Dr. M.N.Radhakrishnan Nair Infrared Spectroscopy Infra means beyond and infrared i.e. beyond red region.

IR-region: 12,800 - 10 cm-1.Covers

that part of the spectrum between visible and microwave regions.
REGION WAVE LENGTH (m) WAVE NUMBER
-1

(cm )

FREQUENCY RANGE Hz
14 14

NEAR MIDDLE FAR MOST USED

0.78 - 2.5 2.5 - 50 50 - 1000 2.5 - 15

12800 - 4000 4000 - 200 200 -10 4000 - 670

3.8x10 - 1.2x10
14 12

1.2x10 - 6x1
12 11

6x10 - 30x10
14 13

1.2x10 - 2x10

IR involves absorption phenomenon. The absorption of radiation depends on increasing energy of vibration or rotation associated with covalent bond in a sample molecule provide that such an increasing in energy causes a change in the dipole moment of molecule. Hence in order to absorb IR radiation a molecule must go a net change in dipole moment due to its vibration or rotation motion.IR absorption of less than 100 cm-1 causes rotational transition ,such transitions are quantised and observed as lines. Similarly absorption in the range 10000100 cm-1 causes vibrational transitions which are also quantised and appears as bands, since a vibrational transition is accompanied by a number of rotational transitions. Vibrational transitions particularly occurring between 4000-400 cm-1 is considered. This means that nearly all molecules containing covalent bond will show some degree of selective IR absorption. Infra red spectra are usually plotted as % transmittance (%T) rather than as absorbance as the ordinate. This makes absorption band appear as dips in the curve than as maxima as in the case of UV-Vis. Each dip in the spectrum is called a band or peak and represented absorption of IR radiation at that frequency by the sample. The transmittance is 0% if all the radiation is absorbed and the transmittance is 100% for no absorption.

Use of Wave numbers than wavelength offer several advantages. Wave number are directly proportional to frequency and are expressed in much more convenient numbers (in this region of the spectrum), 5000-500 cm-1. Because the wave number is directly proportional to frequency and energy, the use of wave numbers allows spectra to be displayed linear in energy, which is a distinct aid in sorting out related vibrational transitions. Infrared theory- Types of vibrations. Stretching and bending vibrations Molecular Vibrations Atoms joined by covalent bonds undergo continual vibrations relative to each other .The energies associated with these vibrations are quantized; within a molecule, only specific vibrational energy levels are allowed the energies associated with transitions between vibrational energy levels correspond to frequencies in the infrared region, 4000 to 400 cm-1. For a molecule to absorb IR radiation the bond undergoing vibration must be polar and its vibration must cause a periodic change in the bond dipole moment. Covalent bonds which do not meet these criteria are said to be IR inactive. The C-C double and triple bonds of symmetrically substituted alkenes and alkynes, for example, are IR inactive because they are not polar bonds. For a nonlinear molecule containing n atoms, there are 3n - 6 allowed fundamental vibrations. For even a relatively small molecule, a large number of vibrational energy levels exist and patterns of IR absorption can be very complex. The simplest vibrational motions are bending and stretching. In stretching vibrations where the distance between the bonded atoms changes but the atoms remains in the same bond axis and in bending vibrations the position of the atom changes with respect to the bond axis. Generally stretching vibrations takes place at higher frequencies than bending absorptions. Consider two covalently bonded atoms as two vibrating masses connected by a spring the total energy is proportional to the frequency of vibration the frequency of a stretching vibration is given by an equation derived from Hookes law for a vibrating spring .K = force constant in dynes, which is a measure of the bonds strength; force constants for single, double, and triple bonds are approximately 5, 10, and 15 x 105 dynes/cm, m = reduced mass of the two atoms, (m1m2)/(m1 + m2), where m is the mass of the atoms in grams. Substituting the values it reduces to the simplified form on the right where m1 and m2 are the atomic masses. From this equation, we see that the position of a stretching vibration is proportional to the strength of the vibrating bond is inversely proportional the masses of the atoms connected by the bond. The above equation permits theoretical calculation of the stretching frequencies. For the C-C bond calculated value is 1682 cm-1 and experimental value is 1650 cm-1 .For the C-H bond the values are 3032 and 3000 cm-1respectively.The intensity of absorption depends primarily on the polarity of the vibrating bond. Stretching vibrations are of two types(a)Symmetric stretching where the movements of the atoms with respect to a particular atom in the molecule is in the same direction.(b) Asymmetric where one atom approaches the central atom while the other departs from it. Different modes of molecular vibrations for the methylene group are shown above. Vibrational frequency of bonds increases as (a) bond strength increases (b) reduced mass increases.
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C-H =3000 : C-C =1200 : C-O = 1100: C-Cl =750 : C-Br = 600 cm-1 Bending vibrations occurs at lower frequencies than stretching because the lower value of the bending force constant K. C-H str.= ~ 3000 C-H def. = ~ 1340

