Infrared spectroscopy(IR) & FTIR (Analytical Technique)
CONTENTS
• SPECTROSCOPY
• INFRARED SPECTROSCOPY
• HISTORY
• PRINCIPLE
• MODES OF VIBRATION
• INSTRUMENTATION
• SAMPLE HANDLING
• FTIR (FOURIER TRANSFORM INFRARED)
SPECTROMETER
• PRINCIPLE
• INSTRUMENTATION
• WORKING
• DISPERSIVE VERSUS FTIR
• ADVANTAGES & DISADVANTAGES OF FTIR WITH
APPLICATIONS
• FACTORS AFFECTING VIBRATIONAL
FREQUENCIES
• IR SPECTRA REGION
• IR SPECTRA INTERPRETATION
• EXAMPLES
• ADVANTAGES AND DISADVANTAGES OF IR
• APPLICATIONS OF IR
• REFERENCE
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SPECTROSCOPY
•SPECTROSCOPY IS DEFINED AS THE INTERACTION
BETWEEN MATTER & ELECTROMAGNETIC
RADIATION(EMR) OR LIGHT.
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CONTD.
•SPECTROMETRY IS THE APPLICATION OF
SPECTROSCOPY SO THAT THERE ARE QUANTIFIABLE
RESULTS THAT CAN THAN BE ASSESSED.
•SPECTROPHOTOMETER OR SPECTROMETER: THE
INSTRUMENT THAT IS USED TO MEASURE THE
AMOUNT OF ELECTRO MAGNETIC RADIATION
ABSORBED BY AN ORGANIC MOLECULE.
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INFRARED SPECTROSCOPY
•IR SPECTROMETER SUBJECTS A COMPOUND TO IR
RADIATION IN THE 5000 − 667𝑐𝑚−1(2𝜇𝑚) RANGE.
•TYPE OF ABSORPTION SPECTROSCOPY.
•DETERMINE FUNCTIONAL GROUPS.
•VIBRATIONAL-ROTATIONAL SPECTRA OCCURS.
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IR SPECTROMETER
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CONTD.
• REQUIREMENTS:
COMPOUND/SAMPLE SHOULD HAVE A DIPOLE MOMENT.
TWO COMPOUNDS WILL NEVER SHOW SIMILAR IR SPECTRA, IF THEY ARE NOT
ENANTIOMERS.
IR CATEGORISED INTO 3 REGIONS
REGIONS WAVELENGTH
(𝜇𝑚)
WAVE NUMBER
(𝑐𝑚−1)
NEAR IR (OVERTONE
REGION)
0.8-2.5 12,500-4000
MID IR (VIBRATION-
ROTATION REGION)
2.5-50 4000-200
FAR IR (ROTATION REGION) 50-1000 200-10
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HISTORY
1800
Chemical IR spectroscopy
was emerged as a science by
SIR WILLIAM HERSCHEL
1880
First real IR spectra
measured by ABNEY &
FESTING
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CONTD.
1881
MICHEALSON INVENTED
INTERFEROMETER.
1901-1940
IR spectroscopy becomes a routine
analytical method as spectra were
measured & instruments developed,
especially by W.COBLENTZ.
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CONTD.
1949
PETER FELLGET
obtained the first IR
spectra by FTIR
1960
Commercial FTIR
spectrometer appeared
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CONTD.
1966
Cooley & Tukey developed an
algorithm, which quickly
does a FT
1980
FTIR instrument become
common, led to great
increase in sensitivity &
resolution.
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PRINCIPLE
•IR ACTIVE COMPOUNDS WILL GET EXCITED & SHOWS
VIBRATIONAL-ROTATIONAL SPECTRA; WHICH IS CHARACTERISTICS
FOR FUNCTIONAL GROUPS & FINGERPRINTING.
•HOOKE’S LAW:
IN ORDER TO UNDERSTAND MOLECULAR VIBRATIONS, A BOND
CAN BE TREATED AS A SIMPLE HARMONIC OSCILLATOR
COMPOSED OF TWO MASSES(AS ATOMS) JOINED BY SPRING.
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CONTD.
𝒗 =
𝟏
𝟐𝝅
𝑲
𝑴 𝟏. 𝑴 𝟐
𝑴 𝟏 + 𝑴 𝟐
𝝁 =
𝑴 𝟏. 𝑴 𝟐
𝑴 𝟏 + 𝑴 𝟐
𝒗 =
𝟏
𝟐𝝅
𝑲
𝝁
Where,
𝑣 =frequency
K= force constant
𝑀1= mass of atom 1
𝑀2=mass of atom 2
• If bond is strong- force constant increases, frequency increases.
• For heavier atom attached- mass increases, frequency increases.
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MODES OF VIBRATION
• ABSORPTION OF LIGHT WILL INCREASE BOTH AMPLITUDE & FREQUENCY
OF MOLECULAR VIBRATIONS.
• TYPES OF VIBRATION:
STRETCHING: BOND LENGTH CHANGES, INCREASES OR DECREASES, BOND
ANGLE REMAIN SAME.
–SYMMETRICAL
–ASYMMETRICAL
BENDING: BOND ANGLE CHANGES, BOND LENGTH REMAINS SAME.
–IN PLANE: SCISSORING & ROCKING
–OUT PLANE: WAGGING & TWISTING
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 SYMMETRICAL STRETCHING
•TWO BONDS INCREASE OR
DECREASE IN LENGTH
SIMULTANEOUSLY.
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 ASYMMETRICAL
STRETCHING
•IN THIS, ONE BOND
LENGTH IS INCREASED &
OTHER IS DECREASED.
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 IN PLANE BENDING:
SCISSORING
•TWO ATOMS APPROACH
EACH OTHER.
•BOND ANGLES ARE
DECREASED.
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 IN PLANE BENDING:
ROCKING
•MOVEMENT OF ATOMS TAKE
PLACE IN THE SAME
DIRECTION.
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 OUT PLANE BENDING:
WAGGING
•TWO ATOMS MOVE TO ONE
SIDE OF THE PLANE. THEY
MOVE UP & DOWN THE
PLANE.
•+’ DENOTES ABOVE THE
PLANE & ‘-’ DENOTES
BELOW THE PLANE.
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 OUT PLANE BENDING:
TWISTING
•ONE ATOM MOVES ABOVE
THE PLANE & ANOTHER
ATOM MOVES BELOW THE
PLANE.
•‘+’ DENOTES ABOVE THE
PLANE & ‘-’ DENOTES BELOW
THE PLANE.
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INSTRUMENTATION
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CONTD.
•DISPERSIVE TECHNIQUE COMPONENTS
RADIATION SOURCE
REFERENCE & SAMPLE
CHOPPER
MONOCHROMATOR
DETECTOR
AMPLIFIER
RECORDER
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 RADIATION SOURCE
•NERNST GLOWER & GLOBAR ARE GENERALLY USED.
