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IR SPECTROSCOPY
Manu Jose First year M.Pharm Pharmaceutical Analysis Dept. National College of Pharmacy
OVERVIEW
INTRODUCTION THEORY FACTORS AFFECTING VIBRATIONAL FREQUENCY
SAMPLING TECHNIQUES
INSTRUMENTATION
INTERPRETATION
APPLICATION
Introduction
Spectroscopy
Spectroscopy is the measurement and interpretation of EMR absorbed or emitted,
Definition
IR spectroscopy can be defined as a method for the identification of substances based on their
absorption of IR wavelength.
IR RADIATION
Electromagnetic spectrum
g-rays
X-rays
UV
IR
Microwave
Radio
Visible
Theory
IR radiation in the range 10,000- 100 cm-1 is absorbed. Frequency of absorption depends on relative masses, the force constant, and geometry of atoms. Converted to energy of molecular vibration. The absorption is quantized. Vibrational spectra is appear as bands.
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2. Correct wavelength
Applied IR frequency =Natural frequency of vibration
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v - vibrational frequency k - force constant = (m1.m2)/(m1+m2) m1 and m2 mass of atom 1 and 2 respectively.
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Molecular vibrations
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The relative positions of atoms in a molecule are not fixed but fluctuate continuously as a
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Stretching vibrations
Involves continuous change in inter atomic distance along the axis.
Two types:
Symmetrical stretching-stretching/ compression in symmetrical way.
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symmetrical
H
C
H
asymmetrical
H
C
H
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Bending vibrations:
Involves change in bond angle between bonds with a common atom or the movement of group of atoms to the reminder of molecule.
Two types:
In-plane
Out-of plane
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In plane bending vibrations Scissoring- atoms move towards and away from each other.
H C H
Rocking- The structural unit swings back and forth in the plane.
H C H
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Wagging: The structural unit swings back and forth out of the plane
Twisting: structural unit rotate about the bond which joins to the rest of the molecule
H C H
H C
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Degree of freedom
Each atom has 3 degrees of freedom N-atom molecule there will be 3N degree of freedom. Translation - the movement of the entire molecule while the positions of the atoms relative to each other remain
fixed
Rotational transitions inter-atomic distances remain constant but the entire molecule rotates with respect to three mutually perpendicular axes.
Translation Non linear linear 3 3 Rotational 3 2
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Linear molecules= 3N -5
Eg : N2 (3x2)-5=1
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Eg:
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Inductive effect:
Electro negative/ Stronger bond Negative inductive Increased force constant Wave number rises Acetone chloroacetone Dichloroacetone Tetrachloroacetone H-CHO Electro positive/ electron attracting Positive inductive effect Weaker bond Decrease force constant Wave number decreases CH3-CHO 1745 Wave no cm-1 1715 1725 1740 1778 1750
electron withdrawing
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Field effect:
Lone pair of electrons on two atoms influences
Eg: O- haloacetophenone
CH3 C = O: :
X:
:
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Ring size
Ring strain causes large shift to higher frequency
7 membered ring 1702 cm-1 6 membered ring 1715 cm-1 5 membered ring 1745 cm-1 4 membered ring 1780 cm-1 3 membered ring 1850 cm-1
Increased s character
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Hydrogen bonding
Remarkable downward frequency shift. Stronger H bond- greater the shift towards lower wave number.
Free alcohol H bonded alcohol - sharp OHstr band - broad OHstr band
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Vibrational coupling
Isolated C-H bond only one str frequency
Fundamental+ fundamental
Amide
1600- 1700cm-1
Fundamental + overtone
Aldehydes
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Sampling techniques
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1) Solid samples:
Mull technique Pressed pellet technique Solids run in solutions Solid film
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Mull technique: Grinding 2-5mg of sample in smooth agitate mortar. Powdered sample + Nujol paste Paste between the two plates of salt. The oil has few absorption bands at 2857, 1449 and 1389 cm-1
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Solids films: Amorphous solid samples melted between salt plates allowed to form solid film. For qualitative purpose.
Solids run in solution Solid + suitable solvent solution Kept in cells for liquids Solvents- non associated solvents- CS2, CCl4,
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Liquid sample:
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Gaseous sample:
Vapors in specially designed cells.
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Instrumentation
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Radiation sources
Consist of inert solid Heated electrically
Nernst glower Globar source Mercury arc Incandescent wire source Tungsten filament
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Nernst glower
Composed of rare earth oxides- zirconium, yttrium and thorium Hollow tube (2-5cm x 1-3mm) Platinum leads at one end Large negative temp. coefficient. Emit radiation over wide range and remains steady over a long period.
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Globar source
Rod of sintered silicon carbide. (5cm x 5mm). Positive coefficient of resistance. Self starting and electrically heated Enclosed in water cooled brass tube
Less intense.
