INFRARED

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

2. Bending - change in bond angle (lower

frequency) Why?

In-plane (Scissoring) Out-plane (Twisting)

 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
Nonlinear molecule with n atoms usually has 3n - 6
fundamental vibrational modes.
E,g. H2O would have

3652 cm-1 3756cm-1 1596 cm-1

=>
 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 :

1. Fundamental frequencies that fall outside the 4000-400 cm-1

region.
2. Fundamental bands that are too weak to be observed.
3. Fundamental bands that are so close that they coalesce.
4. The occurrence of a degenerate band from several absorptions
of the same frequency in highly symmetrical molecules.
5. The failure of certain fundamental vibrations to appear in the
IR because of the lack of change in molecular dipole.
 IR-ACTIVE AND INACTIVE
 A polar bond is usually IR-active.
 A nonpolar bond in a symmetrical molecule
will absorb weakly or not at all.
INFLUENCE OF MASS ON VIBRATION
H2 I2

MM =2 g/mole MM =254 g/mole

The greater the mass - the lower the wavenumber

For a vibration at 4111 cm-1 (the stretch in

H2), how many vibrations occur in a second?
120 trillion vibration per second!!!!
120 x 1012 vibrations/sec or a vibration every 8 x 10-15
seconds!
Hooke’s Law M1 M2

ύ = The vibration frequency (cm-1)

c = Velocity of light (cm/s)
f = force constant of bond (dyne/cm)
m1 and m2 are mass (g) of atom M1 and M2
The relative contributions of bond strength is
also considered in vibrational frequencies.

In general functional groups that have a

strong dipole give rise to strong absorptions in
the IR.
increasing K

=
C=C > C=C > C-C
2150 1650 1200

increasing m

C-H > C-C > C-O > C-Cl > C-Br

3000 1200 1100 750 650
 Conjugation lowers the frequency:
isolated C=C 1640-1680 cm-1
conjugated C=C 1620-1640 cm-1
aromatic C=C approx. 1600 cm-1

Bonds with more s character absorb at a higher

frequency.
 sp3 C-H, just below 3000 cm-1 (to the right)
 sp2 C-H, just above 3000 cm -1 (to the left)
 sp C-H, at 3300 cm-1
 Instrumentation
1. Radiation source 2. Monochromator
3. Solvents, sample cells, samples 4. Readout / Recorder

SOLVENTS, CELLS, SAMPLES

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)

2. Liquid Neat (thin film of liquid between two NaCl plates

solution in CCl4 and put in special NaCl cells.
3. Gas IR spectrum is obtained directly by permitting the sample
to expand into an evacuated special cells.
 INTERFEROGRAM
 The interferogram at the right
displays the interference pattern
and contains all of the spectrum
information.

 A Fourier transform converts the time domain to

the frequency domain with absorption as a
function of frequency.
AN INFRARED SPECTROMETER

=>
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.

The four regions

of the 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

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

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

R R
O H O
H H
Many kinds of OH
bonds of different
lengths and strengths
This leads to a broad
absorption.

R O O
R O
H R
“Neat” solution.
H
O
R H Longer bonds are
weaker and lead to
lower frequency.

Hydrogen bonding occurs in concentrated solutions

( for instance, undiluted alcohol ).
 “FREE” HYDROXYL
The “free” hydroxyl vibrates without interference from any other
molecule.

Distinct bond has a well-defined

CCl4 length and strength.

CCl4
R O CCl4
H
CCl4
CCl4
Solvent molecules
surround but do not
hydrogen bond.

Occurs in dilute solutions of alcohol in an “inert” solvent like CCl 4.

 ALCOHOL

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

O-H bending (OOP)

appearing at 920
broad with medium
intensity
C-O
stretching
as doublet
 CARBOXYLIC ACID

BUTANOIC ACID
neat solution

O-H
H-bond

C-O

CH2 O

C-H C=O CH3 CH2 CH2 C OH

STERIC HINDRANCE TO H-BONDING
O-H AND N-H STRETCHING
 Both of these occur around 3300 cm-1, but
they look different.
 Alcohol O-H, broad with rounded tip.
 Secondary amine (R 2NH), broad with one sharp
spike.
 Primary amine (RNH2), broad with two sharp
spikes.
 No signal for a tertiary amine (R 3N)
N-H STRETCH
 Typical Infrared Absorption Regions

N-H WAVELENGTH (mm)

2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)
THE N-H STRETCHING REGION
N-H 3300 - 3400 cm-1

 Primary amines give two peaks

H H
N N
H H
symmetric asymmetric

 Secondary amines give one peak

 Tertiary amines give no peak
 Shoulder at about 3200; PRIMARY AMINE
fermi resonance with aliphatic
overtone band at 1601
1-Butanamine
CH3 CH2 CH2 CH2 NH2

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

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)
 The C-H stretching region
BASE VALUE = 3000 cm-1

