IR spectroscopy.... Dr.

Paresh Parekh

Infra-red Spectroscopy
Introduction:
• Spectroscopy can be defined as the interaction between matter and light.
Infrared spectroscopy is a very powerful technique which uses
electromagnetic radiation in the infrared region for the determination and
identification of molecular structure as well as having various quantitative
applications within analytical chemistry (Figure 1).
• It is important to note that atoms can absorb energy from electromagnetic
radiation; this absorbed energy alters the state of the atoms within the
molecule. These changes are usually manifest in alterations to the frequency
and amplitude of molecular vibrations, which may be measured and plotted to
produce an infrared spectrum.
• Infrared spectrometers use optical devices for dispersing and focusing
electromagnetic radiation of IR frequency which is passed through the sample
and any changes in absorbance measured against a reference beam.

Fig. 1 The electromagnetic spectrum and the Infra-red region.

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 IR spectroscopy.... Dr. Paresh Parekh

• There are three well defined IR regions (near, mid and far). The boundaries
between them are not clearly defined and debate still persists, but broadly they
are defined as:
• Near infrared (12820-4000 cm-1): poor in specific absorptions, consists of
overtones and combination bands resulting from vibrations in the mid-infrared
region of the spectrum.
• Mid-infrared (4000-400 cm-1): provides structural information for most
organic molecules.
• Far Infrared (400-33 cm-1): has been less investigated than the other two
regions; however, it has been used with inorganic molecules.
• The low energies, typically encountered within the infrared region, are not
sufficient to cause electronic transitions; however, they are large enough to
cause changes in the frequency and amplitude of molecular vibrations.
• Infrared spectroscopy is one of the most useful and widely used methods to perform
structural analysis.
• Given that the molecule under investing is infrared active (i.e. it absorbs Infrared
radiation), then different types of structural information obtained.
• Information achievable with Infrared spectroscopy includes:

• The type of atoms within the molecule.

• The type of bonds between atoms.

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 IR spectroscopy.... Dr. Paresh Parekh

• The molecular structure, more often than not, infrared spectroscopy is

insufficient to determine the complete structure and additional techniques
(such as NMR, Mass spectroscopy etc,) are used to solve the puzzle.

• Both structures have the molecular formula C2H4O

Fig 2 General Infrared region

Selection Rule:
• IR radiation is not energetic enough to bring about the kinds of electronic
transitions that we have encountered in ultraviolet and visible radiation.
Absorption of IR radiation ty thus continued largely to molecular species that
have small energy differences between various vibrational and rotational
states.
• To absorb IR radiation. a molecule must undergo a net change in dipole
moment as if vibrates of rotates. Only under these circumstances can the

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 IR spectroscopy.... Dr. Paresh Parekh

alternating electric field of the radiation interact with the molecule and cause
changes in the amplitude of one of its motions.
• For example, the charge distribution around a molecule such as hydrogen
chloride is not symmetric because the chlorine has a higher electron density
than the hydrogen. Thus. hydrogen chloride has a significant dipole moment
and is said to be polar.
• The dipole moment is determined by the magnitude of the charge difference
and the distance between the two centers of charge. As a hydrogen chloride
molecule vibrates, a regular fluctuation in its dipole moment occurs, and a
field is established that can interact with the electric field associated with
radiation.
• If the frequency of the radiation exactly matches a natural vibrational
frequency of the molecule, absorption of the radiation takes place that
produces a change in the amplitude of the molecular vibration. Similarly, the
rotation of asymmetric molecules around their centers of mass results in
Periodic dipole moment fluctuations that allow interaction with the radiation
field.
• No net change in dipole moment occurs during the vibration of rotation of
homo nuclear species such as O2, N2 or Cl2. As a result, such compounds
cannot absorb IR radiation. With the exception of a few compounds of this
type, all other molecular species absorb IR radiation.
Types of Molecular Vibrations
• The relative positions of atoms in a molecule are not fixed but instead
fluctuate continuously as a con- sequence of a multitude of different types of
vibrations and rotations about the bonds in the molecule. For a simple

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 IR spectroscopy.... Dr. Paresh Parekh

diatomic or triatomic molecule, it is easy to define the number and nature of

such vibrations and relate these to energies of absorption.
• An analysis of this kind becomes difficult if not impossible for molecules
made up of many atoms. Not only do large molecules have a large number of
vibrating centers. but also interactions among several centers can occur and
must be taken into account for a complete analysis.
• Vibrations fall into the basic categories of stretching and bending. A
stretching vibration involves a continuous change in the interatomic distance
along the axis of the bond between two atoms. Bending vibrations are
characterized by a change in the angle between two bonds and are of four
types: scissoring. rocking wagging. and twisting. These are shown
schematically in Figure 3.
• All of the vibration types shown in Figure 3 may be possible in a molecule
containing more than two atoms. In addition, interaction or coupling of
vibrations can occur if the vibrations involve bonds to a single central atom.
The result of coupling is a change in the characteristics of the vibrations
involved.

