Infrared Spectros
Infrared Spectros
Infrared Spectros
SPECTROSCOPY
ELECTROMAGNETIC SPECTRUM
THE IR REGION
Just below red in the visible region.
Wavelengths usually 2.5-25 mm.
More common units are wavenumbers,
or cm-1, the reciprocal of the
wavelength in centimeters.
Wavenumbers are proportional to
frequency and energy.
IR RADIATION
IR absorbed by organic molecules
600-4000cm-1
Photon energy=hc (wn)= 1.2-8.0×10 -20 J
Molar photon energy=7.4-49 KJ /mol
=1.8-12kcal/mol
IR photon energy <<< covalent bond energy.
Absorbing IR radiation cannot trigger substantial
chemical changes. But IR radiation contains more
energy than random thermal motion at room
temperature.
MOLECULAR VIBRATIONS
There are two main vibrational modes :
1. Stretching - change in bond length
(higher frequency)
Covalent bonds vibrate at only certain
allowable frequencies.
STRETCHING TYPES
Symmetric Asymmetric
=>
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, a photons excites 2 different vibration
modes) increase the no. of bands.
Following will reduce the theoretical no. of bands :
=
C=C > C=C > C-C
2150 1650 1200
increasing m
Solvents
1. Must be transparent in the region studied: no single solvent is
transparent throughout the entire IR region
2. Water and alcohols are seldom employed to avoid O-H band of
water .
3. Must be chemically inert (does not react with substance or cell
holder).
CCl4, CS2, or CHCl3; may be used but we should consider its IR
spectrum
Cells
- NaCl or KCl cells may be used (moisture from air and sample
should be avoided: even with care, their surfaces eventually
become fogged due to absorption of moisture)
- Very thin (path length = 0.1 to 1.0 mm)
- Sample concentration = about 0.1 – 10%
Samples
1. Solid KBr disk (1 mg solid sample + 100 mg KBr pressed into a
disk)
Mull: 1 mg solid sample suspended in Nujol (heavy liquid
hydrocarbon)
=>
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.
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, can do
quantitative analysis
Determination of purity
Study of kinetics of the reaction
Detection of water in the sample
Shape and symmetry of the molecule
IR Absorptions
• Bonds absorb in four predictable regions of an IR spectrum.
22
IR CORRELATION DIAGRAM
Region I Region II
3600-2700 cm-1 1800-1600 cm-1
100
O-H N-H C-H C=O
bond stretching
80 Fingerprint
Transmittance (%)
alcohols
acid chlorides Region
60 phenols
anhydrides (below 1500 cm-1)
esters
carboxylic acids
ketones
40 amines aldehydes
amides carboxylic acids
amides
20 alkynes C-H
alkenes =C-H
alkanes -C-H
0
4000 3500 3000 2500 2000 1500 1000
2.5 3.0 4.0 5.0 6.0 10.0
Frequency (cm-1) / Wavelength (microns, mm)
BASE VALUES
(+/- 10 cm-1)
O-H 3600
N-H 3400
C-H 3000
C N 2250
C C 2150
C=O 1715
C=C 1650
C O ~1100 large range
O-H STRETCH
Typical Infrared Absorption
Regions
O-H WAVELENGTH (mm)
2.5 4 5 5.5 6.1 6.5 15.4
FREQUENCY (cm-1)
The O-H stretching region
O-H 3600 cm-1 (alcohol, free)
O-H 3300 cm-1 (alcohols & acids, H-bonding)
broadens
shifts
FREE H-BONDED
3600 3300
HYDROGEN-BONDED HYDROXYL
Many kinds of OH
R R bonds of different
lengths and strengths
O H O This leads to a broad
H H
absorption.
R O O
R O
H R
“Neat” solution.
H
O
R H Longer bonds are
weaker and lead to
lower frequency.
CCl4
R O CCl4
H
CCl4
CCl4
Solvent molecules
surround but do not
hydrogen bond.
