INFRARED SPECTROSCOPY:

Fundamentals and Interpretation of

Organic Compounds

Prof. Mrs. H. M. Nimje

Assistant Professor,
JSPM Charak College of Pharmacy
and Research, Wagholi, Pune.
 THE ELECTROMAGNETIC SPECTRUM
High Frequency (n) Low
High Energy Low

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY

WAVE

Nuclear
Vibrational
Ultraviolet Visible magnetic
infrared
resonance
2.5 mm 15 mm 1m 5m
200 nm 400 nm 800 nm
BLUE RED

short Wavelength (l) long

 INFRA RED REGIONS
Region Wavelength Wavenumber
λ[μm] [cm-1]
Near IR 0.78-2.5 12800-4000
Mid IR 2.5-50 4000-200
(2.5-15)
Functional 2.5-7.7 4000-1300
group
Finger Print 7.7-11.0 1300-900
Aromatic 11.0-15.0 900-670
Far IR 50-1000 200-10
3
 CRITERIA FOR IR ABSORPTION
The frequency of IR radiation should exactly
•

match with the natural vibrational frequency

of the molecule.
A molecule must undergo a net change in
•
dipole moment
Eg:HCl
δ+ δ-

H Cl
4
 DIPOLE MOMENT

Only bonds which have significant dipole moments will absorb IR radiation.

Bonds which do not absorb IR include:

•Symmetrically substituted alkenes and alkynes
R R
R C C R
R R
•Many types of C-C Bonds
C C
•Symmetric diatomic molecules + + d+
O
O
H-H Cl-Cl
- - d-

Oscillating dipoles couple and

energy is transferred
 BOND VIBRATIONAL ENERGY LEVELS
Bonds do not have a fixed distance.
They vibrate continually even at 0oK (absolute).
The frequency for a given bond is a constant.
Vibrations are quantized as levels.
The lowest level is called the zero point energy.

Vibrational
E modes
n •Fundamental
Bond Vibration
e
dissociation bands
r
energy
g Vibrational •Overtone
y bands
energy levels
•Combination
bands
zero point energy

rmin rmax
distance
ravg
(Average bond length)
 MOLECULAR VIBRATIONS
Stretching vibrations : Change in inter-atomic distance along bond axis.

Bending vibrations: Change in angle between two bonds. There are four
types of bend:

In-plane-Scissoring and Rocking Out of plane- Wagging and Twisting

8
Plot of I.R. Spectra: % T vs Wavenumber

%
T

Wave number

ν= c / λ =c x n
ν =frequency
c = speed of light = 3 x 1010 cm/sec
λ= wavelength (cm)
ν =Wavenumber in cm-1
9
HOOKE’S LAW Larger K, higher frequency

1 K
n =
2pc m Larger atom masses,
lower frequency
where
K = force constant
in dynes/cm increasing K
m1 m2
m = > C=C > C-C
=
m1 + m2 C=C
m= reduced mass 2150 1650 1200
m= atomic mass
increasing m

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

3000 1200 1100 750 650
Vibrational coupling (Fermi Resonance)
Coupling between two fundamental vibrations
C-H STRETCHING VIBRATION : Methyl and Methylene
H
H C
C H
H
H
Symmetric Stretch ~2872 cm-1 Symmetric Stretch ~2853 cm-1
H
H
C H C
H H

Asymmetric Stretch ~2962 cm-1 Asymmetric Stretch ~2962 cm-1

Also observed incase of NO2 and NH2 groups

CO2: Coupling of two C=O stretching vibrations, C=O stretch at 2350 cm-1
Carboxylic anhydrides:
O O
O O

CH3 C C CH3 CH3 C C CH3

O
O

Symmetric Stretch ~1760cm-1 Asymmetric Stretch~1820cm-1

 Vibrational coupling (Fermi Resonance)
Amides: O H

R C N R
Amide-I band :C=O stretch
C-N stretch is of similar frequency to N-H bend. Interaction between these two
vibrations gives rise to two bands , one at higher ν and one at lower ν than
uncoupled vibration.
Amide II band: N-H bend at 1550-1510 cm -1
Amide III band : C-N stretch at 1250cm-1(w)