•NERNST GLOWER:
A SPINDLE OF RARE EARTH OXIDE(THORIUM,
ZIRCONIUM, ETC.)
FOR SHORTER WAVELENGTH.
GLOBAR
RESISTANCE ROD OF SILICON CARBIDE
FOR LONGER WAVELENGTH.
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 REFERENCE & SAMPLING
•REFERENCE:
GENERALLY 𝑲𝑩𝒓 IS USED.
•SAMPLING
•SOLID SAMPLING TECHNIQUE
•LIQUID SAMPLING TECHNIQUE
•GAS SAMPLING TECHNIQUE
•SOLUTION SAMPLING TECHNIQUE
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 CHOPPER
•COMBINES BOTH RADIATIONS & PASSES TO
MONOCHROMATOR.
 MONOCHROMATOR
• PRISM (ALKALI METAL HALIDES USED) OR GRATINGS OR BOTH ARE
USED.
• SPLITS POLYCHROMATIC RADIATION TO COMPONENT WAVELENGTHS.
• RESOLUTION DEPENDS ON SLIT WIDTH & QUALITY OF MIRRORS.
• ROCK SALT PRISM IS GENERALLY USED IN THE RANGE OF 650-4000𝑐𝑚−.
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 DETECTORS
•BOLOMETER, THERMOCOUPLE, THERMISTOR, GOLAY DETECTORS
ARE GENERALLY USED.
•MEASURE THE RADIANT ENERGY BY ITS HEATING EFFECT.
•RADIATION IS ALLOWED TO FALL ON PHOTO CONDUCTING
MATERIAL & THE CONDUCTIVITY OF THE MATERIAL IS MEASURED
CONTINUOUSLY BY A BRIDGE NETWORK.
•ONCE THE SAMPLE ABSORBS RADIATION, THEIR WILL BE
INEQUALITY BETWEEN THE TWO RADIATIONS & SIGNAL WILL BE
PRODUCED.
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 AMPLIFIER & RECORDER
•THE AMPLIFIED SIGNAL IS USED TO MOVE AN ATTENUATOR WHICH
CUTS DOWN THE RADIATION COMING OUT OF THE REFERENCE
BEAM UNTIL ENERGY BALANCE IS RESTORED.
•THIS IS ACHIEVED BY A MOTOR WHICH DRIVES THE COMB INTO
THE REFERENCE BEAM WHEN AN ABSORBING BAND IS
ENCOUNTERED & OUT OF THE BEAM WHEN THE BAND IS PASSED
OVER.
•THE RECORDER IS ALSO COUPLED TO THIS MOTOR SO THAT THE
COMB MOVEMENT IS FOLLOWED EXACTLY BY THE PEN.
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SAMPLE HANDLING•SOLID SAMPLING TECHNIQUES:
–DIRECT SAMPLING
–PALLETISATION TECHNIQUE
 𝑲𝑩𝒓 𝑜𝑟 𝑵𝒂𝑪𝒍 USED FOR PREPARATION OF PELLET WITH
SAMPLE.
ACTS AS DILUENT
TRANSPARENT FOR IR RADIATION
𝑺𝒂𝒎𝒑𝒍𝒆 + 𝑲𝑩𝒓 𝒐𝒓 𝑵𝒂𝑪𝒍 → 𝑩𝒚 𝒂𝒑𝒑𝒍𝒚𝒊𝒏𝒈 𝒑𝒓𝒆𝒔𝒔𝒖𝒓𝒆 → 𝑷𝒆𝒍𝒍𝒆𝒕𝒔 𝒇𝒐𝒓𝒎𝒆𝒅
PARTICLE SIZE: LESS THAN 𝟐𝝁𝒎
SAMPLE SHOULD BE 1-2% OF 𝑲𝑩𝒓 𝑜𝑟 𝑵𝒂𝑪𝒍.
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CONTD.
–MULLING(PASTE)
MULLING AGENTS: NUJOL(HIGH MOLECULAR WEIGHT
LIQUID PARAFFIN HYDROCARBON), CHLOROFLUOROCARBON,
HEXACHLOROBUTADIENE.
𝑺𝒂𝒎𝒑𝒍𝒆 + 𝑴𝒖𝒍𝒊𝒏𝒈 𝒂𝒈𝒆𝒏𝒕 → 𝑷𝒂𝒔𝒕𝒆
–SOLID SAMPLING FOR SOLUTION
SAMPLE PRESENT IN VOLATILE SOLVENT WILL PUT IN
𝑲𝑩𝒓 𝑜𝑟 𝑵𝒂𝑪𝒍 SURFACE.
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CONTD.
• LIQUID SAMPLING TECHNIQUE:
–SAMPLE PRESENT IN VOLATILE SOLVENT WILL PUT IN 𝑲𝑩𝒓 𝑜𝑟 𝑵𝒂𝑪𝒍 SURFACE.
–LIQUID FILM→A DROP OF NEAT LIQUID→PLACE BETWEEN 2 PLATES OF 𝑵𝒂𝑪𝒍 →
TO GIVE A THIN FILM.
• GAS SAMPLING TECHNIQUE:
–GAS CELLS ARE USED, MADE UP OF 𝑵𝒂𝑪𝒍 𝑖. 𝑒. 𝟏𝟎𝒄𝒎 LONG.
• SOLUTION SAMPLING TECHNIQUE:
–1-5% OF SOLUTION INTRODUCED IN A SPECIAL CELL MADE OF ALKALI HALIDE.
– 𝑪𝑯𝑪𝒍 𝟑, 𝑪𝑪𝒍 𝟒, 𝑪𝑺 𝟐, SOLVENTS ARE GENERALLY USED TO DISSOLVE SAMPLES.
AFTER THAT SAMPLE IS ANALYSED IN THE FORM OF SOLUTION.
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FTIR (FOURIER TRANSFORM
INFRARED) SPECTROMETER
•FTIR OBTAINS A IR SPECTRA BY COLLECTING AN INTERFEROGRAM
OF A SAMPLE SIGNAL USING AN INTERFEROMETER, THAN
PERFORM ‘FT’ ON THE INTERFEROGRAM TO OBTAIN THE SPECTRA.
•INTERFEROMETER:
IT IS AN INSTRUMENT THAT USES THE TECHNIQUE OF SUPER
IMPOSING TWO OR MORE WAVES, TO DETECT DIFFERENCE
BETWEEN THEM.
FTIR SPECTROMETER USES A “MICHAELSON INTERFEROMETER”.
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CONTD.
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PRINCIPLE
•BASED ON INTERFEROMETRY & INTERFEROGRAM WILL BE
OBTAINED WHICH IS A COMPLEX SIGNAL OCCURS IN WAVE
LIKE PATTERN.
