IR spectroscopy

 Infrared spectroscopy (IR

spectroscopy) is the subset of
spectroscopy that deals with the
infrared region of the
electromagnetic spectrum
 IR Spectroscopy
 Infraredradiation stimulates molecular
vibrations.

 Infrared
spectra are traditionally
displayed as %T (percent transmittance)
versus wavenumber (4000-400 cm-1).
Two important parameters in all IR spectra:

The frequency of the signal, ν

The intensity of the signal, I

 IR Spectroscopy
Molecular rotations

 Rotational transitions are of little use to the spectroscopist.

Rotational levels are quantized, and absorption of IR by gases
yields line spectra. However, in liquids or solids, these lines
broaden into a continuum due to molecular collisions and other
interactions.

Molecular vibrations

 The positions of atoms in a molecules are not fixed; they are

subject to a number of different vibrations. Vibrations fall into
the two main catagories of stretching and bending.
 Infrared Spectroscopy (IR)
Molecular Vibrations
1. Absorption of infrared radiation corresponds to energy
changes on the order of 8-40 KJ/mole (2-10 Kcal/mole
 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
 Scissoring (in-plane bending)
 Rocking (in-plane bending)
 Wagging (out-of-plane bending)
 Twisting (out of plane bending)
Stretching Vibrations of a CH2 Group

Symmetric Antisymmetric
 Bending Vibrations of a CH2 Group

   

In plane In plane
 Bending Vibrations of a CH2 Group

 
 

   

Out of plane Out of plane

 Infrared Spectrum of 1-Hexene

bending
C—H stretching
bending bending

CH3CH2CH2CH2CH2CH3

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright © 2000 The McGraw­Hill Companies, Inc. All rights reserved.
 Infrared Spectrum of 1-Hexene

C=C

C=C—H H—C
H2C=C

H2C=CHCH2CH2CH2CH3

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright © 2000 The McGraw­Hill Companies, Inc. All rights reserved.
 Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Stretching vibrations (single bonds)
sp C—H 3310-3320
sp2 C—H 3000-3100
sp3 C—H 2850-2950
sp2 C—O 1200
sp3 C—O 1025-1200
 Infrared Absorption Frequencies

Structural unit Frequency,

cm-1
Stretching vibrations (multiple
bonds)
C C 1620-1680

—C C— 2100-2200

—C N 2240-2280
 Infrared Absorption Frequencies

Structural unit Frequency, cm-1 C O

Stretching vibrations (carbonyl groups)
Aldehydes and ketones 1710-1750
Carboxylic acids 1700-1725
Acid anhydrides 1800-1850 and 1740-
1790
Esters 1730-1750
 Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Bending vibrations of alkenes
RCH CH2 910-990

R2C CH2 890

cis-RCH CHR' 665-730

trans-RCH CHR' 960-980

R2C CHR' 790-840
 Infrared Absorption Frequencies

Structural unit Frequency, cm-1

Bending vibrations of derivatives of
benzene
Monosubstituted 730-770 and 690-710
Ortho-disubstituted 735-770
Meta-disubstituted 750-810 and 680-730
Para-disubstituted 790-840
 Infrared Spectrum of tert-butylbenzene

Ar—H
C6H5C(CH3)3

H—C Monsubstituted
benzene

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright © 2000 The McGraw­Hill Companies, Inc. All rights reserved.
Infrared Absorption Frequencies: functional
groups
Structural unit Frequency,
cm-1
Stretching vibrations (single bonds)
O—H (alcohols) 3200-3600
O—H (carboxylic acids) 3000-3100
N—H 3350-3500
 Infrared Spectrum of 2-Hexanol

H—C

O—H
CH3CH2CH2CH2CHCH3

OH

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright © 2000 The McGraw­Hill Companies, Inc. All rights reserved.
 Infrared Spectrum of 2-Hexanone

CH3CH2CH2CH2CCH3

O
H—C

C=O

3500 3000 2500 2000 1500 1000 500

Wave number, cm-1
Francis A. Carey, Organic Chemistry, Fourth Edition. Copyright © 2000 The McGraw­Hill Companies, Inc. All rights reserved.
 IR-REGION: 12,800 - 10 cm-1

