PART

D
INFRARED
ABSORPT
ION
SPECTRO
 SUBTOPICS
Introduction
Molecular vibration
Molecular species that absorb
infrared radiation
Operations of FTIR
Sample handling techniques
Qualitative analysis
Structural analysis
 INTRODUCTION
Comparison between UV-Vis and IR:
Energy : UV>Vis>IR
Frequency : UV>Vis>IR
Wavelength : UV<Vis<IR

More common units are wavenumbers,

or cm-1, the reciprocal of the wavelength
in centimeters.
Wavenumbers are proportional to
frequency and energy.
Wavelength measured in microns (m) or
micrometer.
IR region of EM spectrum:
- Wavelength: 780 nm 1000 m
- Wavenumber: 12, 800 10 cm-1
IR region subdivided into 3 subregions:
1. Near IR region (Nearest to the visible)
- 780 nm to 2.5 m (12, 800 to 4000
cm-1)
2. Mid IR region
- 2.5 to 50 m (4000 200 cm-1)
3. Far IR region
- 50 to 1000 m (200 10 cm-1)
IR Spectral Region
Infrared (IR) spectroscopy
measures the bond vibration
frequencies in a molecule and is
used to determine the functional
group.

Applications of IR:
Analysis of organic materials
Polyatomic inorganic molecules
Organometallic compounds
 Advantages of
FTIR
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.
Reproducible.
High resolution (<0.1 cm-1).
Inexpensive.
 MOLECULAR VIBRATIONS
Covalent bonds vibrate at only certain allowable
frequencies.
Imagine a covalent bond between two atoms
acts like a spring.
- If the bond is stretched, a restoring force pulls
the two atoms together towards equilibrium
bond length.
- If the bond is compressed, the restoring force
pushed the two atoms apart.
- if the bond is stretched or compressed and
then released, the atoms vibrate.
 Stretching Frequencies

Frequency decreases with increasing atomic

weight.
- heavier atoms vibrate more slowly than lighter
atoms.
- example: C-D bond had lower frequency than a C-
H bond.
Frequency increases with increasing bond energy.
- stronger bonds are stiffer, requiring more force to
stretch or compress.
- stronger bands usually vibrate faster than weaker
bands (assuming the atoms have similar masses)
- example: O-H bonds are stronger than C-H bonds
and O-H bonds vibrate at higher frequencies.
- strengthens of bonds: triple bonds > double
bonds > single bonds
Bond Stretching Frequencies
 Vibrational Modes
When the molecule absorb IR radiation, the
energy that were absorbed will increased
the vibrational amplitude of the atoms.

Infrared spectra contain many different

absorptions:
- One bond can absorb energy with more
than one frequencies.
- the absorptions results from stretching
vibrations of the molecule or from bending
vibrations.
A) STRETCHING VIBRATIONS:
- causes by vibration of the bond
length.
- two vibrational stretching modes:
i) symmetric stretching
ii) asymmetric stretching
Symmetric stretching Asymmetric stretching
B) BENDING VIBRATIONS:

- causes by the vibration of the bond

angles.

- four bending vibrations modes:

i) in-plane rocking
ii) in-plane scissoring
iii) out-of-plane wagging
iv) out-of-plane twisting
Bending

