Chapter 16 – Infrared

Spectroscopy
Principles of Instrumental Analysis

Course CMA

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 Introduction
• Useful range from about 2.5 mm to 50 mm.
• Infrared used to determine the major functional groups present.
(Functional groups are groups of one or more atoms of distinctive
chemical properties no matter what they are attached to, e.g. –OH)
• Quantitative measurements possible but subject to large amount of
error.
• Atoms or groups of atoms in molecules are in continuous motion
with different modes of vibration relative to each other.
• Absorption of radiation changes amplitude of vibration but not
frequency.

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 Infrared Spectrum
Fig. 16-1, pg. 382 “Infrared absorption spectrum of a thin polystyrene film
recorded with a modern infrared spectrometer. Note that the abscissa scale
changes at 2000 cm-1.” Polystyrene film is commercially used for calibration of
wave numbers. (3026, 3002, 2924, 1602, 1495 & 906)

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Bands of PS found in the ATR spectra and their
assignment.

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 Vibrational Modes
• Increased amplitude produces a change in
dipole moment.
•  = q×r. where  = dipole moment, q =
change displacement, and r = displacement
from equilibrium.
• Only vibrations that cause this change in
electric dipole moment will be associated
with an absorption of infrared radiation.
• E.g. Symmetric and antisymmetric modes
of vibration are possible with CO2;
• symmetric mode of vibration has no net
change in its dipole moment, while
antisymmetic mode has net change in
dipole moment. The antisymmetric mode
would be infrared active and the symmetric
mode would not.
• See
https://en.wikipedia.org/wiki/Infrared_spectroscopy

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Theory of Infrared Absorption Spectroscopy

• In order for IR absorbance to occur two conditions must be met:

1. There must be a change in the dipole moment of the molecule as

a result of a molecular vibration (or rotation). The change (or
oscillation) in the dipole moment allows interaction with the
alternating electrical component of the IR radiation wave.
Symmetric molecules (or bonds) do not absorb IR radiation since
there is no dipole moment.

2. If the frequency of the radiation matches the natural frequency of

the vibration (or rotation), the IR photon is absorbed and the
amplitude of the vibration increases.

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DE = hn
• There are three types of molecular transitions that occur in IR
a) Rotational transitions
• When an asymmetric molecule rotates about its center of mass, the
dipole moment seems to fluctuate.
• DE for these transitions correspond to n < 100 cm-1
• Quite low energy, show up as sharp lines that subdivide vibrational
peaks in gas phase spectra.
b) Vibrational-rotational transitions
• complex transitions that arise from changes in the molecular dipole
moment due to the combination of a bond vibration and molecular
rotation.
c) Vibrational transitions
• The most important transitions observed in qualitative mid-IR
spectroscopy.
• n = 13,000 – 675 cm-1 (0.78 – 15 mM)

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IR Sources and Detectors
Sources - inert solids that heat electrically to 1500 – 2200
K.
• Emit blackbody radiation produced by atomic and molecular oscillations
excited in the solid by thermal energy.
• The inert solid “glows” when heated.
• Common sources:

1. Nernst glower - constructed of a rod of a rare earth

oxide (lanthanide) with platinum leads.

2. Globar - Silicon carbide rod with water cooled contacts to

prevent arcing.

3. Incandescent wire - tightly wound wire heated

electrically. Longer life but lower intensity.

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 Detectors – measure minute changes in temperature.
1. Thermal transducer
• Constructed of a bimetal junction, which has a temperature dependant
potential (V). (similar to a thermocouple)
• Have a slow response time, so they are not well suited to FT-IR.
2. Pyroelectric transducer
• Constructed of crystalline wafers of triglycine sulfate (TGS) that have a
strong temperature dependent polarization.
• Have a fast response time and are well suited for FT-IR.
3. Photoconducting transducer
• Constructed of a semiconducting material (lead sulfide,
mercury/cadmium telluride, or indium antimonide) deposited on a glass
surface and sealed in an evacuated envelope to protect the
semiconducting material from the environment.
• Absorption of radiation promotes nonconducting valence electrons to a
conducting state, thus decreasing the resistance (W) of the semiconductor.
• Fast response time, but require cooling by liquid N2.
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(FT) Spectrometers
• Collect data in the time domain and convert to the frequency domain by
Fourier Transform.