𝑰𝒏𝒕𝒆𝒓𝒇𝒆𝒓𝒐𝒈𝒓𝒂𝒎 𝒔𝒊𝒈𝒏𝒂𝒍 𝑰𝒏𝒕𝒆𝒏𝒔𝒊𝒕𝒚 𝒗𝒔 𝑻𝒊𝒎𝒆
𝑴𝒂𝒕𝒉𝒆𝒎𝒂𝒕𝒊𝒄𝒂𝒍 𝒄𝒂𝒍𝒄𝒖𝒍𝒂𝒕𝒊𝒐𝒏 𝒃𝒚 𝑭𝑻.
𝑭𝑻𝑰𝑹 𝒔𝒑𝒆𝒄𝒕𝒓𝒂(𝑰𝒏𝒕𝒆𝒏𝒔𝒊𝒕𝒚 𝒗𝒔 𝑭𝒓𝒆𝒒𝒖𝒆𝒏𝒄𝒚)
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INSTRUMENTATION
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WORKING
• RADIATION SOURCE:
NERNST GLOWER OR GLOBAR ARE GENERALLY USED.
• BEAM SPLITTER:
POSITIONED AT 45°
SPLITS RADIATION INTO TWO PARTS:
a.DEFLECTED
b.UNDEFLECTED
BEAM SPLITTER RECOMBINES THE RADIATION & SEND TO SAMPLE.
• SAMPLE:
IT WILL ABSORB THE RADIATION TRANSMITTED RADIATION WILL BE PASSED
THROUGH THE SAMPLE TO DETECTOR
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CONTD.• DETECTOR:
GENERALLY USED DETECTORS ARE:
a.PYROELECTRIC DETECTOR: DEUTERATED TRIGLYERINE SULPHATE (DTGS)
b.PHOTON SENSITIVE SEMICONDUCTOR DETECTOR : MERCURY CADNIUM
TELLURIDE (MCT)
IT WILL DETECT THE RADIATION & INTERFEROGRAM IS FORMED.
• COMPUTER & RECORDER:
FURTHER CALCULATIONS ARE DONE BY ‘FT’.
THEN FTIR SPECTRA IS RECORDED.
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DISPERSIVE 𝑉𝑠 FTIR
SPECTROMETER
DISPERSIVE
•TAKES SEVERAL MINUTES TO
MEASURE.
•ALSO THE DETECTOR
RECEIVES ONLY A FEW
PERCENT OF ENERGY OF
ORIGINAL LIGHT SOURCE.
FTIR
•TAKES FEW SECONDS TO
MEASURE.
•THE DETECTOR RECEIVES UP
TO 50% OF THE ENERGY OF
ORIGIN LIGHT SOURCE(MUCH
LARGER THAN DISPERSIVE
SPECTRA ).
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ADVANTAGES OF FTIR
• FELLGETT’S ADVANTAGE-
INFORMATION FROM ALL WAVELENGTHS IS COLLECTED SIMULTANEOUSLY.
RESULTS IN HIGHER SIGNAL TO NOISE RATIO
• JACQUINOT’S ADVANTAGE(THROUGHPUT)
INTERFEROMETER THROUGHPUT(THE AMOUNT OF MATERIAL OR ITEMS
PASSING THROUGH A SYSTEM OR PROCESS) IS DETERMINED ONLY BY THE
DIAMETER OF THE COLLINATED BEAM COMING FROM THE SOURCE SO NO
SLITS ARE NEEDED(AS A MONOCHROMATOR)
• CONNE’S ADVANTAGE(WAVELENGTH ACCURACY)
WAVELENGTH SCALE IS CALIBRATED BY A LASER BEAM OF KNOWN
WAVELENGTH THAT PASSES THROUGH INTERFEROMETER.
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DISADVANTAGES OF FTIR
•CANNOT DETECT ATOMS/ MONOATOMIC IONS:-
SINGLE ATOMIC ENTITIES CONTAIN NO CHEMICAL BONDS.
•COMPLEX MIXTURE:-
 SAMPLE GIVE RISE TO COMPLEX SPECTRA.
•AQUEOUS SOLUTIONS ARE VERY DIFFICULT TO ANALYSE -WATER IS
A STRONG IR ABSORBER.
•CANNOT DETECT MOLECULES COMPRISED OF 2 IDENTICAL ATOMS
SYMMETRIC 𝑒𝑔. 𝑁2 𝑜𝑟𝑂2
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APPLICATIONS OF FTIR
•IDENTIFICATION OF AN ORGANIC COMPOUND
•STRUCTURE DETERMINATION
•STUDY OF CHEMICAL REACTION
•DETECTION OF IMPURITIES
•STUDY OF KETO-ENOL TAUTOMERISM
•CONFORMATIONAL ANALYSIS
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FACTORS AFFECTING
VIBRATIONAL FREQUENCIES
•HYDROGEN BONDING
•COUPLED VIBRATIONS
•FERMI RESONANCE
•ELECTRONIC EFFECT
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 HYDROGEN BONDING•IT OCCURS IN ANY SYSTEM CONTAINING A PROTON DONOR
GROUP(X-H) & A PROTON ACCEPTOR. IF THE S-ORBITAL OF THE
PROTON CAN EFFECTIVELY OVERLAP THE P OR 𝝅 ORBITAL OF THE
ACCEPTOR GROUP.
•STRONGER HYDROGEN BOND: LONGER O-H BOND, LOWER THE
VIBRATION FREQUENCY, BROADER & MORE INTENSE WILL BE THE
ABSORPTION BAND.
•THE N-H STRETCHING FREQUENCIES OF AMINES ARE ALSO
AFFECTED BY HYDROGEN BONDING AS THAT OF THE HYDROXYL
GROUP BUT FREQUENCY SHIFTS FOR AMINES ARE LESSER THAN
THAT FOR HYDROXYL COMPOUNDS.
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CONTD.
•BECAUSE NITROGEN IS LESS ELECTRONEGATIVE THAN OXYGEN SO
THE HYDROGEN BONDING IN AMINES IS WEAKER THAN THAT IN
HYDROXY COMPOUNDS.
•INTERMOLECULAR HYDROGEN BONDS: BROAD BANDS
•INTRAMOLECULAR HYDROGEN BONDS: SHARP AND WELL DEFINED
BANDS
•THE INTER & INTRAMOLECULAR HYDROGEN BONDING CAN BE
DISTINGUISHED BY DILUTION.
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CONTD.• INTRAMOLECULAR HYDROGEN BONDING REMAINS UNAFFECTED ON
DILUTION & AS A RESULT THE ABSORPTION BAND ALSO REMAINS
UNAFFECTED WHERE AS IN INTERMOLECULAR, BONDS ARE BROKEN ON
DILUTION AND AS A RESULT THERE IS A DECREASE IN THE BONDED O-H
ABSORPTION.
• THE STRENGTH OF HYDROGEN BONDING IS ALSO AFFECTED BY:
• RING STRAIN
• MOLECULAR GEOMETRY
• RELATIVE ACIDITY & BASICITY OF THE PROTON DONOR & ACCEPTOR
GROUPS
• DUE TO HYDROGEN BONDING WAVE NUMBER SHIFT TOWARDS LOWER
END.