Hybridisation affects the force constant. Bonds are stronger in the order sp>sp2> sp3 Resonance also affects the strength and length of a bond and hence its force constant. Resonance has the effect of reducing force constant and the absorption lowered to lower frequency. E.g A normal ketone has its C=O stretching vibration at 1715cm-1,a ketone that is conjugated with a C=C absorbs at a lower frequency,near1675 to 1680 cm-1.this is because resonance lengthens C=O bond distance and gives it more single bond character. Fundamental ,overtone and combination bands. Fundamental absorptions arise from excitation from the ground state to the lowest energy excited state. Overtones results from excitation from the ground state to higher energy states which corresponds to integral multiples of the fundamental i.e 1 ,2 etc. When two vibrational frequencies in a molecule couple to give rise to a vibration of a new frequency it is called a combination band. If the observed frequency is the difference between the combining bands it is a difference band. When fundamental vibrations couple with an overtone or a combination band, the coupled vibration is called a Fermi resonance. Fermi resonance is often observed in carbonyl compounds. Fingerprint Region Spectral region ranging from 1500-667 cm-1which is rich in absorption bands caused by the numerous bending and C-X (X=C,N,O,Cl etc) single bond stretching vibrations. This band pattern of vibration is uniquely characteristic of each molecule, gives rise to uniquely characteristic set of absorption band in the spectrum. This band serves as a finger print of the molecule and comprises of unassigned vibrations roughly from1500-667 cm-1 ( C-H str ~1400 , C-H def ~900-700). Applications of finger print region- (1) Similar compounds with same functional groups gives discernable differences in the finger print region. By comparing the IR spectra of a compound with a set of standard IR spectra recorded under identical conditions, we can identify the compound. Thus the finger print region is the most useful in distinguishing between similar
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compounds which can conclusively establish the identity of two samples (e.g. a synthetic material and a natural product- Samples which give identical pattern in same medium.) (2)The finger print region is important in the detection of functional groups like ethers, esters etc. They give characteristic C-O str. at ~1125 cm -1. (3) Substitution pattern in aromatics. The substitution pattern in disubstituted benzene can be

detected by the characteristic absorption in the finger print region. The aromatic out of plane C-H def. bands depends on the number of adjacent nuclear H atoms in the benzene ring. Un substituted and monosubstituted benzenes give two strong bands at 800 and 900 cm -1 and at 700 and 750 cm -1 respectively. Ortho-disubstituted benzenes gives a single band at ~750 cm -1, m- substituted gives two bands at 800 and 900 cm -1 and p- substituted gives a single band at 825 cm -1. Hydrogen bonding- Distinction between intra and intermolecular H- bonding. Intermolecular H bonding, e.g Formic acid dimer and intra molecular H-bonding E.g. o-nitro phenol. Intermolecular and intramolecular H-bonding can be differentiated with the use of IR spectra. The inter and intramolecular H-bonding can be distinguished by dilution. O-H stretching vibration in the range 3400-3200cm-1 which appears as a broad band indicates intermolecular hydrogen bonds. Sharp band at ~ 3600 cm-1 show free O-H stretching. As the sample is diluted with a non polar solvent like CCl4, the broad intermolecular hydrogen bonded band reduces considerably. As intermolecular H-bonding is dependent on dilution the H-bonds are broken on dilution (or at low conc.) and hence there is decrease in the bonded OH absorption on successive dilution the intensities of the bands due to intermolecular Hbonding gradually decrease and finally disappears. Intermolecular hydrogen bond weakens the O-H bond, thereby shifting stretching absorption band to lower frequency. Alcohols, phenols, amines and carboxylic acids show intermolecular hydrogen bonds. The intramolecular H-bonding, present in ortho carbonyl substituted phenols, usually shifts the broad O-H band to lower frequencies as intramolecular hydrogen bonds are stronger than intermolecular hydrogen bond. For example the O-H band in methyl salicylate is centered at about 3200cm-1,while O-H bands in phenols are centered at about 3350cm-1.Intra molecular H-bonds are independent of the concentration. Because it is an internal effect and hence intramolecular H-bonds remains unaffected on dilution and so absorption band also remains unaffected giving bonded O-H absorption.

