Infrared spectroscopy

Analytical infrared studies are based on the absorption (or

reflection) of the
electromagnetic radiation that lies between 1 and 1000m.
This is one of
the most common spectroscopic techniques used for
compound
identification and measuring of concentrations in many
samples
This spectral range is sub-divided into three smaller areas:
- the near infrared (near-IR, 125m),
- the mid infrared (mid-IR, 2550m) and
- the far infrared (beyond 25m).
Infrared spectroscopy is certainly one of the most important
analytical
techniques available to todays scientists.
One of the great advantages of infrared spectroscopy is that
virtually any
sample in virtually any state may be studied.
Liquids, solutions, pastes, powders, films, fibres, gases and

Molecular effects of infrared absorption

1) IR radiation does not have enough energy to induce
electronic transitions
as seen with UV. Absorption of IR is restricted to
compounds with small
energy differences in the possible vibrational states.
2)
For a molecule to absorb IR, the vibrations within a
molecule must cause
a net change in the dipole moment of the molecule.
3) The alternating electrical field of the radiation interacts
with fluctuations
in the dipole moment of the molecule.
Molecular vibration induced by IR adsorption
4)
If the frequency of the radiation matches the vibrational
The positions of atoms in molecules are not fixed; they are subject
frequency of the
to a
molecule (resonance), radiation will be absorbed,
number of different vibrations. Vibrations fall into the two main
causing a change in
categories
the amplitude of molecular vibration.
of stretching and bending.
Stretching:
Molecular
Change
vibrations
in inter-atomic distance along bond
axis Molecular vibrations

Molecular vibration induced by IR absorption

Molecular vibration induced by IR absorption

Molecular vibration induced by IR absorption

Molecular vibration induced by IR absorption

Dipole moment induced by IR absorption

Instrumentation

Schematic diagram of spectrometers and analysers in the infrared. (a)

Single beam
analyser containing a fixed monochromator or a filter used when a
measurement at a single
wavelength will suffice; (b) dispersive spectrometer, double beam system.
In contrast to spectrophotometers in the UV/Vis, the sample, located prior
to the monochromator is permanently exposed to the full radiation of the

Instrumentation

Perkin ElmerT
Spectrum On

BRUKE TENSORTM
Series

Instrumentation
Dispersive instruments: with a monochromator
to be used in the mid-IR region for spectral
scanning and quantitative analysis.
Fourier transform IR (FTIR) systems: widely
applied and quite popular in the far-IR and mid-IR
spectrometry.
Nondispersive instruments: use filters for
wavelength selection or an infrared-absorbing
gas in the detection system for the analysis of
gas at specific wavelength.

The Infrared Spectrometer Dispersive

Infrared Spectrometers

Dispersive Infrared Spectrometers

Dispersive Infrared Spectrometers

Dispersive Infrared Spectrometers

Processes of IR spectroscopic measurement Using

Dispersive Infrared Spectrometers
Chemists often obtain a spectrum in this type of
spectrometer by
dissolving the sample in a solvent
The solution is placed in the sample beam, while the
pure solvent
is placed in the reference beam.
The instrument then subtracts the solvent
spectrum from that
of the sample, along with any IR-active atmospheric
components.
The spectrum is recorded as percent transmittance
(%T):

Processes of IR spectroscopic
measurement Using Dispersive
Infrared Spectrometers
Modern IR spectrometers (spectrophotometers)
have an
optical pathway that produces a pattern called an
interferogram.
An interferogram is a complex wave-like pattern
that contains
all the frequencies that make up an IR spectrum,
as a plot of
intensity vs. time.
A Fourier transform (FT) can separate the
individual
absorption frequencies, producing a spectrum that
is virtually
identical to that obtained by the dispersive

