Theory of infra red absorption

IR radiation does not have enough energy to induce electronic transitions as seen with UV. Absorption of IR is restricted to compounds with small energy differences in the possible vibrational and rotational states. For a molecule to absorb IR, the vibrations or rotations within a molecule must cause a net change in the dipole moment of the molecule. The alternating electrical field of the radiation (remember that electromagnetic radation consists of an oscillating electrical field and an oscillating magnetic field, perpendicular to each other) interacts with fluctuations in the dipole moment of the molecule. If the frequency of the radiation matches the vibrational frequency of the molecule then radiation will be absorbed, causing a change in the amplitude of molecular vibration.
1

Theory of infra red absorption
Molecular rotations Rotational transitions are of little use to the spectroscopist. Rotational levels are quantized, and absorption of IR by gases yields line spectra. However, in liquids or solids, these lines broaden into a continuum due to molecular collisions and other interactions. Molecular vibrations The positions of atoms in a molecules are not fixed; they are subject to a number of different vibrations. Vibrations fall into the two main catagories of stretching and bending. 2

Some General Trends:
• Stretching frequencies are higher than corresponding bending frequencies. (It is easier to bend a bond than to stretch or compress it.) • Bonds to hydrogen have higher stretching frequencies than those to heavier atoms • Triple bonds have higher stretching frequencies than corresponding double bonds, which in turn have higher frequencies than single bonds.(Except for bonds to hydrogen).
3

double or triple) the frequency of the vibration is low for a bond between heavy atoms.Vibrations as a Key to Structure • Each type of vibration has a frequency that depends upon the: THE MASS OF THE VIBRATING ATOMS AND THE NATURE OF THE BOND BETWEEN THEM • For a constant bond type (single. • Multiple bonds vibrate at a higher frequency than do single bonds 4 . for a given bond type the frequency of vibrations is high for light atoms. Conversely.

IR Spectroscopy • deal with the interaction of infrared radiation with matter IR spectrum (%T against Frequency) • chemical nature and molecular structure of compound Applications • organic materials • polyatomic inorganic molecules • organometallic compounds 5 .

6 .

Mid-infrared region 3.900 to 10 cm-1) IR region is often further subdivided into three subregions 1.IR region of the electromagnetic spectrum • wavelength 770 nm to 1000 mm (wave number 12. Far-infrared region 7 . Near-infrared region (nearest to the visible) 2.

5 to 15 wavenumber Range.5 to 50 50 to 1000 2.78 to 2.0x1012 6.0x1013 8 .2x1014 to 2.5 2. mm 0.2x1014 to 6.0x1011 1. Hz 3.2x1014 1. cm-1 12800 to 4000 4000 to 200 200 to 10 4000 to 670 Frequency (v) Range.0x1012 to 3.8x1014 to 1.Table Infrared Spectral Regions Region Near Middle Far Most used Wavelength (l) Range.

IR Spectrum 9 .

Group-frequency region • wavenumber 4000 to 1300 cm-1 (2. Finger print region • wavenumber 1300 to 650 cm-1 10 .Mid-infrared region 1.5 to 8 mm) • functional group 2.

The frequency of the radiation must satisfy. The natural frequency of vibration of the molecules must equal the frequency of the incident radiation 2. E = hv.1  E vib . where E is the energy difference between the vibrational states involved E  E vib . The change in vibration must stimulate changes in the dipole moment of the molecule 11 .2  hn 3.Requirements for the absorption of IR radiation 1.

H d+ – Cl dDipole moment HCl. The degree of absorption is proportional to the square of the rate of change of the dipole during excitation. H2O IR active O–O No dipole moment Atoms. Cl2 IR inactive 12 .Requirements for the absorption of IR radiation 4. • Molecules with permanent dipole moments (μ) are IR active. H2. The energy difference between the vibrational energy levels is modified by the addition or subtraction of rotational energy levels. O2. 5.

The movement of atoms and chemical bonds like spring and balls (vibration) 13 .Molecules are made up of atoms linked by chemical bonds.

change in bond length (higher frequency) Stretching vibration 14 .stretching of bonds. bending of bonds. or internal rotation around single bonds There are two main vibrational modes : 1.Vibrations What is a vibration in a molecule? Any change in shape of the molecule. Stretching .