REGION WAVE WAVE NUMBER FREQUENCY

LENGTH υ (cm-1) RANGE
λ (μm) Hz

NEAR 0.78 - 2.5 12800 - 4000 3.8x1014-1.2x1014

MIDDLE 2.5 - 50 4000 - 200 1.2x1014 - 6x112

FAR 50 - 1000 200 -10 6x1012- 30x1011

MOST 2.5 - 15 4000 - 670 1.2x1014-2x1013

USED
 Fingerprint region
 Theregion to the right-hand side of
the diagram (from about 1500 to 500
cm-1) usually contains a very
complicated series of absorptions.
These are mainly due to all manner
of bending vibrations within the
molecule. This is called the
fingerprint region.
Most the organic compound are fairly large &
their resultant vibration spectra are complex.

-To introduce the basic concept governing vibrational spectra a

simple diatomic covalent bond will be consider as a spring with
atomic masses at either end

-The stiffness of the spring is described by a force constant, K

M1 Force constant, k M2
Ball
and spring representation of 2 atom of
molecule vibrating in the direction of bond
 If such a simple system is put in to motion ( by
stretching and releasing) the induced vibration of the
masses are adequately described by Hooke’s law of
simple harmonic motion

Frequency of motion
m1 m2
Hooke’s law :
1 k
ν= mr =
2π mr m1 +m2
ν = frequency
K : Force constant (dynes /cm)
mr = reduced mass (mass of largest atom)
INSTRUMENTATION
 INFRARED SOURCE

IR source consist of an inert solid that is heated

electrically to a temperature between 1500 and 2200 K

The material is chosen so that its emission approximates

As closely as possible to that of black body radiator.
(in candescent solid-the glow due to the great heat)
 THE NERNST GLOWER

 Nernst Glower is Fabricated from rare earth oxides

 (e.g. ZrO2+Y2O3)

 Diameter 1-2mm length 20mm

 Pt. leads are sealed to the end of cylinder

to permit electric connection

 When electric current pass it glows ,at

temp 1200-2200 k
 SAMPLE HANDLING
TECHNIQUE
(SAMPLING)
INTRODUCTION
 In
1965 Miller has developed
appropriate method to handle
sample in the gas ,liq and solid phase
 IR
spectroscopy can be used to
examine gas ,liq and solid.
 Sample preparation

Gaseous samples require little preparation beyond purification, but

a sample cell with a long pathlength (typically 5-10 cm) is
normally needed, as gases show relatively weak absorbances.

Liquid samples can be sandwiched between two plates of a high

purity salt (commonly sodium chloride, or common salt, although
a number of other salts such as potassium bromide or calcium
fluoride are also used). The plates are transparent to the infrared
light and will not introduce any lines onto the spectra. Some salt
plates are highly soluble in water, so the sample and washing
reagents must be anhydrous (without water).
In liquid sampling the solvent generally used are

Acetone Methane Cyclohexane

CS2 Toluene Benzene

CCl4 Hexane Dioxane

CHCl3 Ether Tetrachloro

ethylene
 Solid samples can be prepared in four major ways.

 The first is to crush the sample with a mulling agent (usually nujol) in a
marble or agate mortar, with a pestle. A thin film of the mull is applied onto
salt plates and measured.

 Mulling agents are substance that transmit a wide range of IR

frequency and help to minimize scattering by surrounding the
analyte with a medium whose refractive index more closely
matches to that of the sample than does air.

 The second method is to grind a quantity of the sample with a specially

purified salt (usually potassium bromide) finely (to remove scattering effects
from large crystals). This powder mixture is then crushed in a mechanical
die press to form a translucent pellet through which the beam of the
spectrometer can pass.

 The third technique is the Cast Film technique, which is used mainly for
polymeric materials.

 The final method is to use microtomy to cut a thin (20-100 micrometre) film
from a solid sample. This is one of the most important ways of analysing
failed plastic products for example because the integrity of the solid is
preserved
 APPLICATIONS

Useful in identifying presence or absence of functional

groups.

Can be used to molecular geometry and bond lengths

in small molecules (eg:-HCl,C2H2..etc)
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

– IR can be used to distinguish one compound from another.

– 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.
 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

 Provides information about the vibrations of functional

groups in a molecule

 Therefore, the functional groups present in a molecule

can be deduced from an IR spectrum
IR spectroscopy can identify functional
groups!
THANK
YOU