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 COUPLED VIBRATIONS
•CH STRETCHING: WE ARE EXPECTING ONE VIBRATIONAL
FREQUENCIES.
•ASYMMETRIC VIBRATIONS OCCUR AT HIGHER FREQUENCIES OR
WAVE NUMBERS THAN SYMMETRIC STRETCHING VIBRATIONS.
•IF 𝐶𝐻2 METHYLENE GROUP IS TAKEN(2 ABSORPTION FREQUENCIES)
SYMMETRICAL
ASYMMETRICAL
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 FERMI RESONANCE
•OVERTONE BAND: SPECTRAL BAND OCCURS IN
VIBRATIONAL SPECTRUM OF A MOLECULE WHEN THE
MOLECULES MAKES TRANSITION FROM GROUND STATE TO
SECOND EXCITED STATE.
•CHANCE OF ENERGY OF OVERTONE BAND &
FUNDAMENTAL FREQUENCY WILL COINCIDE, RESONANCE
WILL OCCUR KNOWN AS FERMI RESONANCE.
•WAVE NUMBER IS INCREASED BY FERMI RESONANCE.
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 ELECTRONIC EFFECT
• ABSORPTION FREQUENCY WILL CHANGE WHEN CHANGE IN THE SUBSTITUENTS
OF NEIGHBOURHOOD GROUP.
• VARIOUS ELECTRONIC EFFECT OCCURS:
INDUCTIVE EFFECT: 𝐈+= DECREASING WAVE NUMBER & 𝐈−=INCREASING
WAVE NUMBER.
MESOMERIC EFFECT: LENGTHENING OF BOND, BOND WILL BE WEAK,
DECREASE IN FORCE CONSTANT, DECREASE WAVE NUMBER.
FIELD EFFECT: OCCURS IN ORTHO SUBSTITUENT, 2 ATOMS INTERACT
THROUGH SPACE INTERACTION & WAVE NUMBER WILL INCREASE OR
DECREASE.
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IR SPECTROSCOPY REGION
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IR SPECTRUM STUDIED UNDER 2
SECTIONS
•FUNCTIONAL GROUP REGION: THE AREA FROM
5000𝑐𝑚−1
TO 1300𝑐𝑚−1
IS CALLED FUNCTIONAL GROUP REGION.
THE BAND IN THIS REGION ARE PARTICULARLY USEFUL IN
DETERMINING THE TYPE OF FUNCTIONAL GROUPS.
•FINGERPRINTING REGION: THE AREA FROM 1300𝑐𝑚−1TO 667𝑐𝑚−1
IS CALLED FINGERPRINTING REGION. A PEAK BY PEAK MATCH
OF AN UNKNOWN SPECTRUM WITH THE SPECTRUM OF THE
SUSPENDED COMPOUND IN THIS REGION CAN BE USED, MUCH
LIKE FINGERPRINT, TO CONFIRM ITS IDENTITY.
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IR SPECTRA INTERPRETATION
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SOME IMPORTANT ABSORPTIONS OF
IR
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AROMATIC HYDROCARBON
(TOLUENE)
E
X
A
M
P
L
E
S
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ALCOHOL (CYCLOHEXANOL)
E
X
A
M
P
L
E
S
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CARBOXYLIC ACID (BUTANOIC
ACID)
E
X
A
M
P
L
E
S
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KETONE (ACETONE)
E
X
A
M
P
L
E
S
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PRIMARY AMINE (1-
BUTANAMINE)
E
X
A
M
P
L
E
S
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SECONDARY AMINE (N-
ETHYLBENAZAMINE)
E
X
A
M
P
L
E
S
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ADVANTAGES & DISADVANTAGES OF
IR SPECTROSCOPY
ADVANTAGES
•EASY TO USE
•ANALYSIS TIME TYPICALLY
< 10 MINUTES
•INEXPENSIVE
DISADVANTAGES
•SENSITIVE TO THE
ABSORPTION OF WATER. IF
THERE IS SIGNIFICANT
MOSITURE IN THE SAMPLE
PENETRATION DISTANCE
OF THE LIGHT DECREASES.
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APPLICATIONS OF IR
SPECTROSCOPY
• IDENTIFICATION OF FUNCTIONAL
GROUPS.
• STRUCTURE ELUCIDATION OF
ORGANIC COMPOUNDS.
• QUANTITATIVE ANALYSIS OF A
NUMBER OF ORGANIC COMPOUNDS.
• STUDY OF COVALENT BONDS IN
MOLECULES.
• STUDYING THE PROGRESS OF
REACTIONS.
• DETECTION OF IMPURITIES IN A
COMPOUND.
• RATIO OF CIS-TRANS ISOMERS IN A
MIXTURE OF COMPOUNDS.
• SHAPE OF SYMMETRY OF AN
INORGANIC MOLECULE.
• STUDY THE PRESENCE OF WATER IN
A SAMPLE.
• MEASUREMENT OF PAINTS &
VARNISHES.
22-12-2019V.K. VIKRAM VARMA 60
REFERENCE
• INTRODUCTION TO SPECTROSCOPY BY PAVIA.
• A TEXTBOOK OF ORGANIC CHEMISTRY BY BAHL ARUN & BAHL B.S.
