3.1.1. Introduction Infrared (IR) spectroscopy deals with the infrared region (12800 -10cm") of electromagnetic spectrum. The term infra means beyond, thus infrared means beyond red. It covers. range of techniques, the most common being a form of absorption spectroscopy. This spectroscopic technique is used for identifying compounds and determining the sample compesition. Infrared spectrophotometer is a common laboratory instrument used for this technique. ‘The infrared region in electromagnetic spectrum is divided into the following three regions named for their relation with the visible spectrum (figure 3.1): 1) The far-infrared, approximately 400 -10em"' (1000-30 m), lies adjacent to the microwave region, has low energy and is used for rotational spectroscopy. 2) The mid-infrared, approximately 4000 -400cm™' (30-2.5 m) is used to study the fundamental vibrations and associated rotational -vibrational structure. This region has wavelengths between 3x10-* and 3<10°em. 3) The near- infrared, approximately 14000-4000cm* (2.5-0.8 m) has higher energy and can excite overtone or harmonic vibrations, 2 (em) Alem) 2 (um | (Wavenumber) | Energy (E) Visite N © | 78% 10%t03% 104 [251008 | 14.0001 4.000 | 10-87Kcavmole | (@.000078-0.0003) M VY] sxto*to3%10° | 301025 | 400010400 | 1-10Kealmoe Invrared a] 10.0003-0.003) F a | 3*10%3% 10% ]1000030} 400010 | 0.1-1Kealmote 1 | @ocs-0.03) Microwave pm = 10°%m Figure 2.1: IR Regions of the Electromagnetic Spectrum IR spectra are mostly reported in jum; however, V_ (nu bar or wavenumber) is another currently preferred unit. Organic molecules absorb the IR radiation and convert them into energy of molecular vibrations. In IR spectroscopy, an organic molecule is exposed to IR radiation, and absorption occurs when the radiant energy matches a specific molecular vibration energy. 3.1.2. Principle Infrared spectroscopy works on the principle that all molecules vibrate and absorb energy in the infrared region. Most ofthe vibrational absorption states correspond to 2.5. -25ym (4000-400cm") wavelength. The vibrational frequency (v) in a two atomic systom containing two masses (m , and m.) (figure 3.2) is related to the force constant (k) and reduced mass (1) by the following equation: mm, m, +m, va | wim p= 2a Ve An IR spectrum represents transmission versus wave number (cm), Le., frequency () divided by the speed of light. Absorption occurs only at those frequencies at which higher ‘vibrational states can be reached. Ifa molecule absorbs energy, the signal at this frequency decreases and forms a peak in the spectrum, Oru) «m) w (mw) Figure 2.2: Atomic System Consisting of Two Masses (ma and m,)‘As per the formula, larger the force constant (k) of the bond between two atoms, higher is the vibrational frequency. Thus, indicating that a C =C bond will absorb at a higher frequency than a C —C bond, forming a peak at 1600cm “ and 1000cm" respectively. If lighter atoms will be involved in the vibration, the frequency will be higher. The stretching vibrations of CH bond can be found in the 3000crH region of IR spectrum. 3.1.2.1. Selection Rule Given below are the selection rules for IR spectroscopy: 1) Absorption of Correct Wavelength of Radiation (Matching of Frequency): When a molecule’s natural vibration frequency matches with the frequency of incident radiation, it will absorb the radiation (ie., anet transfe _ r of energy occurs, and changes the amplitude of molecular vibration). Natural frequency of HCL molecule is 8.7 x 10 "Hz (vib/sec) or 2890cm"'. When HCI sample is exposed to IR radiation, the transmitted radiation is analysed and itis observed that parto this, radiation having the same frequency (8.7 x 10 '“Hz) is absorbed and the remaining is transmitted to give the characteristic value of HCL 2) Dipole Moment: When the change in the vibrational state of a molecule is related to the change in its dipole moment, it absorbs IR radiation. A heteronuclear diatomic molecule consists of two different atoms having different electron withdrawing capacity. The electron density shifts towards the more electronegative atom, and such molecule possesses an electric dipo Ie moment and is said to be polar. Dipole ‘moment arises due to asymmetrical partial charge distribution, fy 5 weqxr Where, 11 = Dipole moment q= Magnitude of charge. Distance between charges. 1.602 x 10°C But atomic charge is q = € b=qxexr Here charge is measured in Coulomb and distance in meters: so, ST unit of is Coulomb meter (ie., Cm ). But for convenience 11 is often given in unit Debye (ID = 3.336 x 10 “cx. IF HCI has dipole moment of 1.83D bond length and r is 92pm: naqvexr 041 This value indicates that charge in HCI molecule is asymmetrically distributed ina manner that Cl atom effectively gains 0.41 of an eleciron and H atom loses 0.41 of an electron. The total dipole moment ina polyatomic molecule isthe vector sum of the dipole moment of the individual bond. _No dipole moment exists in a symmetrical molecule (like CC1,), however the C—CI bond is polar.3.1.2.2. Overtones Oxertone bands (harmonics) appear at integer multiples of fundamental vibrations, thus the s trong absorptions at 800em and 1750cm give rise to weaker absorptions at 1600cm™' and 3500cm ~', respect ively. Two frequencies interact and give beats, (combination or difference frequ encies); thus, absorptions at x cm and yem* interact and produce two weaker beat frequencies at x yem! On absorbing IR radiation, transitions from the ground state (V — 0) to the second excited state (V = 2) give rise to weak bands, termed overtones. If all the vibrational bands are equally spaced (which actually are not), the energy of first overtone is given by: {5.1 (2 | 24— hv-[ Or hv =2 hv 2 2 On adding reagent, the chemical shift of each proton or proton group of the sample molecule changes and the extent of this induced shift is measured. The resultant induced shift is plotted against the ratio of shift reagent to substrate to give a straight line at low ratio values. Structural information for each proton group in a molecule can be obtained from these plots. They may be used to resolve overlapping signals from different proton groups ina molecule, or canbe used in more quantita tive studies to provide information on molecular configuration. For example , chiral | anthanide shift reagents are used for quantitative estimation of enantiomer mixtures. ‘The actual IR spectrum becomes quite complicated due to the _ presence of additional bands at various wavelengths. For example, additional bands can appear at 1/2. 