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 IR spectroscopy.... Dr. Paresh Parekh

Fig. 3 Different types of molecular vibration

Vibration Modes:
• It is ordinarily possible to deduce the number and kinds of vibrations in simple
diatomic and triatomic molecules and whether these vibrations will lead to
absorption. Complex molecules may contain several types of atoms as well as
bonds. For these molecules, the many types of possible vibrations give rise to
IR spectra that are much more difficult to analyze.

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 IR spectroscopy.... Dr. Paresh Parekh

• The number of possible vibrations in a polyatomic molecule can be calculated

as follows. Three coordinates are needed to locate a point in space. To fix N
points requires a set of three coordinates for each point, for a total of 3N. Each
coordinate corresponds to one degree of freedom for one of the atoms in a
polyatomic molecule. For this reason, a molecule containing N atoms is said
to have 3N degrees of freedom.
• In defining the motion of a molecule. we need to consider (1) the motion of
the entire molecule through space (that is, the translational motion of its center
of gravity); (2) the rotational motion of the entire molecule around its center
of gravity; and (3) the motion of each of its atoms relative to the other atoms,
or in other words, its individual vibrations, because all atoms in the molecule
move in concert through space, definition of translational motion requires
three coordinates and thus this common motion requires three of the 3N
degrees of freedom.
• Another three degrees of freedom are needed to describe the rotation of the
molecule as a whole. The remaining 3N — 6 degrees of freedom involve
interatomic motion and hence represent the number of possible vibrations
within the molecule. A linear molecule is a special case because by definition,
all of the atoms lie on a single, straight line. Rotation about the bond axis is
not possible, and two degrees of freedom suffice to describe rotational motion,
Thus, the number of vibrations for a linear molecule is given by 3N - 5. Each
of the 3N – 6 or 3N - 5 vibrations are called a normal mode.
• E.g. Carbon dioxide is a linear molecule and thus has (3 x 3)-5=4 normal
modes. Two stretching vibrations are possible; furthermore, interaction
between the two can occur because the bonds involved are associated with
common carbon atom. As can be seen, one of the coupled vibrations is
symmetric and the other is asymmetric.
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 IR spectroscopy.... Dr. Paresh Parekh

Fig. 4 CO2 vibration modes.

• The symmetric vibration causes no change in dipole moment, because the (wo
oxygen atoms simultaneously move away from or toward the central carbon
atom. Thus, the symmetric vibration is IR inactive. In the asymmetric
vibration, one oxygen Moves away from the carbon atom as the carbon alom
moves toward the other oxygen. As a consequence, a net change in charge
distribution occurs periodically, producing a change in dipole moment, so
absorption at 2350 cm -1 results.
• These two bending vibrations are the resolved components at 90° to one
another of the bending motion in all possible planes around the bond axis. The
two vibrations are identical in energy and thus produce a single absorption
band at 667 cm-1. Quantum states that are identical, as these are, are said to be
degenerate.
• Triatomic molecule such as water, sulfur dioxide. or nitrogen dioxide. These
molecules have (3 X 3) - 6 = 3 vibrational modes that take the following
forms:

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 IR spectroscopy.... Dr. Paresh Parekh

Fig. 5 Vibration modes of Water molecules.

• Because the central atom is not in line with the other two, the symmetric
stretching vibration produces a change in dipole moment and is thus IR active.
For ex- ample, stretching peaks at 3652 and 3756cm-1 appear in the IR
spectrum for the symmetric and asymmetric stretching vibrations of the water
molecule.
• There is only one component to the scissoring vibration for this nonlinear
molecule because motion in the plane of the molecule constitutes a rotational
degree of freedom. For water, the bending vibration causes absorption at 1596
cm-1.
• The difference in behavior of linear and nonlinear triatomic molecules with
two and three absorption bands, respectively. Illustrates how IR absorption
spectroscopy can sometimes be used to deduce molecular shapes.