Bending .Stretching Types Symmetric Bending Types Asymmetric 2.change in bond angle (lower frequency) In-plane (Scissoring) Out-plane (Twisting) 15 .

Scissoring or Deformation • The two atoms connected to a central atom move toward and away from each other with deformation of the valence angle 16 .

Rocking or In-plane bending • The structural unit swings back and forth in the symmetry plane of the molecule 17 .

Wagging or out-of-plane bending • The structural unit swings back and forth in the plane perpendicular to the molecules symmetry plane 18 .

Twisting • The structural unit rotates back and forth around the bond that joins it to the rest of the molecule 19 .

Occurs at lower energy: 1400-666 cm 1. Bending: change in bond angle.  H 2O -CH2- 20 . Occurs at higher energy: 4000-1250 cm1.Modes of vibrations Stretching: change in bond distance.

 More complex types of stretching and bending are possible  Can a vibration change the dipole moment of a molecule?  Asymmetrical stretching/bending and internal rotation change the dipole moment of a molecule. Not IR active  Infrared active vibrations (those that absorb IR radiation) must result in a change of dipole moment 21 . Asymmetrical stretching/bending are IR active.  Symmetrical stretching/bending does not.

6 = 3 H O H H O H H O H Symmetrical Stretching (υs OH) 3652 cm-1 Asymmetrical Stretching (υas OH) 3756 cm-1 Scissoring (δs HOH) -1 1596 cm22 . • Each atom has 3 degree of freedom (x. H2O) Vibrational degrees of freedom or Fundamental Vibrations = 3n – 6 = 3(3) .g.y.z) • A molecule of n atoms therefore has 3n degrees of freedom. • Non linear molecules (e.Fundamental Vibrations (Absorption Frequencies) A molecule has as many as degrees of freedom as the total degree of freedom of its individual atoms.

g. CO2) : Vibrational degrees of freedom or Fundamental Vibrations = 3n – 5 = 3(3)-5 = 4 O C O O C O Symmetrical Stretching (υs CO2) 1340 cm-1 Asymmetrical Stretching (υas CO2) 2350 cm-1 O C O O C O Scissoring (bending out of the plane of the paper) (δs CO2) 666 cm -1 Scissoring (bending in the plane of the paper) (δs CO2) 666 cm -1 23 .For linear molecule (e.

24 .

Fundamental bands that are so close that they coalesce. Fundamental bands that are too weak to be observed. 5. The theoretical no. of bands including: 1. of fundamental vibrations will seldom be observed because overtones (multiples of a given frequencies) and combination tones (sum of two other vibrations) increase the no. Other phenomena reduce the no. Fundamental frequencies that fall outside the 4000-400 cm-1 region. 4. 3. 25 . The failure of certain fundamental vibrations to appear in the IR because of the lack of change in molecular dipole. The occurrence of a degenerate band from several absorptions of the same frequency in highly symmetrical molecules. 2. of bands.

0 3000 2500 4.0 6.5 alcohols phenols carboxylic acids amines amides O-H N-H C-H bond stretching alkynes alkenes alkanes C-H =C-H -C-H C= O acid chlorides anhydrides esters ketones aldehydes carboxylic acids amides Fingerprint Region (below 1500 cm-1) 3500 3. mm) .0 1500 26 1000 10.IR Correlation Diagram Region I 3600-2700 cm-1 100 Region II 1800-1600 cm-1 Transmittance (%) 80 60 40 20 0 4000 2.0 2000 5.0 Frequency (cm-1) / Wavelength (microns.

