Infrared (IR) Spectroscopy

Lies between microwaves and visible light.

Most used units: m and wave number
Most useful range: 2.5m - 16m
IR region is lower in photon energy than visible light (below red
produces heating as with a heat lamp)
2.5 106 m to 2.5 105 m region used by organic chemists for
identifying functional groups.
IR energy in a spectrum is usually measured as wavenumber (cm -1),
the inverse of wavelength and proportional to frequency:
Wavenumber (cm-1) = 1/(cm)
Specific IR absorbed by organic molecule related to its structure

IR region and vicinity

Infrared Energy Modes

IR energy absorption corresponds to

specific modes, corresponding to
combinations of atomic movements,
such as bending and stretching of
bonds between groups of atoms called
normal modes
Energy is characteristic of the atoms in
the group and their bonding
Corresponds to vibrations and
rotations

Hukum Hooke :

3700 - 2500 cm-1: X-H stretching (X = C,N,O,S)

2300 - 2000 cm-1: C X stretching (X = C or N)
1900 - 1500 cm-1: C=X stretching (X = C, N, O)
1300 - 800 cm-1: C-X stretching (X = C, N, O)

Molecular Vibrations
1. Absorption of infrared radiation corresponds to energy
changes on the order of 8-40 KJ/mole (2-10 Kcal/mole
2. The frequencies in this energy range correspond to the
stretching and bending frequencies of the covalent
bonds with dipole moments.
3. Stretching (requires more energy than bending)
a. Symmetrical
b. Asymmetrical
4. Bending
a. Scissoring (in-plane bending)
b. Rocking
(in-plane bending)
c. Wagging
(out-of-plane bending)
d. Twisting
(out of plane bending)

Infrared Energy Modes

Stretching A rhythmical movement along the bond axis

such that the interatomic distance is
increasing or decreasing.
In any group of three or more atoms at least two of which
are identical - there are two modes of stretching or
bending: Symmetric and Asymmetric
For the Methylene Group (CH2):
CH

H
C
H
Symmetric
Stretch
(2853 cm-1)

H
C
H
Asymmetric
Stretch
(2926 cm-1)

Bending A change in bond angle between bonds with a

common atom or
A movement of a group of atoms with respect
to the remainder of the molecule
H

Wagging
~1250 cm-1

(In Plane)

(Out of Plane)

Rocking
~750 cm-1

Twisting
~1250 cm-1

Scissoring
~1450 cm-1

(In Plane)

C
H

(Out of Plane)

H
C

H
C

 Thus, no two molecules of different structure will have

exactly the same natural frequency of vibration, each will
have a unique infrared absorption pattern or spectrum.
Two Uses:
1. IR can be used to distinguish one compound from
another.
2. Absorption of IR energy by organic compounds will
occur in a manner characteristic of the types of bonds
and atoms in the functional groups present in the
compound; thus, infrared spectrum gives structural
information about a molecule.
The absorptions of each type of bond (NH, CH, OH,
CX, C=O,CO, CC, C=C, CC, CN, etc.) are regularly
found only in certain small portions of the vibrational
infrared region, greatly enhancing analysis possibilities.

Common Structural Units

Stretching Vibrations
O

H (alcohols)

Stretching Vibrations (Double Bonds)

3200-3600
C

H (carboxylic
acids)

2500-3600

3350-3500

3310-3320

sp2 C

3000-3100

sp

sp3 C

C
1620-1680

2850-2950

sp2 C

1200

sp3 C

1025-1200

Aldehydes and ketones

1710-1750

Carboxylic acids

1700-1725

Acid anhydrides

1800-1850 and 1740-1790

Acyl halides

1770-1815

Esters

1730-1750

Amides

1680-1700

Bending Vibrations (Diagnostic)

Alkenes:
cis-disubstituted

665-730

trans-disubstituted

960-980

trisubstituted

790-840

Stretching Vibrations Triple Bonds)

C

2100-2200

2240-2280

Substituted derivatives of benzene

monosubstituted

730-770 and 690-710

ortho-disusbstituted
meta-disubstituted
para-substituted

735-770
750-810 and 680-730
790-840

Serapan gugus fungsional pada Infra merah

Regions of the Infrared Spectrum

4000-2500

cm-1 N-H, C-H, O-H (stretching)

2500-2000

cm-1 CC and C N (stretching)