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 IR spectroscopy.... Dr. Paresh Parekh

Instrumentation of FTIR:

Fig. 6 Instrument of FTIR

Sources:
• IR sources consist of an inert solid that is heated electrically to a temperature
between 1500 and 2200 K. These sources produce continuum radiation
approximating that of a blackbody.
• The maximum radiant intensity at these temperatures occurs between 3000
and 5900 cm-1. At longer wavelengths, the intensity falls off smoothly until it
is about 1% of the maximum at 670 cm-1.
• On the short wavelength side, the decrease is much more rapid. and a similar
reduction in intensity is observed at about 10,000 cm-1.
The Nernst Glower
• The Nernst glower is composed of rare earth oxides formed into a cylinder
having a diameter of 1 to 3 mm and a length of 2 to 5 cm. Platinum leads are
sealed to the ends of the cylinder to permit electrical connections to what
amounts to a resistive heating element.

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 IR spectroscopy.... Dr. Paresh Parekh

• As current passes through the device, its temperature increases to between

1200 K and 2200 K. The Nernst glower has a large negative temperature
coefficient of electrical resistance. and it must be heated externally to a dull
red heat before the current is large enough to maintain the desired temperature.
• Because the resistance decreases with increasing temperature. the source
circuit must be designed to limit the current or the glower rapidly becomes so
hot that it is destroyed.
The Globar
• A Globar is a silicon carbide rod. usually about 5 cm long and 5 mm in
diameter. lt also is electrically heated (1300 to 1500 K) and has the advantage
of a positive coefficient of resistance. On the other hand, water cooling of the
electrical contacts is required to prevent arcing.
• Spectral energies of the Globar and the Nernst glower are comparable except
in the region below 5 µm, where the Globar provides a significantly greater
output.
Incandescent Wire Source
• A source with somewhat lower intensity but with longer life than the Globar
or Nernst glower is a tightly wound spiral of nichrome wire heated to about
1100K by an electrical current.
• A rhodium wire heater sealed in a ceramic cylinder has similar properties,
although it is more expensive, Nichrome wire sources are less intense than
many IR sources.
• However, the incandescent wire source requires no cooling and is nearly
maintenance free. For this reason, the nichrome wire source is often used
where reliability is paramount, such as in process analyzers.

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 IR spectroscopy.... Dr. Paresh Parekh

The Mercury Arc

• For the far-IR region of the spectrum (A > 50 µm). none of the thermal sources
just described provides sufficient radiant power for convenient detection.
Here, a high-pressure mercury arc is used.
• This device consists of a quartz-jacketed tube containing mercury vapor at a
pressure greater than 1 atmosphere. Passage of electricity through the vapor
forms an internal plasma source that provides continuum radiation in the far-
IR region,
The Carbon Dioxide Laser Source:
• A tunable carbon dioxide laser is used as an IR source for monitoring the
concentrations of certain atmospheric pollutants and for determining
absorbing species in aqueous solutions.
• A carbon dioxide laser produces a band of radiation in the range of 900 to
1100 cm-1, which consists of about 100 closely spaced discrete lines. Although
the range of wavelengths available is limited, the region from 900 to 1100 cm-
1
is one particularly rich in absorption bands arising from the interactive
stretching modes of CO2.
• Thus, this source is useful for quantitative determination of a number of
important species such as ammonia, butadiene, benzene, ethanol, nitrogen
dioxide, and trichloroethylene. An important property of the laser source is
the radiant power available in each line, which is several orders of magnitude
greater than that of blackbody sources.
• Carbon dioxide lasers are widely used in remote sensing applications such as
light detection and ranging (lidar). The operating principle of lidar is similar
to that of radar. The lidar system transmits radiation out to a target where it
interacts with and is altered by the target.