Hooke’s Law states that two masses joined by a spring will vibrate such that

k

m

(1)

where  = the frequency (rad/sec), but since   2n we have
1 n  2 k

m

(2)
27

where n = the frequency of vibration, k is the force constant of the bond (dynes/cm), and m is the reduced mass, or
M1M 2 m M1  M 2

(3)

where M1 is the mass of one vibrating body, M2 the mass of the other. But n is in cyles per second (cps). During this time light travels a distance measured in cm/sec (I.e., the speed of light).
28

Therefore, if one divides n by c, the result is the number of cycle per cm. This is n , the wavenumber of an absorption peak (cm-1) and
n  n
c

(4)

It can be deduced that
1 n  2c
n  5.3x 10

k

m
12

(5)
k

m

(6)
29

Hooke’s Law M1 M2 ύ = The vibration frequency (cm-1) c = Velocity of light (cm/s) f = force constant of bond (dyne/cm) M1 and M2 are mass (g) of atom M1 and M2 30 .

THE EQUATION OF A SIMPLE HARMONIC OSCILLATOR n = frequency in cm-1 c = velocity of light ( 3 x 1010 cm/sec ) K = force constant in dynes/cm C C n = 2c where 1 K m m m1 m2 = m1 + m2 >C C >C C multiple bonds have higher K’s This equation describes the vibrations of a bond. m= atomic masses m = reduced mass 31 .

lower frequency increasing K = C=C > C=C > C-C 2150 increasing m 1650 1200 C-H > C-C > C-O > C-Cl > C-Br 3000 1200 1100 750 65032 . higher frequency n = 2c constants 1 K m larger atom masses.larger K.

• Frequency increases with increasing bond energy. 33 .Stretching Frequencies • Frequency decreases with increasing atomic mass.

Frequencies of various group vibrations in the group frequency region and in fingerprint region 34 .

Block diagram of IR spectrophotometer source sample monochromator Grating Filter detector readout Nernst Glower Globar Incandescent wire source Hg Arc Recorder Thermal D Thermocouple XY plotter Thermopile Printer Thermister Bolometer Pneumatic D Pyroelectric D 35 .

Instrumentation Three distinct types of instruments employed for IR absorption spectrometry 1. Nondispersive instruments that use filters for wavelength selection or an infrared-absorbing-gas in the detection system are often used for gas analysis at specific wavelength 36 . Fourier transform IR systems are widely applied in the far-IR region and becoming quite popular for mid-IR spectrometry 3. Dispersive instruments with a monochromator are used in the midIR region for spectral scanning and quantitative analysis 2.

IR sources: general • an inert solid that is heated electrically to a temperature between 1500 and 2200 K (provide continuous radiant) • the maximum radiant intensity at these temperatures occurs at between 5000 and 5900 cm-1 (2 to 1.7 mm) 37 .

it must be used with ballast resistor in the heating circuit to prevent burnout 38 .The Nernst Glower (Continuous source) IR sources • It is a useful and inexpensive source • It is composed of rare earth oxides formed into a cylinder having a diameter of 1 to 2 mm and a length of 20 mm • Platinum leads are sealed to the ends of the cylinder to permit passage of electricity. temperatures between 1200 and 2200 K results • Because of a negative temperature coefficient of electrical resistance.

The Nernst Glower (Continuous source) (cont.) IR sources • it is rather fragile. and its lifetime depends on the operating temperature and the care taken in handling it 39 .

The globar (continuous source) IR sources • A globar is a silicon carbide rod. usually about 50 mm in length and 5 mm in diameter • current through the globar causes the rod to heat and emit radiation at temperature exceeding 1000 oC • the power consumption is normally higher than that of the Nernst Glower • water cooling is needed to cool the metallic electrodes attached to the rod • less convenient to use and more expensive because of the necessity for water cooling 40 .

8 mm dia. G 15 mm 650 cm -1 NG NG 10 mm 1 mm -1 G 1000 cm 10000 cm -1 41 . of resistance 6 .c) Globar SiC rod heated to 1300oC watercooled brass tube with slot 5 cm + temp coeff.

IR sources Incandescent wire source • A source somewhat lower intensity but longer life than the Globar or Nernst glower • It is a tightly wound spiral of nichrome wire heated to about 1100 K by an electrical current • A rhodium-wire heater sealed in a ceramic cylinder has a similar properties as a source 42 .

The Mercury arc IR sources • For the far-infrared region of the spectrum (l> 50 mm) • It provides sufficient energy for convenient detection • It consist of a quartz-jacketed tube containing mercury vapor at a pressure greater than one atmosphere • Passage of electricity through the vapor forms an internal plasma source that provides continuous radiation in the far-infrared region 43 .

