CHAPTER 3

INSTRUMENTATION AND SAMPLE HANDLING TECHNIQUES

OF FT-IR AND FT-RAMAN SPECTROSCOPY

Abstract

The experimental techniques of infrared and Raman

spectroscopy and sample handling techniques are briefly dealt

with. The advantages of FT techniques are also explained.

 CHAPTER 3

INSTRUMENTATION AND SAMPLE HANDLING TECHNIQUES

OF FT-IR AND FT-RAMAN SPECTROSCOPY

3.1 INTRODUCTION

The infrared and Raman spectroscopic techniques are based on different

principles. A change in electric dipole moment is necessary for IR active whereas the

Raman criterion depends on the change in poiarizability during vibration. The intensity

of the infrared and Raman spectra mainly depends on the magnitude of the change in

dipole moment and the poiarizability respectively. The infrared and Raman methods are

used to study the materials existing in various states. The molecular vibrational

frequencies obtained by these methods have been used in the molecular mechanics]

and they yield considerable information about the interatomic forces in varioug

molecules [67].

3.2 INFRARED SPECTROSCOPY

Infrared spectroscopy is one of the most powerful analytical techniques which

offers the possibility of chemical identification. IR technique when coupled with intensity

measurements may be used for quantitative analysis. Infrared has been of tremendous

use to chemists and its currently more popular as compared to other physical techniques

(X-ray diffraction, electron spin resonance, etc.) in the elucidation of the structure of

unknown compounds.
 The infrared radiation refers broadly to that part of the electro magnetic spectrum

which lies between the visible and microwave regions. The infrared region of the

spectrum encompasses radiation with wave numbers ranging from about 12,800 to 10

cm"^ or wavelengths from 0.78 to 1000 jj.m. From instrumentation and application point

of view, the infrared region has been subdivided into near IR region (overtone region),

mid IR region (vibration rotation region) and far IR region (rotation region). The

techniques and the applications of methods based upon the three infrared spectral

regions differ considerably. An infrared spectrum shows downward peaks corresponding

to absorption, plotted against wavelength (A,) or wave number (v). In the infrared

spectrum, apart from the prominent modes of vibrations, there are other vibrations due

to coupling and overtones which may lead to additional bands in the spectrum. The

various bands can be interpreted according to the characteristic functional groups

present in the substance [68].

Infrared absorption, emission and reflection spectra for molecular species can be

rationalized by assuming that all arise from various changes in energy brought about by

transitions of molecules from one vibrational or rotational energy state to another.

Absorption of infrared radiation is thus confirmed largely to molecular species that have

small energy differences between various vibrational and rotational states. In order to

absorb infrared radiation, a molecule must undergo a net change in dipole moment as a

consequence of its vibrational or rotational motion. Only under these circumstances can

be alternating electrical field of the radiation interact with the molecule and course

changes in the amplitude of one of its motions [69,7D].

31
3.2.1 INSTRUMENTATION

a. Introduction

The basic components of an infrared spectrometer are shown in Fig.3.1. A

source provides radiation over the whole range of the infrared spectrum. The

monochromator disperses the light and then selects a narrow wave number

range. The detector measures the energy and transforms it into an electric

signal. This signal is further amplified and registered by a recorder.

Radiation Sample
source Monochromator —• Detector Amplifier
Area -
i
Recorder

Fig,3.1 Block diagram of major components of an infrared spectrometer

Source

Infrared radiation is produced by electrically heating a source, usually a Nernst

filament or a Globar to 1000 - 1800°C. The Nernst filament is fabricated from a

binder and oxides of thorium, cerium, zirconium and yttrium. The Globar is a

small rod of silicon carbide usually 5 cm in length and 0.5 cm in diameter. The

maximum radiation for the Globar occurs in the 5500 - 5000 cm"^ region.

Nichrome wire, carbon arc, rhodium wire and tungsten filament lamp are also

used as light source.

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 In a commercial infrared spectrometer either a nichrome wire or a platinum

filament contained in a ceramic tube is commonly used as infrared source for the

range 4000 - 400 cm'^

0. Monochromator

A monochromator is a means of separating wavelengths of the source radiation.

Prisms and gratings are used for this purpose. A grating or a prism disperses the

radiation from the source into its spectral elements. The monochromators

perform three functions, which are basic to the operation of the instrument.

)^. It disperses the radiation according to its wavenumber components.

)*• It restricts the radiation falling on the detector into a narrow wavenumber

range and

W. It maintains the energy incident on the detector to an approximately

constant level when no sample is present throughout the wave number

range of the instrument [71].