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 IR spectroscopy.... Dr. Paresh Parekh

• Some of the radiation is then reflected back to the lidar instrument where it is
analyzed and used to obtain information about the target. By means of lidar,
distance, speed. rotation, chemical composition. and concentration of remote
targets can be obtained.
Transducers:
IR transducers are of three general types: (1) pyro- electric transducers. (2) photo
conducting transducers. and (3) thermal transducers.
Pyroelectric transducers:
• They are constructed front single crystalline wafers of pyroelectric materials,
which are insulators (dielectric materials) with very special thermal and
electrical properties. Triglycine sulfate (NIf2CH2COOH)3 H2SO4 (usually
deuterated or with a fraction of the glycines replaced with alanine), is the most
important pyroclectric material used for IR- detection systems.
• When an electric field is applied across any dielectric material, polarization
takes place, with the magnitude of the polarization being a function of the
dielectric constant of the material.
• For most dielectrics. this induced polarization rapidly decays to zero when the
external field is removed. Pyroelectric substances. in contrast, retain a strong
temperature-dependent polarization after removal of the field.
• Thus, by sandwiching the pyroelectric crystal between two electrodes, one of
which is IR transparent, a temperature- dependent capacitor is produced.
• Changing its temperature by irradiating it with IR radiation alters the charge
distribution across the crystal, which can be detected as a current in an external
electrical circuit connecting the two sides of the capacitor.
• The magnitude of this current is proportional to the surface area of the crystal
and the rate of change of polarization with temperature. Pyroelectric crystals

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 IR spectroscopy.... Dr. Paresh Parekh

lose their residual polarization when they are heated to a temperature called
the Curie point. For triglycine sulfate. the Curie point is 47°C.
• Pyroclectric transducers exhibit response times that are fast enough to allow
them to track the changes in the time domain signal from an interferometer.
For this reason, many FTIR spectrometers for the mid-IR region employ this
type of transducer.
Photo conducting Transducers:
• IR photo conducting transducers consist of a thin film of a semiconductor
material, such as lead sulfide, mercury telluride-cadmium telluride (MCT), or
indium antimonide, deposited on a nonconducting glass surface and sealed in
an evacuated envelope to protect the semiconductor from the atmosphere.
• Absorption of radiation by these materials promotes nonconducting valence
electrons to a higher energy-conducting state, thus decreasing the electrical
resistance of the semiconductor. Typically, a photoconductor is placed in
series with a voltage source and load resistor, and the voltage drop across the
load resistor serves as a measure of the power of the beam of radiation.
• A lead sulfide photoconductor is the most widely used transducer for the near-
IR region of the spectrum from 10.000 to 3333 cm-1 (1 to 3 pm). It can be
operated at room temperature. For mid- and far-IR radiation, MCT
photoconductor transducers are used. They must be cooled with liquid
nitrogen (77 K) to minimize thermal noise. The long-wavelength cut off, and
many of the other properties of these transducers, depend on the ratio of the
mercury telluride to cadmium telluride, which can be varied continuously.
• The MCT transducer is faster and more sensitive than the deuterated triglycine
sulfate transducer discussed in the previous section. For this reason, the MCT
transducer also finds widespread use in FTIR spectrometers, particularly those

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 IR spectroscopy.... Dr. Paresh Parekh

requiring fast response times, such as spectrometers interfaced to gas

chromatographs.
Thermal Transducers:
• Thermal transducers, whose responses depend on the heating effect of
radiation, are found in older dispersive spectrometers tor detection of all but
the shortest IR wavelengths.
• With these devices, the radiation is absorbed by a small blackbody and the
resultant temperature rise is measured.
• The radiant power level from a spectrophotometer beam is minute (107 to 109
W), so that the heat capacity of the absorbing element must be as small as
possible if a detectable temperature change is to be produced.
• Under the best of circumstances, temperature changes are continued to a few
thousandths of a kelvin.
• The problem of measuring IR radiation by thermal means is compounded by
thermal noise from the surroundings.
• For this reason, thermal transducers are housed in a vacuum and are carefully
shielded from thermal radiation emitted by other nearby objects.
• To further minimize the effects of extraneous heat sources, the beam from the
source is always chopped.
• In this way, the analyte signal, after transduction, has the frequency of the
chopper and can be separated electronically from extraneous noise signals.
which are ordinarily broad band or vary only slowly with time.
Michelson Interferometer:
• Instead of using a monochromator, the IR radiation after passage through a
sample can be analysed by means of a scanning Michelson interferometer. It
consists of a moving mirror, a fixed mirror and a beam splitter.