The Mercury arc IR sources 44 .

78 mm) 45 .800 cm-1 (2.IR sources The Tungsten filament lamp • the near-infrared region of 4000 to 12.5 to 0.

which consists of a dispersion element and a slit system. Gratings 46 . • This is done by monochromator. Prisms 2. • Two types of dispersion elements are 1.Monochromators • To select radiation of any desired frequency from source and eliminate other frequencies.

The most common materials used to make prism are metal salts.Prisms Requirements: • It must be transparent to IR radiation.5 mm. • The material used must be strong enough to be shaped & polished. This eliminates common materials like glass & quartz. such as – – – – Potassium bromide Calcium fluoride Sodium chloride (Rock salt) Thallous bromide 47 . which are not transparent to IR at wavelengths longer than 3.

Prisms • Sodium chloride is transparent to radiation between 2. the better the resolution. • The larger the crystal.4 – 7. • Surfaces must be smooth to prevent random scattering of 48 the radiation by the prism surfaces.26 mm. • Calcium fluoride in the range of 2.5 and 15 mm. .1 .7 mm • The prism is prepared from a single large crystal of the metal salt which is cut and polished to the required shape. This wavelength range is sometimes termed the rock salt region. • Potassium bromide or cesium bromide can be used over the range 2.

• The metal salts used to make prisms are water soluble.Prisms • The crystal must be high quality otherwise scattering of radiation takes place and hence a loss of signal and resolution. On drying it is left etched. it is necessary to keep the prisms dry. 49 . so if the surface becomes wet it dissolves. So.

• Resolution is constant over the operable range. 50 .Gratings The advantages of gratings are: • They can be made with materials such as aluminum that is stable in the atmosphere and not attacked by moisture. • They can be used over a wide wavelength range.

51 . they lose transparency at longer wavlengths. Problems involved in IR Spectroscopy: • At longer wavelengths. the energy of each proton is decreased.Slit systems The radiation from the source is dispersed by the dispersion element. This small section is separated from the rest of the beam by the exit slit. • The power from the light source drops off at long wavelengths and the response of the detector becomes poor. which a small part is used. • If prisms are used.

The disadvantage is that use of wider slits results in an automatic loss in resolution.Slit systems The problem is reduced by the use of a “PROGRAMMED SLIT SYSTEM” In this system. This may lead to interference from unresolved bands in quantitative analysis. 52 . the slit opens up automatically to permit a wider wavelength range to reach the detector and therefore to increase the intensity of the signal. and loss of fine structure in qualitative analysis. The advantage is that more radiation falls on the detector and the instrument responds more reliably.

Thermal Detectors 2. Photoconducting Detectors Fourier Transform IR 53 . Pyroelectric Detectors Dispersive spectrophotometer 3.Infrared Detectors General types of infrared detectors: 1.

Infrared Detectors Thermal Detectors • widely used in the IR region of the spectrum • responses depends upon the heating effect of radiation Problem: The problem of measuring infrared radiation by thermal means is compounded by thermal noise from surrounding Solution: Thermal detectors are usually encapsulated and carefully shielded from thermal radiation emitted by other nearby objects 54 .

• If one welded joint (called the hot junction) becomes hotter than the other joint (the cold junction).Thermal detectors: Thermocouples Infrared Detectors • a thermocouple is made by welding together at each end two wires made from different metals. a small electrical potential develops between the joints Metal A welded junction (hot) Metal B welded junction (cold) 55 .

56 . which increases the temperature of the junction. the cold junction is carefully screened in a protective box and kept at a constant temperature.Thermal detectors: Thermocouples Infrared Detectors In IR spectroscopy. The hot junction is exposed to the IR radiation. of the intensity of IR radiation falling on the hot junction. The potential difference generated in the wires is a function of the temperature difference between the junctions and. therefore.

Thermal detectors: Thermocouples Infrared Detectors A well-designed thermocouple detector is capable of responding to temperature difference of 10-6 K. This figure corresponds to a potential difference of about 6 to 8 mV/mW To enhanced sensitivity. several thermocouples may be connected in series to give what is called a ‘thermopile’ 57 .

