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SPECTROSCOPY
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COMPARISON BETWEEN TRANSMITTANCE (UPPER) VS
ABSORBANCE (LOWER) PLOT
The transmittance
spectra provide better
contrast btw
intensities of strong
and weak bands
compared to
absorbance spectra
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ELECTROMAGNETIC SPECTRUM
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INFRARED SPECTROSCOPY
IR spectrum provides:
Important information about its chemical nature
and molecular structure
IR applicability:
Analysis of organic materials
Polyatomic inorganic molecules
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Organometallic compounds
IR region of EM spectrum:
λ: 780 nm – 1000 μm
Wavenumber: 12,800 – 10cm-1
2. Mid IR region M
infrared
- 2.5 to 50 μm (4000 – 200 cm-1) I
D
3. Far IR region F
- 50 to 1000 μm (200 – 10cm-1) A
R
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When IR absorption occur?
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What is a dipole moment?
δ-
O
H H
δ+ δ+
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Inheteronuclear diatomic molecule, because
of the difference in electronegativities of the
two atoms, one atom acquires a small positive
charge (q+), the other a negative charge (q-).
This
molecule is then said to have a dipole
moment whose magnitude, μ =qd
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Theory
Covalent bonds in organic molecules are not rigid sticks – rather, they behave
more like springs.
At room temperature, organic molecules are always in motion, as their bonds
stretch, bend, and twist. These complex vibrations can be broken down
mathematically into individual vibrational modes.
The energy of molecular vibration is quantized rather than continuous,
meaning that a molecule can only stretch and bend at certain 'allowed'
frequencies.
If a molecule is exposed to electromagnetic radiation that matches the
frequency of one of its vibrational modes, it will in most cases absorb energy
from the radiation and jump to a higher vibrational energy state – what this
means is that the amplitude of the vibration will increase, but the vibrational
frequency will remain the same.
The difference in energy between the two vibrational states is equal to the
energy associated with the wavelength of radiation that was absorbed. It turns
out that it is the infrared region of the electromagnetic spectrum which contains
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frequencies corresponding to the vibrational frequencies of organic bonds.
The power of infrared spectroscopy - that different functional groups have
different characteristic absorption frequencies.
Some bonds absorb infrared light more strongly than others, and some bonds
do not absorb at all.
In order for a vibrational mode to absorb infrared light, it must result in a
periodic change in the dipole moment of the molecule. Such vibrations are said
to be infrared active.
In general, the greater the polarity of the bond, the stronger its IR
absorption.
The carbonyl bond is very polar, and absorbs very strongly. The carbon-
carbon triple bond in most alkynes, in contrast, is much less polar, and thus a
stretching vibration does not result in a large change in the overall dipole
moment of the molecule. Alkyne groups absorb rather weakly compared to
carbonyls.
Some kinds of vibrations are infrared inactive. The stretching vibrations of
completely symmetrical double and triple bonds, do not result in a change in
dipole moment, and therefore do not result in any absorption of light (but other
bonds and vibrational modes in these molecules do absorb IR light).
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On the horizontal axis we see IR wavelengths expressed in terms of a unit called
wavenumber (cm-1), which tells us how many waves fit into one centimeter. On
the vertical axis we see ‘% transmittance’, which tells us how strongly light
was absorbed at each frequency (100% transmittance means no absorption
occurred at that frequency).
You will notice that there are many additional peaks in this spectrum in the
longer-wavelength 400 -1400 cm-1 region. This part of the spectrum is called the
fingerprint region. The pattern of absorbance peaks in the fingerprint region is
unique to every molecule, meaning that the data from an unknown sample can be
compared to the IR spectra of known standards in order to make a positive
identification.