2000-1500

cm-1 double bonds (stretching)

3300-3600 N-H, O-H

3000 C-H

C=O 1680-1750
C=C 1640-1680 cm-1
Below

1500 cm-1 fingerprint region

The Infrared Spectrum

A plot of absorption intensity (% Transmittance) on the yaxis vs. frequency on the x-axis.
Transmittance (T) - the ratio of the radiant power
transmitted by a sample to the radiant power incident on
the sample.
Absorbance (A) - the logarithm to base 10 of the
reciprocal of the Transmittance.
A = log10 (1 / T)
Frequency - The x-axis is represented by two scales:
1. Wavelength (2.5 to 25 )

(Bottom)

2. Wavenumber (4000 cm-1 to 400 cm-1) (Upper)

Spectra Infrared

Methyl Isopropyl Ketone

Regions of the Infrared

Spectrum

Spectra Infrared
IR Spectrum Peak Characteristics
1.Primary Examination Regions of the Spectrum
High Frequency Region

- 4000 to 1300 cm-1

Intermediate (Fingerprint Region) - 1300 to 900 cm-1

2.High Frequency Region (Functional Group Region)
Characteristic Stretching frequencies of such groups
as:
=CH, OH, NH, C=O, CO, CN, CC, C=C
3.The Fingerprint Region
Absorption patterns frequently complex
Bands originate from interacting vibrational modes
Valuable when used in reference to other regions
Absorption unique for every molecular species
Effective use comes from experience

Infrared Spectroscopy (IR)

IR Spectrum Peak Characteristics (cont)
Shape
Sharp (narrow)
Broad
Intensity
Weak
(w)
Medium (m)
Strong (s)
Note: Peak intensity is dependent on amount of sample
and sensitivity of instrument; therefore, the actual
intensity can vary from spectrum to spectrum

Infrared Spectra of Hydrocarbons

C-H, C-C, C=C, C C have characteristic peaks

Hexane

Alkenes

1-Hexene

Alkynes

IR: Aromatic Compounds

Weak CH stretch at 3030 cm 1
Weak absorptions 1660 - 2000 cm 1 range
Medium-intensity absorptions 1450 to 1600 cm 1

Phenylacetylene

Cyclohexane or Cyclohexene?

The infra-red spectrum for a

simple carboxylic acid
Ethanoic acid
carbon-oxygen double, C=O
carbon-oxygen single, C-O
oxygen-hydrogen, O-H
carbon-hydrogen, C-H
carbon-carbon single, C-C

IR: Alcohols

Infrared Absorption Spectrum of

Ethanol

dilute t-butanol in choloroform

t-butanol

IR: Carbonyl Compounds

Strong, sharp C=O peak 1670 to 1780 cm1
Exact absorption characteristic of type of
carbonyl compound
1730 cm1 in saturated aldehydes
1705 cm1 in aldehydes next to double bond or
aromatic ring

C=O in Ketones
1715 cm1

in six-membered ring and acyclic ketones

1750 cm1 in 5-membered ring ketones
1690 cm1 in ketones next to a double bond or an aromatic ring

C=O in Esters

1735 cm1 in saturated esters

1715 cm1 in esters next to aromatic
ring or a double bond

The infra-red spectrum for an ester

Ethyl ethanoate

Practice problem:

Phenylacetaldehyde

The infra-red spectrum for a ketone

Propanone

Amines

The infra-red spectrum for a primary amine

1-aminobutane

Analyzing the Spectrum A Suggested Approach

Step 1. Check for the presence of the Carbonyl group (C=O) at
1715 cm-1. If molecule is conjugated, the strong (C=O)

absorption will be shifted to the right by ~30 cm-1,

i.e. ~1685 cm-1

If the carbonyl absorption is present, check for:

Carboxylic Acids - Check for OH group (broad absorption
near 3300-2500 cm-1)
Amides
- Check for NH group
(1 or 2 absorptions near 3500 cm-1)
Esters
- Check for C-O group (medium
absorptions near 1300-1000 cm-1)
Anhydrides
- Check for 2 C=O absorptions near
1810 and 1760 cm-1
Aldehydes
- Check for Aldehyde CH group (2 weak
absorptions near 2850 and 2750 cm-1)
Ketones
- Ketones (The above groups have been
eliminated)