IR radiation heats up this conductor which causes its electrical resistance to change. or from a semi conductor.Thermal detectors: Bolometer Infrared Detectors A bolometer is a type of resistance thermometer constructed of thin metal conductor such as platinum wire or nickel. 58 . A germanium bolometer operated at 1. is an ideal detector for radiation in the 5 to 400 cm-1 (2000 to 25 mm) range.5 K. The degree of change the conductor’s resistance is a measure of the amount of radiation that has fallen on the detector.

• The strip is not exposed to IR radiation. • A similar strip of metal is used as the balancing arm of the bridge. • When no radiation falls on the bolometer. • The amount of current flowing through the galvanometer is a measure of the intensity of the radiation falling on the 59 detector. the bridge becomes unbalanced due to change in the electrical resistance which causes a current to flow through the galvanometer G. • If radiation falls on the bolometer. the bridge remains balanced. .Thermal detectors: Bolometer Infrared Detectors • A bolometer is made one arm of the wheatstone bridge.

The thermistor is normally placed in a bridge circuit with a reference thermistor that is not irradiated. The resistance can be measured by a null-comparison method 60 .Thermal detectors: Thermistor Infrared Detectors A thermistor is made of a fused mixture of metal oxides which show a negative thermal coefficient of electrical resistance.

•The resulting pressure increase in the gas deforms the metalized diaphragm which separates two chambers. • It is filled with a nonabsorbing gas such as xenon and sealed. .Golay detector • It consists of small hollow cylinder which is closed by a blackened film at one end and by a flexible metalized diaphragm at the other. • Light from a lamp is made to fall on the diaphragm 61 which reflects the light on to a photocell. • IR radiation falls on the blackened film and heats the enclosed gas in the confined space.

much faster than that of the bolometer. thermistor or thermocouple.Golay detector • Motion of the diaphragm changes the output of cell. • The advantage of this detector is that its useful wavelength range is very wide. • The response time is about 10-2 sec. 62 . • The signal seen by the phototube is modulated in accordance with the power of the radiant beam incident on the gas cell. • The response is linear.

Golay detector 63 .

a temperature dependent capacitor is produced. One electrode is IR transparent. • Changing its temperature by irradiating it with infrared radiation alters the charge distribution across the crystal. • The current across the electrodes is Temperature dependent. 64 . which can be detected as a current in an external electric circuit connecting the two sides of the capacitor. • Triglycine sulfate is sandwiched between two electrodes.Pyroelectric Transducers (PTs) or Detector • Pyroelectric substances act as temperature-dependent capacitors and are constructed from single crystalline wafers of pyroelectric materials.

. which is why most of the FT-IR instruments uses them. • The curie point for triglycine sulfate is 470c. • Pyroelectric detectors exhibit fast response times. • Pyroelectric crystals lose their residual polarization when they are heated to a temperature called the curie point. 65 .Pyroelectric Transducers (PTs) or Detector continued. • The magnitude of this current is proportional to the surface area of the crystal and the rate of change of polarization with temperature.

DTGS Tc~50oC. Fast response time: 1ms-1ms Ignore steady background 66 . by IR absorption changes lattice spacing and polarization – charge moves.Pyroelectric detector TGS. LiTaO3 Tc~610oC Change in detector temp.

liquid and gas samples.SAMPLE CELLS • IR Spectrometry deals with the measurement of the IR spectrum. • Samples of different phases must be treated differently. • This limits the selection to certain salts. • It is used for the characterization of solid. 67 . • The material used to contain the sample must always be transparent to IR radiation. such as Sodium chloride & Potassium bromide.

68 .Solid Samples Four techniques are available for preparing solid samples for IR spectrometry: 1. Solids run in solution: • Solution of solid is prepared in a suitable solvent then the solution is run in one of the cells for liquids. • When solids are in solutions. the absorption due to solvent has to be compensated by keeping the solvent in a cell of same thickness as that containing the sample.

Solid Samples 2. • Useful for rapid qualitative analysis and difficult to carryout quantitative analysis. 69 . Solids films: • Sample is deposited on the surface of a KBr or NaCl cell by evaporating a solution of the solid to dryness. • IR radiation is then passed through the thin layer deposited.

