the cut-off
frequencies. It provides a constant output (gain) from zero to cut-off
frequency.

High Pass Filters

It is a type of Filter which attenuates all the frequencies below the
cut-off frequencies. It provides a constant output (gain) above the
cut-off frequency.
Band Pass Filters
It is a type of filter which allows specific Band of frequencies to pass through
and all other frequencies outside the band are attenuated.

Band Stop Filters

Specific Band of frequencies gets rejected and allows passing of frequencies
outside the Band.
 All Pass Filters
It is a type of filter which passes all frequencies equally. It is also
known as Phase-Shift filter, time-delay filter as the output voltage shifts
in phase with respect to input voltage but they are equal in magnitude.

Applications of Filters:

 Filter Circuits are used to eliminate background Noise.

 They are used in Radio tuning to a specific frequency.
 Used in Pre-amplification, Equalization, Tone Control in Audio
Systems.
 They are also used in Signal Processing Circuits and Data Conversion.
 Filter Circuits are extensively used in Medical Electronic Systems.
 3. Diffraction gratings
Evolved from Young’s Double Slit experiment, diffraction gratings are
the preferred method of light scattering in many spectrometers. A
diffraction grating is a device that splits electromagnetic radiation into its
constituent wavelengths. In a nutshell, a diffraction grating comprises
slits of varying widths to match the wavelengths of the different colors of
the visible spectrum. When white light is incident on the grating, its
constituent colors are separate as they bend through the slit that matches
their respective wavelengths.

Types of Diffraction Gratings

In general, there are four types of diffraction gratings: ruled gratings,
holographic gratings, transmission gratings, and reflection gratings.

Ruled Gratings:
Ruled gratings are created by physically etching several parallel grooves
onto a reflective surface. Applications that require a narrow wavelength,
such as spectrometers and monochromators, often benefit from having a
ruled grating blazed at that specific wavelength.
Commons applications for ruled gratings are:
 Fluorescence Excitation
 Telecommunications
 Analytical Chemistry
 Life Sciences
 Physics
 Space Sciences
 Education

Note: The wavelength of electromagnetic radiation that yields the

greatest absolute efficiency of the ruled diffraction grating is referred to
as the blaze wavelength.
Holographic Gratings:
Holographic gratings are developed by using a photolithographic process
to generate an interference pattern between two UV beams, creating a
sinusoidal index of refraction variation in a piece of optical glass.
Generally, ruled diffraction gratings are lighter and cheaper than
holographic gratings but they exhibit more stray light. On the other hand,
holographic diffraction gratings are better for stray light performance but
tend to have lower efficiency.
Transmission Gratings:
One popular style of grating is the transmission grating. This type of
grating is created by scratching or etching a transparent substrate with a
repetitive, parallel structure. In a transmission diffraction grating, light
passes through the material on which the grating is etched.
Transmission gratings are particularly useful in fixed grating applications
such as spectrographs. Transmission gratings have relatively low
polarization sensitivity when compared to reflection gratings because
incident light is not reflected by a mirror coating. Transmission gratings are
particularly effective in compact, in-line configurations because light is
transmitted through the grating. Transmission gratings are great in
monochromators and spectrometers.

Reflection Gratings:
A reflective grating is traditionally made by depositing a metallic coating
on an optic and ruling parallel grooves in the surface. Reflective gratings
are also commonly made by replicating a master diffraction grating
version with epoxy and/or plastic. In all cases, light is reflected off of the
ruled surface at different angles corresponding to different orders and
wavelengths.
As evident in their descriptions, the four types of diffraction gratings
listed are not necessarily mutually exclusive, and diffraction gratings are
capable of incorporating components of multiple different types.
Diffraction Gratings for Spectrometry
Diffraction gratings are commonly used in monochromators,
spectrometers, lasers, wavelength division multiplexing devices, optical
pulse compression devices, and many other optical instruments. CDs
and DVDs are good, easily observable examples of diffraction gratings.
Reflecting sunlight off a CD or DVD onto a white wall will yield light
of different colors i.e., different wavelengths of the visible spectrum.

Spectrometers:
Perhaps the most elementary application of diffraction gratings for
spectrometry tools, spectrometers are used to separate white light into its
constituent wavelengths.

Monochromators:
In some ways, monochromators are kind of the reverse of spectrometers.
While spectrometers separate white light into all its constituent colors,
monochromators are devices used to filter out all but a narrow band of
electromagnetic energy. This particular application of diffraction
gratings for spectrometry tools is very useful when tunable
monochromatic light is needed.

Lasers:
Diffraction gratings are often used in lasers for wavelength tuning. That
is, calibrating the laser to emit a specific wavelength of electromagnetic
radiation.

Optical Communications:
Holographic diffraction gratings have widespread use in optical
communications and industrial measurement across near infrared
spectral regions in which high performance and environment resistance
are necessary.

Pulse Compression:
Diffraction gratings have also found a foothold in the pulse compression
technology. The gratings used for these applications tend to be made of
high-purity monolithic fused silica, which is ideal for certain laser
wavelengths.
 4. Flame emission photometry
Photoelectric flame photometry, a branch of atomic spectroscopy is used
for inorganic chemical analysis for determining the concentration of
certain metal ions such as sodium, potassium, lithium, calcium, Cesium,
etc. In flame photometry the species (metal ions) used in the spectrum are
in the form of atoms. The International Union of Pure and Applied
Chemistry (IUPAC) Committee on Spectroscopic Nomenclature has
recommended it as flame atomic emission spectrometry (FAES).