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IR VIBRATIONAL MODES
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Molecular vibration
divided
back & into involves
forth change in
movement bond angles
stretching bending
wagging
scissoring
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BENDING
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Vibrational spectra (I): Harmonic oscillator model
• Infrared radiation in the range is absorbed and converted by an organic molecule into
energy of molecular vibration, this absorption is quantized:
Consider diatomic molecule A and B with mass m1 and m2
Two atoms connected by covalent bond as a spring,stiffness of bond is force constant k
If spring struck with force,vibrations are produced described by HOOKS law of simple
harmonic motion
Liquid
sodium chloride windows
“neat” liquid
Solid
Pellet (KBr)
Mull
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PELLETING
(KBr PELLET)
spectrometer.
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MULLS
What is Nujol
A trade name for a heavy medicinal liquid paraffin.
Extensively used as a mulling agent in spectroscopy
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INSTRUMENTATION
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IR INSTRUMENT
Dispersive spectrometers
sequential mode
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IR INSTRUMENT (DISPERSIVE)
Important components in IR dispersive
spectrometer
1 2 3 4 5
source sample λ signal processor
detector & readout
lamp holder selector
Detector:
Source:
- Thermocouple
- Nernst glower
- Pyroelectric transducer
- Globar source
- Thermal transducer
- Incandescent wire
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RADIATION SOURCES
generate a beam with sufficient power in the
λ region of interest to permit ready detection
& measurement
provide continuous radiation; made up of all
λ’s with the region (continuum source)
stable output for the period needed to
measure both P0 and P
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SCHEMATIC DIAGRAM OF A DOUBLE BEAM
INFRARED SPECTROPHOTOMETER
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FTIR
FOURIER TRANSFORM INFRARED
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FTIR
Why is it developed?
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Interferometer
Special instrument which can read IR frequencies
simultaneously
faster method than dispersive instrument
interferograms are transformed into frequency spectrums
by using mathematical technique called Fourier
Transformation
FT
Calculations
interferograms
IR spectrum
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COMPONENTS OF FOURIER TRANSFORM INSTRUMENT
5 2
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Instrumentation
Perkin ElmerTM
Spectrum One
BRUKE TENSORTM
Series
Advantages (over dispersive instrument)
high sensitivity
high resolution
speed of data acquisition ( data for an entire spectrum can
be obtained in 1 s or less)
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C) Instrumentation
1.) Basic Design
- normal IR instrument similar to UV-vis
- main differences are light source & detector
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i.) Light Source:
- must produce IR radiation
- can’t use glass since absorbs IR radiation
- several possible types
a) Nernst Glower
Zr, Ce, Th
b) Globar
- similar to Nernst Glower but uses silicon carbide rod
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instead of rare earth oxides
- similar range
c) Incandescent Wire Source
e) Others
- mercury arc (l > 50 mm) (far IR) 61
- tungsten lamp (4000 -12,800cm-1) (near IR)
ii.) Detectors:
- two main types in common IR instruments
a) Thermal Detectors
1.) Thermocouple
- two pieces of dissimilar metals fused together at the ends
- when heated, metals heat at different rates
- potential difference is created between two metals that varies
with their difference in temperature
- usually made with blackened surface (to improve heat
absorption)
- placed in evacuated tube with window transparent to IR (not
glass or quartz)
- IR “hits” and heats one of the two wires.
- can use several thermocouples to increase sensitivity.
metal1 metal2
hn
- + 62
IR transparent
material (NaCl)
V
2.) Bolometer
- strips of metal (Pt, Ni) or semiconductor that has a large change in
resistance to current with temperature.
- as light is absorbed by blackened surface, resistance increases and
current decreases
- very sensitive
hn
A
b) Photoconducting Detectors
- thin film of semiconductor (ex. PbS) on a nonconducting glass surface
and sealed in a vacuum.
- absorption of light by semiconductor moves from non-conducting to
conducting state
- decrease in resistance increase in current hn
-1
- range: 10,000 -333 cm at room temperature
semiconductor 63
glass
c) Pyroelectric Detectors
- pyroelectric (ceramic, lithium tantalate) material get polarized
(separation of (+) and (-) charges) in presence of electric field.