• Good for qualitative studies. • Disadvantage is the absorption band of sample will coincide with absorption band of nujol mull. viscous liquid. their use in combination permits the recording of IR spectrum. the solid sample in the nujol has to be used in combination with hexachlorobutadiene because the absorption band of nujol and hexachlorobutadiene appear in different regions. • So.Solid Samples 3. 70 . such as Nujol (paraffin oil) or chlorofluorocarbon greases and spread between IR transmitting windows. but not for quantitative analysis. Mull technique: • The sample may be ground to a powder. • The powder can be made into a thick slurry or mull by grinding it with a greasy.

Pressed pellet technique or KBr pellet method: • A finely ground solid sample is mixed with about 100 times its weight of dried powdered potassium bromide (other alkali metal halides can also been used).000 to 15. • Cesium iodide absorbs below 200 cm-1 and is used because of its 71 greater transparency at low frequencies. • The disk is then held in the instrument beam for spectroscopic examination. • Being ionic. .000 pounds per square inch) to yield a transparent disk about 1 cm in diameter and 1-2 mm thick. • The disk is prepared in vacuum to eliminate air or moisture. • Mixing is carried out using pestle and mortar or a small ball mill. • The mixture is compressed under very high pressure (10. KBr transmits most of the IR region with a lower cutoff of about 400 cm-1.Solid Samples 4.

which may cause complications in IR spectrum. • High pressure involved during the formation of pellets may bring about polymorphic changes in crystallinity in the samples. it can be used for quantitative analysis. Disadvantages: • Not suitable for some polymers which are difficult to grind with KBr. • As concentration of sample can be suitably adjusted in the pellets.Solid Samples Advantages of pellet technique over Nujol method: • KBr pellets can be stored for long periods of time. • Resolution of the spectrum in KBr is superior to that obtained with mulls. . so care must be taken while 72 investigating the region of the OH band in the sample. • It always has a absorption band at 3450 cm-1 from the OH group of moisture present in the sample.

01 – 0.Liquid Samples • Liquid samples are poured without any preparation into circular or rectangular cells made of NaCl.05 mm in thickness. • The sample thickness should be so selected that the transmittance lies between 15 and 70 percent. KBr or ThBr and their IR spectrum determined directly. 73 . • For most liquids this will represent a thin layer of 0.

• Organic liquid samples should be dried before being poured into the cells. otherwise the cell surfaces become opaque and cause erroneous results to be obtained.Liquid Samples For double beam work. • All cells must be protected from water. 74 . because they are water soluble. • One cell is used to contain the sample and the other cell to contain a reference material. • Matched cells are similar in total thickness and in cell wall thickness. matched cells are used.

75 . • The gas must not react with the cell windows or the reflecting surfaces. • Gas analysis are performed with IR but the method is not commonly used because of its lack of sensitivity. but they may be up to 1 mt long. so that constituents of the gas can be determined. usually they are about 10 cm long. NaCl or ThBr. • Multiple reflections can be used to make the effective path length as long as 40 mt. • The cells are larger. • Larger cells are used for the small number of molecules of a sample that is contained in a gas.Gas Samples • The gas sample cell are similar to liquid sample cell and are made of KBr.

An Infrared Spectrometer 76 .

IR Spectrometer 77 .

Has better sensitivity.FT-IR Spectrometer • • • • • • Uses an interferometer. Takes several scans and averages them. Less energy is needed from source. Components • Source • Michelson Interferometer • Sample 78 • Detector . Has a laser beam that keeps the instrument accurately calibrated. Completes a scan in 1-2 seconds.

sampling interval. control mirror velocity 79 .Michaelson Interferometer • • • • • Beam splitter Stationary mirror Moving mirror at constant velocity Motor driven Micrometer screw He/Ne laser.