1/3. of the wavelength (or two times, three times,..... the frequency) of the fundamental absorption bands; such bands are termed overtones. These are present in the spectra of carbonyl co mpounds, in the range 3200 -3500cm''. This value is two times the characteristic absorption frequency due to C=O stretching vibrations. ple) a4 3.2.1. Introduction Infrared spectroscopy relies on the theory that molecules ab sorb specific frequencies that are characteristic of their structure. These absorptions are resonant frequencies, as the frequency of absorbed radiation matches the frequency of the vibrating bond or ‘group. The eneegies are determined by the shape of molecular potential energy susfaces, the masses of atoms, and the associated vibronic coupling, Inthe IR spectroscopy (region 2.5151), the absorbed energy causes major changes in the vibrational energy that depends on the following factors: 1) Masses of the atoms in the molecule, 2) Bond strengths, and 3) Arrangement of atoms in the molecule. No two compounds, except the enantiomers, can have similar IR spectra. 3.2.2. Fundamental Modes of Vibrations in Polyatomic Molecules The molecular atoms are not tightly held. A molecule appears to be consisting of different sized balls (atoms) tied with springs (chemical bonds) of variable strengths. On passing IR light through the sample, the vibrational and rotational energies of the molecules increase.3.2.2. Fundamental Modes of Vibrations in Polyatomic Molecules ‘The molecular atoms are not tighily held. A molecule appears to be consisting of different sized balls (atoms) tied with springs (chemical bonds) of variable strengths. On passing IR light through the sample, the vibrational and rotat _ional energies of the molecules increase. Fundamental vibrations are of the following two types: 1) Stretching Vibrations: In this type, the distance between the two atoms increases or decreases, however, keeping the atoms in the same bond axis. Stretching vibrations are of the following two types: i) Symmetric Stretching Vibrations: In this type, the movement of atoms with respect to a particular atom in a molecule is in the same direction. il) Asymmetric Stretching Vibrations: In this type, one atom approaches an d the other atom moves apart from the central atom. 2) Bending or Deformation Vibrations : In this type. the positions of atoms change with respect to the original bond axis. The stretching absorptions of a bond appear at higher frequencies (.e., higher energy) than tie bending absorptions of the same bond. Bending vibrations are of the following four types: i) Scissoring: In this type, two atoms approach each other. ii) In this type, the movement of atoms is in the same direction. au) in this type, {Wo atoms move up and down the plane with respect to the central atom iv) Twisting: In this type, one atom moves up the plane and the other moves down with respect to the central atom, In bending vibrations, the bond lengths change if required to do so by the centre of gravity resisting displacement. Bending vibrations describe two dimensional motions, thus there is 2n-5 bending vibration for non -cyclic and linear molecules. These vibrations appear at lower frequencies than the stretching vibrations (appear at h igher frequencies). Since the force constants of bending vibrations are also less than those of the stretching vibrations, the former are more sensitive to environmental conditions. Ina polyatomic molecule, the same bond can perform stretching and bendin 8 vibrations simultaneously. YT © @ Figure 3.8: Stretching Vibrations Symmetric stretching vibration of AB, molecule symmetric stretching vibration of AB. molecule symmetric stretching vibration of AB,malecule symmetric stretching vibration of AB, molecule The two types of stretching vibrations, ‘e., symmetric and asymmetric, are denoted by ‘v’. The symmetric and asymmetric stretching vibrations of AB» molecule are illustrated by the figure 3.3 (a) and (b); while th e symmetric and asymmetric stretching vibrations of ABs molecule are represented in figure 3.3 (0) and (d). The ‘most important bending vibrations are illustrated in figure 3.4 try yy? Figure 3.4: Bending Vibrations of AB, and AB Molecules. The in-plane deformation vibrations -(a) Scissoring and (b) Rocking Vibrations of AB, Molecule; The out-o- plane deformation vibrations - (c) Twisting and (d) Wazging Vibrations of ABs ‘Molecule; (@) Symmetric and (f) Asymmetric Vibrations of AB; Molecule. Bending vibrations are of the following two types: ').Incplane deformation vibrations, and ii) Out-of- plane deformation vibrations.The in-plane deformation vibrations include scissoring [figure 3.4 (a)] and rocking vibrations [figure 3.4 (b)]; andthe out-of-plane deformation vibrations include twisting [ figure 3.4 (0)] and wagging vibration [ figure 3.4 (@)]. This may also comprise symmetric [ figure 3.4 (e)] and asymmetric [ figure 3.4 (f)] vibrations. ‘Water is atriatomic non -linear molecule with 3x3 -6 or 3(8n-6) normal modes of vibrations, which can be calculated by applyinghe following two primary forces: 4) The force acting against stretching or shortening of O-H bond, and ii) The force acting against the bending of H-O-H molecule. ‘These forces are applied to the water molecule and the nature of three normal modes of