FTIR

SPECTROSCOPY
Assoc Prof Dr Kamariah Noor Ismail
PhD (UiTM), MSc (Leeds,UK), BSc (UKM)
Faculty of Chemical Engineering UiTM
 To understand the basic principal of FTIR
Analysis

To explain the procedure of FTIR Analysis

OBJECTIVES

To analyze the FTIR spectra and determine

their functionality and structure of unknown
substance
 Common Applications:
• Identification of compounds by matching spectrum of unknown
compound with reference spectrum (fingerprinting)
Objective 1 • Identification of functional groups in unknown substances
• Identification of reaction components and kinetic studies of
Basic reactions
• Identification of molecular orientation in polymer films
Principal of
• Detection of molecular impurities or additives present in amounts of
FTIR Analysis 1% and in some cases aslow as 0.01%
• Identification of polymers, plastics, and resins
• Analysis of formulations such as insecticides and copolymers
 Spectroscopy and Electromagnetic Radiation a.k.a EMR

Objective 1

Basic
Principal of
FTIR Analysis
Objective 1

Basic
Principal of
FTIR Analysis
 Molecular vibrations when the heteroatoms molecule absorb an IR radiation

Objective 1

Basic
Principal of
FTIR Analysis
 What type of samples can FTIR analyses?
● Organic powders in pellet or mull form (paste)
● Thermoplastic powders
● Soluble polymers
Objective 2 ● Thin polymer films
● Regular-shaped polymers (with preparation)
Procedure for ● Irregular-shaped polymers (with preparation)
FTIR Analysis ● Dark polymer films (not carbon-filled)
● Liquids (free-flowing or viscous)
● Gases (high concentrations to trace amounts)
● Liquid, Solid, Gaseous and Solution form
 Solid: direct sampling,
Objective 2 pellatization, and Liquid: direct
mulling (paste)…KBr measurement
Procedure for and NaCl
FTIR
Type of
Analysis: sample
Type of
Sample and Solution: sample is
Sampling dissolved in chloroform, Gas: Used gas cell made
carbon tetrachloride and up of NaCl
carbon disulphide
 Fourier Transform
Instrumentation

Objective 2

Procedure for
FTIR Analysis
 How does interferometer work?
• The light passes through a beamsplitter, which sends the light
in two directions at right angles.
• One beam goes to a stationary mirror then back to the beamsplitter,
the other goes to a moving mirror.
• The motion of the mirror makes the total path length variable versus that
Objective 2 taken by the stationary-mirror beam.
• When the two meet up again at the beamsplitter, they recombine, but the difference
in path lengths, hence creates constructive and destructive interference
Procedure for known as an interferogram
• The recombined beam passes through the sample and absorbs all the different
FTIR Analysis wavelengths characteristic of its spectrum, and this subtracts specific wavelengths
from the interferogram.
• The detector now reports variation in energy versus time for all wavelengths simultaneous
• A mathematical function called a Fourier transform allows us to convert
an intensity-vs.-time spectrum into an intensity-vs.-frequency spectrum
 Interferograme vs FTIR
Spectrum

Objective 2

Procedure for
FTIR Analysis
 Primary Functional Group, Is it
VOC?
Objective 3

FTIR spectra
and determine
their
functionality
and structure of
unknown
substance..
Spectrum
Interpretation
 Example of Functional Group in Organic
Molecule
Objective 3

FTIR spectra
and determine
their
functionality
and structure of
unknown
substance..
Spectrum
Interpretation
 Dipole changes During Vibrations and Rotations
● IR absorption - a molecule must undergo a net change in dipole moment due
to vibrational or rotational motion.
● Homonuclear species such as O2, N2 or Cl2 – no net change in dipole
moment occurs during vibration or rotation.
● Eg. The charge distribution around a molecule of HCl is not symetric
because the Cl has a higher electron density than the hydrogen.
Theory of ● HCl has a significant dipole moment and known as polar molecule
Infrared ● Dipole moment: determined by the magnitude of the charge difference and
the distance between the two centre of centre of charge.
● as a HCl vibrates, a regular fluctuation in dipole moment occurs, an a field is
established that can interact with the electrical field associated with radiation.
If the frequency of the radiation exactly matches a natural vibrational
frequency of the molecule, a net transfer of energy takes place that results in
a change in the amplitude of the molecular vibration, absorption of the
radiation is the consequence. Similarly, the rotation of asymmetric molecules
around their centres of mass result in a periodic dipole fluctuation that can
interact with radiation.
 Rotational Transitions
● The energy required to cause a change
-1
in rotational is minute (small) and
corresponds to radiation of 100 cm or less (>100μm)
● Rotational levels are quantized;
i) Absorption by gases in the far IR region is characterized by discrete,
well-defined line
ii) Absorption by liquids or solids intramolecular collisions and
interactions cause broadening of the lines in to a continuum.
Theory of Vibrational/Rotational Transitions
Infrared ● Vibrational energy levels are also quantized for most molecules the energy
differences between quantum states correspond to the mid-IR region.
● The IR spectrum of a gas usually consists of closely spaced lines, because
there are several rotational energy state for each vibrational state.
● On the other hand, rotation is highly restricted in liquids and solids, in such
sample, discrete vibrational/rotational lines disappear, leaving only
somewhat broadening vibrational peaks.
 i) Stretching: involves a continues change in the inter atomic
distance along the axis of the bond between two atoms. 2 types:
Types of Symetric stretching and asymetric stretching

molecular ii) Bending: characterized by a change in the angle between two

vibration bonds. 4 types of bending vibrations: scissoring(bending),
rocking, wagging and twisting.
Stretching and
Bending
Objective 3