Stationary mirror HeNe laser Source PMT Beam Splitter Moving mirror Sample Detector 80 .

thus decreases the electrical resistance of the semiconductor. • The voltage drop across the thin film is a measure the power of the IR radiation. such as lead sulfide. 81 .Photoconducting detector • Consists of a thin film of a semi-conducting material. • Absorption of IR radiation promotes nonconducting electrons to a higher energy conducting state. mercury/cadmium telluride or indium antimonide deposited on a nonconducting glass surface and sealed into an evacuated envelope to protect the semiconductor from the atmosphere.

• Mercury/cadmium telluride can be used in the mid-IR and far IR. 82 . • It provides superior response characteristics. • Great for GC-Irs. but must be cooled with liquid nitrogen (77 K) to minimize thermal noise.Photoconducting detector • A lead sulfide photoconductor for near IR can be operated at room temperature.

Principle of operation of FTIR spectrometer Determines datapoint sampling interval Photodiode 83 .

liquids. solids 84 .1 cm-1) • Inexpensive IR (especially FTIR) very widely used for Qualitative & quantitative analysis of • Gases.Advantages of FTIR • High S/N ratios .high throughput • Rapid (<10 s) • Reproducible • High resolution (<0.

01 cm-1) frequency Stray light does not affect the Stray light within the instrument detector. since all signals are causes spurious readings modulated In order to improve resolution only A much larger beam may be used a small amount of the IR beam at all times. Only the mirror moves during an resulting in mechanical slippage experiment and wear Calibration against reference Use of a laser provides high spectra is required to measure frequency accuracy (to 0. DISPERSIVE IR FOURIER TRANSFORM IR (FTIR) 1 There are a many moving parts. Data collection is may be allowed to pass through the easier 85 slits 2 3 4 .Comparison of Fourier Transform & Dispersive IR SL. NO.

NO.Comparison of Fourier Transform & Dispersive IR SL. DISPERSIVE IR FOURIER TRANSFORM IR (FTIR) 5 Only radiation of a narrow All frequencies of radiation fall on frequency range falls on the the detector simultaneously detector at any one time Slow scan speeds make dispersive Rapid scan speeds permit instruments too slow for monitoring samples undergoing monitoring systems undergoing rapid change rapid change The sample is subject to thermal The sample is not subject to effects from the focused beam thermal effects Any emission of IR radiation by An emission of IR radiation by the the sample will fall on the detector sample will not be detected 86 6 7 8 .

can do quantitative analysis 87 .IR Interpretation Use of IR spectra • Identification of functional groups on a molecule – this is a very important tool in organic chemistry • Spectral matching can be done by computer software and library spectra • Since absorbance follows Beer’s Law.

The dip is often called an absorption peak or absorption band. the intensity of transmitted radiation decreases. • Different types of groups of atoms (C-H. This results in a decrease of per cent transmittance and hence a dip in the spectrum. O-H. N-H. . etc…) absorb infrared radiation at 88 different characteristic wavenumbers. • A 100 per cent transmittance in the spectrum implies no absorption of IR radiation. When a compound absorbs IR radiation. A typical infrared spectrum is shown below.FEATURES OF AN IR SPECTRUM • An IR spectrum is a plot of per cent transmittance (or absorbance) against wavenumber (frequency or wavelength).

called the 89 “fingerprint region” .IR Spectrum Baseline Absorbance /Peak • No two molecules will give exactly the same IR spectrum (except enantiomers) • Simple stretching: 1600-3500 cm-1 • Complex vibrations: 400-1400 cm-1.

Describing IR Absorptions IR absorptions are described by their frequency and appearance. • Frequency (n) is given in wavenumbers (cm-1) • Appearance is qualitative: intensity and shape • conventional abbreviations: vs s m w br sh very strong strong medium weak broad sharp OR shoulder 90 .

g.g. the IR spectrum can be split into four regions for interpretation: • 4000  2500 cm-1: Absorption of single bonds formed by hydrogen and other elements e. C≡N • 2000  1500 cm-1: Absorption bonds e. complicated bands. This part of the spectrum is unique to each compound and is often called the fingerprint region. NH.g. OH. C=O of double • 1500  400 cm-1: This region often consists of many different.• In general. C≡C. 91 . C=C. It is rarely used for identification of particular functional groups. CH • 2500  2000 cm-1: Absorption of triple bonds e.