Fourier Transform
Spectrometers

Fourier Transform Spectrometers

Fourier Transform Spectrometers

Fourier Transform Spectrometers

Fourier Transform Spectrometers

Fourier Transform Spectrometers

There are three major advantages in the performance of an FTIR spectrometer over a dispersive infrared spectrometer.
1) Multiplex: An interferometer in an FT-IR instrument does not
separate
energy into individual frequencies for measurement
of the infrared spectrum. In contrast, every wavelength across
the spectrum must be measured individually in a dispersive
spectrometer. Many scans can be completed and combined
on an FT-IR in a shorter time than one scan on a dispersive
Instrument.
2) Throughput: Overall, more energy reaches the sample and
hence the detector in an FT-IR spectrometer than in a
dispersive spectrometer. This means that the signal-to-noise
ratio of an infrared spectrum measured on an FT-IR is higher
than the signal-to-noise ratio attained on a dispersive
instrument. Also, in a dispersive instrument, the process is
extremely slow due to the coordination of the grating and slit
systems to collect the large number of data points required.

Fourier Transform Spectrometers

3) Precision: An FT-IR spectrometer requires the use of a laser
to control the velocity of the moving mirror and to time the
collection of data points throughout the mirror stroke length
for each scan. This laser is also available
as a source of wavelength calibration within the instrument.
External calibration standards are required to control the
accuracy of a dispersive instrument, making spectra less
comparable. Accuracy and precision in infrared spectra are
much higher when collected on an FT-IR.

Preparation of Samples for Infrared

Spectroscopy
Infrared spectra may be obtained for gases, liquids or
solids (neat or in solution)
The preparation of samples for infrared spectrometry is often the
most
challenging task in obtaining an IR spectrum. Since almost all
substances
absorb IR radiation at some wave length, and solvents must be
carefully
chosen for the wavelength region and the sample of interest.
Practical considerations:
Samples must go in sample holders.
Glass and plastic absorb throughout the IR region.
Ionic salts must therefore be used; normally NaCl or KBr
KBr is more expensive than NaCl, but they are useful across
the
entire IR range of 400 4000 cm-1 (NaCl is limited to
650 4000 cm-1).

Preparation of Samples for Infrared

Spectroscopy
Gas samples
A gas sample cell consists of a cylinder of glass or sometimes a metal. The cell is
closed at both ends with an appropriate window materials (NaCl/KBr) and
equipped with valves or stopcocks for introduction of the

sample.

Long pathlength (10 cm) cells used to study dilute (few molecules) or weakly
absorbing samples.
Multipass cells more compact and efficient instead of long-pathlength cells.
Mirrors are used so that the beam makes several passes through the sample
before exiting the cell. (Effective pathlength 10 m).
To resolve the rotational structure of the sample, the cells must be capable of
being evacuated to measure the spectrum at reduced pressure.
For quantitative determinations with light molecules, the cell is sometimes
pressurized in order to broaden the rotational structure and all simpler
measurement.

Preparation of Samples for Infrared

Spectroscopy

Preparation of Samples for Infrared

Spectroscopy
Liquid samples
Pure or soluted in transparent solvent not water (attacks windows)
The sample is most often in the form of liquid films (sandwiched
between two NaCl plates)
Adjustable pathlength (0.015 to 1 mm) by Teflon spacer

Preparation of Samples for Infrared

Spectroscopy

Preparation of Samples for Infrared Spectroscopy

Regions of transparency for common
infrared solvents.

The horizontal lines indicate regions where solvent transmits at

least 25% of the incident radiation in a 1-mm cell.

Solid samples
Spectra of solids are obtained as alkali halide discs (KBr), mulls
(e.g. Nujol, a highly refined mixture of saturated hydrocarbons) and
films (solvent or melt casting)
1. Mix finely ground sample with
KBr, and press under high
pressure to create KBr pellet
that can be inserted into a
holder
2. Grind the sample with mineral
oil (Nujol) to create a Nujol mull,
which is then pressed between
salt plates (Note: Nujol absorbs
in the IR, at 2924, 1462 and
1377 cm-1)
3. Dissolve the sample in an
organic solvent and treat like a
liquid sample (Note: Most
organic solvents absorb in the IR

Preparation of Samples for Infrared

Spectroscopy
FT-IR ATR: Attenuated Total Reflectance enables
samples to
be examined directly in the solid or liquid state
without
further preparation.
This operates by measuring the changes that occur
in a totally
internally reflected infrared beam when the beam
comes into contact with a sample

Basic Concept in IR
1.