vibration of water is determined with the help of Herzberg method. The normal modes of vibrations of water determined by these calculations are shown in met UA ANY A Figure 3.5: Normal Modes of Vibration of Water Molecule In figure 3.5, v, is the symmetric siretching move, v, is the in -plane deformation (scissoring) vibration, and v, is the asymmetric stretching mode. The three vibrations are infrared active. The stretching vibrations (v, and v3) appear at 3652 and 3756cm'', whereas the in -plane deformation vibration (~ vz) appears at 1515em in the IR spectrum of water. Carbon dioxide isa linear triatomic molecule with 3x3 —5 or 4(8n-5) modes of vibrations, which are shown in figure 3.6 as calculated with Herzberg method, o-e+0 p—t—p O—@—O O++@—O> Figure 2.6: Normal Modes of Vibration of Carbon Diaxide Molecule In figure 3.6, v, is the symmetrical stretching vibration, which does not appear in the infrared spectrum (i.e, its inactive) as it produces no change in the dipole moment of the molecule. The vz and vs are in -plane deformation vibrations and appear perpendicularly to the surface of page. These two kinds of vibrations occur independently of each other, but have similar frequencies because the frequency cannot be altered on turning the plane of vibrations. Thus.. the deformation vibrations (v2 and vs) of CO » are degenerate and appear at 666cm “' region in the infrared spectrum. The v4 is asymmetrical stretching vibration and appears in the infrared spectrum in 2350em"' region. The number of modes of vibrations in polyatomic molecules is different from those calculated theoretically due to the following reasons 1) Theovertones (multiples of a given frequency) and combination of tones (sum of two other vibrations) increase the number of modes of vibrations. 2) Some other phenomenon may reduce the number of bands ‘While determining the number of modes of vibrations in the IR spectrum, the following experimental limitations are observed 1) Vibrations not falling in the IR region do not appear in the IR spectrum. 2) Weak vibrational bands are not observed in the IR spectrum 3) The vibrational bands with same or slightly different frequencies overtap each oth er and are observed as a single band in the IR spectrum. 4) Some vibrational bands may degenerate and appear at the same place in IR spectrum.5) No band appears in the IR spectrum of a molecule if no change occurs in its dipole ‘momeat. 3.2.3. Translational Energy Translational energy and the uniform velocity of a molecule are associated. This motion is described with respect to the molecule’s centre of mass. The classical energy due to ‘translational motion is given by: elim? a) 2 ‘Where, E, = translational energy of molecular mass (m) moving with velocity (v) with respect to the centre of mass (m). A molecule moves freely in three perpendicular directions (Le, x, and z) due to translational motion, thus indicating that it has three degrees of freedom . As per the quantum mechanical equations of translational motion of an isolated molecule of mass M ina rectangular box of dimensions ax bx , the translational energy value is given by (2) {3 +{%2) ] @ a) b Le vo “8M | ‘Where. n = integer values. Continuous ranges of translational energies are available as the number of translational energy levels is large and the difference between them is small 3.2.4. Rotational Frequencies Absorption occurs in the IR region due to changes in the vibrational and rotational levels When radiations of less than 100em ~ frequency are absorbed, molecular rotation occurs in the substance. As this absorption is quantized, discrete lines appear in the spectrum due to molecular rotation. Along with a single change in vibrational energy, a large number of ‘changes occur in the rotational energy; thus, vibrational spectra appear as vibrational rotational changes. On passing IR light through a sample, the molecule’ vibrational rotational energies increase. The three different ways in which molecules can store ‘energy as a result of motion of atoms in anon -lincar triatomic molecule are shown in the figure 3.7. J Translational Zs Rotational ee fe Figure 3.7: Three Different Ways in Which Molecules Can Store Energy ‘as a Result of Motion of Atoms in aNon-Liner Triatomic Malecule. Rotational frequencies are the result of rotation of a molecule about an axis through the centre of gravity. This energy is associated with the overall rotation of the molecule with the atoms considered as fixed point ma _sses. As per the classical theory, the rotational energy value is given by: )Where, I = Moment of inertia. © = Angular velocity of the rotating molecule. However, the quantum mechanical formula for rotatio nal energy of asimple linear molecule is given by: @ Where, I = Moment of inertia of a simple linear molecule. J = 0 ora positive integer (the rotational quantum number) Each rotational level has a (2J + 1) fold degeneracy. Ina monoatomic molecule only one rotational degree of freedomexists. But a nonlinear trior poly-etomic molecule rotates about the three perpendicular axes passing through the centre of gravity, thus, indicating that it has three rotatial degrees of freedom. 