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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.
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IR Spectroscopy
deal with the interaction of infrared radiation with matter
Applications
organic materials polyatomic inorganic molecules organometallic compounds
IR Spectrum
Mid-infrared region
1. Group-frequency region wavenumber 4000 to 1300 cm-1 (2.5 to 8 mm) functional group 2. Finger print region wavenumber 1300 to 650 cm-1
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3. The change in vibration must stimulate changes in the dipole moment of the molecule
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OO
No dipole moment
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Molecules are made up of atoms linked by chemical bonds. The movement of atoms and chemical bonds like spring and balls (vibration)
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Vibrations
What is a vibration in a molecule? Any change in shape of the molecule- stretching of bonds, bending of bonds, or internal rotation around single bonds
There are two main vibrational modes : 1. Stretching - change in bond length (higher frequency)
Stretching vibration
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Stretching Types
Asymmetric
In-plane (Scissoring)
Out-plane (Twisting)
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Scissoring or Deformation
The two atoms connected to a central atom move toward and away from each other with deformation of the valence angle
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Twisting
The structural unit rotates back and forth around the bond that joins it to the rest of the molecule
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Modes of vibrations
Stretching: change in bond distance. Occurs at higher energy: 4000-1250 cm1. Bending: change in bond angle. Occurs at lower energy: 1400-666 cm 1.
H 2O
-CH2-
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Asymmetrical stretching/bending and internal rotation change the dipole moment of a molecule. Asymmetrical stretching/bending are IR active. Symmetrical stretching/bending does not. Not IR active
Infrared active vibrations (those that absorb IR radiation) must result in a change of dipole moment
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Fundamental Vibrations (Absorption Frequencies) A molecule has as many as degrees of freedom as the total degree of freedom of its individual atoms.
For linear molecule (e.g. CO2) : Vibrational degrees of freedom or Fundamental Vibrations = 3n 5 = 3(3)-5 = 4
O C O O C O
Symmetrical Stretching (s CO2) 1340 cm-1 Asymmetrical Stretching (as CO2) 2350 cm-1
(s
CO2) 666 cm
-1
CO2) 666 cm
-1
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The
theoretical no. 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. of bands. Other phenomena reduce the no. of bands including:
5. The failure of certain fundamental vibrations to appear in the IR because of the lack of change in molecular dipole.
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IR Correlation Diagram
Region I 3600-2700 cm-1
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Transmittance (%)
80 60 40 20 0 4000 2.5
C= O
acid chlorides anhydrides esters ketones aldehydes carboxylic acids amides
Fingerprint Region
(below 1500 cm-1)
3500 3.0
3000
2500 4.0
1500
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1000 10.0
Hookes Law states that two masses joined by a spring will vibrate such that
(1)
(2)
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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).
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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)
m
12
(5)
k
(6)
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Hookes Law
M1
M2
= The vibration frequency (cm-1) c = Velocity of light (cm/s) f = force constant of bond (dyne/cm)
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n = frequency
in cm-1 c = velocity of light ( 3 x 1010 cm/sec )
K = force constant in dynes/cm
C C
n = 2c
where
m1 m2 = m1 + m2
>C
>C
m=
n = 2c
constants
2150
increasing m
1650
1200
Stretching Frequencies
Frequency decreases with increasing atomic mass. Frequency increases with increasing bond energy.
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Frequencies of various group vibrations in the group frequency region and in fingerprint region
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sample
monochromator
Grating Filter
detector
readout
Recorder Thermal D Thermocouple XY plotter Thermopile Printer Thermister Bolometer Pneumatic D Pyroelectric D
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Instrumentation
Three distinct types of instruments employed for IR absorption spectrometry 1. Dispersive instruments with a monochromator are used in the midIR region for spectral scanning and quantitative analysis 2. Fourier transform IR systems are widely applied in the far-IR region and becoming quite popular for mid-IR spectrometry
3. 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
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)
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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, it must be used with ballast resistor in the heating circuit to prevent burnout
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IR sources
it is rather fragile, and its lifetime depends on the operating temperature and the care taken in handling it
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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
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c) Globar
SiC rod heated to 1300oC
watercooled brass tube with slot
5 cm
6 - 8 mm dia.