Correlation Tables-Characteristic group frequencies Characteristic IR absorptions for the types of bonds and functional groups we deal with most often are given below.

Alcohols and Phenols O-H ---The free O-H stretch is a sharp peak at 3650-3600cm-1. This band appears in combination with the H- bonded O-H peak when the alcohol is dissolved in a solvent. The H- bonded O-H band is a broad peak at 3400-3300 cm-1. For neat samples generally this is the only O-H band and dissolved in a solvent free and bonded bands are present ,with the relatively free O-H band on the left. C-O-H Bending appears as a broad and weak peak at 1440-1220 cm-1 often obscured by
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the CH3 bendings. C-O -- Stretching vibration usually occurs in the range 1200-1600 cm-1.This band can be used to assign a primary ,secondary or tertiary structure to an alcohol or to determine whether a phenolic compound is present. Compound Phenol 30 Alcohols 20 Alcohols 10 Alcohols
0

C-O stretch (cm-1) 1220 1150 1100 1050(decreases)

O-H stretch (cm-1) 3610 3620 3630 3640(increases)

The spectrum of 1-hexanol, a 10 alcohol has its C-O absorption at 1058cm-1,butanol a 2 alcohol has its C-O absorption at 1109cm-1. Phenols -OH stretching vibrations of phenols occurs at 3610 cm-1.In addition to this phenol gives characteristic CCstr and C-H def of the aromatic residue . C-O str. absorption of phenols occurs at about 1220cm-1 and 1410-1310 cm -1 because of conjugation of the oxygen with the ring which shifts the band to higher energy due to more double bond character. In addition to this band, an O-H in-plane bending absorption is usually found near1360 cm-1for neat samples of phenol. The C-O absorptions are shifted to lower frequencies when unsaturation is present on adjacent carbon atoms or when the O-H is attached to a ring. Shifts of 30 to40 cm-1 from the base values are observed. E.g 1050-1017-benzyl alcohol 1050-1030cm-1 C6H11-OH- 1100-1070 CH2=CHCHCH3-1100-1060 cm-1 / CH3

Carbonyl compounds The carbonyl group is present in aldehydes, ketones , acids, esters,amides,and anhydrides. This group absorbs strongly in the range of1850-1650 cm-1 because its large change in dipole moment. Factors influencing carbonyl absorption. 1810 1800 Anhydride Acid band1 chloride 1760 1735 Anhydride Ester band2 1725 1715 Aldehyde Ketone 1710 1690 Carboxylic Amide acid

The range of values given in the above table can be explained by the polar effects, i.e., inductive, resonance and hydrogen bonding.

IR of Molecules with C=O Groups

The position of C=O stretching vibration is determined by the following factors Physical state, electronic and mass effect of the neighbouring substituents, conjugation ,hydrogen bonding and ring strain. Conjugation shifts the C=O absorption to lower frequency. Conjugation with a C=C bond results in delocalisation of the pi electrons of the C=O group reduces its double bond character causing absorption at lower wave numbers. Conjugation with an alkene or a phenyl group causes absorption in the 1685-1666 cm -1 region. Additional conjugation causes further lowering in wave number. Acetophenone the C=O stretch is at 1685 cm -1 which is lower than that of 2pentanone 1717 cm -1. Ring size-Acetone and cyclohexanone absorbs at 1715 cm-1 .As ring size decreases and angle strain increases, absorption shifts to a higher frequency.