3.2.5. Vibrational Energy Vibrational energy and the oscillation of atoms of a molecule (considered as point masses) about equilibrium positions are associated. This energy canbe tr _eatedona {quantum mechanical basis. ‘The vibrational energy of a molecule is given by: Where, v = Vibrational frequency O ora positive integer (the vibrational quantum number) Non-Linear molecules ( eg, HO, NO », and CH ,) have 3n-6 vibrational degrees of freedom; while the Ii sar molecules ( €g CO; C aH, andl) have 3n-5 vibrational degeees of freedom. Vibrational frequency or wave number is influenced by the bond strength and reduced mess. With increase in bond strength or decrease in the reduced mass, the value of vibrational frequency increases. ‘The C=C stretching gets absorbed at a frequency higher than the C_—C stretching, since the bond strength (value of k) of double bond is higher than that of the single bond, 3.2.6. Factors Affecting Vibrations Discussed below are the factors under the effect of which the vibrational frequencies of some groups shift from their normal values: 1) Coupled Interactions: Two bond oscil lators sharing a common atom never behave as individual oscillators , except when they exhibit different oscillation frequencies. This behaviour is the result of mechanical coupling interaction between the oscillators. For example, CO, consists of two C=O bonds (O=C=0) with a common carbon atom. Thus, CO 2 has two fundamental stretching vibrations, of Which one is asymmetrical and the other is symmetrical stretching vibration. The symmetrical stretching vibration mode consists of an in-phase stretching or contracting of the C to © bond. This absozption occurs at a wavelength longer than the wavelength for C=O group in aliphatic ketones. This mode also does not alter the molecule’s dipole moment; hence is infrared inactive, but can be observe din the Raman spectrum near 1340cm 7 region. In asymmetrical stretching vibration mode, the two C to O bonds stretch out of plane; and one C=O bond stretches as the other contracts. This mode alters the molecule’s dipole moment, and hence is infrared active. This absorption occurs at a wavelength shorter or a frequency higher (2350cm'') than that for a C=O (carbonyl) group in aliphatic ketones. This difference in C=O absorption frequencies in CO, molecule is due to strong ‘mechanical coupling or interaction. show ‘The two ketonic carbonyl groups separated by one or more carbon ator normal carbonyl absorptions near 1715cm_~ region because appreciable coupling has been prevented by the intervening carbon atom(s)2) Labelling of symmetric or asymmetric vibrations is done with reference to the axis of symmetry about which if molecule is rotated, an identical view is presented more than once in a complete rotation. The vibrational mode is labelled as symmetric if rotation about this axis does not alter the natur e of vibration, while if itis altered the vibrational mode is labelled as asymmetric. The modes are either parallel or perpendicular depending on whether the change in dipole moment is along the axis of symmetry or perpendicular to it. Modes are numbered 5 v,, V2, V3, inorder of decreasing frequency within each symmetry group, starting from the symmetric ‘mode of vibration. Coupling also accounts fort wo N-H stretching bands in 3497 -3077cm" region in primary amine and primary amide spectra, for two C=O stretching bands in 1818- 1720cm' region in carboxylic anhydride and imide spectra, and for two C -H stretching bands in 3000 -2760cm' region for methylene and methyl groups. Characteristic group frequency bands involve coupled vibrations, The important requirements for effective coupling interactions are: i) The vibrations should be of the same symmetry species for the interactions to ii) There should be a common atom between the groups for strong coupling between stretching vibrations. i), Maximum interaction occurs when the coupled groups individually absorb near the same frequency. iv) Coupling between bending and stretching vibrations occurs when stretching bond forms one side of the changing angle. v) Acommon bond is required for the coupling of bending vibrations. vi) Separation of groups by one or more carbon atoms and/or mutually perpendicular vibrations causes no coupling, Hydrogen Bonding: This gives rise to downward frequency shifts. Stronger the hydrogen bonding, greater is the absorption shift. from the normal value towards the lower wave number. With the help of infrared technique, the two types of hydrogen bonds can be distinguished. The inter-molecular hydrogen bonds give rise to broad bands, while the intra-molecular hydrogen bonds give tise to sharp and well-defined bands. Inter-molecular hydrogen bonds depend upon concentration. The intensities of such bands decrease and ultimately disappear on dilution. Intra -molecular hydrogen bonds do not depend on concentration. The frequency difference between free and associated molecules in intra -molecular hydrogen bonding is smaller than that in inter-molecular hydrogen bonding, wolecular hydrogen bonds depend upon concentration, The intensities of bands decrease ard ultimately disappear on dilution, Intra-molecular hydrogen bonds do not depend an concentration, The frequency difference between Free and associated molecules in intra -molecular hydrogen bonding is smaller than that in {nter- molecular hydrogen bonding, ‘Non-associating solvents (eg, CS,,CHC1,, and CCl, are most commonly used because solvenis, lke benzene, acetone, etc, highly 4nfluence the -H and N -H ‘compounds. The electronegativity of nitrogen atom is less chan thar of oxygen atom, ths the hydrogen bonding in amines is weaker than that in aleobols al the frequency shifs in amines are loss drastic For example, amines show N-H stretching at 2500cm “region in dilute solutions, while absorption in condensed phase spectra occurs at 3300cm “region. Alcohols with intermolecular hydrogen bonding are absorbed between 3400 -3200em" region, hile O- Hy in fre aleohol absorbs near 3600em "region ‘The hydrogen bonding in enols and cholates is very strong and absorption due to H stretching oceurs at very low values. As these bonds are not breken on dilution \with an inert solvent, free O-H streicing is not observed at low concentrations. This is because the bonded ¢ is stabilised hy resonance, Consider acetyl acetone.3) ‘The O-H group involved in chelation gives rise to broad absorptions between 3000 and 2500cm * region. The vCO absorption in enolic and ketonic for ms occurs at 1630em"' and 1725cm' region, respectively . The quantities of enolie and ketonic forms can be determined from the intensities of two peaks. Fermi Resonance: Coupling of two fundamental vibrational modes give rise to two new modes of vibration having higher and lower frequencies than that observed in the absence of interaction. Interactions that may occur between fundamental vibrations and overtones or combination tone vibrations are known as Fermi resonance, For an isolated C -H bond only one C -H stretching vibration takes place. The C -H. stretching vibrations in CH. groups combine together to exhibit two coupled vibrations (asymmetric and symmetric) of different frequencies. The vibrational frequencies of C -H coupled vibrations of CH_ 3 groups will be different than CH 2 groups, and thus the detection of all the four CH stretching vibrations in the high resolution IR spectra of the compounds having CH. and CH, groups becomes easy. A.C-H stretching absorption can be detected from its position (around 2925 cm’') in the IR spectra. However, atleast three of these C_ —H stretching bands (in the same spectra) due t0 CH » and CH groups, eg., in the spectrum of propionic anhydride, should be visible. Vibrational coupling occurs between two bonds (close inth ¢ molecule) vibrating individually at the same frequency. The coupling vibrations may be fundamentals or there may be a coupling of a fundamental vibration with the overtone of some other vibration (this is called Fermi resonance). This type of coupling al so accounts for wo N-H stretching bands in the spectra of primary amines and amides For strong vibrational coupling between stretching vibrations, presence of a common atom between the two groups is necessary. This type of coupling is seen in acid anhydrides (R-CO-O-CO-R), in which two C—O stretching absorptions takes place with a separation of 60cm ~'. Coupling occurs between two C =O groups indirectly linked via O. This interaction is effective due to a slight double bo nd character in the (C=0}-0 (carbonyl-oxygen) bonds arising due to resonance. The system becomes, coplanar due to resonance. 9° g 9 f i fab teh AS A Ye Figure 3. ‘easonance Forms of Anhydride (C=0 stretching absorption bands for acyclic saturated acid anhydrides occur at 1850cm' region due to asymmetric and symmetric stretching. The high frequency band is more intense in acyclic anhydrides, while the lower frequency band is more intense in cyclic anh ydrides. Hence, the acyclic and cyclic anhydrides can be easily differentiated. In conjuga ted anhydrides, a decrease in C=O stretching is observed due to resonance. The acid anhydrides exhibit C-O stretching vibration as one or two bands near 1300-1050cem ' region. Fermi resonance isan apparent splitting of a fundamental, such as C=O stretching into two bands. It has its 0 rigin in the sharing of intensity between the fundamental and an overtone or combination tone of almost similar frequency. Fermi resonance can also be explained with the help of the absorption pattern of COz, The symmetrical stretching band of CO; appears in the Raman spectrum at 1340cm"' region. Two bands are observed at 1286cm * and 1388cm " regions. Splitting is caused by the coupling between the fundamental C =0 stretching vibration near 1340cm ~! region and first overtone of the be nding vibration. The fundamental bending vibration occurs in 666cm' region and the first overtone occurs near 1334em ' region Fermi resonance commonly occuts in the IR and Raman spectra. For Fermi resonance to occur: 4) The vibrational levels should be of same symmetry species, and ii) The interacting gr oups should be in the molecule so that mechanical coupling can take place.4) Electronic Effects: Let us assume a saturated aliphatic ketone, Be» acetone (CH3COCH,), in which =O stretching absorption occurs at 1715 "This absorption frequency changes due to the changes in the environment of carbonyl group (C=0) The vibrational frequency of absorption is increased by a halogen on a carbon atom a: to the ketone functional gr oup. For example, o-chloroacetone (CH,COCH,C)) gives C=O absorption in 1725em’' region . This halogen effect can be seen when C-X (X= halogen) bond becomes coplanar with the C=O bond. For example, a,<- dichloroacetone (CICH;COCH.C!) shows C=O absorption in 1725cm’' region (just asin CH sCOCH,C)); but the 0,0” dichloroacetone (CICH ,COCH,C!) shows twice the effect and absorbs at 1740cm ‘ region. Adding a halogen atom and an electronegative atom causes inductive effect, which either shortens or strengthens the band. As a result, the force constant increases along With the increase in frequency or wave number of absorption. On attaching an alkyl gtoup at c-position of C=O group, a +I effect is produced and the wave number of absorption is decreased (as force _ constant decreases as a result of lengthening or weakening of bond). For example, the C=O stretching absorption of HCHO and CHsCHO occurs at 1735em' and 1730cm region, respectively. ‘The C=O group of acetone (CH sCOCH,) is lined by two ~CHs groups. Thus two +1 ‘methyl groups weaken the C=0 bond strength than that in acetaldehyde (CH_ ;CHO) in which only one ~CH; group is present. Hence, acetone C=O absorption occurs at ower frequency (1715em !) and acetaldehyde C=O absorption occurs at higher frequency (1730cm"). The aldehydes in comparison to ketones absorb at higher wave number because of C=O stretching vibrations. 