CYCLOHEXANOL
neat solution
CH2
O-H OH
H-bond
C-O
1260-1000
C-H
O-H STRETCH OF A
CARBOXYLIC ACID
This O-H absorbs broadly, 2500-3500 cm-1, due to
strong hydrogen bonding.
C-O-H in plane
bending
BUTANOIC ACID
neat solution
O-H
H-bond
C-O
CH2 O
NH2
scissor CH3
CH2 N-H wagging
NH2
NH2 PRIMARY AMINE
aromatic
3-Methylbenzenamine
CH3
-CH3
Ar-H
NH2
benzene
Ar-H
SECONDARY AMINE
N -Ethylbenzenamine
NH
NH CH2 CH3
CH3
Ar-H
benzene
TERTIARY AMINE
N,N -Dimethylaniline
Ar-H
-CH3
CH3
no N-H
N
CH3
CH3
benzene Ar-H
C-H STRETCH
Typical Infrared Absorption Regions
WAVELENGTH (mm)
C-H
2.5 4 5 5.5 6.1 6.5 15.4
HEXANE
CH bending vibration
CH includes
stretching CH3 sym and asym
vibrations CH2 sym and asym
CH3 CH2 CH2 CH2 CH2 CH3
C-H BENDING
THE C-H BENDING REGION
H-1
~1465 cm
H H H ~1250 cm-1
C C C
H H
~720 cmH
-1
H H H ~1250 cm-1
C C C
H H
Rocking Twisting
in-plane out-of-plane
Bending
Vibrations
METHYLENE AND METHYL BENDING VIBRATIONS
CH2 CH3
C-H Bending, look near
1465 and 1375 cm-1
asym sym
asym sym
C CH3
one peak
1465 1460 1375
CH3
geminal dimethyl 1380 1370 C two peaks
(isopropyl) CH3
CH2
rocking
CH3
CH2 bend
bend
CH
stretch
no 1375 cm-1
no –CH3
ALKENE
1-HEXENE
=CH
C=C CH2
CH3
bend
CH CH
CH2 CH CH2 CH2 CH2 CH3
1-decene
unsat’d
C-H
3020-
3080
cm-1 910-920 &
990-1000
C=C 1640-1680 RCH=CH2
4-methyl-1-pentene
910-920 &
990-1000
RCH=CH2
2,3-dimethyl-1-butene
880-900
R2C=CH2
IR spectra BENZENEs
=C—H bond, “unsaturated” “aryl”
(sp2) 3000-3100 cm-1
+ 690-840
mono-substituted + 690-710, 730-770
ortho-disubstituted + 735-770
meta-disubstituted + 690-710, 750-810(m)
para-disubstituted + 810-840(m)
C=C bond 1500, 1600 cm-1
AROMATIC
TOLUENE
Ar-H CH3
C=C ring
strectching
benzene
CH3
Ar-H
ethylbenzene
Overtones or
3000- Combination
3100 bands from
2000-1667
cm-1
Unsat’d
1500 & 1600
C-H 690-710,
Benzene ring
730-770
mono-
o-xylene
735-770
ortho
p-xylene
810-840(m)
para
m-xylene
meta
690-710,
750-810(m)
ALKYNE
1-HEXYNE
=
C=C
CH2, CH3
Similar
C10H22 But Not
Identical
C12H26
C N AND C C STRETCH
Typical Infrared Absorption
Regions
C=N
=
WAVELENGTH (mm)
2.5 4
C=C
= 5 5.5 6.1 6.5 15.4
R C C R
NITRILE
=
C=N
CH3 CH2 C N
C=O STRETCHING
Typical Infrared Absorption
Regions
WAVELENGTH (mm)
C=O
2.5 4 5 5.5 6.1 6.5 15.4
overtone
2x C=O
C-H CH bend
O
C=O
C=O
CH3 C CH2 CH3
C=O IS SENSITIVE TO ITS ENVIRONMENT