Absorption of an infrared photon results in the excitation of the

molecule to a higher vibrational quantum state.
2. For a stretching vibration, a photon is absorbed and the molecule
excited to a higher vibrational quantum state only if that vibration
results in a change in bond dipole. The bond dipole is a product of
bond length and charge difference of the bonded atoms.
3. As a bond vibrates, the bond length changes, so this criterion is met.
The charge difference is determined by the electronegativity of the
bonded atoms. If these atoms are not identical then they have a
difference in electronegativity and thus a difference in charge. If these
atoms are identical, they have equal electronegativity and thus no
charge difference.
4. In this case, the product of bond length change and charge difference
(zero) is zero, so no photon is absorbed. If the atoms are even slightly
different, then a small change in bond dipole occurs, along with the
corresponding absorption of an infrared photon.

Basic Concept in IR.

5. E.g. all bond stretches of H2C=O show up on the IR spectrum
because all of the bonds consist of unequal atoms. For
H2C=CH2, the CH bond stretches give IR bands, but the
C=C bond (which is made up of two identical carbon atoms)
does not. The C=C bonds of H2C=CHCH=CH2 show up in
the IR because the carbons are not equal. One carbon is a
CH2 and the other is a HCCH.
6. In summary, asymmetrical bonds give IR absorptions
whereas symmetrical bonds do not.
7. The energy of the photon necessary to excite the molecule to
a higher vibrational quantum level is controlled by the masses
of the attached atoms and the bond strength. Similar
functional groups are made up of similar atoms. Thus
molecules with similar functional groups absorb photons of
similar energies. This is why we can use IR spectroscopy to
determine what functional groups are present or absent in a
compound by simply looking at the positions of the IR peaks.

Basic Concept in IR.

8. We divide the IR spectrum into five zones, based upon the energy of
photons absorbed by twelve common functional groups. The zones
and functional groups therein are summarized below :
The absence of functional groups as indicated by the IR
spectrum is just as important as their presence. Students
often forget to list the functional groups not contained in the
unknown, and therefore lose exam points! Avoid this by
listing all the functional groups in each zone before
beginning the five zone analysis, and then it is an easy
matter to label each possible functional group
as absent or present.
a) Zone 1 (37003200 cm-1): alcohol OH, amide, or amine NH,
terminal alkyne CH
b) Zone 2 (32002700 cm-1): alkyl CH, aryl or vinyl CH, aldehyde C
H, carboxylic acid OH
c) Zone 3 (23002000 cm-1): alkyne and nitrile triple bonds
d) Zone 4 (18501650 cm-1): carbonyl functional groups
e) Zone 5 (16801450 cm-1): alkene, benzene ring

Basic Concept in IR.

9. - Alcohol, Amine: the OH and NH stretches are usually broadened
due to hydrogen bonding.
- Carboxylic acid: must have two bands: broad OH stretch in zone 2
and C=O stretch in Zone 4.
- Aldehyde: must have two sets of bands: 2900 and 2700 cm-1 in zone
2 (2900 cm-1 often hidden by alkyl CH stretches), and C=O stretch
in zone 4.
- Alkyne: a peak caused by the triple bond stretch is not observed
when the alkyne is symmetric or nearly so.
- Carbonyl: often the most intense peak in the entire spectrum.
- Benzene ring: must have bands at about 1600 cm-1 (may be two
bands close together) and another at about 1500 cm-1. Since most
benzene ring compounds have at least one hydrogen atom attached
to the benzene ring, an sp2 CH stretch peak is also seen in Zone 2.

Basic Concept in IR.