All infrared monochromators use mirror optics. Fortunately, the reflection from

most metallic surfaces is good in the infrared region and consequently

monochromator mirrors are normally worked in glass and finished with a thin

reflecting coating of aluminium.

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d. Thermal detectors

The detector must produce an electrical signal, which is proportional to the

intensity of the incident radiation over the whole spectral range of the instrument.

The most desirable features of the detectors are the closeness with which they

approach the behaviour of a black body, high sensitivity, high speed and

robustness.

The infrared detectors may be selective or non-selective. The selective detectors

are those whose response is markedly dependent upon the wavelength of the

incident radiation. Examples of this type are photocells, photographic plates,

photoconductive ceils and infrared phosphors. The non-selective detectors are

those whose response is directly proportional to incident energy but relatively

independent of wavelength. Common examples include thermocouples,

bolometers and pneumatic cell.

Recent detectors are fabricated from crystals such as lithium niobate, barium

titanate and triglycine sulphate. These crystals are known as pyroelectrics and

take less time than other thermal detector. Hence with these crystals, radiation

can be chopped at a higher rate. However, these are more expensive and not

widely employed.

e. Amplifiers and Recorders

The radiant energy received by the detector is converted into measurable

electrical signal and is amplified by the amplifiers. The amplified signal is

34
 registered by a recorder or a plotter. The recorder is driven with a speed which is

synchronised with that of a monochromator, so that, the pen moving across the

chart, records the transmittance of the sample as a function of the wave number.

3.2.2 SAMPLE HANDLING TECHNIQUES

Sample handling is considered as an important technique in the infrared

spectroscopy. There are various methods of sample preparation to enable almost any

type of sample to be examined.

Some significant problems arise when trying to construct sample containers for

vibrational spectrometry, because every material has some vibrational absorption. What

is done is to use material that has a minimum interference in the regions of interest. The

material of choice for IR spectrometry is a solid potassium bromide plate. Such plates

are used in a number of ways. Polyethylene pellets are used for recording the far IR

spectra.

a. Solids

A sample of a solid of low melting point can be melted on one plate and its

spectrum may be obtained. A solid into small particles and suspend them in a

viscous liquid that is placed in the light beam between KBr or NaCI plates. A

liquid commonly used for this purpose is mineral oil - also called Nujol. The

mixture of the solid particles suspended in the viscous liquid is called a mull.

Another popular method to use for solids is to form an intimate mixture by

35
 grinding the sample together with dry KBr. A measured amount of this finely

ground powder is then pressed under several hundred kgs/cm^ to form a

transparent KBr disk about 1cm in diameter and less than 1mm thick. The KBr

can, however, interact with some groups (such as - NH2) to cause distortion of the

spectrum. In addition, water in the KBr can be hard to eliminate and the water

absorption interferes with -OH and -NH2 bands. A third approach is to deposit the

solid as a film on a single KBr plate by allowing the solvent to evaporate from a

solution of the sample.

b. Liquids

When a liquid is placed in the form of thin film, a complete spectrum of it may be

obtained. A liquid can be spread as a film on an IR transparent plate if it is

concentrated enough and will not evaporate. Otherwise, the liquid., is placed

between two KBr or NaCI plates fixed in a holder and the corresponding spectrum

can be obtained.

Solvents

Solvents of good infrared transparency over a convenient frequency range are

available and the spectra of the sample dissolved in carbon tetrachloride and

carbondisulphide provide the complete range. Chloroform is considered to be an

important solvent and is frequently used because it shows more absorptions

through it is less symmetrical molecule -than carbon tetrachloride and

carbondisulphite.

36
d. Gases

Absorption spectra of gases can be measured in a wide variety of gas cells

ranging from a few centimetres to several metres.

3.3 FOURIER TRANSFORM INFRARED SPECTROSCOPY

The discovery of the fast Fourier transform algorithm and the concurreni

introduction of sophisticated computers permitted the new generation of infrarec

instrumentation, called Fourier transform infrared spectrometers. The Fourier transfomr

infrared spectrographs have replaced the conventional infrared spectrographs. A FT-

infrared spectrometer consists of two parts : (a) an optical system which uses an

interferometer and (b) a dedicated computer which stores data, performs computations

on data and plots the spectra. A schematic diagram of the essential components of a

FT spectrometer based on Michelson interferometer is shown in Fig.3.2. It consists of

two perpendicular mirrors; one of which is a stationary, mirror and other a movable mirror

which can be displaced perpendicularly to the fixed mirror at a constant velocity.