• Detectors are not fast enough to respond to power variations at high

frequency (1012 to 1015 Hz) so the signal is modulated by a Michelson
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interferometer to a lower frequency that is directly proportional to the high
B. Multiplexing (FT) Spectrometers
1. Michelson Interferometer

• The source beam is split into two

beams.

• One beam goes to a stationary

mirror and the other goes to a
moveable mirror.

• Movement of the mirror at a

constant rate and recombination of
the two beams results in a signal
that is modulated by constructive
and destructive interference
(Interferogram).

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Multiplexing (FT) Spectrometers

• The frequency of the

radiation (n) is directly
related to the frequency
of the interferogram (f).

ν = frequency of radiation
f = frequency of inteferogram
νM = velocity of the mirror
c = speed of light (3.00 x 1010 cm/s)
δ = retardation 2(M-F), the
difference in path lengths for
the two beams

• FT-IR spectrometers use a polychromatic source and collect the entire

spectrum simultaneously and decode the spectrum by Fourier Transform.
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 FT-IR summary

Time axis decoding Wavenumber

Frequency domain
Time domain by FFT 14
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Multiplexing (FT) Spectrometers
2. FT-IR instrument
• Mirror length of travel ranges
from 1 to 20 cm.

• Scan rates from 0.1 to 10 cm/s

• Detectors are usually pyroelectric

or photoconducting.

• Use multiple scans and signal

averaging to improve S/N.

• Cost $10,000 - $20,000

• Have virtually replaced

dispersive instruments.

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Performance Characteristics
• Range: 7800 to 350 cm-1 (less expensive)
25,000 to 10 cm-1 (Near to far IR, expensive)
• Resolution: 8 cm-1 to 0.01 cm-1

• Qualitative: Very good, functional groups are

identifiable
• Quantitative: Dispersive – poor
FTIR - fair

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Table 26-5 is from Skoog, Fundamentals of Analytical
Chemistry, 9th edition. Table 2-4 is from Pavia, p.30
The detailed table is given in Skoog, principles of Instrumental
Analysis, 7th edition.

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Abbreviated Table of Group Frequencies for Organic Groups (adapted from Skoog)
Bond Type of Compound Frequency Range, cm-1 Intensity
C-H Alkanes 2850-2970 Strong
C-H Alkenes H 3010-3095 Medium
C C 675-995 strong
C-H Alkynes 3300 Strong
C C H
C-H Aromatic rings 3010-3100 Medium
690-900 strong
O-H Monomeric alcohols, phenols 3590-3650 Variable
Hydrogen-bonded alchohols, phenols 3200-3600 Variable, sometimes broad
Monomeric carboxylic acids 3500-3650 Medium
Hydrogen-bonded carboxylic acids 2500-2700 broad
N-H Amines, amides 3300-3500 medium
Nitriles 2210-2280 Strong
Alkynes 2100-2260 Variable
C N
C=O
C C Aldehydes, ketones, carboxylic acids, esters 1690-1760 Strong
C=C Alkenes 1610-1680 Variable
C=C Aromatic rings 1500-1600 Variable
C-N Amines, amides 1180-1360 Strong
C-O Alcohols, ethers,carboxylic acids, esters 1050-1300 Strong
NO2 Nitro compounds 1500-1570 Strong
1300-1370
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 Quantitative Analysis
• IR has traditionally been used for qualitative
analysis.
• Difficult to use quantitatively due to chemical
or instrumental effects.
• Large sloping background often interferes
with normal spectrum.
• The base line method corrects involves
selection of absorption band of the
substance under analysis which is
sufficiently separated from other matrix
peaks and corrected as shown below.
• Mixtures can be determined by same
methods described earlier. Need to set up
the correct number of simultaneous
equations. Instrumental Analysis, Christian & O’Reilly, p. 241.

• Convenient for measuring concentrations of

gases

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