• HTTP://WWW.CHEM.UCALGARY.CA/COURSES/350/CAREY5TH/CH13/CH13-0.HTML
• HTTP://PREMIERBIOSOFT.COM/TECH_NOTES/MASS-SPECTROMETRY.HTML
• HTTPS://EN.WIKIPEDIA.ORG/WIKI/MASS_SPECTROMETRY
• WWW.YOUTUBE.COM
• WWW.SLIDESHARE.COM
• WWW.GOOGLE.COM
• HTTPS://ORGSPECTROSCOPYINT.BLOGSPOT.COM/2014/12/INFRARED-SPECTROSCOPY.HTML
• HTTPS://WWW.COMPOUNDCHEM.COM/2015/02/05/IRSPECTROSCOPY/
• HTTPS://WWW.SCIENCEDIRECT.COM/TOPICS/EARTH-AND-PLANETARY-
SCIENCES/SPECTROSCOPY
22-12-2019V.K. VIKRAM VARMA 61
22-12-2019V.K. VIKRAM VARMA 62

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Infrared spectroscopy(IR) & FTIR (Analytical Technique)

  • 2. CONTENTS • SPECTROSCOPY • INFRARED SPECTROSCOPY • HISTORY • PRINCIPLE • MODES OF VIBRATION • INSTRUMENTATION • SAMPLE HANDLING • FTIR (FOURIER TRANSFORM INFRARED) SPECTROMETER • PRINCIPLE • INSTRUMENTATION • WORKING • DISPERSIVE VERSUS FTIR • ADVANTAGES & DISADVANTAGES OF FTIR WITH APPLICATIONS • FACTORS AFFECTING VIBRATIONAL FREQUENCIES • IR SPECTRA REGION • IR SPECTRA INTERPRETATION • EXAMPLES • ADVANTAGES AND DISADVANTAGES OF IR • APPLICATIONS OF IR • REFERENCE 22-12-2019V.K. VIKRAM VARMA 2
  • 3. SPECTROSCOPY •SPECTROSCOPY IS DEFINED AS THE INTERACTION BETWEEN MATTER & ELECTROMAGNETIC RADIATION(EMR) OR LIGHT. 22-12-2019V.K. VIKRAM VARMA 3
  • 4. CONTD. •SPECTROMETRY IS THE APPLICATION OF SPECTROSCOPY SO THAT THERE ARE QUANTIFIABLE RESULTS THAT CAN THAN BE ASSESSED. •SPECTROPHOTOMETER OR SPECTROMETER: THE INSTRUMENT THAT IS USED TO MEASURE THE AMOUNT OF ELECTRO MAGNETIC RADIATION ABSORBED BY AN ORGANIC MOLECULE. 22-12-2019V.K. VIKRAM VARMA 4
  • 5. INFRARED SPECTROSCOPY •IR SPECTROMETER SUBJECTS A COMPOUND TO IR RADIATION IN THE 5000 − 667𝑐𝑚−1(2𝜇𝑚) RANGE. •TYPE OF ABSORPTION SPECTROSCOPY. •DETERMINE FUNCTIONAL GROUPS. •VIBRATIONAL-ROTATIONAL SPECTRA OCCURS. 22-12-2019V.K. VIKRAM VARMA 5
  • 7. CONTD. • REQUIREMENTS: COMPOUND/SAMPLE SHOULD HAVE A DIPOLE MOMENT. TWO COMPOUNDS WILL NEVER SHOW SIMILAR IR SPECTRA, IF THEY ARE NOT ENANTIOMERS. IR CATEGORISED INTO 3 REGIONS REGIONS WAVELENGTH (𝜇𝑚) WAVE NUMBER (𝑐𝑚−1) NEAR IR (OVERTONE REGION) 0.8-2.5 12,500-4000 MID IR (VIBRATION- ROTATION REGION) 2.5-50 4000-200 FAR IR (ROTATION REGION) 50-1000 200-10 22-12-2019V.K. VIKRAM VARMA 7
  • 8. HISTORY 1800 Chemical IR spectroscopy was emerged as a science by SIR WILLIAM HERSCHEL 1880 First real IR spectra measured by ABNEY & FESTING 22-12-2019V.K. VIKRAM VARMA 8
  • 9. CONTD. 1881 MICHEALSON INVENTED INTERFEROMETER. 1901-1940 IR spectroscopy becomes a routine analytical method as spectra were measured & instruments developed, especially by W.COBLENTZ. 22-12-2019V.K. VIKRAM VARMA 9
  • 10. CONTD. 1949 PETER FELLGET obtained the first IR spectra by FTIR 1960 Commercial FTIR spectrometer appeared 22-12-2019V.K. VIKRAM VARMA 10
  • 11. CONTD. 1966 Cooley & Tukey developed an algorithm, which quickly does a FT 1980 FTIR instrument become common, led to great increase in sensitivity & resolution. 22-12-2019V.K. VIKRAM VARMA 11
  • 12. PRINCIPLE •IR ACTIVE COMPOUNDS WILL GET EXCITED & SHOWS VIBRATIONAL-ROTATIONAL SPECTRA; WHICH IS CHARACTERISTICS FOR FUNCTIONAL GROUPS & FINGERPRINTING. •HOOKE’S LAW: IN ORDER TO UNDERSTAND MOLECULAR VIBRATIONS, A BOND CAN BE TREATED AS A SIMPLE HARMONIC OSCILLATOR COMPOSED OF TWO MASSES(AS ATOMS) JOINED BY SPRING. 22-12-2019V.K. VIKRAM VARMA 12
  • 13. CONTD. 𝒗 = 𝟏 𝟐𝝅 𝑲 𝑴 𝟏. 𝑴 𝟐 𝑴 𝟏 + 𝑴 𝟐 𝝁 = 𝑴 𝟏. 𝑴 𝟐 𝑴 𝟏 + 𝑴 𝟐 𝒗 = 𝟏 𝟐𝝅 𝑲 𝝁 Where, 𝑣 =frequency K= force constant 𝑀1= mass of atom 1 𝑀2=mass of atom 2 • If bond is strong- force constant increases, frequency increases. • For heavier atom attached- mass increases, frequency increases. 22-12-2019V.K. VIKRAM VARMA 13
  • 14. MODES OF VIBRATION • ABSORPTION OF LIGHT WILL INCREASE BOTH AMPLITUDE & FREQUENCY OF MOLECULAR VIBRATIONS. • TYPES OF VIBRATION: STRETCHING: BOND LENGTH CHANGES, INCREASES OR DECREASES, BOND ANGLE REMAIN SAME. –SYMMETRICAL –ASYMMETRICAL BENDING: BOND ANGLE CHANGES, BOND LENGTH REMAINS SAME. –IN PLANE: SCISSORING & ROCKING –OUT PLANE: WAGGING & TWISTING 22-12-2019V.K. VIKRAM VARMA 14