The basis of flame photometric working is that, the species of alkali

metals (Group 1) and alkaline earth metals (Group II) metals are
dissociated due to the thermal energy provided by the flame source. Due
to this thermal excitation, some of the atoms are excited to a higher energy
level where they are not stable. The absorbance of light due to the
electrons excitation can be measured by using the direct absorption
techniques. The subsequent loss of energy will result in the movement of
excited atoms to the low energy ground state with emission of some
radiations, which can be visualized in the visible region of the spectrum.
The absorbance of light due to the electrons excitation can be measured
by using the direct absorption techniques while the emitting radiation
intensity is measured using the emission techniques. The wavelength of
emitted light is specific for specific elements.
Parts of a flame photometer

1. Sourceof flame:
A burner that provides flame and can be maintained in a constant form
and at a constant temperature.

2. Nebulizer and mixing chamber:

Helps to transport the homogeneous solution of the substance into the
flame at a steady rate.

3. Optical system (optical filter):

The optical system comprises three parts: convex mirror, lens and
filter. The convex mirror helps to transmit light emitted from the
atoms and focus the emissions to the lens. The convex lens help to
focus the light on a point called slit. The reflections from the mirror
pass through the slit and reach the filters. This will isolate the
wavelength to be measured from that of any other extraneous
emissions. Hence it acts as interference type color filters.

4. Photo detector:
Detect the emitted light and measure the intensity of radiation emitted
by the flame. That is, the emitted radiation is converted to an electrical
signal with the help of photo detector. The produced electrical signals
are directly proportional to the intensity of light.
Mechanism of working:
The working of the flame photometer involves a series of steps which is
discussed in the following sections.

Nebulization:
The solution of the substance to be analyzed is first aspirated into the
burner, which is then dispersed into the flame as fine spray particles.

A brief overview of the process:

 The solvent is first evaporated leaving fine divided solid particles.
 This solid particles move towards the flame, where the gaseous
atoms and ions are produced.
 The ions absorb the energy from the flame and excited to high energy
levels.
 When the atoms return to the ground state radiation of the characteristic
element is emitted.
 The intensity of emitted light is related to the concentration of the
element.
 5. Absorption spectroscopy
Absorption spectroscopy is useful in chemical analysis because of its
specificity and its quantitative nature. The specificity of absorption spectra
allows compounds to be distinguished from one another in a mixture, making
absorption spectroscopy useful in wide variety of applications. For instance,
Infrared gas analyzers can be used to identify the presence of pollutants in the
air, distinguishing the pollutant from nitrogen, oxygen, water and other
expected constituents.
The specificity also allows unknown samples to be identified by
comparing a measured spectrum with a library of reference spectra. In
many cases, it is possible to determine qualitative information about a
sample even if it is not in a library. Infrared spectra, for instance, have
characteristics absorption bands that indicate if carbon-hydrogen or
carbon-oxygen bonds are present.
An absorption spectrum can be quantitatively related to the amount of
material present using the Beer-Lambert law. Determining the absolute
concentration of a compound requires knowledge of the compound's
absorption coefficient. The absorption coefficient for some compounds
is available from reference sources, and it can also be determined by
measuring the spectrum of a calibration standard with a known
concentration of the target.

Remote sensing
One of the unique advantages of spectroscopy as an analytical technique
is that measurements can be made without bringing the instrument and
sample into contact. Radiation that travels between a sample and an
instrument will contain the spectral information, so the measurement can
be made remotely. Remote spectral sensing is valuable in many
situations. For example, measurements can be made in toxic or hazardous
environments without placing an operator or instrument at risk. Also,
sample material does not have to be brought into contact with the
instrument—preventing possible cross contamination .
 Remote spectral measurements present several challenges compared to
laboratory measurements. The space in between the sample of interest and the
instrument may also have spectral absorptions. These absorptions can mask
or confound the absorption spectrum of the sample.
These background interferences may also vary over time. The source of
radiation in remote measurements is often an environmental source, such as
sunlight or the thermal radiation from a warm object, and this makes it
necessary to distinguish spectral absorption from changes in the source
spectrum. To simplify these challenges, Differential optical absorption
spectroscopy has gained some popularity, as it focusses on differential
absorption features and omits broad-band absorption such as aerosol
extinction and extinction due to Rayleigh scattering. This method is applied
to ground-based, air-borne and satellite based measurements. Some ground-
based methods provide the possibility to retrieve tropospheric and
stratospheric trace gas profiles.
Astronomy
Astronomical spectroscopy is a particularly significant type of remote
spectral sensing. In this case, the objects and samples of interest are so
distant from earth that electromagnetic radiation is the only means
available to measure them. Astronomical spectra contain both absorption
and emission spectral information. Absorption spectroscopy has been
particularly important for understanding interstellar clouds and
determining that some of them contain molecules.
Absorption spectroscopy is also employed in the study of extrasolar
planets. Detection of extrasolar planets by the transit method also
measures their absorption spectrum and allows for the determination of
the planet's atmospheric composition, temperature, pressure, and scale
height, and hence allows also for the determination of the planet's mass.
Atomic and molecular physics

Theoretical models, principally quantum mechanical models, allow for

the absorption spectra of atoms and molecules to be related to other
physical properties such as electronic structure, atomic or molecular
mass, and molecular geometry. Therefore, measurements of the
absorption spectrum are used to determine these other properties.
Microwave spectroscopy, for example, allows for the determination of
bond lengths and angles with high precision.

In addition, spectral measurements can be used to determine the accuracy

of theoretical predictions. For example, the Lamb shift measured in the
hydrogen atomic absorption spectrum was not expected to exist at the
time it was measured. Its discovery spurred and guided the development
of quantum electrodynamics, and measurements of the Lamb shift are
now used to determine the fine-structure constant.