Vibratio
ns
Modes
 MOLECULAR
VIBRATIONS

STRECTHING BENDING

IN-PLANE
SYMMETR ASYMMETR IN-PLANE
SCISSORIN
IC IC ROCKING
G
OUT-OF- OUT-OF-
PLANE PLANE
WAGGING TWISTING
 Fingerprint of Molecule
Whole-molecule vibrations and bending
vibrations are also quantitized.
No two molecules will give exactly the same
IR spectrum (except enantiomers).
Simple stretching: 1600-3500 cm-1.
Complex vibrations: 600-1400 cm-1, called
the fingerprint region.
IR spectra is called fingerprints because
no other chemical species will have identical
IR spectrum.
Significant of fingerprint region:
- The complex vibrations found in this
region are used to confirm the identity of an
Infrared Spectra
 MOLECULAR SPECIES THAT ABSORB INFRARED
RADIATION
IR absorption only occurs when IR radiation
interacts with a molecule undergoing a change
in dipole moment when the molecule is
vibrate.
What happen when a molecule absorbs
infrared radiation?
Absorption of IR radiation corresponds to
energy changes on the order of 8 to 40
kJ/mole.
- Radiation in this energy range corresponds
to stretching and bending vibrational
frequencies of the bonds in most covalent
molecules.
In the absorption process, those frequencies
NOT ALL bonds in a molecule are capable
of absorbing IR energy. Only those bonds
that have change in dipole moment are
capable to absorb IR radiation.

The larger the dipole change, the stronger

the intensity of the band in an IR spectrum.
 MOLECULAR SPECIES THAT DO NOT
ABSORB INFRARED RADIATION
A bond is symmetrical and has zero dipole
moment.
- example: the triple bond of acetylene, has zero
dipole moment, and dipole moment remains zero
if the bond is stretched or compressed. The
vibration produces no change in the dipole
moment, thus no absorption of energy is
occurred.

- examples: O2, N2, Cl2 cannot absorb IR radiation

because no net change in dipole moment occurs
during the vibration or rotation.
 OPERATIONS OF FTIR
Purging with dry nitrogen:
- IR is often purged with dry nitrogen to
remove atmospheric CO2 and H2O which
may cause significant absorption peaks in
the IR spectrum.

Running Background spectrum

- Before run sample
- Reason: to substrate absorption bands
due to H2O moisture, CO2 and anything else
that is not in the sample to produce the
actual spectrum.
- Sources of traces: solvent in the sample
 Example of FTIR background spectrum

H2 O
CO2 CO2

H2 O

Ambient water (two irregular groups of lines at

about 3600 cm1and about 1600 cm1) and CO2
(doublet at 2360 cm1and sharp spike at 667 cm
 SAMPLE HANDLING TECHNIQUES
Gases or low boiling point liquid
Permitting the sample to expand into
an evacuated cylindrical cells equipped
with suitable windows.
Path length of cylindrical cells: a few
cm to 10 m or more.
Liquid
o Method:
i) A drop of the pure (neat) liquid is squeezed
between two salt (NaCl) plates to give a layer
that has thickness 0.01 mm or less.
ii) Two plates held together by capillary
mounted in the beam path.
** Can also use KBr (common), KCl, AgBr etc
plates.

o Neat liquid:
- A pure liquid that do not contain any solvent
or water.
o This method is applied when amount of liquid is
small or when a suitable solvent is unavailable.
PREPARATI
ON OF
LIQUID
SAMPLES
(NEAT
LIQUIDS) Clean the Use a Pasteur pipette
USING plates with a to place a drop of
SALT small amount liquid on one salt
PLATE of acetone. plate

o
r

Put the second salt

Place the sandwich in the IR salt plate on top so that
plate holder and then in the the liquid spreads into
a thin film.
Salt plates
salt plate holder Demountabl salt plate holder
e cell (mull
cell) for
round
windows

Liquid cells
 The correct Never do this
way to hold a !!
salt plate
Solid
There are three ways to prepare solid
sample for IR spectroscopy:

i) Dissolve solid sample (solid is soluble

in solvent) in IR solvents such as CCl4
and put between salt plates for analysis.