Between these two mirrors is a beam splitter set at 45° from the initial position of the

movable mirror. A parallel beam of radiation from an infrared source is passed to the

mirrors through the beam splitter. The beam splitter reflects about half of the beam to

the fixed mirror which reflects it back to the beam splitter and transmits the other half to

the movable mirror which reflects it back to the beam splitter. The returning beams are

again split and mixed about half going back to source and half passing through the

sample compartment. The composition of the beam splitter depends on the spectral

37
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region of interest. For example, in the mid-infrared region (4000 - 400 cm"^), a beam

splitter of germanium coated on KBr plate (substrate) is often used. Germanium reflects

the radiation while KBr transmits most of the desirable radiation. In the far infrared

region, germanium coated on CSI (800 - 200 cm'^) or germanium coated on Mylar

(polyethylene terephthalate) (650-10 cm"^) are used as beam splitters. A thin film of the

beam splitter material is coated on an optically flat substrate.

The return beams from both the mirrors along the same path length as their

incident path are recombined into a single beam at the beam splitter. The path length of

one of the return beams is changed in order to create an overall phase difference to

cause an interference pattern. The recombined radiation is then directed through the

sample and focussed on to the detector. The detector measures the amount of energy

at discrete inten/als mirror movement.

The movable mirror can be moved in a range of say ± 5 cm. The mirror velocities

from 0.05 to 5 cm s"^ are used. Interferometric instruments need detectors with response

times short enough to detect and transmit rapid energy changes to the recorder. The

detector used in conjunction with rapid scanning interferometers in the mid-infrared

region at room temperature is triglycine sulfate with KBr windows as pyroelectric

bolometer. It has a high response time. Other most common detectors used such as

thermocouples, bolometers and Golay detectors have short response time.

The design of the Michelson interferometer is such as to make measurement in

any infrared region possible by simply changing the beam splitter and the detector.

38
3.4 ADVANTAGES OF FT-TECHNIQUE

The greater advantage of FT technique is its speed. The entire spectrum is

contained in the interprogram and can be recorded within few seconds using powerful

computers. In FT method, all the source energy passes through the instrument and the

resolving power is constant over the entire spectrum. The signal to noise ratio is also

improved [72]. The smoothening of peaks and the vertical and horizontal expansion of

selective region is also possible.

3.5 RAMAN SPECTROSCOPY

The Raman spectroscopy is made sophisticated with the advent of gas lasers and

computers. The advantages of lasers are their high intensity, high monochromaticity,

narrow band width, high resolution and coherence. From the time of Invention of Raman

effect, both infrared and Raman spectra of chemical compounds have been effectively

used for the determination of molecular structure and also for the quick identification of

the presence of the characteristic group frequencies in the compound as discussed in

the literature [73-75]. In order that for a molecular vibration to be Raman active there

must be a change in the polarizability of the molecule.

An important advantage of Raman spectra over infrared lies in the fact that water

does not cause interference; indeed, Raman spectra can be obtained from aqueous

solutions. In addition, glass or quartz cells can be employed, thus avoiding the

inconvenience of working with sodium chloride or other atmospherically unstable window

39
materials. Raman spectra ^f® acquired by irradiating a sample with a powerful laser

source of visible or near-infraf^ed monochromatic radiation.

3.5.1 INSTRUMENTATION

In Raman spectromet^'' the sample is in'adiated with monochromatic light and the

scattered light is observed at f'Qht angles to the incident radiation. Raman spectrometer

consists of a source samP'® holder, a monochromator and a detector. Fig.3.3

represents schematic diagrafi^ of a Raman spectrometer.

Light Source

yr y
Sample Monochromator Detector

^r y Filter
Light Source

Fig.3.3 Sche'^^t'c diagram for a Raman spectrometer

(a) Source

The sources used in modern Raman spectroscopy are nearly always lasers

because their high intensity is necessary to produce Raman scattering of

sufficient intensity to b® rneasured with a reasonable signal-to-noise ratio. Five of

the most common las^f^ used for Raman spectroscopy are listed below :

40
 Type source Wave length (nm)

Argon ion 488.0 or 514.5

Krypton ion 530.9 or 647.1

Helium / Neon 632.8

Diode laser 782 or 830

mrYAG 1064

Because the intensity of Raman scattering varies as the fourth power of the

frequency, argon and krypton ion sources that emit in the blue and green region

of the spectrum have an advantage over the other sources shown in the table.