Summary of IR Absorptions 92 .

93 .

C=O C=C C O 1715 1650 ~1100 large range 94 .10 cm-1) O-H N-H C-H C N C C 3600 3400 3000 2250 2150 These are the minimum number of values to memorize.BASE VALUES (+/.

H-bonding) broadens shifts FREE H-BONDED 3600 3300 95 .The O-H stretching region • O-H • O-H 3600 cm-1 (alcohol. free) 3300 cm-1 (alcohols & acids.

The N-H stretching region N-H 3300 .3400 cm-1 • Primary amines give two peaks H N H symmetric asymmetric H N H • Secondary amines give one peak • Tertiary amines give no peak 96 .

The C-H stretching region BASE VALUE = 3000 cm-1 •C-H sp stretch ~ 3300 cm-1 •C-H sp2 stretch > 3000 cm-1 •C-H sp3 stretch < 3000 cm-1 UNSATURATED 3000 divides SATURATED •C-H aldehyde. two peaks (both weak) ~ 2850 and 2750 cm-1 97 .

THE C-H BENDING REGION • CH2 bending ~ 1465 cm-1 • CH3 bending (asym) appears near the CH2 value ~ 1460 cm-1 • CH3 bending (sym) ~ 1375 cm-1 98 .

sharp peak due to its large dipole moment. The carbon-carbon triple bond gives a sharp peak. This is especially true if it is at the center of a symmetric molecule.The triple bond stretching region • C =N • C =C 2250 cm-1 2150 cm-1 The cyano group often gives a strong. but it is often weak due to a lack of a dipole. R C C R 99 .

 C=O is often one of the strongest peaks in the spectrum 100 .RIGHT IN THE MIDDLE OF THE SPECTRUM  The base value is 1715 cm-1 (ketone)  The bands are very strong !!! due to the large C=O dipole moment.THE CARBONYL STRETCHING REGION  This region stretches from about 1800 to 1650 cm-1 .

C=O IS SENSITIVE TO ITS ENVIRONMENT EACH DIFFERENT KIND OF C=O COMES AT A DIFFERENT FREQUENCY acid chloride ester aldehyde ketone carboxylic acid amide O R C Cl O R C OR' O R C H O R C R O R C OH O R C NH2 1800 anhydride 1735 O 1725 1715 1710 BASE VALUE 1690 O R C O C R 1810 and 1760 ( two peaks ) THESE VALUES ARE WORTH LEARNING all are +/.10 cm-1 101 .

weights the two factors (resonance/ e-withdrawal) differently in esters than in amides.SUMMARY Ketones are at lower frequency than Aldehydes because of the second electron-donating alkyl group. The electron-withdrawing effect of nitrogen is less important than the resonance. Acids are at lower frequency than ketones due to H-bonding. O versus N. Note the electronegativity difference. 102 . This is more important than resonance with the electron pair on the oxygen. Amides are at lower frequencies than ketones due to resonance involving the unshared pair on nitrogen. Esters are at higher frequencies than ketones due to the electron-withdrawing oxygen atom. Acid chlorides are at higher frequency than ketones because of the electron-withdrawing halide.

The C=C stretching region
• C=C double bond at 1650 cm-1 is often weak or not even seen. • C=C benzene ring shows peak(s) near 1600 and 1400 cm-1 , one or two at each value CONJUGATION LOWERS THE VALUE.
• When C=C is conjugated with C=O it is stronger and comes at a lower frequency.
103

The C-O stretching region
• The C-O band appears in the range of 1300 to 1000 cm-1

• Look for one or more strong bands appearing in this range! • Ethers, alcohols, esters and carboxylic acids have C-O bands
104

The N=O stretching region
• N=O stretching -- 1550 and 1350 cm-1 asymmetric and symmetric stretchings

• Often the 1550 cm-1 peak is stronger than the other one

105

The C-X stretching region • C-Cl 785 to 540 cm-1. 106 . but are not that common. often hard to find amongst the fingerprint bands!! • C-Br and C-I appear outside the useful range of infrared spectroscopy. • C-F bonds can be found easily.

107 .

108 .

108 .

Sign up to vote on this title
UsefulNot useful