** Common IR solvents: carbon

disulfide, carbon tetrachloride,
tetrachloroethylene, chloroform,
dimethylformamide, dioxane,
cyclohexane and benzene.
** Cannot use water or alcohol as a solvent
because:
i) water shows several strong absorption
bands in IR region and will cover up a lot
of other peaks.
ii) water and alcohol attack alkali-metal
halides (materials used for cell windows).
Barium fluoride must be used with this
solvents.
iii) water will dissolve the salt plates.
 ii)Solid that is insoluble in CCl4 or any
other IR solvents can be prepared either
by KBr pellet or mulls.

a) KBr pellet
i) mix solid sample with powdered
KBr (IR grade) for ratio 1:80 in agate
mortar and grind the mixture until it
become homogeneous and powdered.
ii) Press into a transparent disk using
hydraulic press (10,000-15,000 psi) in
special die.
iii) Put in the pellet holder for
analysis.
 Preparation of KBr pellet

Grind
sample Put the Put the die set into
with KBr sample into hydraulic press gauge.
(1:80) die set. Press until pressure
up to 7000 psi.

Put the KBr

pellet into a
pellet holder
for analysis.
Transparent
disk
 b) Mulls
i) 2-5 mg solid sample is grind into fine
powdered sample. Mix the fine sample with 1
or 2 drops of a heavy hydrocarbon oil (Nujol)
or mineral oil or fluorinated hydrocarbon
mull to obtain a pasty mull.
ii) The mull is examined as a film between
flat salt plates for analysis.

This method applied when solid not soluble

in an IR transparent solvent and not
conveniently
** pelleted
Mull = A thick pastein KBr. by grinding
formed
an insoluble solid with an inert liquid and
used for studying spectra of the solid
 Preparation of Nujol mulls

Mix the fine sample with

1 or 2 drops of a heavy Add a Put the second
hydrocarbon oil. The drop of salt plate on top
resulting mull should be mixture to so that the
transparent with no one salt liquid spreads
Attenuated total reflection (ATR)
spectroscopy
 How an ATR accessory works?
Internal reflection spectroscopy passes
infrared radiation through an infrared-
transmitting crystal of high refractive
index, allowing the radiation to reflect in
the crystal one or more times.
An attenuated total reflection accessory
measures the totally reflected infrared
beam when the beam comes in contact
with a sample.
In this way, an evanescent wave
penetrates into the sample in contact
with the crystal, producing a spectrum of
 ATR Data Collection
When collecting ATR data, samples
are run as % Reflectance or
log (1/R)
% Reflectance is equivalent to %
Transmittance
Log (1/R) is equivalent to
Absorbance
In summary, % Reflectance is
similar to Absorbance
 Crystal Composition
Crystals are typically made of:
Zinc Selenide (ZnSe)
Germanium (Ge)
Zinc Sulfide (ZnS)
Silicon (Si)
Diamond
AMTIR: Germanium, Arsenic,
Selenium (GeAsSe)
 Advantages
ATR versus. Transmission
When an ATR accessory is used, most
samples can be run neat, which means
in their natural state.
ATR sampling is fast and easy because
little or no sample preparation is
required.
Other techniques, such as infrared
transmission, often require the sample
to be heated, pressed or ground in order
to collect the spectrum.
 QUALITATIVE ANALYSIS

IR spectra gives more specific

qualitative information.
Absorption spectra is recorded as
transmittance spectra.
- Reason: the transmittance
spectra provide better contrast
between intensities of strong and
weak bands compared to
absorbance spectra.
absorbance (lower) plot
transmittan
ce spectra
provide
better
contrast
between
intensities
, cm-1 of strong
and weak
bands
compared
to
absorbance
spectra
 STRUCTURAL ANALYSIS

IR spectra is due to specific structural

features, a specific bond, within the
molecule, since the vibrational states
of individual bonds represent one
vibrational transition.