3. INSTRUMENTATION 3.3.1. Introduction ‘The usual optical materials (glass or quartz) absorb strongly in the IR region, and thus the apparatus for mea suring IR spectra is different from that for the visible and UV regions. ‘The main components of an IR spectrometer are: 1) Sources of radiation, 2) Monochromators, 3) Sample cells, and 4) Detectors.IR spectrophotometers are of two types: 1) Dispersive spectrophotometewith monochromator single beamIR spectrophotomete}, 2) Fourier Transform Infrared Spectrometer (FTIR) 3.3.2. Sources of Radiation The IR spectrometer requires a source of radiant energy for isolating narrow frequency bands. The IR radiation emitted by the source should be steady, of intensity sufficient for detection, and should extend over the desired wavelengths, Infrared sources are hot bodies that emit continuously throughout the IR region, and which approx imate a black body radiator in their emission properties. An incandescent solid is chosen as a source of IR radiation so that its emission closely approaches that of a black body radiator . This solid is electrically heated at 1200. - 1500°C temperatu re. ‘The following sources can be used as a source of IR radiation: 1) Nernst Glower: It consists of a rod or hollow tube (2cm long and Imm in diameter) ‘made by sintering a mixture of cer ium, zitconium, thorium and ytt rium oxides. It is heated between 10001800°C temperature. It provides maximum radiation at 7100 crit! region 2) Globar: It isa silicon carbide rod (Sem long and 0.5cm in diameter) which is also electrically heated between 1300 -1700°C temperature and has a positive coefficient of resisiance 3) Nichrome Wire: A coil of this wire is heated by passing current and is used as a source when the required wavelength range and intensity are not sufficient. 4) Rhodium Wire: This wire is sealed in a cylinder. 5) Tungsten Filament Lamp: It is used for near infrared region. 3.3.3. Monochromators (Wavelength Selectors) Radiations of various frequencies are emitted by the radiation source. Since the sample in IR spectroscopy absorbs at certain frequencies, desired frequencies from the radiation source should be selected and the radiations of other frequencies should be rejected. This selection is achieved using monochromators of the following two types: 1) Prism monochromator, and 2) Grating monochromator. 3.3.3.1. Prism Monochromator A prism to be used as a dispersive element should be made up _of materials that transmit in the infrared region (e.g., various metal halide salts). Glass and quartz are utilised in the visible and UV region, but they are usatisfactorily absorbed in the IR region, Sodium chloride isthe most common prism salt due to its high dispersion inthe 4 - 154m region (a region significantly important in the study of functional groups). Many of these salt materials are inappropriately subjected to mechanical and thermal instability and/or water solubility; thus, protection agai _nst damage should be continuously implemented. A single- or mono-pass monochromator is shown in the figure 3.9:Plane oO Exit slit (©) Littrow Source mirror Entrance 8 slit (A) Figure 3.9: Single-Pass Monochromator ‘Source: Adapted from Instrumental Methods of Chemical Analysis (pp 2.42), by Chatwal G.R. (2006) (Himalaya Publishing House) ‘The sample is placed at or near the beam focus, just before the entrancesslit (A) to the mochromator. The radiation from th e source pass through the sample and the entrance slit, and then strikes the off-axis parabolic Littrow mirror (B) which makes the radiation parallel and sends it to prism (C). ‘The dispersed radiation reflects from the plane mirror (D) and returns through the prism a second time and focuses into the exit slit (E) of the monochromator. Through this sit, 1 finally passes into the detector section, Prism Littrow Off-axis parabolic smircor \ Exit slit * Entrance slit Plane mirrors Figure 3.10: Double-Pass Monochromator Source: Adapted from Insirumental Methods of Chemical Analysis (pp 2.42), by Chatwal G.R. (2006) (Himalaya Publishing House) ‘The double-pass monochromator is shown in the figure 3.10. In this monochromator, the radiation passes four times through the prism as shown (1), (2), (3) and (4) in figure 3.10. ‘The double pass monochromator produces more resolution than the monochromator in the radiation, before reaching to the detector. Inboth mono - and double -pass monochromators, sodium chloride —(rock-salt) prism is used for 4000 -650cm’? (2.5015.4,)) region. Prisms of lithium fluoride or calcium fluoride give more resolution in the region of significant stretching vibrations. 3.3.3.2. Grating Monochromator Gratings are made up of vari ous materials and cause linear dispersion, On replacing the prism in a prism monochromator with a grating, higher dispersion is achieved. Reflection gratings are preferred over transmittance gratings. Some gratings with different rulings (Lines/cm) are u sed for covering the wide wavelength (energy) range associated with IR radiation. Different combinations of transmission or interference filters with or without gratings are usedGrating is a series of parallel straight lines cut into a plane surface. Dispersion by a grating follows the law of diffraction (figure 3.11), and also the following mathematical relation: nA = d(sin i « sin 0) Where, n = The order (a whole number) 4. = Wavelength of the radiation, d = Distance between grooves i = Angle of incidence of IR radiation beam. 0 = Angle of dispersion of light of a particular wavelength. Vertical ra¢iation Incident beam radiation Diffracted radiation Figure 2.11: Path of IR Radiation Diffracted by a Grating ‘Monochromator 3.3.4. | Sample Cells and Sample Handling IR spectroscopy is used for the characterisation of solid, liquid or gas samples, thus the samples of different phases have to be handled and differently treated. But, the only ‘common point to the sampling of different phases is that the material containing the sample should be transparent to IR radiation. ‘This condition restricts only to certain salts like potassium bromide (KBr) or sodium chloride (NaC). However, the salt is sele cted depending on the wavelength range to be studied, ‘The sampling processes of different samples are discussed below: 1) Sampling of Solids: Solid whose IR spectrum is to be recorded is sampled as follows: i) Solid Dissolved in Solvent: The solid sample is d_issolved ina solvent ( e.g., carbon tetrachloride, chloroform, alcohol, acetone, cyclohexane, and carbon disulphide), and the resulting solution is used in one of the cell2) 