  • 15.  SYMMETRICAL STRETCHING •TWO BONDS INCREASE OR DECREASE IN LENGTH SIMULTANEOUSLY. 22-12-2019V.K. VIKRAM VARMA 15
  • 16.  ASYMMETRICAL STRETCHING •IN THIS, ONE BOND LENGTH IS INCREASED & OTHER IS DECREASED. 22-12-2019V.K. VIKRAM VARMA 16
  • 17.  IN PLANE BENDING: SCISSORING •TWO ATOMS APPROACH EACH OTHER. •BOND ANGLES ARE DECREASED. 22-12-2019V.K. VIKRAM VARMA 17
  • 18.  IN PLANE BENDING: ROCKING •MOVEMENT OF ATOMS TAKE PLACE IN THE SAME DIRECTION. 22-12-2019V.K. VIKRAM VARMA 18
  • 19.  OUT PLANE BENDING: WAGGING •TWO ATOMS MOVE TO ONE SIDE OF THE PLANE. THEY MOVE UP & DOWN THE PLANE. •+’ DENOTES ABOVE THE PLANE & ‘-’ DENOTES BELOW THE PLANE. 22-12-2019V.K. VIKRAM VARMA 19
  • 20.  OUT PLANE BENDING: TWISTING •ONE ATOM MOVES ABOVE THE PLANE & ANOTHER ATOM MOVES BELOW THE PLANE. •‘+’ DENOTES ABOVE THE PLANE & ‘-’ DENOTES BELOW THE PLANE. 22-12-2019V.K. VIKRAM VARMA 20
  • 22. CONTD. •DISPERSIVE TECHNIQUE COMPONENTS RADIATION SOURCE REFERENCE & SAMPLE CHOPPER MONOCHROMATOR DETECTOR AMPLIFIER RECORDER 22-12-2019V.K. VIKRAM VARMA 22
  • 23.  RADIATION SOURCE •NERNST GLOWER & GLOBAR ARE GENERALLY USED. •NERNST GLOWER: A SPINDLE OF RARE EARTH OXIDE(THORIUM, ZIRCONIUM, ETC.) FOR SHORTER WAVELENGTH. GLOBAR RESISTANCE ROD OF SILICON CARBIDE FOR LONGER WAVELENGTH. 22-12-2019V.K. VIKRAM VARMA 23
  • 24.  REFERENCE & SAMPLING •REFERENCE: GENERALLY 𝑲𝑩𝒓 IS USED. •SAMPLING •SOLID SAMPLING TECHNIQUE •LIQUID SAMPLING TECHNIQUE •GAS SAMPLING TECHNIQUE •SOLUTION SAMPLING TECHNIQUE 22-12-2019V.K. VIKRAM VARMA 24
  • 25.  CHOPPER •COMBINES BOTH RADIATIONS & PASSES TO MONOCHROMATOR.  MONOCHROMATOR • PRISM (ALKALI METAL HALIDES USED) OR GRATINGS OR BOTH ARE USED. • SPLITS POLYCHROMATIC RADIATION TO COMPONENT WAVELENGTHS. • RESOLUTION DEPENDS ON SLIT WIDTH & QUALITY OF MIRRORS. • ROCK SALT PRISM IS GENERALLY USED IN THE RANGE OF 650-4000𝑐𝑚−. 22-12-2019V.K. VIKRAM VARMA 25
  • 26.  DETECTORS •BOLOMETER, THERMOCOUPLE, THERMISTOR, GOLAY DETECTORS ARE GENERALLY USED. •MEASURE THE RADIANT ENERGY BY ITS HEATING EFFECT. •RADIATION IS ALLOWED TO FALL ON PHOTO CONDUCTING MATERIAL & THE CONDUCTIVITY OF THE MATERIAL IS MEASURED CONTINUOUSLY BY A BRIDGE NETWORK. •ONCE THE SAMPLE ABSORBS RADIATION, THEIR WILL BE INEQUALITY BETWEEN THE TWO RADIATIONS & SIGNAL WILL BE PRODUCED. 22-12-2019V.K. VIKRAM VARMA 26
  • 27.  AMPLIFIER & RECORDER •THE AMPLIFIED SIGNAL IS USED TO MOVE AN ATTENUATOR WHICH CUTS DOWN THE RADIATION COMING OUT OF THE REFERENCE BEAM UNTIL ENERGY BALANCE IS RESTORED. •THIS IS ACHIEVED BY A MOTOR WHICH DRIVES THE COMB INTO THE REFERENCE BEAM WHEN AN ABSORBING BAND IS ENCOUNTERED & OUT OF THE BEAM WHEN THE BAND IS PASSED OVER. •THE RECORDER IS ALSO COUPLED TO THIS MOTOR SO THAT THE COMB MOVEMENT IS FOLLOWED EXACTLY BY THE PEN. 22-12-2019V.K. VIKRAM VARMA 27
  • 28. SAMPLE HANDLING•SOLID SAMPLING TECHNIQUES: –DIRECT SAMPLING –PALLETISATION TECHNIQUE  𝑲𝑩𝒓 𝑜𝑟 𝑵𝒂𝑪𝒍 USED FOR PREPARATION OF PELLET WITH SAMPLE. ACTS AS DILUENT TRANSPARENT FOR IR RADIATION 𝑺𝒂𝒎𝒑𝒍𝒆 + 𝑲𝑩𝒓 𝒐𝒓 𝑵𝒂𝑪𝒍 → 𝑩𝒚 𝒂𝒑𝒑𝒍𝒚𝒊𝒏𝒈 𝒑𝒓𝒆𝒔𝒔𝒖𝒓𝒆 → 𝑷𝒆𝒍𝒍𝒆𝒕𝒔 𝒇𝒐𝒓𝒎𝒆𝒅 PARTICLE SIZE: LESS THAN 𝟐𝝁𝒎 SAMPLE SHOULD BE 1-2% OF 𝑲𝑩𝒓 𝑜𝑟 𝑵𝒂𝑪𝒍. 22-12-2019V.K. VIKRAM VARMA 28
  • 29. CONTD. –MULLING(PASTE) MULLING AGENTS: NUJOL(HIGH MOLECULAR WEIGHT LIQUID PARAFFIN HYDROCARBON), CHLOROFLUOROCARBON, HEXACHLOROBUTADIENE. 𝑺𝒂𝒎𝒑𝒍𝒆 + 𝑴𝒖𝒍𝒊𝒏𝒈 𝒂𝒈𝒆𝒏𝒕 → 𝑷𝒂𝒔𝒕𝒆 –SOLID SAMPLING FOR SOLUTION SAMPLE PRESENT IN VOLATILE SOLVENT WILL PUT IN 𝑲𝑩𝒓 𝑜𝑟 𝑵𝒂𝑪𝒍 SURFACE. 22-12-2019V.K. VIKRAM VARMA 29
  • 30. CONTD. • LIQUID SAMPLING TECHNIQUE: –SAMPLE PRESENT IN VOLATILE SOLVENT WILL PUT IN 𝑲𝑩𝒓 𝑜𝑟 𝑵𝒂𝑪𝒍 SURFACE. –LIQUID FILM→A DROP OF NEAT LIQUID→PLACE BETWEEN 2 PLATES OF 𝑵𝒂𝑪𝒍 → TO GIVE A THIN FILM. • GAS SAMPLING TECHNIQUE: –GAS CELLS ARE USED, MADE UP OF 𝑵𝒂𝑪𝒍 𝑖. 𝑒. 𝟏𝟎𝒄𝒎 LONG. • SOLUTION SAMPLING TECHNIQUE: –1-5% OF SOLUTION INTRODUCED IN A SPECIAL CELL MADE OF ALKALI HALIDE. – 𝑪𝑯𝑪𝒍 𝟑, 𝑪𝑪𝒍 𝟒, 𝑪𝑺 𝟐, SOLVENTS ARE GENERALLY USED TO DISSOLVE SAMPLES. AFTER THAT SAMPLE IS ANALYSED IN THE FORM OF SOLUTION. 22-12-2019V.K. VIKRAM VARMA 30