15 mm 650 cm -1
NG NG 10 mm 1 mm -1 G 1000 cm 10000 cm -1
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IR sources
IR sources
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
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IR sources
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IR sources
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Monochromators
To select radiation of any desired frequency from source and eliminate other frequencies. This is done by monochromator, which consists of a dispersion element and a slit system. Two types of dispersion elements are 1. Prisms 2. Gratings
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Prisms
Requirements:
It must be transparent to IR radiation. This eliminates common materials like glass & quartz, which are not transparent to IR at wavelengths longer than 3.5 mm. The material used must be strong enough to be shaped & polished. The most common materials used to make prism are metal salts, such as
Potassium bromide Calcium fluoride Sodium chloride (Rock salt) Thallous bromide
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Prisms
Sodium chloride is transparent to radiation between 2.5 and 15 mm. This wavelength range is sometimes termed the rock salt region. Potassium bromide or cesium bromide can be used over the range 2.1 - 26 mm. Calcium fluoride in the range of 2.4 7.7 mm
The prism is prepared from a single large crystal of the metal salt which is cut and polished to the required shape. The larger the crystal, the better the resolution. Surfaces must be smooth to prevent random scattering of 48 the radiation by the prism surfaces.
Prisms
The crystal must be high quality otherwise scattering of radiation takes place and hence a loss of signal and resolution. The metal salts used to make prisms are water soluble, so if the surface becomes wet it dissolves. On drying it is left etched. So, it is necessary to keep the prisms dry.
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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. Resolution is constant over the operable range.
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Slit systems
The radiation from the source is dispersed by the dispersion element, which a small part is used. This small section is separated from the rest of the beam by the exit slit. Problems involved in IR Spectroscopy: At longer wavelengths, the energy of each proton is decreased. The power from the light source drops off at long wavelengths and the response of the detector becomes poor. If prisms are used, they lose transparency at longer wavlengths.
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Slit systems
The problem is reduced by the use of a PROGRAMMED SLIT SYSTEM In this system, the slit opens up automatically to permit a wider wavelength range to reach the detector and therefore to increase the intensity of the signal. The advantage is that more radiation falls on the detector and the instrument responds more reliably. The disadvantage is that use of wider slits results in an automatic loss in resolution. This may lead to interference from unresolved bands in quantitative analysis, and loss of fine structure in qualitative analysis.
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Infrared Detectors
General types of infrared detectors:
1. Thermal Detectors
2. Pyroelectric Detectors
Dispersive spectrophotometer
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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
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Infrared Detectors
a thermocouple is made by welding together at each end two wires made from different metals. If one welded joint (called the hot junction) becomes hotter than the other joint (the cold junction), a small electrical potential develops between the joints
Metal A welded junction (hot) Metal B welded junction (cold)
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Infrared Detectors
In IR spectroscopy, the cold junction is carefully screened in a protective box and kept at a constant temperature. The hot junction is exposed to the IR radiation, which increases the temperature of the junction. The potential difference generated in the wires is a function of the temperature difference between the junctions and, therefore, of the intensity of IR radiation falling on the hot junction.
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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
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Infrared Detectors
A bolometer is a type of resistance thermometer constructed of thin metal conductor such as platinum wire or nickel, or from a semi conductor. IR radiation heats up this conductor which causes its electrical resistance to change. The degree of change the conductors resistance is a measure of the amount of radiation that has fallen on the detector. A germanium bolometer operated at 1.5 K, is an ideal detector for radiation in the 5 to 400 cm-1 (2000 to 25 mm) range.