3) il) As Solid Film: The sample solution is placed on KBr or NaCI surface and the solvent is evaporated. AS a resull, the solid sample leaves behind a thin film on the call surface. This technique is used for rapid qualitative analysis, iii) Mull Technique: ‘The solid sample is mixed with heavy mineral oil (Nujol) to form a paste, which is sandwiched between two salt plates and then used for spectral measurement. Nujol is transparent in most part of the IR region, but has absorption maxima at 2915, 1462, 1376 and 719 cm “regions. This is the limitation in the use of Nujol for compounds having absorption in the region similar to Nujol. The mull technique is used for qualitative analysis iv) Pressed Pellet Technique (Disk Method): A small amount of finely ground solid sample is mixed with powdered potassium bromide (of 100 times its weight). The obtained finely ground mixture is passed under very high pressure ina press (at least 25,000 psig) to form small 1 “2mm thick pellets (of Im. diameter). These pellets are transparent to IR radiation and are run as such, Figure 3.12 shows device used for preparing small pellets by pressing the mixture of KBrand solid sample. The powdered mixture of KBr and sample is introduced andthe upper screw (A) is Tal tightened tll the powder is compressed into a thin disc. When the sample is sufficiently 2B ‘KBr (powder) compressed, the bolts (AandA ‘are Q sree removed and the steel cylinder with the sue sample disc is put inside it in the path of the = B cylinder beam of IR spectrometer. A blank poiassium bromide pellet of same thi ckness Il is also put in the path of the reference beam. This method has some advantages over ‘Nujol Mull method: a) Due to the use of KBr, no bands appear in the IR spectrum that used to appear due to the mulling agent. b) KBr pellets can be stored for prolong time periods. ©) The pellets can be used for quantitative analysis as the sample concentration can be adjusted. 4) The spectrum resolution in the KBr is superior to that obtained with mulls. However, the pellet technique has a few disadvantages also: 1) _Itshows a band at 3400cm”' region due to the OH group of moisture present inthe sample. Thus, care should be taken during investigations related to the OH band region in the sample. b) The high pressure involved in the formation of pellets causes polymorphic changes int he crystallinity of samples (especially, inorganic complexes), and this may further complicate the IR spectrum. ©) This method is not suitable for polymers that are difficult to grind with KBr. Figure 3.12: Device for Preparing Potassium Bromide Dises ‘Thus, it can be concluded that the Nujol method is suitable for running crystalline compounds (including complexes) in the solid state and the KBr pellet method is used for the remaining solid samples. Sampling of Liquids: The simplest way of sampling a liquid is in a thin film (0.1 0.3mm) squeezed between two sodium chloride plates (sodium chloride is transparent to IR light). Calcium fluoride plates are used for water -containing samples. A drop of liquid sample is placed on the top of sodium chloride plate and another sodium chloride plate is placed over it. This pak of sodium chloride plates enclosing the liquid film is placed in the path of sample beam. In the same way. a drop of the low melting substance is placed betweenthe two plates for spectral analysis. Sampling of Gases: ‘The gaseous sample is introduced int oa gas cell (10cm long) having sodium chloride walls. Sodium chloride windows allow the cell to be placed directly in the path of the sample beam. The low frequency rotational changes in the gaseous phase split the high frequency vibrational bands. Very f ew organic compounds are examined as gases.3.3.5. Detectors Except in the near IR region, where a photoconductivity cell is basically used, no better choice than thermal detectors is available. These give responses for all frequencies. If the radiant power for the IR region is low, the detector signal will also be low. The various types of detectors are as follows: 1) Golay cell, 2) Bolometer, 3) Thermocouple, 4) ‘Thermistor, and 5) Pyroelectrie detector. 3.3.5.1. Golay Cell ‘The golay ce Il is used in some commercial spectrophotometers. It has a small metal cylinder, whose one end is closed by a blackened metal plate and the other end is closed bya flexible metalised diaphragm. The cylinder is filled with xenon and sealed. Then IR radiation is allowed to fall on the blackened metal plate. As a result, the gas heats up and expands. The resulting pressure increases and deforms the metalised diaphragm that separates into two chambers. A light from a lamp is allowed to fall on the diaphragm th at reflects the light on to a photocell. The diaphragm motion changes the output of cell. The signal seen by the phototube is modulated with respect to the power of the radiant beam incident on the gas cell. 3.3.5.2. Bolometer A bolometer (figure 3.13) works on the principle that the electrical resistance of a metal increases by 0.4% for every Celsius degree increase of temperature. 