  • 31. FTIR (FOURIER TRANSFORM INFRARED) SPECTROMETER •FTIR OBTAINS A IR SPECTRA BY COLLECTING AN INTERFEROGRAM OF A SAMPLE SIGNAL USING AN INTERFEROMETER, THAN PERFORM ‘FT’ ON THE INTERFEROGRAM TO OBTAIN THE SPECTRA. •INTERFEROMETER: IT IS AN INSTRUMENT THAT USES THE TECHNIQUE OF SUPER IMPOSING TWO OR MORE WAVES, TO DETECT DIFFERENCE BETWEEN THEM. FTIR SPECTROMETER USES A “MICHAELSON INTERFEROMETER”. 22-12-2019V.K. VIKRAM VARMA 31
  • 33. PRINCIPLE •BASED ON INTERFEROMETRY & INTERFEROGRAM WILL BE OBTAINED WHICH IS A COMPLEX SIGNAL OCCURS IN WAVE LIKE PATTERN. 𝑰𝒏𝒕𝒆𝒓𝒇𝒆𝒓𝒐𝒈𝒓𝒂𝒎 𝒔𝒊𝒈𝒏𝒂𝒍 𝑰𝒏𝒕𝒆𝒏𝒔𝒊𝒕𝒚 𝒗𝒔 𝑻𝒊𝒎𝒆 𝑴𝒂𝒕𝒉𝒆𝒎𝒂𝒕𝒊𝒄𝒂𝒍 𝒄𝒂𝒍𝒄𝒖𝒍𝒂𝒕𝒊𝒐𝒏 𝒃𝒚 𝑭𝑻. 𝑭𝑻𝑰𝑹 𝒔𝒑𝒆𝒄𝒕𝒓𝒂(𝑰𝒏𝒕𝒆𝒏𝒔𝒊𝒕𝒚 𝒗𝒔 𝑭𝒓𝒆𝒒𝒖𝒆𝒏𝒄𝒚) 22-12-2019V.K. VIKRAM VARMA 33
  • 35. WORKING • RADIATION SOURCE: NERNST GLOWER OR GLOBAR ARE GENERALLY USED. • BEAM SPLITTER: POSITIONED AT 45° SPLITS RADIATION INTO TWO PARTS: a.DEFLECTED b.UNDEFLECTED BEAM SPLITTER RECOMBINES THE RADIATION & SEND TO SAMPLE. • SAMPLE: IT WILL ABSORB THE RADIATION TRANSMITTED RADIATION WILL BE PASSED THROUGH THE SAMPLE TO DETECTOR 22-12-2019V.K. VIKRAM VARMA 35
  • 36. CONTD.• DETECTOR: GENERALLY USED DETECTORS ARE: a.PYROELECTRIC DETECTOR: DEUTERATED TRIGLYERINE SULPHATE (DTGS) b.PHOTON SENSITIVE SEMICONDUCTOR DETECTOR : MERCURY CADNIUM TELLURIDE (MCT) IT WILL DETECT THE RADIATION & INTERFEROGRAM IS FORMED. • COMPUTER & RECORDER: FURTHER CALCULATIONS ARE DONE BY ‘FT’. THEN FTIR SPECTRA IS RECORDED. 22-12-2019V.K. VIKRAM VARMA 36
  • 37. DISPERSIVE 𝑉𝑠 FTIR SPECTROMETER DISPERSIVE •TAKES SEVERAL MINUTES TO MEASURE. •ALSO THE DETECTOR RECEIVES ONLY A FEW PERCENT OF ENERGY OF ORIGINAL LIGHT SOURCE. FTIR •TAKES FEW SECONDS TO MEASURE. •THE DETECTOR RECEIVES UP TO 50% OF THE ENERGY OF ORIGIN LIGHT SOURCE(MUCH LARGER THAN DISPERSIVE SPECTRA ). 22-12-2019V.K. VIKRAM VARMA 37
  • 38. ADVANTAGES OF FTIR • FELLGETT’S ADVANTAGE- INFORMATION FROM ALL WAVELENGTHS IS COLLECTED SIMULTANEOUSLY. RESULTS IN HIGHER SIGNAL TO NOISE RATIO • JACQUINOT’S ADVANTAGE(THROUGHPUT) INTERFEROMETER THROUGHPUT(THE AMOUNT OF MATERIAL OR ITEMS PASSING THROUGH A SYSTEM OR PROCESS) IS DETERMINED ONLY BY THE DIAMETER OF THE COLLINATED BEAM COMING FROM THE SOURCE SO NO SLITS ARE NEEDED(AS A MONOCHROMATOR) • CONNE’S ADVANTAGE(WAVELENGTH ACCURACY) WAVELENGTH SCALE IS CALIBRATED BY A LASER BEAM OF KNOWN WAVELENGTH THAT PASSES THROUGH INTERFEROMETER. 22-12-2019V.K. VIKRAM VARMA 38
  • 39. DISADVANTAGES OF FTIR •CANNOT DETECT ATOMS/ MONOATOMIC IONS:- SINGLE ATOMIC ENTITIES CONTAIN NO CHEMICAL BONDS. •COMPLEX MIXTURE:-  SAMPLE GIVE RISE TO COMPLEX SPECTRA. •AQUEOUS SOLUTIONS ARE VERY DIFFICULT TO ANALYSE -WATER IS A STRONG IR ABSORBER. •CANNOT DETECT MOLECULES COMPRISED OF 2 IDENTICAL ATOMS SYMMETRIC 𝑒𝑔. 𝑁2 𝑜𝑟𝑂2 22-12-2019V.K. VIKRAM VARMA 39
  • 40. APPLICATIONS OF FTIR •IDENTIFICATION OF AN ORGANIC COMPOUND •STRUCTURE DETERMINATION •STUDY OF CHEMICAL REACTION •DETECTION OF IMPURITIES •STUDY OF KETO-ENOL TAUTOMERISM •CONFORMATIONAL ANALYSIS 22-12-2019V.K. VIKRAM VARMA 40
  • 41. FACTORS AFFECTING VIBRATIONAL FREQUENCIES •HYDROGEN BONDING •COUPLED VIBRATIONS •FERMI RESONANCE •ELECTRONIC EFFECT 22-12-2019V.K. VIKRAM VARMA 41
  • 42.  HYDROGEN BONDING•IT OCCURS IN ANY SYSTEM CONTAINING A PROTON DONOR GROUP(X-H) & A PROTON ACCEPTOR. IF THE S-ORBITAL OF THE PROTON CAN EFFECTIVELY OVERLAP THE P OR 𝝅 ORBITAL OF THE ACCEPTOR GROUP. •STRONGER HYDROGEN BOND: LONGER O-H BOND, LOWER THE VIBRATION FREQUENCY, BROADER & MORE INTENSE WILL BE THE ABSORPTION BAND. •THE N-H STRETCHING FREQUENCIES OF AMINES ARE ALSO AFFECTED BY HYDROGEN BONDING AS THAT OF THE HYDROXYL GROUP BUT FREQUENCY SHIFTS FOR AMINES ARE LESSER THAN THAT FOR HYDROXYL COMPOUNDS. 22-12-2019V.K. VIKRAM VARMA 42