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Infrared Detectors
A bolometer is made one arm of the wheatstone bridge. A similar strip of metal is used as the balancing arm of the bridge. The strip is not exposed to IR radiation. When no radiation falls on the bolometer, the bridge remains balanced. If radiation falls on the bolometer, the bridge becomes unbalanced due to change in the electrical resistance which causes a current to flow through the galvanometer G. The amount of current flowing through the galvanometer is a measure of the intensity of the radiation falling on the 59 detector.
Infrared Detectors
A thermistor is made of a fused mixture of metal oxides which show a negative thermal coefficient of electrical resistance. 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
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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. It is filled with a nonabsorbing gas such as xenon and sealed.
IR radiation falls on the blackened film and heats the enclosed gas in the confined space. The resulting pressure increase in the gas deforms the metalized diaphragm which separates two chambers. Light from a lamp is made to fall on the diaphragm 61 which reflects the light on to a photocell.
Golay detector
Motion of the diaphragm changes the output of cell.
The signal seen by the phototube is modulated in accordance with the power of the radiant beam incident on the gas cell. The response time is about 10-2 sec, much faster than that of the bolometer, thermistor or thermocouple. The advantage of this detector is that its useful wavelength range is very wide. The response is linear.
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Golay detector
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Pyroelectric detector
TGS, DTGS Tc~50oC; LiTaO3 Tc~610oC
Change in detector temp. by IR absorption changes lattice spacing and polarization charge moves. Fast response time: 1ms-1ms Ignore steady background
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SAMPLE CELLS
IR Spectrometry deals with the measurement of the IR spectrum. It is used for the characterization of solid, liquid and gas samples. Samples of different phases must be treated differently. The material used to contain the sample must always be transparent to IR radiation. This limits the selection to certain salts, such as Sodium chloride & Potassium bromide. 67
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.
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Solid Samples
2. 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. Useful for rapid qualitative analysis and difficult to carryout quantitative analysis.
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Solid Samples
3. 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, viscous liquid, such as Nujol (paraffin oil) or chlorofluorocarbon greases and spread between IR transmitting windows. Disadvantage is the absorption band of sample will coincide with absorption band of nujol mull. So, 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, their use in combination permits the recording of IR spectrum. Good for qualitative studies, but not for quantitative analysis.
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Solid Samples
4. 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). Mixing is carried out using pestle and mortar or a small ball mill. The mixture is compressed under very high pressure (10,000 to 15,000 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. The disk is then held in the instrument beam for spectroscopic examination. Being ionic, KBr transmits most of the IR region with a lower cutoff of about 400 cm-1. Cesium iodide absorbs below 200 cm-1 and is used because of its 71 greater transparency at low frequencies.
Solid Samples
Advantages of pellet technique over Nujol method: KBr pellets can be stored for long periods of time. As concentration of sample can be suitably adjusted in the pellets, it can be used for quantitative analysis. Resolution of the spectrum in KBr is superior to that obtained with mulls. Disadvantages: Not suitable for some polymers which are difficult to grind with KBr. High pressure involved during the formation of pellets may bring about polymorphic changes in crystallinity in the samples, which may cause complications in IR spectrum. It always has a absorption band at 3450 cm-1 from the OH group of moisture present in the sample, so care must be taken while 72 investigating the region of the OH band in the sample.
Liquid Samples
Liquid samples are poured without any preparation into circular or rectangular cells made of NaCl, KBr or ThBr and their IR spectrum determined directly.
The sample thickness should be so selected that the transmittance lies between 15 and 70 percent. For most liquids this will represent a thin layer of 0.01 0.05 mm in thickness.
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Liquid Samples
For double beam work, matched cells are used. 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. All cells must be protected from water, because they are water soluble. 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.