Steric effect steric effect that reduces coplanarity of the conjugated system reduces the effect of conjugation. In the absence of steric hindrance ,a conjugated system will tend toward a planar conformation. The stericaly hindered cis isomer is less conjugated and shows a higher absorption. Benzal acetone in CS2 shows two C=O stre. Indicating that the cis and trans forms exists at room temperature the higher absorption is that of S-cis (1699) and 1674 of S-trans

Intermolecular hydrogen bonding between a ketone and a hydroxylic solvent such as methanol causes a slight decrease in absorption frequency of the carbonyl group .For e.g a neat sample of ethyl- methyl ketone absorbs at 1715 cm-1 where as 10 % solution of it in methanol absorbs at 1706 cm-1. Stretching and bending vibrations Ketones shows absorption in the region of 1300-1100 cm-1 as a result of C-C-C- stretching and bending in the group. The absorption may consist of multiple bands. Aliphatic ketones absorbs in the range1230-1100and aromatic ketones absorb at the higher frequency end. Aldehydes C=O stretching vibrations of aldehydes occurs at slightly higher frequencies than that of the corresponding methyl ketones. Aliphatic aldehydes absorbs near 1740-1720 cm-1. Acetaldehyde absorbs at1730 cm-1, CCl3 CHO absorbs at 1768 cm-1. C-H stretching vibrations Aldehydic C-H stretching vibrations occurs at 2830-2695 cm-1. (Generally appears as two bands due to Fermi resonance between the fundamental C-H bending and its first overtone). Aromatic aldehydes with strongly electronegative groups in the o- position absorb at higher wave number ~2900 cm-1.An absorption of medium intensity near 2720 cm-1accompanied by a carbonyl absorption band is an indication of an aldehyde group. Carboxylic acids C=O stretching bands of acids are intense .Monomers shows band at 1760 cm-1 and dimmers shows bands near 1720-1706 cm-1 . Intra molecular h- bonding decreases the C=O frequency than intermolecular. E.g salicylic acid absorbs at 1665 cm-1 where as the p-isomer absorbs at 1680 cm-1 . O-H Displays broad OH bands in the region 3300-2500 cm-1 centered around 3000 cm-1. Absorptions of Other compounds

Carbon - Nitrogen Stretching C N absorbs around 1200 cm1.

C = N absorbs around 1660 cm-1 and is much stronger than the C = C absorption in the same region. C N absorbs strongly just above 2200 cm-1. The alkyne C C signal is much weaker and is just below 2200 cm-1

IR Instrumentation 2 Types of IR spectrometer: Dispersive Grating Spectrophotometers Multiplex Instruments employing Fourier Transform (FTIR) As infrared is an absorption technique, infrared radiation passes through the sample, and is detected. A dispersive spectrometer works as follows:

FTIR spectrometer (2-dimensional IR spectroscopy ) FEATURES and USE * Simplify complex IR spectra with many overlapping peaks* Enhancement of spectral resolution by spreading peaks over the second dimension. * Establishing unambiguous assignments through correlation analysis of bands selectively coupled by various interaction mechanisms. FTIR spectrometers are very different to dispersive spectrometers and more complicated. All FTIR spectrometers are based on the Michelson interferometer. Layout of an FTIR instrument is given below.