  • 43. CONTD. •BECAUSE NITROGEN IS LESS ELECTRONEGATIVE THAN OXYGEN SO THE HYDROGEN BONDING IN AMINES IS WEAKER THAN THAT IN HYDROXY COMPOUNDS. •INTERMOLECULAR HYDROGEN BONDS: BROAD BANDS •INTRAMOLECULAR HYDROGEN BONDS: SHARP AND WELL DEFINED BANDS •THE INTER & INTRAMOLECULAR HYDROGEN BONDING CAN BE DISTINGUISHED BY DILUTION. 22-12-2019V.K. VIKRAM VARMA 43
  • 44. CONTD.• INTRAMOLECULAR HYDROGEN BONDING REMAINS UNAFFECTED ON DILUTION & AS A RESULT THE ABSORPTION BAND ALSO REMAINS UNAFFECTED WHERE AS IN INTERMOLECULAR, BONDS ARE BROKEN ON DILUTION AND AS A RESULT THERE IS A DECREASE IN THE BONDED O-H ABSORPTION. • THE STRENGTH OF HYDROGEN BONDING IS ALSO AFFECTED BY: • RING STRAIN • MOLECULAR GEOMETRY • RELATIVE ACIDITY & BASICITY OF THE PROTON DONOR & ACCEPTOR GROUPS • DUE TO HYDROGEN BONDING WAVE NUMBER SHIFT TOWARDS LOWER END. 22-12-2019V.K. VIKRAM VARMA 44
  • 45.  COUPLED VIBRATIONS •CH STRETCHING: WE ARE EXPECTING ONE VIBRATIONAL FREQUENCIES. •ASYMMETRIC VIBRATIONS OCCUR AT HIGHER FREQUENCIES OR WAVE NUMBERS THAN SYMMETRIC STRETCHING VIBRATIONS. •IF 𝐶𝐻2 METHYLENE GROUP IS TAKEN(2 ABSORPTION FREQUENCIES) SYMMETRICAL ASYMMETRICAL 22-12-2019V.K. VIKRAM VARMA 45
  • 46.  FERMI RESONANCE •OVERTONE BAND: SPECTRAL BAND OCCURS IN VIBRATIONAL SPECTRUM OF A MOLECULE WHEN THE MOLECULES MAKES TRANSITION FROM GROUND STATE TO SECOND EXCITED STATE. •CHANCE OF ENERGY OF OVERTONE BAND & FUNDAMENTAL FREQUENCY WILL COINCIDE, RESONANCE WILL OCCUR KNOWN AS FERMI RESONANCE. •WAVE NUMBER IS INCREASED BY FERMI RESONANCE. 22-12-2019V.K. VIKRAM VARMA 46
  • 47.  ELECTRONIC EFFECT • ABSORPTION FREQUENCY WILL CHANGE WHEN CHANGE IN THE SUBSTITUENTS OF NEIGHBOURHOOD GROUP. • VARIOUS ELECTRONIC EFFECT OCCURS: INDUCTIVE EFFECT: 𝐈+= DECREASING WAVE NUMBER & 𝐈−=INCREASING WAVE NUMBER. MESOMERIC EFFECT: LENGTHENING OF BOND, BOND WILL BE WEAK, DECREASE IN FORCE CONSTANT, DECREASE WAVE NUMBER. FIELD EFFECT: OCCURS IN ORTHO SUBSTITUENT, 2 ATOMS INTERACT THROUGH SPACE INTERACTION & WAVE NUMBER WILL INCREASE OR DECREASE. 22-12-2019V.K. VIKRAM VARMA 47
  • 49. IR SPECTRUM STUDIED UNDER 2 SECTIONS •FUNCTIONAL GROUP REGION: THE AREA FROM 5000𝑐𝑚−1 TO 1300𝑐𝑚−1 IS CALLED FUNCTIONAL GROUP REGION. THE BAND IN THIS REGION ARE PARTICULARLY USEFUL IN DETERMINING THE TYPE OF FUNCTIONAL GROUPS. •FINGERPRINTING REGION: THE AREA FROM 1300𝑐𝑚−1TO 667𝑐𝑚−1 IS CALLED FINGERPRINTING REGION. A PEAK BY PEAK MATCH OF AN UNKNOWN SPECTRUM WITH THE SPECTRUM OF THE SUSPENDED COMPOUND IN THIS REGION CAN BE USED, MUCH LIKE FINGERPRINT, TO CONFIRM ITS IDENTITY. 22-12-2019V.K. VIKRAM VARMA 49
  • 52. SOME IMPORTANT ABSORPTIONS OF IR 22-12-2019V.K. VIKRAM VARMA 52
  • 59. ADVANTAGES & DISADVANTAGES OF IR SPECTROSCOPY ADVANTAGES •EASY TO USE •ANALYSIS TIME TYPICALLY < 10 MINUTES •INEXPENSIVE DISADVANTAGES •SENSITIVE TO THE ABSORPTION OF WATER. IF THERE IS SIGNIFICANT MOSITURE IN THE SAMPLE PENETRATION DISTANCE OF THE LIGHT DECREASES. 22-12-2019V.K. VIKRAM VARMA 59
  • 60. APPLICATIONS OF IR SPECTROSCOPY • IDENTIFICATION OF FUNCTIONAL GROUPS. • STRUCTURE ELUCIDATION OF ORGANIC COMPOUNDS. • QUANTITATIVE ANALYSIS OF A NUMBER OF ORGANIC COMPOUNDS. • STUDY OF COVALENT BONDS IN MOLECULES. • STUDYING THE PROGRESS OF REACTIONS. • DETECTION OF IMPURITIES IN A COMPOUND. • RATIO OF CIS-TRANS ISOMERS IN A MIXTURE OF COMPOUNDS. • SHAPE OF SYMMETRY OF AN INORGANIC MOLECULE. • STUDY THE PRESENCE OF WATER IN A SAMPLE. • MEASUREMENT OF PAINTS & VARNISHES. 22-12-2019V.K. VIKRAM VARMA 60
  • 61. REFERENCE • INTRODUCTION TO SPECTROSCOPY BY PAVIA. • A TEXTBOOK OF ORGANIC CHEMISTRY BY BAHL ARUN & BAHL B.S. • HTTP://WWW.CHEM.UCALGARY.CA/COURSES/350/CAREY5TH/CH13/CH13-0.HTML • HTTP://PREMIERBIOSOFT.COM/TECH_NOTES/MASS-SPECTROMETRY.HTML • HTTPS://EN.WIKIPEDIA.ORG/WIKI/MASS_SPECTROMETRY • WWW.YOUTUBE.COM • WWW.SLIDESHARE.COM • WWW.GOOGLE.COM • HTTPS://ORGSPECTROSCOPYINT.BLOGSPOT.COM/2014/12/INFRARED-SPECTROSCOPY.HTML • HTTPS://WWW.COMPOUNDCHEM.COM/2015/02/05/IRSPECTROSCOPY/ • HTTPS://WWW.SCIENCEDIRECT.COM/TOPICS/EARTH-AND-PLANETARY- SCIENCES/SPECTROSCOPY 22-12-2019V.K. VIKRAM VARMA 61