10. The region from about 1450 to 400 cm-1 is called the fingerprint
region. This region is often complex because it contains many
absorptions. It is usually ignored in routine IR analysis because it
can be difficult to make precise assignments. For example, a peak
at 1360 cm-1 could be a CH2 bend or a CN stretch. Without precise
assignments, it can be difficult to determine the absence or
presence of functional groups from the fingerprint region. However,
the fingerprint regions of two IR spectra of the same compound are
identical, in the same way that two fingerprints left by the same
person in different places are identical. Thus the fingerprint region
of an unknown compound can be compared with the fingerprint
region of a known sample, and if they match exactly, the unknown
and known are identical

Main uses of IR spectroscopy:

1. Fundamental chemistry
Determination of molecular structure/geometry.
e.g. Determination of bond lengths, bond angles of
gaseous molecules
2. Qualitative analysis simple, fast, nondestructive
Monitoring trace gases: NDIR.Rapid, simultaneous
analysis of GC, moisture, N in soil. Analysis of fragments
left at the scene of a crime
Quantitative determination of hydrocarbons on filters, in
air, or in water

Practice Problems
1. Several functional groups have absorptions in more than
one of the five
zones. To conclude that the functional group is present,
both absorptions must be seen. Prepare a table listing these
functional groups and the corresponding absorptions. Hint:
There are at least six such functional groups. Some of them
require three distinct absorptions.

Functional Group Absorptions

terminal alkyne 3300 cm-1 (CH stretch)

z1
22602000 cm-1 (CC stretch)
- z3
aromatic ring 31003000 cm-1 (sp2 CH stretch)
-z2
~1600 cm-1 and 15001450 cm-1 (benzene ring
stretch)
- z5
aldehyde ~2900 and ~2700 cm-1 (CH stretch)
- z2
17401720 cm-1 (C=O stretch)
- z4
carboxylic acid 30002500 cm-1 (OH stretch)
-z1
17251700 cm-1 (C=O stretch)
-z4
aryl ketone 17001680 cm-1 (C=O stretch)
-z4
~1600 cm-1 and 15001450 cm-1 (benzene ring
stretch) z5
enone 16851665 cm-1 (C=O stretch)
-z4
16801620 cm-1 (C=C stretch)
-z5
There are a few uncommon exceptions to this table. For
example, acetylene is a terminal alkyne that displays a zone 1
CH stretch, but not a zone 3 CC stretch, due to the
symmetry of the triple bond. A benzene ring in which all six
ring hydrogens have been substituted (e.g.,

2. What is the effect of conjugation on the energy of an

infrared absorption band?
Conjugation shifts a band to lower energy. For example, a ketone
typically absorbs in the region of 17501705 cm-1, whereas an enone
(alkene-carbonyl conjugation O=CC=C; also called an ,unsaturated ketone) absorbs at 16851665 cm-1, and an aryl ketone
(ketone conjugated with a benzene ring) absorbs at 17001680 cm -1.
This shift to a lower energy is seen when any functional group is
conjugated.
3. Perform five zone analyses for the following IR spectra.

When given only a formula and an IR spectrum it may not be

possible to determine the exact structure of a molecule. The
actual compound answers given here are meant to help you
verify how the structure corresponds to the particular
spectrum.
(a) IHD = 4 pi bonds and/or rings. Possible benzene ring Zone
1: 3388 cm-1: alcohol OH No NH: no nitrogen in formula No
terminal alkyne: no zone 3 absorption

Zone 2: > 3000 cm-1: vinyl or aryl CH

< 3000 cm-1: alkane CH
No carboxylic acid or aldehyde: no zone 4 carbonyl
Zone 3: No triple bonds: no absorptions
Zone 4: No C=O or aromatic ring: no absorptions
Zone 5: 1599 cm-1 and 1494 cm-1: benzene ring
No alkene: not enough IHD for alkene plus benzene ring

It is usually very difficult or impossible to determine the exact structure of

an unknown based only on the formula and IR. The structure is given in
these solutions so you can verify your five zone analysis.
The use of information from more than one source, such as formula
(from mass spectrum) and IR spectral features, is a common and
useful practice when solving spectroscopy problems. Think
"outside the spectrum"!

Solution

Solution