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 IR spectroscopy.... Dr. Paresh Parekh

• Radiation from the infrared source B is collimated by a mirror, split into two
beams. One beam is passed through a fixed mirror and another to a moving
mirror.
• After reflection the two beams are recombined at the beam splitter. The two
beams interact at any particular wavelength constructively or destructively
depending on the difference in the optical paths.
• The intensity of the emerging radiation modulates in a sinusoidal manner. In
the case of a broad band infrared source the emerging beam is a complex
mixture of modulation frequencies, which after passing through the sample
compartment is focused onto the detector.
• The detector signal is sampled at very precise intervals during the mirror scan.
Both the sampling rate and mirror velocity are controlled by a reference signal
from the detector produced by the modulation of the beam from a He — Ne
laser. The resulting signal is known as an interferogram which contains all the
information required to reconstruct the spectrum using a mathematical process
known as Fourier Transformation.
Working of Interferometer:
• At position 1, the moving mirror and fixed mirror are equidistant from the
beam splitter. In this situation both light beams travel the same distance and
when they recombine at the beam splitter they are mutually in phase and
constructive interference occurs.
• This is observed as a maximum signal being passed through to the detector.
Let this signal be unity (zero path difference).

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 IR spectroscopy.... Dr. Paresh Parekh

Fig. 7 Michelson Interferometer.

• As the mirror moves away from ZPD (zero position displacement) to 1/4 ,
the signal reaches a minimum value or zero (out of phase). Further on, when
it reaches 1/2  OPD (optical path difference), it again reaches a maximum
value with constructive interference. This pattern continues where a series of
maxima and minima are produced at /4 and /2 to yield an overall sine wave
pattern or more accurately, a cosine wave.
• If a second wavelength is selected now, a similar wave form is generated but
the maxima and minima are separated by a distance equivalent to the new
wavelength.
• In this way a unique cosign wave is generated for each wavelength. The
observed signal at the detector is a summation of all these cosign waves which
gives a maximum at ZPD and rapidly decays to a complex overlapped signal
which continues to decay with increasing distance from ZPD.

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 IR spectroscopy.... Dr. Paresh Parekh

Sample Handling:
• Infrared instrumentation has reached a remarkable degree of standardization
but sample handling itself presents a number of problems. No rugged window
material for cuvettes exist that is transparent and inert over the entire infrared
region.
• Alkali halides such as NaCl are widely used since they are transparent up to
625 cm-1. Cell windows are easily fogged by exposure to moisture and require
frequent polishing.
• Glass and quartz absorb strongly in infrared region, so they cannot be used as
cell containers or optical prisms. Almost invariably in all dispersive
instruments, the sample compartment is positioned before the monochromator
to conserve weak IR energy and reduce stray radiation and optical aberrations.
• AgCl is often used for moist samples but it is not entirely satisfactory. It easily
deforms, is too soft and darkens on exposure to light. For frequencies under
600 cm-1, a polyethylene cell is useful. Characteristics of other useful window
materials are shown in the next table.
Table 1: IR Transmitting Materials
Windows Materials Useful Frequency
NaCl 40000-625 cm-1
KBr 40000-400 cm-1
AgCl 25000-435 cm-1
AgBr 20000-286 cm-1
CaF2 6670-1110 cm-1
BaF2 50000-870 cm-1
CsBr 10000-270 cm-1
ZnSe (Vaccum Deposited) 10000-55 cm-1
Polyethylene 625-33 cm-1

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 IR spectroscopy.... Dr. Paresh Parekh

Gases:
• Gases can be directly scanned in 10 cm path length cells. For trace analysis,
cells of 1.5 - 120 meter are used. Such cells are constructed with folded light
paths and gold surfaced mirrors.
Liquids:
• Liquid samples are usually scanned in their neat form or in solution. The
sample thickness should be 0.001 - 0.05 mm thickness which provides
transmittance of 15-70%.
• For solutions, a 10% carbon tetrachloride(CCl4) is ideal for 4000-1333 cm-1
range. Carbon disulphide (CS2) is useful for 13333 - 650 cm-1. Methylene
chloride, acetonitrile and acetone are the other useful solvents.
• IR cells are constructed with sealed windows which are separated by thin
gaskets copper and lead gaskets which are wetted with mercury. The whole
assembly is securely clamped in a stainless steel holder. As the mercury
penetrates a gasket it expands producing a tight seal.
Polymer film:
• For polymers, resins and amorphous solids the sample is dissolved in a
volatile solvent and a drop of the solution is placed on the window and sealed.
As the solvent evaporates, a thin homogeneous film is deposited which can be
scanned directly. For liquids and polymers, a drop of the solution may be
placed and squeezed between the windows.
Solid:
Mull:
• Powders can be examined as a thin paste or mull. About 5 mg of the sample
is mixed with nujol (a high molecular weight liquid paraffin). Nujol has peaks
around 3030 – 2860 cm-1, ~ 1460 cm-1 and 1374 cm-1.