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Gas Samples
The gas sample cell are similar to liquid sample cell and are made of KBr, NaCl or ThBr. Larger cells are used for the small number of molecules of a sample that is contained in a gas. The cells are larger, usually they are about 10 cm long, but they may be up to 1 mt long. Multiple reflections can be used to make the effective path length as long as 40 mt, so that constituents of the gas can be determined. 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.75
An Infrared Spectrometer
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IR Spectrometer
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FT-IR Spectrometer
Uses an interferometer. Has better sensitivity. Less energy is needed from source. Completes a scan in 1-2 seconds. Takes several scans and averages them. Has a laser beam that keeps the instrument accurately calibrated. Components Source Michelson Interferometer Sample 78 Detector
Michaelson Interferometer
Beam splitter Stationary mirror Moving mirror at constant velocity Motor driven Micrometer screw He/Ne laser; sampling interval, control mirror velocity
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Beam Splitter
Moving mirror
Sample Detector
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Photoconducting detector
Consists of a thin film of a semi-conducting material, such as lead sulfide, 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. Absorption of IR radiation promotes nonconducting electrons to a higher energy conducting state, thus decreases the electrical resistance of the semiconductor. The voltage drop across the thin film is a measure the power of the IR radiation. 81
Photoconducting detector
A lead sulfide photoconductor for near IR can be operated at room temperature. Mercury/cadmium telluride can be used in the mid-IR and far IR, but must be cooled with liquid nitrogen (77 K) to minimize thermal noise. It provides superior response characteristics. Great for GC-Irs.
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Photodiode
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Advantages of FTIR
High S/N ratios - high throughput Rapid (<10 s) Reproducible High resolution (<0.1 cm-1) Inexpensive IR (especially FTIR) very widely used for Qualitative & quantitative analysis of Gases, liquids, solids
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There are a many moving parts, 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 0.01 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. Data collection is may be allowed to pass through the easier 85 slits
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
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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 Beers Law, can do quantitative analysis 87
FEATURES OF AN IR SPECTRUM
An IR spectrum is a plot of per cent transmittance (or absorbance) against wavenumber (frequency or wavelength). A typical infrared spectrum is shown below.
Different types of groups of atoms (C-H, O-H, N-H, etc) absorb infrared radiation at 88 different characteristic wavenumbers.
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, called the 89 fingerprint region
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
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In general, 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.g. OH, NH, CH 2500 2000 cm-1: Absorption of triple bonds e.g. CC, CN 2000 1500 cm-1: Absorption bonds e.g. C=C, C=O of double
1500 400 cm-1: This region often consists of many different, complicated bands. This part of the spectrum is unique to each compound and is often called the fingerprint region. It is rarely used for identification of particular functional groups.
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Summary of IR Absorptions
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BASE VALUES
(+/- 10 cm-1)
C=O C=C C O
broadens
shifts
FREE H-BONDED
3600
3300
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H N H
3000 divides
SATURATED
C-H aldehyde, two peaks (both weak) ~ 2850 and 2750 cm-1
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CH3 bending (asym) appears near the CH2 value ~ 1460 cm-1
CH3 bending (sym) ~ 1375 cm-1
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The cyano group often gives a strong, sharp peak due to its large dipole moment.
The carbon-carbon triple bond gives a sharp peak, but it is often weak due to a lack of a dipole. This is especially true if it is at the center of a symmetric molecule.
R C C R
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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
1690
R C O C R
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SUMMARY
Ketones are at lower frequency than Aldehydes because of
the second electron-donating alkyl group.
Esters
are at higher frequencies than ketones due to the electron-withdrawing oxygen atom. 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. The electron-withdrawing effect of nitrogen is less important than the resonance.
Note the electronegativity difference, O versus N, weights the two factors (resonance/ e-withdrawal) differently in esters than in amides.
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Look for one or more strong bands appearing in this range! Ethers, alcohols, esters and carboxylic acids have C-O bands
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Often the 1550 cm-1 peak is stronger than the other one
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C-Br and C-I appear outside the useful range of infrared spectroscopy.
C-F bonds can be found easily, but are not that common.
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