Example: IR spectrum can tell the

molecule has an O H bond or a
C=O or an aromatic ring.
Example of Infrared
Spectra
Intensities: s = strong, m = medium, w =
weak, b = broad
Intensities: s = strong, m = medium, w =
weak, b = broad
Summary of IR
Absorptions
 IR Spectrum of hydrocarbonds

Carbon-Carbon Bond Stretching

Stronger bonds absorb at higher frequencies:
C-C 1200 cm-1
C=C 1660 cm-1
CC 2200 cm-1 (weak or absent if internal)

Conjugation lowers the frequencies:

- isolated C=C 1640-1680 cm-1
- conjugated C=C 1620-1640 cm-1
- aromatic C=C approx. 1600 cm-1
 Carbon-Hydrogen Stretching

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
 An Alkane IR Spectrum

H H H H H H
H C C C C C C H

H H H H H H n -hexane
 CH2
C-H
rocking
bending
C-H
stretching

C-H stretching for sp3 hybridized: around

3000 2840 cm-1
Methylene groups (CH2): bending absorption
at approx 1465 cm-1.
Methyl groups (CH3): bending absorption at
approx 1375 cm-1.
CH2 the bending (rocking) motion associated
 An Alkene IR Spectrum
H H H H H H
H C C C C C C H

H H H H

C-H stretching corresponds to =C-H bonds

involving sp2 hybrid C:
3080 cm-1
stretching C=C: 1642 cm-1
 An Alkyne IR Spectrum
H H H H H H
H C C C C C C C C H

H H H H H H

C-H stretching (sp hybrid C) : 3313 cm-1

CC stretching: 2119 cm-1
 An Aromatic IR Spectrum

=C-H Stretch for sp2 hybrid: values

greater than 3000 cm-1.
C=C ring stretch absorptions: occur
in pairs at 1600 cm-1 and 1475 cm-1
=C-H bending: 900 - 690 cm-1.
Examples: IR spectrum for
toluene
 C-H Bending (for Aromatic Ring)

Monosubstituted rings
- This substitution pattern always gives a
strong absorption near 690 cm-1. If this band is
absent, no monosubstituted ring is present. A
second strong band usually appears near 750
cm-1.
Ortho-Disubstituted rings
- One strong band near 750 cm-1.
Meta-Disubstituted rings
- Gives one absorption band near 690 cm-1 plus
one near 780 cm-1. A third band of
medium intensity is often found near 880 cm-1.
Para-Disubstituted rings
Ortho-Disubstituted Rings

=C-H bending
Meta-Disubstituted Rings

=C-H
para-Disubstituted Rings

=C-H
 An Alcohol IR Spectrum

O-H bond stretching: broad peak at 3400 -

3300 cm-1. Broad peak present is due to the
hydrogen bonding arrangements.
C-O stretching absorption (unreliable): broad
-1
 IR Spectrum of phenol

OH

C-O
stretching
O-H Aromatic
stretchi C=C
ng
 IR Spectrum of ether
R O R'
C-O-C stretching: The most prominent
band at 1300 - 1000 cm-1.
Absence of C=O and O-H is required to
ensure that C-O stretching is not due to
an ester or an alcohol.
Phenyl alkyl ethers give two strong
bands at about 1250 - 1040 cm-1.
While aliphatic ethers give one strong
band at about 1120 cm-1 .
IR spectrum of diethyl ether
CH3CH2 O CH2CH3

C-O
stretching
~ 1120 cm-1
 C=O stretching
Compounds Frequencies (cm-1)
Amides 1670-1650
Aldehydes 1740-1720
Ketones 1725-1705
Carboxylic acids 1725-1700
Esters 1750-1730
Acid halides 1810-1780
Anhydrides 1830-1800 and
1775-1740
 1) IR spectrum of aldehydes
O C=O
stretching:
1740-1720
R C H cm-1 (s)

Two C-H stretching: 2860-

2800 cm-1 and at 2760-
2700 cm-1(w)

O Conjugation of C=O with phenyl;

i) 1700-1660 cm-1 for C=O
Ar C H ii) 1600,1450 cm-1 for ring (C=C)
IR spectrum of
butyraldehyde
2) IR spectrum of ketones

O
C=O stretch appear in
range 1720-1708 cm-1
R C R'