The last two sources in the table, which emit near-infrared radiation, are finding

more and more use as excitation sources. Near-infrared sources have two major

advantages over shorter wavelength lasers. The first is that they can be operated

at much higher power (upto 50 W) without causing photodecomposition of the

sample. The second is that they are not energetic enough to populate a

significant number of fluorescence producing excited electronic energy states in

most molecules. Consequently, fluorescence is generally much less intense or

nonexistent with these lasers. The Nd/YAG line at 1064 nm is particularly

effective in eliminating fluorescence. The two lines of the diode array laser at 782

and 830 nm also markedly reduce fluorescence in most cases.

41
(b) Sample handling techniques

Sample handling for Raman spectroscopic measurement is simpler than for

infrared spectroscopy because glass can be used for windows, lenses and other

optical components instead of the more fragile and atmospherically less stable

crystalline halides. In addition, the laser source is easily focussed on a small

sample area and the emitted radiation efficiently focussed on a slit. Consequently,

very small samples can be investigated. In fact, a common sample holder for

nonabsorbing liquid samples is an ordinary glasslnelting - point capillary.

Liquid samples

The spectrum of a liquid can be recorded as neat or in solution. Ordinarily about

0.3 ml of a liquid may be required. The sample could be taken in glass or silica

containers or capillaries. The spectra can be measured directly from the reaction

vessel. Water is a good solvent for recording the Raman spectra. Water absorbs

strongly in the infrared but it is a poor Raman scatterer. Raman spectroscopy is

thus a valuable tool for studying water soluble biological materials.

Solid samples

The Raman spectra of solids as polycrystalline material or as a single crystal can

be recorded. No medium such as null, KBr or solvent is needed. A few milligrams

of the solid samples are required. Solid can be packed into a capillary tube as a

powder. The crystal can be mounted in a goniometer on a glass or silica fiber.

42
 The spectra can be measured for different orientations of the crystal. For single

crystals, the Raman spectrum varies depending on the direction of the crystal

axis, when polarized light is used as incident radiation. Raman spectra of

adsorbed species can be recorded at different temperatures and pressures.

Gas Samples

The Raman spectra of gases are generally weaker than those of liquids or solids

and hence may require cells of larger path length. The gas may be filled in a

glass or silica tube of 1 to 2 cm diameter. If the resolving power of the instrument

is good and if the molecule has sufficiently low moment of inertia, the rotational

fine structure may be observed on either side of the Rayleigh line. Generally a

broad band contour may be observed.

In this study the spectral data were recorded on BRUKER IFS 66V, FTIR with

FRA 106 FT - Raman spectrophotometer and the block diagram of the instrument

is shown in Fig. 3.4.

(c) Filter

Liquid filters are placed between the source and the sample tube. Different filters

are used for different excitation radiation. Filters made of quartz glass or nickel

oxide glass is used for getting monochromatic radiations. The functions of filters

are:

43
 >i^ To isolate a single exciting line

,¥ To remove high energy radiation that might cause photo decomposition or

fluorescence.

'^ To remove the continuous spectrum in the region occupied by the Raman

lines.

(d) Monochromators

In the monochromator, both lenses and miri-ors have been used. Most Raman

Spectrometers use a diffraction grating as the dispersing element. A grating

instrument has a wide aperture and a medium dispersion. A double

monochromator Is used to avoid stray light problem from scattering by dust

particles in the sample.

(e) Detectors

Raman spectrum can be photographed with an ordinary spectrograph. Basically

there are two different ways to detect and record Raman lines. The easiest way Is

to gather the scattered light emerging through a glass window at the end of the

Raman sample tube. It is passed through a prism or grating and then focussed on

a photographic plate. The plate is then developed and both the line frequencies

and intensities can be measured using external equipment. Modern

spectrometers have photomultiplier tubes for direct measurement and automatic

scanning of a spectrum. The spectrum produced by the monochromator is

44
 passed through a slit which allows a narrow wavelength region to pass through

which is focussed on to a photomultiplier type detector. This detector employs an

amplifier and a recorder. It directly provides the Raman spectrum.

3.5.2 Interpretation of spectra

The assignments of fundamental modes of vibrations and interpretation of the

spectra have been carried out by following empirical correlation of group frequencies,

infrared and Raman selection rules, the magnitude and relative intensities of the spectra

[76-78]. In the case of polyatomic molecules, the interpretation of spectra is highly

complex due to the appearance of combination and overtone bands.

45