Coupling between a fundamental vibration and an overtone

O

Aldehydes:
CH3 C H
Fermi resonance between the Fundamental aldehydic C-H stretch(2850 cm-1) and
the first overtone of the aldehydic C-H bend(1390 cm-1) : Doublet between 2850-
2720 cm-1)
 Typical IR Absorption Regions
• Functional Group region : 3600-1300cm-1
1.Hydrogen stretching : 3600-2700 cm-1
2. Triple Bond : 2500-2000 cm-1 3. Double Bond region: 2000-1500cm-1
• Finger print region : 1500-650 cm-1
BASE VALUES These are
the minimum
(+/- 10 cm-1) number of
values to
memorize.
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
 The C-H stretching region
BASE VALUE = 3000 cm-1
UNSATURATED

•C-H sp stretch in Alkynes ~ 3300 cm-1

•C-H sp2stretch C=C-H in Alkenes/Aromatics> 3000 cm-1
3000 divides

•C-H sp3 stretch in Alkanes < 3000 cm-1

SATURATED

•C-H aldehyde, two peaks

~ 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 sp2 sp3 aldehyde

Increasing s character in bond

Increasing CH Bond Strength

Increasing force constant K
CH BASE VALUE = 3000 cm-1
 C-H STRETCHING VIBRATIONS
METHYL GROUP METHYLENE GROUP
Three C-H bonds share a central carbon Two C-H bonds share a central carbon
(hydrogens attached to the same carbon) H
H C
C H H
H Symmetric Stretch ~2853 cm-1
Symmetric Stretch ~2872 cm-1 H
H C
C H H
H Asymmetric Stretch ~2926 cm-1
Asymmetric Stretch ~2962 cm-1
 THE C-H BENDING REGION
Methylene and Methyl Bending Vibrations
CH2 CH3 CH2 bending ~ 1465 cm-1

CH3 bending (asym) appears near

asym sym
the CH2 value ~ 1460 cm-1

CH3 bending (sym) ~ 1375 cm-1

1465 1460 1375

These two peaks

frequently overlap
C
and are not resolved
H H
H
 METHYLENE GROUP BENDING VIBRATIONS
Scissoring Wagging

H ~1465 cm-1 H H ~1250 cm-1

H
C C C
H H

H ~720 cm-1 ~1250 cm-1

H H H
C C C
H H

Rocking Twisting
in-plane out-of-plane
Bending
Vibrations
ALKANE C – H stretching: 3000-2850 cm-1
C – H bending(scissoring) : 1450-1375 cm-1
C – H bending(rocking) : 725-720 cm-1
Hexane

CH2
CH3 rocking
CH2 bend
bend
CH
stretch

CH3 CH2 CH2 CH2 CH2 CH3

C–H alkene stretching vibrations : 3100-3000cm-1 ALKENE
C=C stretching vibrations are seen at 1680-1600cm-1
Out of plane C–H bending vibrations between 1000-650 cm-1
1-Hexene

=CH
C=C CH2
CH3
bend

CH CH bend
CH2 CH CH2 CH2 CH2 CH3
C≡C stretching vibrations : 2260 -2100 cm-1 ALKYNE
C–H stretching vibrations : 3300 -3270 cm-1
C–H bending vibrations : 700-610 cm-1

1-Hexyne

=
C=C

CH2, CH3

==C-H C-H HC C CH2 CH2 CH2 CH3

Aromatic C–H stretching :3100-3000 cm-1 AROMATIC
Weak combination and overtone bands : 2000-1665 cm-1
Ring C–H oop bend: 900-675 cm-1

Toluene

CH3 str
Ar-H str
C=C
benzene

CH3

Ar-H oop
 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“FREE” HYDROXYL

Many kinds of OH bonds of different

Distinct bond has a
lengths and strengths
well-defined length
This leads to a broad absorption.
R R and strength.
O H O CCl4
H H CCl4
R O R O O R O CCl 4
H R H
H
O CCl4
R H CCl4
Longer bonds are weaker and lead to
lower frequency.
Solvent molecules
Hydrogen bonding occurs in concentrated surround but do not
solutions (undiluted alcohol ) hydrogen bond.
Occurs in dilute solutions of alcohol /
in an “inert” solvent like CCl4.
 Effect of Hydrogen-Bonding
on O-H Stretching