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 IR spectroscopy.... Dr. Paresh Parekh

• Therefore, no useful information can be obtained in these regions. Hexa

chloro butadine is another mulling agent. It has no CH bonds.
Pellet:
• A solid sample can also be handled by mixing with KBr and pressing at 25000
psi into a small disc of 10 mm diameter and 2mm thickness. Quantitative
analysis can be performed by the pellet technique.
Advantages of FTIR:
1. Only one moving part is involved which is mounted on a frictionless air
bearing.
2. Slits and filters are not needed which saves energy especially in the far IR
region.
3. Near absolute frequency accuracy (better than 0.01cm-1).
4. Same S/N ratio as in a dispersive spectrometer obtained in a fraction of time
(Fellgets advantage).
5. Saves time as many as 32 scans can be done per minute.
6. Single beam spectrum is ratioed against stored background in the memory
which gives the double beam accuracy.
Application of IR:
1. In general IR peaks will occur at the same frequencies for specific groups
except in molecules where steric or electrical effects are predominant. For
example, carbonyl (C=O) stretching vibration is same for acetone or di-n-
hexyl ketone. But it is different for acetic acid (electrical effect) and for
cyclobutane (steric effect). Also IR spectrum cannot distinguish a pure
sample from impure sample. Thus a crude product will show infrared
peaks of all the reactants and side products. Even high molecular weight
chemicals generally give poor spectra.

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 IR spectroscopy.... Dr. Paresh Parekh

2. The progress of a chemical reaction can be followed by drawing an aliquot

and checking the IR spectra for a specific functional group. Chemical
separations also can be followed by the same principle.
Example:
(R)2-CH-OH (R)2-C=O
OH frequency 3570 cm-1 decreases and C=O appears at 1725 cm-1.
3. The most powerful function of IR is in establishing the identity of a sample
by comparison using same medium. The region 1430 — 910 cm-1 contains
many C-C, C-O, C-N stretching vibrations and bending vibrations. This is
known as finger print region. Thus even if similar compounds show similar
spectra, discernible differences can be identified in the finger print region.
4. Identification of functional groups & structure elucidation of organic
compounds.
5. Quantitative analysis of a number of organic compounds.
6. Study of covalent bonds in molecules.
7. Detection of impurities in a compound.
8. Ratio of cis-trans isomers in a mixture of compounds.
9. Shape of symmetry of an inorganic molecule.
10. Study the presence of water in a sample.
11. Measurement of paints and varnishes.
12. Inter molecule and Intra molecule hydrogen bonding can easily identified.
o Hydrogen bonding gives rise to downward frequency shifts.
o Stronger the bonding, greater the absorption shifts towards lower wave
number from normal value.
o Generally, intermolecular hydrogen bonds are sharp and
well defined.

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 IR spectroscopy.... Dr. Paresh Parekh

o Intermolecular hydrogen bonds are concentration dependent. On

dilution, intensities of such bands decreases and finally disappears.

Limitation of IR spectroscopy:
1. Cannot determine the molecular weight of the compound.
2. Does not give information about the relative position of different
functional groups in a molecule.
3. From the single IR spectrum of an unknown substance, it is not possible to
know whether it is pure compound or a mixture of compound.
4. Sample cells are made of halaogen salts which are susceptible to moisture.
5. Gas samples cannot be analyzed as they lack sensitivity.
Reflection Spectroscopy:
• Reflection of radiation is of four types: specular reflection. diffuse reflection.
internal reflection, and attenuated total reflectance (ATR).
• Specular reflection occurs when the reflecting medium is a smooth polished
sur- lace. Here, the angle of reflection is identical to the incident angle of the
radiation. If the surface is made up of an IR absorber, the relative intensity of

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 IR spectroscopy.... Dr. Paresh Parekh

reflection is less for wavelengths that are absorbed than for wave- lengths that
are not.
• Thus. a plot of reflectance R. which is the fraction of the incident radiant
energy reflected, versus wavelength or wavenumber provides a spectrum for
a compound similar in general appearance to a transmission spectrum for the
species.
• Specular reflection spectra find some use for examining and characterizing
the smooth surfaces of solids and coated solids but are not as widely used as
diffuse- and total-reflection spectra.
Diffuse Reflection Spectroscopy:
Introduction:
• Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) is a
technique that collects and analyzes scattered IR energy. It is used for
measurement of fine particles and powders, as well as rough surface (e.g., the

Fig. 8 Diffuse reflection Spectroscopy

interaction of a surfactant with the inner particle, the adsorption of molecules
on the particle surface). Sampling is fast and easy because little or no sample
preparation is required.