O Conjugation of C=O with

phenyl;
i) 1700-1680 cm-1 for C=O
Ar C R' ii) 1600, 1450 cm-1 for
ring (C=C)
IR spectrum of 2-
butanone
 3) IR spectrum of carboxylic acids

R C OH
O-H stretching: usually very broad (strongly
hydrogen-bonding), occurs at 3400-2400 cm -1
and often overlaps the C-H absorptions.
C=O stretching: broad, occurs at 1730-1700
cm-1. Conjugation moves the absorption to a
lower frequency.
C-O stretching: 1320-1210 cm-1 (medium
IR spectrum of hexanoic
acid
 4) IR spectrum of esters

R C O R
C=O stretching: 1750-1735 cm-1 for
normal aliphatic esters. Conjugation
moves the absorption to a lower
frequency (1740-1715 cm-1 ).
C-O stretching: two or more bands, one
stronger and broader than the other,
occurs in the range 1300-1000 cm-1.
IR spectrum of ethyl
acetate
IR spectrum of ethyl
benzoate
 5) IR spectrum of amides
O O H O R
H

R C N R C N R C N

H R R
1 2 3
C=O stretching: approximately at 1680-1630
cm-1.
N-H stretching:
i) primary amides (-NH2) gives two bands
near 3350 and 3180
cm-1.
ii) Secondary amides have one band (-NH) at
about 3300 cm-1.
-1
 IR spectrum of acetamide
(primary amide)

N-H
stretching

C-N
C=O stretching
stretching
IR spectrum of N-methyl-1-
piperidinecarboxamide
(secondary amide)
CH3
O N
H
N

N-H C=O
stretching stretching
IR spectrum of tertiary amide

** No N-H
stretching

C=O
stretching
 6) IR spectrum of acid chlorides

R C Cl

C=O stretching: appear in range 1810-

1775 cm-1 in conjugated chlorides.
Conjugation lowers the frequency to
1780-1760 cm-1.

C-Cl stretching: range 730-550 cm-1.

 IR spectrum of 3,3-
dimethylbutyryl chloride

C=O
stretching C-Cl
stretching
 7) IR spectrum of anhydrides
O
O
C R
R C O

C=O stretching:
- two bands, 1830-1800 cm-1 and 1775-1740
cm-1 with variable
relative intensity.
- Conjugation moves the absorption to a lower
frequency.
- Ring strain (cylic anhydride) moves
absorptions to a higher
IR spectrum of acetic anhydride

C=O
stretching
C-O
stretching
 IR spectrum of amines
H H
R N R N
H R
1 2

R
R N
R
3

 N-H stretching:
- occurs in the range 3400-3250 cm-1.
- Primary amines have two bands from 3400-
3300 and 3330-3250 cm-1.
- Secondary amines have one band; a
vanishingly weak one for aliphatic compounds
and a stronger one for aromatic secondary
amines from 3350-3310 cm-1.
-Tertiary amines have no N-H stretch (no
bands in this region ).
N-H bending:
- primary amines results in a broad band in
the range 1640-1560 cm-1.
- Secondary amines absorb near 1500 cm-1.
N-H out-of-plane bending: near 800 cm-1
C-N stretching: range 1350-1000 cm-1.
IR spectrum of 1-aminobutane
(primary amine)

N-H
N-H bendin
stretchi g N-H
ng
oop
IR spectrum of diethylamine
(secondary amine)

N-H
oop
 IR spectrum of N,N-diethyl-1-
butanamine (tertiary amine)

CH2
bend
C-N
CH3 stretc
bend h

CH3
C-H H3C CH2 CH2 CH2 N
stretc CH3
h
Example: The following is the IR spectrum of a
carboxylic acid, which has the molecular formula
C2H4O2. Select two significant peaks associated
with the carboxylic acid from the given
spectrum. State the wavenumber and the bond
associated with each peak you selected.
 O-H C=O
stretching stretchin
g

Answers:
Wavenumber Types of
(cm-1) Bond
3100 O-H
stretching