Free
OH
Free C-H
OH

H-bonded H-bonded
OH C-H OH C-H

4000 3600 3200 2800 4000 3600 3200 2800 4000 3600 3200 2800

(a) Pure Liquid (b) Dilute Solution (c) Very Dilute Solution
“neat”

1-Butanol
O–H stretching vibrations( Dilute samples): ~ 3600cm-1
O–H stretching vibrations( Neat samples): 3400-3200 cm-1 ALCOHOL
C–O stretching vibrations occur at 1260 -1000 cm-1
O–H bending vibrations occur at 1420-1330 cm-1
Cyclohexanol
Neat solution

O-H str OH CH2 bend

H-bond
C-O str

C-H str
O–H stretching: 3300-2700( broad band) CARBOXYLIC ACID
C=O absorption bands at 1720 -1670 cm-1
C – O stretching occur at 1320-1210cm-1
O–H bending at 1440-1395 cm-1
Butanoic Acid
Neat solution

O-H str
H-bond

C-O str
CH2bend O

C-H str C=O str CH3 CH2 CH2 C OH

 The N-H stretching region
N-H 3400 -3250 cm-1
• Primary amines give two peaks
H H
N N
H H
Symmetric, 3330-3250 cm-1 Asymmetric, 3400- 3300cm-1

• Secondary amines give one peak 3350-3310cm-1

• Tertiary amines give no peak
• N–H bending vibrations occur in the 1650-1580 cm-1
• C –N stretching: 1250-1020 cm-1
 PRIMARY AMINE
aliphatic
1-Butanamine

NH2 bend CH3 bend

CH2 bend
NH2 str

CH3 CH2 CH2 CH2 NH2

 PRIMARY AMINE
aromatic

3-Methylbenzenamine

-CH3 str

Ar-H str
NH2
NH2 str

Benzene
Ar-H
CH3 C=C str
oop
 SECONDARY AMINE

N -Ethylbenzenamine

NH str

NH CH2 CH3
CH3 bend

Ar-H
Benzene
oop
 TERTIARY AMINE

N,N -Dimethylaniline

Ar-H str

-CH3 str

CH3
no N-H str
N
CH3 CH3 bend
benzene Ar-H
oop
The Triple bond stretching region: 2500-2000cm-1

• C =N 2260-2220 cm-1 (2250 cm-1)

• C =C 2260-2120 cm-1 (2150 cm-1)

•The cyano group : Strong, sharp peak due to its large

dipole moment.
•The carbon-carbon triple bond: Sharp peak, but it is
often weak due to a lack of dipole.
•Symmetric alkynes: IR inactive due to center of a
symmetry.
R C C R
 NITRILE

Propanenitrile BASE = 2250

= str
C=N
CH3 CH2 C N
 ALKYNE

BASE = 2150
1-Hexyne

==C-H str
= str
C=C

HC C CH2 CH2 CH2 CH3

THE CARBONYL STRETCHING REGION
• Amides Carboxylic acids Aldehydes Ketones Esters
• Acid Chlorides Anhydrides

• 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 large C=O
dipole moment.
• C=O is often one of the strongest peaks in the
spectrum
 KETONE

BASE = 1715
2-Butanone
1715

C-H str CH bend

O
C=O
C=Ostr
CH3 C CH2 CH3
 C=O IS SENSITIVE TO ITS ENVIRONMENT
Each different kind of C=O absorbs 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
FACTORS THAT INFLUENCE THE C=O ABSORPTION

•INDUCTIVE EFFECT
O
Electron-donating groups
R C weaken the carbonyl
A
Lower its absorption frequency
R = Me, Et, etc.
Aldehydes , Ketones

O Electron-withdrawing groups
B C X strengthen the carbonyl

Raises its absorption frequency

X = F, Cl, Br, OR
Acid halides, Esters
 O EFFECTS and HYDROGEN BONDING
RESONANCE
C X
-
O O
+ Resonance
C Y C Y weakens the carbonyl