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 IR spectroscopy.... Dr. Paresh Parekh

Principle:
• When the IR beam enters the sample, it can either be reflected off the surface
of a particle or be transmitted through a particle. The IR energy reflecting off
the surface is typically lost.
• The IR beam that passes through a particle can either reflect off the next
particle or be transmitted through the next particle.
• This transmission‐reflectance event can occur many times in the sample,
which increases the path length. Finally, such scattered IR energy is collected
by a spherical mirror that is focused onto the detector.
• The detected IR light is partially absorbed by particles of the sample, bringing
the sample information.
• A number of models have been developed to de- scribe in quantitative terms
the intensity of diffuse reflected radiation. The most widely used of these
models was developed by Kubelka and Munk. Fuller and Griftiths in their
discussion of this node! show that the relative reflectance intensity for a
powder f(Rs) is given by
(1 − 𝑅𝑠 )2 𝑘
𝑓(𝑅𝑠 ) = =
2𝑅𝑠 𝑠
• where Rs, is the ratio of the reflected intensity of the sample to that of a non-
absorbing standard. such as finely ground potassium chloride.
• The quantity k is the molar absorption coefficient of the analyte. and s is a
scattering coefficient.
• For a diluted sample, k is related to the molar absorptivity  and the molar
concentration of the analyte c by the relationship.
𝑘 = 2.303𝜀𝑐

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 IR spectroscopy.... Dr. Paresh Parekh

Instrumentation:
• Currently, most manufacturers of FTIR instruments offer adapters that fit in
cell compartments and permit diffuse-reflectance measurements. Figure 9
illustrates one type of adapter. The collimated beam from the interferometer
is directed to an ellipsoidal mirror and then to the sample.

Fig. 9 DRS adaptor in FTIR

• The sample is usually ground and mixed with KBr or KCl as a diluent. The
mixture is then placed in a sample cup 3.4 mm deep and about 10-15 mm in
diameter. A complex combination of reflection, absorption, and scattering
occurs before the beam is directed to the detector.
• To obtain a spectrum with a single-beam instrument, the signal for the sample
is first stored. A reference signal with a good reflector, such as finely ground
KBr or KCI, is then recorded in place of the sample. The ratio of these signals
is then taken to give the reflectance.
Sample Preparation:
• Fill the micro‐cup with the powder (or the mixture of the powder and KBr).
The diffuse reflectance accessory uses a focusing mirror to focus the beam on
the sample surface and collect the IR energy. The micro‐cup needs to be filled
consistently in order to keep the focus.
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 IR spectroscopy.... Dr. Paresh Parekh

• Scratch the sample surface with a piece of abrasive (SiC) paper and then
measuring the particles adhering to the paper.
• Place drops of solution on a substrate. If colloids or powders are dissolved or
suspended in a volatile solvent, you can place a few drops of the solution on
a substrate, and then evaporate the solvent, subsequently analyze the
remaining particles on the substrate.
• It is well known that particle size is a key variable in a transmission
measurement with the pellet method. Large particle will result in the
scattering of the energy, leading to the shift of the spectrum baseline and the
broadening of IR bands. The scenario becomes worse in a diffuse reflectance
measurement, because the infrared light travels in the sample for a long period
and the optics collects a large portion of the distorted energy. It is important
to grind the sample particles to 5 microns or less.
Attenuated Total reflection spectroscopy:
Introduction:
• Attenuated total reflectance (ATR) accessories are especially useful for
obtaining IR spectra of difficult samples that cannot be readily examined by
the normal transmission method. They are suitable for studying thick or highly
absorbing solid and liquid materials, including films, coatings, powders,
threads, adhesives, polymers, and aqueous samples. ATR requires little or no
sample preparation for most samples and is one of the most versatile sampling
techniques.
Principle:
• When a beam of radiation enters from a more-dense (with a higher refractive
index) into a less-dense medium (with a lower refractive index).