Michelson Interferometer

As the name implies it relies on the interference of infrared waves At the interferometer, the light strikes a beam splitter (thin gold on KBr plate) which passes 50% of the light to mirror 1 and 50% to mirror 2 Mirror 1 is a moving mirror which oscillates back and forth, whilst mirror 2 is stationary On reflection from these mirrors, the beam splitter recombines the light which is then guided on towards the sample This light is absorbed by the sample, and passes to the detector. The moving mirror must travel smoothly; a frictionless bearing is used with electromagnetic drive. The position of the mirror is measured by a laser shining on a corner of the mirror. A simple sine wave interference pattern is produced. Each peak indicates mirror travel of one half the wavelength of the laser. The accuracy of this measurement system means that the IR frequency scale is accurate and precise. The detector used in an FTIR instrument must respond quickly because intensity changes are rapid (the moving mirror moves quickly). Pyroelectric detectors or liquid nitrogen cooled photon detectors must be used. Thermal detectors are too slow. Unlike the dispersive spectrometer, all frequencies from the source are measured atone time. This has major advantages that will be discussed later. Because of the interference between the light reflecting from the stationary mirror, and that from the moving mirror, the energy observed by the detector shows an unusual pattern over time. This is called an interferogram. The maximum occurs when the moving mirror is at the same distance as the stationary mirror. We get constructive interference. Fourier Transform Any waveform can be shown in one of two ways; either in frequency domain or time domain. A Fourier transform is a mathematical operation used to translate a complex curve into its component curves. In a Fourier transform infrared instrument, the complex curve is an interferogram, or the sum of the constructive and destructive
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interferences generated by overlapping light waves, and the component curves are the infrared spectrum. The standard infrared spectrum is calculated from the Fourier-transformed interferogram, giving a spectrum in percent transmittance (%T) vs. light frequency (cm-1). Because of the complicated nature of the signal, it must be converted back to a spectrum by a computer. This is the FOURIER TRANSFORM. The FTIR is a single beam spectrometer. That is, it does not automatically measure a background. You should measure a background spectrum before your sample. As the sample and background are collected separately, a laser (usually He Ne at 632nm) is used to ensure the background and sample frequencies are identical. Because of the need for computers, and lasers, FTIR is very new compared to dispersive infrared spectroscopy. Commercial instruments became available in the 1980s. If we consider a single wavelength, , then if M2B M1B= (n+) destructive interference. If mirror M1 is moved with constant speed, v, towards the beam splitter then the optical signal (in the absence of a sample) due to the recombined beam will vary sinusoidal. Since the mirror is moving with constant speed, then the sinusoidal variation can be mapped as a function of path length difference or time. The signal recorded by the detector as a function of time is then fed into a computer which performs a FT to convert it into the frequency regime. If the beam consists of two well defined wavelengths. The signal vs. time spectrum is known as the "interferogram"

FTIR Advantages The first advantage of FTIR is known as the Fellget advantage. The Fellgett, or multiplex advantage arises because all of the spectral elements are measured simultaneously. Thus, a spectrum can be obtained very quickly. This leads to a spectrum better signal to noise ratio (S/N) in the same time compared to a dispersive instrument. Alternatively, it makes FTIR a quicker technique to achieve the same quality spectrum. FTIR is better for kinetic work, and where S/N is poor. The second advantage of FTIR is known as the Jacquinot advantage. The Jacquinot, or throughput advantage, arises because unlike dispersive spectrometers, FTIR spectrometers have no slits which attenuate the infrared light. This means the spectrometer has greater optical throughput, and again, a higher S/N than dispersive infrared spectrometers. The third advantage of FTIR is known as the Connes advantage. The Connes advantage arises because the frequency scale of the spectrum is known very accurately. This control over the calibration of the wavelength domain means mirror movement averaging is possible. This means the collection many spectra and their co-addition. The addition of many spectra increases signal to noise ratio in FTIR spectroscopy. An additional advantage of the accurate wavelength calibration is that because the wavelength is known absolutely,
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techniques such as spectral subtraction can be used easily. For example, you might remove the spectrum of a solvent, to obtain that of the solute. FTIR Disadvantages 1. FTIR instruments do not measure spectra; they measure interferograms. Interferograms are difficult to interpret without first performing a Fourier transform to produce a spectrum. This used to be a major problem, but since the dramatic increase in computing power, performing a Fourier transform is now a quick and easy process. However, the way the interferogram is transformed can affect the results, and so care must be taken. Instrumentation-Components Sample Cells and Preparation Conventional sampling techniques used in IR depends on the physical state and nature of the sample. Sample cells To obtain an IR spectrum, the sample must be placed in a container or cell that is transparent in the IR region of the spectrum. Sodium chloride or salt plates are a common means of placing the sample in the light beam of the instrument. Solids(i) Mull - make a mull with nujol, fluorolube and/or hexachlorobutadiene, so that mulling agent bands do not overlap sample bands. (ii) Make a KBr disc (1-3 mg sample in 250-300 mg KBr). KBr Pellet - few mg sample + 0.5 to 1 g dry KBr ground +compressed at very high pressure Disposable polyethylene film strips (dissolve solid in volatile solvent, paint on the film or on a salt plate) Liquids: (i) place as a film between halide plates; (ii) use a fixed path length cell. Determine pathlength, b, when empty by counting interference fringes. Gases: Introduce into long-path length gas cell Optics - dessicated salts such as NaCl, CsBr, LiF, KBr and front surface mirrors. Glass and quartz lenses cannot be used because they absorb IR radiation
Some typical IR spectra

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