Y = N, O, or C=C, Lowers its absorption frequency

C Amides (Note the lengthening of
the C=O bond! )

O H O Hydrogen bonding
D lengthens and weakens
R C the C=O bond
Lowers its absorption frequency
R
 HOW THESE FACTORS AFFECT C=O FREQUENCY
STRETCHING VIBRATIONS

Acid Carboxylic
chloride Ester Aldehyde Ketone acid Amide
B A C
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
D
Anhydride
O O
BASE
R C O C R VALUE

1810 and 1760

( Two peaks ) A E-donating C Resonance

B E-withdrawing D H-bonding
 CONFIRMATION OF FUNCTIONAL GROUP
Every type of carbonyl compound shows other peaks
you can look to confirm your conclusion based on C=O
frequency alone.

O C=O at 1710 cm-1

O C=O at 1725 cm-1 Also look for OH
Also look for aldehyde CH R C
R C (H-bonded, lower
2850and 2750 cm-1
H O H Frequency) and
2851(unsym doublet)
C-O ~1200 cm-1

O C=O at 1690 cm-1 O C=O at 1735 cm-1

R C R C Also look for two
Also look for
N H NH peaks at O R' C-O at 1200 and
H 3400-3300 cm-1 1000 cm-1

Ketones have C=O at 1715 cm-1 and no NH, OH, C-O or -CHO
Anhydrides have two C=O peaks near 1800 cm-1 and two C-O
 C=O stretching: 1660-1690 cm-1 AMIDE

Two peaks BASE = 1690

sym / asym
Propanamide

C-H str O
C=O str C
NH2str CH bend CH3 CH2 NH2
 CARBOXYLIC ACID
C=O stretching: 1720-1690 cm-1
BASE = 1710

2-Methylpropanoic Acid

O-H str

C-O str C
C-H str C=O str CH3 CH OH

CH3
 CARBOXYLIC ACID DIMER

Lowers
frequency
of C=O

O H O
and also
R C C R 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.
Overtone of strong C=O peak
KETONE
1719 x 2 = 3438
BASE = 1715

2-Butanone

overtone

C-H str CH bend

O
C=O str
CH3 C CH2 CH3

3438
Aldehyde C=O stretching:1740-1720 cm-1 ALDEHYDE

C–H stretching: Doublet between 2850-2720 cm-1 BASE = 1725

Nonanal

CHO

CH bend

C=O str
O

CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 C H

3460
Ester C=O stretching:1750-1735 cm-1 ESTER

C–O stretching: 1300-1000 cm-1 BASE = 1735

Ethyl Butanoate

C-O str
C-H str
O

C=O str C
CH3 CH2 CH2 O CH2 CH3
 ACID CHLORIDE

BASE = 1800
Dodecanoyl Chloride

CH bend

C
C=O str CH3 (CH2)10 Cl
C-H str

3608
 Conjugation of C=O with C=C

• Conjugation of a carbonyl with a C=C bond shifts

values to lower frequencies

• For aldehydes, ketones and esters, subtract about 25-

30 cm-1 for conjugation with C=O

• Conjugated ketone = 1690 to 1680 cm-1

• Conjugated ester = 1710 to 1700 cm-1
• C=C becomes quite strong!!
CONJUGATION LOWERS THE FREQUENCY OF C=O
AND ALSO OF C=C (WHICH IS STRENGTHENED)

Resonance lengthens
(weakens) C=O

-
O
O
+
R C CH CH2 R C CH CH2

O O 1650 1625 cm-1

C=C is also
R C R R C CH CH2 lengthened
….. and
1715 1690 cm-1 polarized !
lowered
 C=O : 1715 - 30 = 1685 KETONE
C=C : 1650 - 25 = 1625 conjugated

4-Methyl-3-penten-2-one

weak

CH3 C CH3
C C doublet =
C=O C=C gem dimethyl
CH3 H
only one
 C=O : 1715 - 30 = 1685 AROMATIC KETONE
conjugated

Acetophenone

benzene
C-H stretch

C CH3 C=O benzene

C-H oop

benzene bonds
1400 - 1600
 ANGLE STRAIN RAISES THE CARBONYL FREQUENCY

2 In response to more p character

in the ring bonds, there is more s
character in the bonds to C=O.