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 IR spectroscopy.... Dr. Paresh Parekh

• The fraction of the incident beam reflected increases when the angle of
incidence increases. All incident radiation is completely reflected at the
interface when the angle of incidence is greater than the critical angle (a
function of refractive index).
• The beam penetrates a very short distance beyond the interface and into the
less-dense medium before the complete reflection occurs. This penetration is
called the evanescent wave and typically is at a depth of a few micrometers
(μm).
• Its intensity is reduced (attenuated) by the sample in regions of the IR
spectrum where the sample absorbs. Fig. 10 illustrates the basic ATR
principles.

Fig. 10 Schematic representation of multiple internal reflection effect in (ATR).

Working:
• The sample is normally placed in close contact with a more-dense, high-
refractive-index crystal such as zinc selenide, thallium bromide–thallium
iodide (KRS-5), or germanium.
• The crystal must have high refractive index n2 (higher than that of sample n1)
• The beam enters the crystal at the incidence angle θ higher than critical angle
𝑛
𝜃𝑐 = 𝑎𝑟𝑐 sin 1; under this condition, the beam is totally caught by the crystal,
𝑛2

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 IR spectroscopy.... Dr. Paresh Parekh

i.e. a complete internal reflection occurs and the beam travels in the crystal;
after one or multiple reflections, the beam leaves the crystal and reaches the
detector
• At the crystal-sample interface, the beam actually penetrates a very short
distance (<2 μm) into the sample and the absorption of specific wavelengths
occurs penetration depth depends on the wavelength:
𝜆
𝑑𝑝 =
𝑛 21
2𝜋 [𝑠𝑖𝑛2 𝜃 − ( 1 ) ] ⁄2
𝑛2

• where , is the wavelength in the crystal.  is the angle of incidence, and n1

and n2 are the refractive indexes of the sample and crystal, respectively.
• Note that the effective penetration depth can be changed by changing the
crystal material, the angle of incidence, or both.
• It is possible to obtain a depth profile of a sur- face using ATR spectroscopy.
In practice, a multi- reflection crystal with a 45° angle can accommodate most
routine samples.
Table 2: Different Crystal used in ATR
Kind of Crystal Spectral Range (cm-1) n at 1000 cm-1
Diamond 30000 – 200 2.4
Sapphire 50000-1750 1.74
NaCl 40000-590 1.49
ZnSe 20000-454 2.4
Ge 5500-600 4.0
Si 8300-6600 3.4
TlBr/TlI 20000-250 2.37

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 IR spectroscopy.... Dr. Paresh Parekh

ATR Instrument

• In traditional ATR instruments the sample was clamped against the vertical
face of the crystal. This design has now been replaced by horizontal ATR
stages where the upper surface of the crystal is exposed. ATR accessory kits
can be purchased which can be used to modify existing IR instruments.
• Similarly to FT-IR instruments a background spectrum must be collected; this
is taken from the clean ATR crystal. The background spectrum which is
obtained can be a useful indication of the cleanliness of the ATR crystal; a
line at 100% T should be obtained with no spectral features.
• In order for total internal reflectance to occur there must be good contact
between the sample and crystal surface. Liquid samples can be placed directly
onto the ATR crystal; the whole crystal must be covered.
• Similarly pastes or other viscous substances can be spread onto the crystal. In
the case of solids, these are more readily analyzed on single reflection ATR
instruments which are often made of diamond.
• High quality spectra can be obtained directly from powder samples placed on
the ATR crystal. The amount of sample should entirely cover the crystal and
does not need to be more than a few millimeters thick.
• In order to ensure that there is good contact with the crystal surface the
instrument pressure arm is positioned over the sample and tightened; it may
be necessary to apply greater pressure when analyzing high density polymers
or coatings on metal surfaces, however, the user manual should always be
consulted for optimum operating parameters.

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 IR spectroscopy.... Dr. Paresh Parekh

Requirements for a sample and a crystal:

a. good adherence of the sample to the crystal

b. mechanical strength of the crystal (when the sample is pressed against
the crystal)
c. inertness of the crystal against samples
d. removal of sample residue from the crystal using various solvents.

Advantages of ATR:

1. Simple preparation of sample before measurements.

2. Non-transparent samples can be analyzed
3. Threads, yarns, fabrics, polymers, rubbers and fibers can be studied by
pressing the sample against dense crystal.
4. Pastes, powders, suspension or aqueous solution can also be easily handled.

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