FTIR spectra IR Correlation Table

and determine
their
functionality
and structure of
unknown
substance..
Spectrum
Interpretation
 The spectra of simple alkanes are characterized by absorptions due to C–H stretching and bending (the
C–C stretching and bending bands are either too weak or of too low a frequency to be detected in IR
spectroscopy). In simple alkanes, which have very few bands, each band in the spectrum can be
assigned.
Objective 3 • C–H stretch from 3000–2850 cm-1
• C–H bend or scissoring from 1470-1450 cm-1
• C–H rock, methyl from 1370-1350 cm-1
• C–H rock, methyl, seen only in long chain alkanes, from 725-720 cm-1
FTIR spectra
and determine
their
functionality
and structure of
unknown
substance..
Spectrum
Interpretation
for Alkane
 Alkenes are compounds that have a carbon-carbon double bond, –C=C–. The stretching vibration of the
C=C bond usually gives rise to a moderate band in the region 1680-1640 cm-1.
Stretching vibrations of the –C=C–H bond are of higher frequency (higher wavenumber) than those of the
–C–C–H bond in alkanes.
Objective 3 ● C=C stretch from 1680-1640 cm-1
● =C–H stretch from 3100-3000 cm-1
● =C–H bend from 1000-650 cm-1
FTIR spectra
and determine
their
functionality
and structure of
unknown
substance..
Spectrum
Interpretation
for Alkene
 The =C–H stretch in aromatics is observed at 3100-3000 cm-1. Note that this is at slightly higher frequency than is the –C–H
stretch in alkanes.
Aromatic hydrocarbons show absorptions in the regions 1600-1585 cm-1 and 1500-1400 cm-1 due to carbon-carbon
stretching vibrations in the aromatic ring.
Objective 3 ● C–H stretch from 3100-3000 cm-1
● overtones, weak, from 2000-1665 cm-1
● C–C stretch (in-ring) from 1600-1585 cm-1

FTIR spectra ● C–C stretch (in-ring) from 1500-1400 cm-1

and determine
their
functionality
and structure of
unknown
substance..
Spectrum
Interpretation
for Aromatics
 Alcohols have characteristic IR absorptions associated with both the O-H and
the C-O stretching vibrations.
● O–H stretch, hydrogen bonded 3500-3200 cm-1

Objective 3 ● C–O stretch 1260-1050 cm-1 (s)

FTIR spectra
and determine
their
functionality
and structure of
unknown
substance..
Spectrum
Interpretation
for Alcohols
 The carbonyl stretching vibration band C=O of saturated aliphatic ketones appears at 1715 cm-1.
Conjugation of the carbonyl group with carbon-carbon double bonds or phenyl groups, as in alpha, -1
beta-unsaturated aldehydes and benzaldehyde, shifts this band to lower wave numbers, 1685-1666 cm
Objective 3 ● C=O stretch:
● aliphatic ketones 1715 cm-1
● α, β-unsaturated ketones 1685-1666 cm-1

FTIR spectra
and determine
their
functionality
and structure of
unknown
substance..
Spectrum
Interpretation
for Ketones
 The carbonyl stretch C=O of saturated aliphatic aldehydes appears from 1740-1720 cm-1. As in ketones, if
the carbons adjacent to the aldehyde group are unsaturated, this vibration is shifted to lower
wavenumbers, 1710-1685 cm-1

Objective 3 ● H–C=O stretch 2830-2695 cm-1

● C=O stretch:
● aliphatic aldehydes 1740-1720 cm-1

FTIR spectra ● alpha, beta-unsaturated aldehydes 1710-1685 cm-1

and determine
their
functionality
and structure of
unknown
substance..
Spectrum
Interpretation
for Aldehydes
Objective 3

FTIR spectra
and determine
their
functionality
and structure of
unknown
substance..
Spectrum
Interpretation &
Practice
Practice for
these
compounds
 ●Absorption spectroscopy is a widely applied
technique for chemical characterisation.
●An extensively used form of absorption
spectroscopy is infrared absorption (IR)
spectroscopy.
●IR measures specific frequencies in the
infrared region of the electromagnetic
Conclusion spectrum at which constituent parts of
molecules corresponding to specific types of
molecular bonds vibrate.
●This makes possible for structural elucidation
and compound identification of materials.
●As a consequence, IR absorption is extensively
used as an analytical tool.
 ●Presentation materials are compiled
Aknowlegdment
from variation of sources: FTIR
and Thank You
Website, Textbooks and Journals