•C-H sp stretch ~ 3300 cm-1

UNSATURATED
•C-H sp2 stretch > 3000 cm-1
3000 divides

•C-H sp3 stretch < 3000 cm-1 SATURATED

•C-H aldehyde, two peaks (both weak)

~ 2850 and 2750 cm-1
 STRONGER BONDS HAVE LARGER FORCE CONSTANTS
AND ABSORB AT HIGHER FREQUENCIES

increasing frequency (cm-1)

3300 3100 3000 2900 2850 2750

==C-H =C-H -C-H -CH=O

(weak)

sp-1s sp2-1s sp3-1s aldehyde

increasing s character in bond

increasing CH Bond Strength

increasing force constant K

C-H BASE VALUE = 3000 cm-1

 ALKANE

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

 CH2 bending ~ 1465 cm-1

 CH3 bending (asym) appears near

the CH2 value ~ 1460 cm-1

 CH3 bending (sym) ~ 1375 cm-1

METHYLENE GROUP BENDING VIBRATIONS
Scissoring Wagging

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

1465 1460 1375

these two peaks

frequently overlap
and are not resolved C
H H
H
METHYLENE AND METHYL BENDING VIBRATIONS
ADDITIONAL DETAILS FOR SYM CH3 The sym methyl peak
splits when you have
CH2 CH3 more than one CH3
attached to a carbon.

asym sym
C CH3
one peak
1465 1460 1375

CH3
geminal dimethyl 1380 1370 C two peaks
(isopropyl) CH3

t-butyl 1390 1370 CH3

C CH 3
CH3 two peaks
 ALKANE
HEXANE

CH2
rocking
CH3
CH2 bend
bend
CH
stretch

CH3 CH2 CH2 CH2 CH2 CH3

2-methylbutane
(isopentane)
cyclohexane

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

= C-H HC C CH2 CH2 CH2 CH3

=C-H
Fingerprinting

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

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)
THE TRIPLE BOND STRETCHING
REGION
 C ≡ N 2250 cm-1
 C ≡ C 2150 cm-1

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
 NITRILE

PROPANENITRILE BASE = 2250

=
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

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)
 THE CARBONYL STRETCHING REGION
 This region stretches from about 1800 to 1650
cm-1 - RIGHT IN THE MIDDLE OF THE SPECTRUM

 The base value is 1715 cm-1 (ketone)

 The bands are very strong !!! due to the large

C=O dipole moment.

 C=O is often one of the strongest peaks in

the spectrum
 KETONE
BASE = 1715
2-Butanone
1715

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

1810 and 1760 THESE VALUES ARE

( two peaks ) WORTH LEARNING
all are +/- 10 cm-1
C=O BOND LENGTHS IN CARBONYL COMPOUNDS

shorter longer

1.225 A 1.231 A 1.235 A 1.248 A

acid ester ketone amide

chloride

1780 cm-1 1735 cm-1 1715 cm-1 1680 cm-1

 SUMMARY
Ketones are at lower frequency than Aldehydes because of
the second electron-donating alkyl group.

Acid chlorides are at higher frequency than ketones because

of the electron-withdrawing halide.
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.

Acids are at lower frequency than ketones due to H-bonding.

 KETONE
overtone of strong C=O peak
1719 x 2 = 3438 BASE = 1715

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

CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 C H

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

Strong hydrogen-bonding in the dimer weakens the O-H and

C=O bonds and leads to broad peaks at lower frequencies.
 AMIDE
two peaks BASE = 1690
sym / asym Propanamide

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

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)
THE C=C STRETCHING
REGION
 C=C double bond at 1650 cm-1 is often weak or not even seen.

 C=C benzene ring shows peak(s) near 1600 and 1400 cm-1 ,
one or two at each value - CONJUGATION LOWERS THE VALUE.

 When C=C is conjugated with C=O it is stronger and comes

at a lower frequency.
 ALKENE

1-HEXENE

=C-H C=C C-H

bend

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

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)
C-O STRETCHING
 THE C-O STRETCHING REGION
 The C-O band appears in the range of 1300 to
1000 cm-1

 Look for one or more strong bands appearing in

this range!

 Ethers, alcohols, esters and carboxylic acids have

C-O bands
 ETHER

Dibutyl Ether BASE = 1100

CH2 CH3
bending
C-H
C-O

CH3 CH2 CH2 CH2 O CH2 CH2 CH2 CH3

 AROMATIC ETHER

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

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)
 THE N=O STRETCHING REGION
 N=O stretching -- 1550 and 1350 cm-1 asymmetric
and symmetric stretchings

 Often the 1550 cm-1 peak is stronger than the other

one
 NITROALKANE

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

O-H C-H C N C=O C=N C-Cl

Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650

FREQUENCY (cm-1)
THE C-X STRETCHING REGION
 C-Cl 785 to 540 cm-1,
often hard to find amongst the fingerprint bands!!

 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.
 Often used as a solvent for IR spectra.
When it is used, spectra show C-Cl absorptions.

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