- temperature dependent polarization
- measure degree of polarization related to temperature of crystal
- fast response, good for FTIR
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iii.) Other Components
a.) Sample Cell
- must be made of IR transparent material (KBr pellets or NaCl)
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v.) Fourier Transfer IR (FTIR) – alternative to Normal IR
- Based on Michelson Interferometer
Principal:
1) light from source is split by central mirror into 2 beams of equal intensity
2) beams go to two other mirrors, reflected by central mirror, recombine and
pass through sample to detector
3) two side mirrors. One fixed and other movable
a) move second mirror, light in two-paths travel different distances
before recombined 66
b) constructive & destructive interference
c) as mirror is moved, get a change in signal
Remember
Destructive Interference can be created when two waves from the
same source travel different paths to get to a point.
This may cause a difference in the phase between the two waves.
• If the paths differ by an integer multiple of a wavelength, the waves will also be in
phase.
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• If the waves differ by an odd multiple of half a wave then the waves will be 180
degrees out of
phase and cancel out.
- observe a plot of Intensity vs. Distance (interferograms)
- convert to plot of Intensity vs. Frequency by doing a Fourier
Transform
- resolution Dn = 1/Dd (interval of distance traveled by mirror)
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Advantages of FTIR compared to Normal IR:
1) much faster, seconds vs. minutes
2) use signal averaging to increase signal-to-noise (S/N)
increase S / N number scans
3) higher inherent S/N – no slits, less optical equipment, higher light intensity
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Application of IR
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Application of IR
Qualitative and quantitative analysis
INTERPRETATION
INFRARED SPECTRA
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INFRARED SPECTRA
e.g.
IR spectrum can tell the molecule has an
O-H bond or a C=O or an aromatic ring
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INFRARED SPECTRA
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HOW TO INTERPRET INFRARED SPECTRA?
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How to analyze IR spectra
Indicates:
alkyl groups (present in most organic
Are any or all to the right of 3000?
molecules)
a C=C bond or aromatic group in the
Are any or all to the left of 3000?
molecule
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2. Look for a carbonyl in the region 1760-1690.
If there is such a band:
Indicates:
Is an O–H band also present? a carboxylic acid group
Is a C–O band also present? an ester
Is an aldehyde C–H band also
an aldehyde
present?
Is an N–H band also present? an amide
Are none of the above present? a ketone
(also check the exact position of the carbonyl band for clues as to the type 78
of carbonyl compound it is)
3. Look for a broad O–H band in the region 3500-3200 cm-1.
If there is such a band:
Indicates:
Is an O–H band present? an alcohol or phenol
4. Look for a single or double sharp N–H band in the region 3400-3250
cm-1.
If there is such a band:
Indicates:
Are there two bands? a primary amine
Is there only one band? a secondary amine
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5. Other structural features to check for:
Indicates:
an ether (or an ester if there is a
Are there C–O stretches?
carbonyl band too)
Is there a C=C stretching band? an alkene
Are there aromatic stretching bands? an aromatic
Is there a C≡C band? an alkyne
Are there -NO2 bands? a nitro compound
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How to analyze IR spectra
Also check the region from 900-650 cm-1. Aromatics, alkyl halides,
carboxylic acids, amines, and amides show moderate or strong
absorption bands (bending vibrations) in this region.
H H H
H C C C H
H H H
n
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C-H Stretch for sp3 C-H around 3000 – 2840 cm-1.
CH2 Methylene groups have a characteristic bending absorption
at approx 1465 cm-1
CH3 Methyl groups have a characteristic bending absorption at
approx 1375 cm-1
CH2 The bending (rocking) motion associated with four or more 85
CH2 groups in an open chain occurs at about 720 cm-1
ALKENE
H H
C C
H H
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ALKENE
=C-H Stretch for sp2 C-H occurs at values greater than 3000 cm-1.