EACH DIFFERENT KIND OF C=O COMES AT A DIFFERENT FREQUENCY
acid carboxylic
chloride ester aldehyde ketone acid amide
O O O O O O
R C R C R C R C R C R C
Cl OR' H R OH NH2
1800 1735 1725 1715 1710 1690
anhydride
O O
BASE
R C O C R VALUE
shorter longer
2-BUTANONE
overtone
C-H CH bend
O
C=O
CH3 C CH2 CH3
3438
ALDEHYDE
NONANAL BASE = 1725
Overtone of 1730
Aldehydic
C-H
CH bend
C=O
O
3460
ACID CHLORIDE
BASE = 1800
DODECANOYL CHLORIDE
CH bend
C
C=O CH3 (CH2)10 Cl
C-H
3608
ESTER
BASE = 1735
ETHYL BUTANOATE
C-O
C-H
O
C=O C
CH3 CH2 CH2 O CH2 CH3
3482
CARBOXYLIC ACID
BASE = 1710
2-METHYLPROPANOIC ACID
O-H
C-O C
C-H C=O CH3 CH OH
CH3
CARBOXYLIC ACID DIMER
RECALL lowers
frequency
of C=O
O H O
R C C R and also
of O-H
O H O
C-H O
C=O C
NH2 CH3 CH2 NH2
CH bend
ALKENES
AROMATICS
C=C STRETCHING
Typical Infrared Absorption
Regions
WAVELENGTH (mm) C=C
2.5 4 5 5.5 6.1 6.5 15.4
C=C benzene ring shows peak(s) near 1600 and 1400 cm-1 ,
one or two at each value - CONJUGATION LOWERS THE VALUE.
1-HEXENE
C-H
aliphatic oops
CH2 CH CH2 CH2 CH2 CH3
AROMATIC
TOLUENE
benzene
C-H CH3 benzene
C=C
oops
Typical Infrared Absorption
Regions
WAVELENGTH (mm) C-O
2.5 4 5 5.5 6.1 6.5 15.4
CH2 CH3
bending
C-H
C-O
BASE = 1100
Anisole
C-H
aromatic
O CH3
Benzene oops
Ring stretch C-O-C
ALCOHOL
BASE = 3600
Cyclohexanol
BASE = 1100
CH2
bend
OH OH
C-O
C-H
CARBOXYLIC ACID
2-Methylpropanoic Acid
OH
C-O C
CH C=O CH3 CH OH
CH3
ESTER
Ethyl Butanoate
CH
O
C-O
C
C=O CH3 CH2 CH2 O CH2 CH3
N=O STRETCHING
Typical Infrared Absorption
Regions
WAVELENGTH (mm)
N-O
2.5 4 5 5.5 6.1 6.5 15.4
2-Nitropropane
C-H
N=O
NO2
gem-dimethyl
CH
CH3 CH3 N=O
Typical Infrared Absorption
Regions
WAVELENGTH (mm) C-Cl
2.5 4 5 5.5 6.1 6.5 15.4
Carbon Tetrachloride
Cl
C-Cl
Cl C Cl
Cl
Chlorobenzene benzene ring
combination
bands
Cl
oops
benzene
C=C C-Cl
=C-H OUT OF PLANE BENDING
OUT-OF-PLANE BENDING
(OOPS)
PLANE
above
H
ALKENES H
H
below
H also with
BENZENES
ALKENES
10 11 12 13 14 15 m
R H
Monosubstituted C C s s
H H
Disubstituted
R R
cis-1,2- C C s
H H
H R
trans-1,2- C C s
R H
R H
1,1- C C s
R H
R R
Trisubstituted C C m
R H
R R
Tetrasubstituted C C =C-H OUT OF PLANE BENDING
R R
1000 900 800 700 cm-1
BENZENES 10 11 12 13 14 15 m
Monosubstituted s s
Disubstituted
s
meta m s s
ortho
para s
RING H’s
Trisubstituted OOPS
1,2,4 m s
1,2,3 s m
1,3,5 s m
combination bands
1000 900 800 700 cm-1