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Mercury arc
For far IR region High pressure Hg arc, enclosed in quartz jacketed tube, at 1 atm Passage of electricity through vapor internal
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Sample holders
Constructed of rock salt. Path length is adjusted with Teflon. Filled and emptied with hypodermic needles.
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Monochromator
To select desired frequency from radiation source.
Prism monochromator Grating monochromator
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Detectors
Thermal detectors
(IR heating potential difference amt of radiation)
Photo detectors
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Thermocouple
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Bolometer
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Golay cell
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Comparison
Dispersion Spectrometer
The dispersion Spectrometer takes several minutes to measure an IR spectrum Also the detector receives only a few % of the energy of original light source.
FT-IR
FT-IR takes only a few seconds, to measure an IR spectrum. The detector receives up to 50% of the energy of original light source.
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Spectrum
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IR spectrum
Each dip- band 100% transmittance- no absorption. Scale of spectrum is not entirely linear.
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ALKANES
General structure :
R- CH2- R
Wave number
C-H (str) 3000-2840 cm-1
C-H (def)
1470-1450 cm-1
C-H (rock)
1370-1350 cm-1
C-H (rock)
725-720 cm-1
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Eg: Octane
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ALKENES
General structure : R-C=C-R
Wave number
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Eg: 1-Octene
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ALKYNES
General structure : R- C C - R
Wave number - C C - H str 3333-3267 cm-1
- C C - H def
700-610 cm-1
-C C str
2260-2100 cm-1
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Eg: 1-Hexyne
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Aromatic Compounds
General structure : Ar-R Wave number
C -H str
3100-3000cm-1
1600-1585cm-1 1500-1400cm-1
C-H bend
900-675cm-1
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Eg: Toluene
Alkyl Halides
General structure : R-X
Wave number
C-H str 3000-2850 cm-1
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C-H def
1300-1150 cm-1
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Eg: 1-Bromopropane
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Alcohols
General structure : R-OH
Wave number
O-H str
3500-3200 cm-1
C-O str
1260-1050 cm-1
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Eg: Ethanol
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KETONES
General structure : R-CO-R
Wave number
C=O str
aliphatic ketones
1715 cm-1
,-unsaturated ketones
1685-1666 cm-1
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Eg: 2-Butanone
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Aldehydes
General structure : R-CHO
Wave number
H-C=Ostr
C=O str
2830-2695 cm-1
aliphatic aldehyde
1740-1720 cm-1
,-unsaturated aldehydes
1710-1685 cm-1
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Eg: Butaraldehyde
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CARBOXYLIC ACIDS
General structure : R-COOH
Wave number O-H str 3300-2500 cm-1
C=O str
1760-1690 cm-1
C-O str
1320-1210 cm-1
O-H bend
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ESTERS
General structure : R-COOR
Wave number
C=O str
aliphatic esters
1750-1735cm-1
,-unsaturated
1730-1715cm-1
C-O str
1300-1100cm-1
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Amines
General structure : R- NH2 Wave number N-H str 1O amines 3400-3250cm-1 3400-3300cm-1 3330-3250cm-1 3350-3310cm-1
2Oamines
3O amines
N-H bend (1O only) N-H wag C-N str aromatic amines aliphatic amines
no bands
1650-1580cm-1 910-665cm-1 1335-1250cm-1 1250-1020cm-1
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Eg: Aniline
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NITRO GROUP
General structure: R-NO2
Wave number
1550-1475cm-1
N-O str(symmetric)
1360-1290cm-1
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Eg: Nitromethane
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Recent Advancements
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Applications
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Quantitative analysis
Based on the determination of the concentration of one of the functional group of the compound being estimated. Concentration is determined using Beer- lamberts law A = I1/I0 = abc A c ;
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Qualitative analysis
By comparison with reference spectra. Group frequency region: (3700-1500cm-1)
Hydrogen bonding region
By str vibration between hydrogen and other atom (O-H)
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Miscellaneous applications
Study of progress of reaction. Detection of impurities. Tautomerism. Functional group identification.
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Conclusion
Infrared spectroscopy is certainly one of the most important analytical techniques available to todays scientists for the determination of identity and molecular structure of organic compounds
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References
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William Kemp; Organic Spectroscopy; 3rd edition; page no:20-94. Robert M Silverstein; Spectrometric Identification of Organic Compounds; 6th edition; page no:71-109. Skoog, Holler, Crouch; Instrumental Analysis; 5th edition; page no:477- 528. John R Dyer; Application of Absorption Spectroscopy; page no:23-33.
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H.Kaur; Instrumental Method of Chemical Analysis; 6th edition; page no:181-184,192-195. P.S Kalsi Spectroscopy of organic compound; 6th
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