=C-H out-of-plane (oop) bending occurs in the range 1000 – 650 cm-1
C=C stretch occurs at 1660 – 1600 cm-1; 87
often conjugation moves C=C stretch to lower frequencies
and increases the intensity
ALKYNE
HC CH
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ALKYNE
C H Stretch for sp2 C-H occurs at values greater than 3000 cm-1.
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C-H Bending ( for Aromatic Ring)
Monosubstituted rings
this substitution pattern always gives a strong absorption near 690
cm-1. If this band is absent, no monosubstituted ring is present. A
second strong band usually appears near 750 cm-1.
Ortho-Disubstituted rings
one strong band near 750 cm-1.
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Meta- Disubstituted rings
- gives one absorption band near 690 cm-1 plus one near 780 cm-1.
C H A third band of medium intensity is often found near 880 cm-1.
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Para- Disubstituted rings
C H - one strong band appears in the region from 800 to 850 cm-
1.
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ALCOHOL
H H
H OH H
H C C OH
H C C C H
H H
H H H
Primary alcohol 10
Secondary alcohol 20
CH3
H3C C OH
CH3 Tertiary alcohol 30
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ALCOHOL
O-H The hydrogen-bonded O-H band is a broad peak at 3400 – 3300 cm-1.
This band is usually the only one present in an alcohol that has not
been dissolved in a solvent (neat liquid).
C-O-H Bending appears as a broad and weak peak at 1440 – 1220 cm-1 often
obscured by the CH3 bendings.
C-O Stretching vibration usually occurs in the range 1260 – 1000 cm-1.
This band can be used to assign a primary, secondary or tertiary 97
structure to an alcohol.
PHENOL
OH
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PHENOL
99
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ETHER
R O R'
C-O The most prominent band is that due to C-O stretch, 1300 – 1000 cm-1.
Phenyl alkyl ethers give two strong bands at about 1250 – 1040 cm-1,
while aliphatic ethers give one strong band at about 1120 cm-1.
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102
CARBONYL COMPOUNDS
cm-1
Normal base values for the C=O stretching vibrations for carbonyl groups
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A. ALDEHYDE
R C H
O
R C H C=O stretch appear in range 1740-1725 cm-1 for normal
O aliphatic aldehydes
R C R'
O
R C R' C=O stretch appear in range 1720-1708 cm-1 for
O normal aliphatic ketones
Ar C R' Conjugation of C=O with phenyl; 1700 – 1680 cm-1 for C=O
O and 1600 – 1450 cm-1 for ring (C=C)
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107
C. CARBOXYLIC ACID
R C OH
O
108
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D. ESTER
R C O R
O
R C O R C=O stretch appear in range 1750-1735 cm-1 for normal
O aliphatic esters
C–O Stretch in two or more bands, one stronger and broader than
the other, occurs in the range 1300 – 1000 cm-1 110
111
E. AMIDE
O O O
H H R
R C N R C N R C N
H R R
10 20 30
112
AMIDE
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F. ACID CHLORIDE
O
R C Cl
Stretch appear in range 1810 -1775 cm-1 in conjugated
C O chlorides. Conjugation lowers the frequency to 1780 – 1760
cm-1
Acid chloride show a very strong band for the C=O group. 114
F. ANHYDRIDE
O O
R C O C R
Stretch always has two bands, 1830 -1800 cm-1 and 1775 – 1740 cm-1,
C O with variable relative intensity.
Conjugation moves the absorption to a lower frequency. Ring strain
(cyclic anhydride) moves absorptions to a higher frequency.
H H R N R
R N R N R
H R
10 20
30
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AMINE
Stretching occurs in the range 3500 – 3300 cm-1.
Primary amines have two bands.
N–H Secondary amines have one band: a vanishingly weak one for
aliphatic compounds and a stronger one for aromatic secondary
amines.
Tertiary amines have no N – H stretch.
Secondary Amine
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TERTIARY AMINE
Aromatic Amine
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