3.3.5.2. Bolometer A bolometer (figure 3.13) works on the principle that the electrical resistance of a metal increases by 0.4% for every Celsius degree increase of temperature. Figure 3.13: Schematic Presentation of a Bolometer-Wheatstone Bridge for Infrared Detection 33.5.3. Thermocouple ‘Thermocouple detector (figure 3.14) works on the principle that when two dissimilar metal wires are connected together at both ends, a temperature differential exists and an electric current flow between the two ends. The end expose d to the IR radiation is _generally a black body so as to increase the energy gathering efficiency , and is called the hhot junction. The other end is thermally insulated and carefully screened from stray light and is called the cold junction . The flowing ele ciicity and the energy differential ‘between the two connections are directly proportional Meal lack hogy bo! jeter Cold junction sy Bp Mata Figure 3.14: Schematic Presentation of a Thermocouple.3.3.5.4. Thermistor Thermistor is made up of a fused mixture of metal oxides. The electrical resistance of the mixture decreases with increase in temperature. This relationship between electrical resistance and temperature allows the thermistors to be used as IR detectors in the same ‘way as bolometers, Thermistor changes resistance by 5% per degree Celsius change in temperature. Its response time is also slow 3.3.5.5. Pyroelectric Detector Pytoclectric detector is made up of anon -centrosymmetrical erystal, which has an internal electrical field along its polar axis. On applying IR radiation, a change in polarisation is observed due to an alteration of the crystal lattice. The pyroelectric detector acts as a capacitator if two electrodes are connected to the crystal. The effects of this detector depend on the rate of temperature change and not on the temperature change itself, Pyroelectric detector also ignores the effects of background radiation. They are usually used in FTIR spectrometers. 3.4. APPLICATIONS 3.4.1. Introduction Infrared spectros copy is widely used in industries and inresearch_ work. itis a simple technique that is effectively used for the measurement, quality control , and dynamic measurement. Itis also. used in forensic analysis in civil and criminal analysis. Quantitatively infrared spectroscopy is used to determine the quantity of a substance either in pure form or asa mixture of two or more compounds. 3.4.2. Qualitative Analysis Qualitative analysis by infrared spectroscopy _ isused for determining the structure of complex molecules. IR spectroscopy helps in detecting Gauche (skew) and staggered conformations. The two conformations of 1,2:dichloroethane are shown below a a H clo. H H ‘H H H 4 | i 1 Gauche (skew) 1235em™ Staggered (trans) (CH rocking) 1291em' (CH, rocking) Infrared spectral studies are used for identifying the presence of various functional ‘groups, like olefinic protons, N-methyl, O-methyl and C-methyl groups. ‘The qualitative applications of IR spectroscopy are discussed below: 1) Identification of an Organic Compound: An organic compoune’s identity can be established from its fingerprint region (1400 -900cm ') that should exactly match with the known spectrum of tat compound. 2) Structure Determination: — This technique helps in determining an unknown compound's structure. All the major functional groups absorb at their characteristic wave numbers. The shifts due to environmental effects are also observed. The data available due to absorption frequencies can be used for predicting the possible structure. The available chemical data can help in the confirmation of the structure. It is known that the IR spectra of amino acids exhibit bands for only ionised carboxylic acids and amine salts ( —NH,), and not for free. +—NH, and —COOH groups. Amino acids exist as Zwitter ions as below:4—cH—coo™ Similarly, from the IR bands of sulphanilic acid it ca be seen that the compound contains NH, and SO;" salts and not NH, and SO3H free groups. 3) Distinction between Two Types of Hydrogen Bonding: This technique is used for differentiating between the types of hydrogen bonding. In hydrogen bonding, the electron cloud in a hydrogen atom transfers to the neighbouring electronegative atom. The s-orbital of proton should overlap the p-orbital of the acceptor group. On dissolving such a substance in non-polar solvent (e.g., CCl), the aggregates or polymers break in dimers and monomers. Due to this, the 0» —H, (stretching vibration) absorption shifts to higher frequencies and sharp peaks are obtained, Intramolecular and intermolecular hydrogen bonding can also he distinguished using, this technique. For example, o-nitrophenol shows intramolecular hydrogen bonding and p-nitrophenol shows intermolecular hydrogen bonding. On dilution, the compounds showing intramolecular hydrogen bonding do not undergo any absorption shifts, while the compounds showing intermolecular hydrogen bonding do so. 3.4.3. Quantitative Analysis ‘Quantitative analysis by infrared spectroscopy helps in evaluating an organic mixture ‘quantitatively. Estimation of mixture components can be done by: 1) Measuring the intensities of absorption bands characteristic of each component, and 2) Knowing the optical density of the absorption band for a pure component. ‘The commercial xylene exists as a mixture of three isomers (i.e., artho-, meta- and para- xylones), and this mixture cannot be separated easily. However, the pe reentage composition of mixture can be determined by taking its IR spectrum. The bands in the spectrum are formed at: 1) 740cm' for ortho isomer, 2) 80cm" for mea isomer, and 3) 830cm" for para isomer. Mixtures of known composition are recorded and the workin _g curves are drawn for the above bands for ortho-, meta- and para-isomers. The quantitative applications of IR spectroscopy are discussed below 1) Study of a Chemical Reaction: This technique is used to study the chemical reactions. For example, a saturate d aliphatic ketone is reduced to form a secondary alcohol. Ketone forms a strong band at 1710cm “region. On reduction, it forms butan-2-ol, which absorbs at 3300cm * region due to O—H,, bond. The reaction can be studied at definite intervals and complete reduction occurs when a strong band due to C=O, will be missing and only a band due to OH is present. ° ou Il Reduction CH; —C—cH,—cH, ——"—+ cH, —c— cH, — cH, Butan-2-one Butan-2-01, 2) Study of Keto -Enol Tautomerism: Diketones and ketoesters show keto -enol tautomerism only ifthey have c-H atom. The IR spectrum of such a comp ound. contains bands due to C =O, O—H and C=C bonds. For example, ethyl acetoacetic ester exists in keto-enol isomers in equilibrium. I S\/™, cHy ‘cnt ‘oat o=0 =o Socatts C=O gy 1733, 1710669) VO, ~ 3300em-"(0) VC =O, 1645em""s)