3
O O More s character
leads to a shorter and
stronger bond and a
C C higher frequency.

Normal Bond angle :120o

1 A smaller angle requires
more p character in the
hybrids forming the ring.
 CONJUGATION AND RING SIZE EFFECTS

O O O O O

1815 1780 1745 1715 1705 1690

RING STRAIN CONJUGATION
O O
R C R C
R CH CH2
O
Normal
aliphatic R C
ketones
 CYCLIC KETONE
5-ring

Cyclopentanone

C-H
aliphatic

O
CH
bend

C=O
The C=C stretching region (Alkenes and
Aromatics)

• C=C str: Weak band at 1675-1600 (1650 cm-1 )

• C=C benzene ring: Peak(s) near 1600 and 1400 cm-1

• 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 oop
CH2 CH CH2 CH2 CH2 CH3
 AROMATIC
Toluene

benzene
C-H benzene
CH3
C=C

oop
 Finger print region :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
BASE = 1100
Dibutyl Ether

CH2 CH3
C-H bending
C-O

CH3 CH2 CH2 CH2 O CH2 CH2 CH2 CH3

The N=O stretching region NITROALKANE
Sym N=O stretch- 1350 cm-1
Asymmetric N=O stretch- 1550 cm-1
2-Nitropropane

C-H

N=O

NO2
gem-dimethyl
CH
CH3 CH3 N=O
 HALIDES: 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 :Below 500 cm-1
• Outside the useful range of infrared
spectroscopy
• C-F bonds : 1000-1400 cm-1, 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
Overtone/
combination
bands

Cl
oop
benzene
C=C C-Cl
=C-H OUT OF PLANE BENDING (OOP)

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 730-770 s s
Disubstituted
ortho 770-735 s

meta 750-810 s 680-725 s

para 790-850 s
RING H’s
Trisubstituted OOPS
1,2,4 m s

1,2,3 s m

1,3,5 s m
YOU DO NOT NEED TO MEMORIZE
THE ALKENE AND AROMATIC OOP
ABSORPTION CHARTS ! 1000 900 800 700 cm-1
 BACKGROUND SPECTRUM:
MODERN FT-IR INSTRUMENTS SUBTRACT THE “BACKGROUND”

Carbon Dioxide and Water

H-O-H
H-O-H

O=C=O
 YES C=O present ? NO MAKING
DECISIONS
YES YES
Anhydride 2 C=O Peaks OH present ? Alcohol

Acid OH present ? NH present ? Amine

Amide NH present ? C-O present ? Ether

Ester C-O present ? = present ?

C=N Nitrile

Aldehyde CHO present ? = present ?

C=C Alkyne

Ketone C=C present ? Alkene

NO
(benzene ?) Aromatic
NO2 present ? Nitro

C-X present ? Halides

How to Use an Infrared Spectrum
•Molecular formula: Calculate index of hydrogen deficiency
•Check for carbonyl: Note any shift from 1715 cm-1

•Check for O-H, N-H

•Check for triple bonds

•Check for C=C, benzene rings
•Look below 1550 cm-1 check for C-O and Nitro group
Go back over spectrum for refinements
•Check the C-H region for aldehydes
and for peaks above 3000 cm-1 (alkenes , aromatics and terminal
alkynes)
Final Summary: The Minimum You Need To Know
BASE VALUES EXPANDED CH
3000
OH 3600
3300 3100 2900 2850
NH 3400 2750
C-H =C-H -C-H -CHO
CH 3000
CH2 and CH3 bend : 1465 and 1365

C N 2250
1800 1735 1725 1715 1710 1690
C C 2150 Aldehyde Acid
Acid Ester Ketone Amide
C=O 1715 chloride
Anhydride : 1810 and 1760
C=C 1650
EXPANDED C=O

C-O 1100 Benzene C=C : between 1400 and 1600

Remember also the effects of H-bonding, conjugation and ring size.

THANK YOU