IR Spectrum
Carboxylic Acids

Isobutyric Acid

C4H8O2

IR Spectrum
Amides

Benzamide

C7H7NO

IR Spectrum
Esters

Methyl Benzoate

C8H8O2

IR Spectrum
Aldehydes

Nonanal

C9H18O

IR Spectrum
Ketones

Methyl Isopropyl Ketone

C5H10O

Step 2. - If the Carbonyl Group is Absent Check for Alcohols,

Amines, or Ethers.
Alcohols & Phenols - Check for OH group (Broad
absorption near 3600-3300 cm-1
Confirm present of CO near
1300-1000 cm-1
Amines
- Check for NH stretch (Medium
absorptions) near 3500 cm-1
Primary Amine

- 2 Peaks

Secondary Amine - 1 Peak

Tertiary Amine

- No peaks

N-H scissoring at 1560 - 1640 cm-1

Ethers

- Check for C-O group near 13001000 cm-1 and absence of OH

IR Spectrum
Alkynes (CC)

Propargyl Alcohol

C3H4O

HC CCH2OH

IR Spectrum
Alcohols & Phenols

2-Naphthol

C10H9O

IR Spectrum
Amines

n-butylamine

C4H11N

IR Spectrum
Ethers

Butyl Ether

C8H18O

CH3(CH2)3 O (CH2)3CH3

Step 3. Refine the Structure Possibilities by Looking for

Double Bonds, Triple Bonds and Nitro Groups
Double Bonds - C=C is weak absorption near 1650 cm-1
Aliphatics occur on right side of
3000 cm-1.
Unsaturated C=C or CC bonds show
an absorption on the left side of 3000
cm-1.
Triple Bonds

- CN (medium, sharp absorption near

2250 cm-1
CC (weak, sharp absorption near
2150 cm-1

Nitro Groups

- Two strong absorptions 1600-1500 cm-1

and 1390-1300 cm-1

Step 3 (Cont)
Aromatic Ring Absorptions
Aromatic unsaturated C=C bonds show an absorption
on the left side of 3000 cm-1, but the aromaticity must
be verified in the overtone region (1667 - 2000cm-1) and
the out-of-plane (OOP) region (900 - 690 cm-1)
Medium to strong absorption in region 1650 - 1450 cm -1
Many weak combination and overtone absorptions
appear between 2000 and 1667 cm-1
The relative shapes and numbers (1 - 4) of the overtone
absorptions can be used to tell whether the aromatic
ring is monosubstituted or di-, tri-, tetra-, penta-, or
hexasubstituted.
Positional (ortho-, meta-, para-) isomers can also be
distinguished.
Note: A strong carbonyl absorption can overlap these
ovetone bands, making them unusable.

Step 3 (Cont)
Aromatic Ring Absorptions (Cont)
The unsaturated =C-H Out-of-Plane (OOP) bending
absorptions in the region 900 690 can also be used
to determine the type of ring substitution.
The number of absorptions and their relative positions
are unique to each type of substitution.
Although these absorptions are in the fingerprint
region they are particularly reliable for rings with alkyl
group substitutions.
They are less reliable for polar substituents.

IR Spectrum
Nitriles

Benzonitrile

C7H5N

IR Spectrum
Alkynes (CC)

Propargyl Alcohol

C3H4O

HC CCH2OH

IR Spectrum
Nitro Compounds

Nitro Benzene

C6H5NO2

Step 4. If none of the above apply then the compound is

most likely a hydrocarbon.
Generally, very simple spectrum
Hydrocarbons

- Check for main absorptions near

right side of 3000 cm-1

IR Spectrum
Alkane

Decane

C H

CH (CH2) CH

Sample Preparation
1.

2.

IR spectra of liquids.
IR spectra of liquid compounds may be obtained either
from the neat liquid or from a solution of the liquid in an
appropriate solvent. It is generally desirable to obtain the
spectrum from the neat liquid, if possible, since
interference by solvent absorption is thereby avoided.
IR spectra of solids.
- The Mull Method. In this method, the solid sample is
thoroughly ground up, using an agate mortar and pestle,
with a weakly absorbing, non-volatile liquid to form a
thick paste, called a mull.
- The KBr pellet Method. In this method, the solid sample
is finely pulverized with pure, dry KBr, the mixture is
pressed in a hydraulic press to form a transparent pellet,
and the spectrum of the pellet is measured.