Chem 3052 Spectroscopy

CHAPTER 6

Infrared Spectroscopy

Outline:

6.1 Introduction
6.2 Energy levels in vibrating and rotating molecules
6.3 Characteristic vibrational frequencies
6.4 Factors affecting group frequencies
6.5 Instrumentation
6.6 Interpretation of some spectra

6.1 Introduction

The simplest instrument for IR absorption spectroscopy is a filter photometer similar to that for
UV/Vis absorption. These instruments have the advantage of portability and typically are used as
dedicated analyzers for gases such as HCN and CO.

Infrared instruments using a monochromator for wavelength selection are constructed using
double-beam optics similar to that shown in Figure 6. Double beam optics are preferred over
single-beam optics because the sources and detectors for infrared radiation are less stable than
that for UV/Vis radiation. In addition, it is easier to correct for the absorption of infrared
radiation by atmospheric CO2 and H2O vapor when using double-beam optics. Resolutions of 1–3
cm–1 are typical for most instruments.

In a Fourier transform, infrared spectrometer, or FT–IR, the monochromator is replaced with an

interferometer. Because an FT–IR includes only a single optical path, it is necessary to collect a
separate spectrum to compensate for the absorbance of atmospheric CO 2 and H2O vapor. This is
done by collecting a background spectrum without the sample and storing the result in the
instrument’s computer memory. The background spectrum is removed from the sample’s
spectrum by ratioing the two signals. In comparison to other IR instruments, an FT–IR provides
for rapid data acquisition, allowing an enhancement in signal-to-noise ratio through signal
averaging.

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Infrared spectroscopy is routinely used for the analysis of samples in the gas, liquid, and solid
states. Sample cells are made from materials, such as NaCl and KBr, which are transparent to
infrared radiation. Gases are analyzed using a cell with a path-length of approximately 10 cm.
Longer path-lengths are obtained by using mirrors to pass the beam of radiation through the
sample several times.

Liquid samples are analyzed in one of two ways. For nonvolatile liquids a suitable sample can
be prepared by placing a drop of the liquid between two NaCl plates, forming a thin film that
typically is less than 0.01 mm thick. Volatile liquids must be placed in a sealed cell to prevent
their evaporation.

The analysis of solution samples is limited by the solvent’s IR-absorbing properties, with CCl4,
CS2, and CHCl3 being the most common solvents. Solutions are placed in cells containing two
NaCl windows separated by a Teflon spacer. By changing the Teflon spacer, path-lengths from
0.015 to 1.0 mm can be obtained. Sealed cells with fixed or variable path-lengths also are
available.

The analysis of aqueous solutions is complicated by the solubility of the NaCl cell window in
water. One approach to obtaining infrared spectra on aqueous solutions is to use attenuated total
reflectance (ATR) instead of transmission. A typical attenuated total reflectance (ATR) sampler
consists of an IR-transparent crystal of high-refractive index, such as ZnSe, surrounded by a
sample of lower-refractive index. Radiation from the source enters the ATR crystal, where it
undergoes a series of total internal reflections before exiting the crystal. During each reflection,
the radiation penetrates into the sample to a depth of a few microns. The result is a selective
attenuation of the radiation at those wavelengths at which the sample absorbs. ATR spectra are
similar, but not identical, to those obtained by measuring the transmission of radiation.

Transparent solid samples can be analyzed directly by placing them in the IR beam. Most solid
samples, however, are opaque and must be dispersed in a more transparent medium before
recording a traditional transmission spectrum. If a suitable solvent is available, then the solid can
be analyzed by preparing a solution, and analyzing as described earlier. When a suitable solvent
is not available, solid samples may be analyzed by preparing a mull of the finely powdered

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sample with suitable oil. Alternatively, the powdered sample can be mixed with KBr and pressed
into an optically transparent pellet.

Solid samples also can be analyzed by means of reflectance. The ATR sampler described for the
analysis of aqueous solutions can be used for the analysis of solid samples, provided that the
solid can be brought into contact with the ATR crystal. Examples of solids that have been
analyzed by ATR include polymers, fibers, fabrics, powders, and biological tissue samples.
Another reflectance method is diffuse reflectance, in which radiation is reflected from a rough
surface, such as a powder. Powdered samples are mixed with a non-absorbing material, such as
powdered KBr, and the reflected light is collected and analyzed. As with ATR, the resulting
spectrum, is similar to that obtained by conventional transmission methods.

6.2 Energy levels in vibrating and rotating molecules

Molecules exhibit two additional types of radiation-induced transitions: vibrational transitions

and rotational transitions. The vibrational energy of a molecule is associated with the bonds that
hold the molecule together. The vibrational energy of a molecule is quantized and can only
assume certain discrete levels. Transitions between vibrational levels are vibrational transitions.

The overall energy E associated with a molecule in a given state can be written as

E = Eelectronic + Evibrational + Erotaitonal

where Eelectronic is the electronic energy of the molecule, E vibrational is its vibrational energy, and
Erotaitonal is its rotational energy.

Energy-Level Diagrams for Molecule

A partial energy-level diagram depicting typical processes that occur when a polyatomic
molecule absorbs infrared, visible and ultraviolet radiation is shown. The energies E 1 and E2 of
the first two of the several electronically excited states of a molecule are shown relative to the
energy of its ground state associated with each electronic state are indicated by the lighter
horizontal lines labeled 1, 2, 3, and 4. The lowest vibrational levels are labeled 0.

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Infrared radiation is generally not of sufficient energy to cause electronic transitions but can
induce transitions in the vibrational and rotational states associated with the ground electronic
state of the molecule. For absorption to occur, the analyte must be irradiated with frequencies
corresponding exactly to the energies indicated by the lengths of the four arrows (wavelengths l1
–l4 as shown).

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6.3 Characteristic vibrational frequencies

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

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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.
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 C–H 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=CH–CH=CH2 show up in the IR because the carbons are not equal. One carbon is a CH 2
and the other is a HC–CH.
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.

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 :
a) Zone 1 (3700–3200 cm-1): alcohol O–H, amide, or amine N–H, terminal alkyne ≡C–H
b) Zone 2 (3200–2700 cm-1): alkyl C–H, aryl or vinyl C–H, aldehyde C–H, carboxylic acid
O–H
c) Zone 3 (2300–2000 cm-1): alkyne and nitrile triple bonds
d) Zone 4 (1850–1650 cm-1): carbonyl functional groups
e) Zone 5 (1680–1450 cm-1): alkene, benzene ring

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

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beginning the five zone analysis, and then it is an easy matter to label each possible functional
group as “absent” or “present.”

9. Alcohol, Amine: the O–H and N–H stretches are usually broadened due to hydrogen
bonding.
Carboxylic acid: must have two bands: broad O–H 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 C–H 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 C–H stretch peak is also seen in Zone 2.

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 C–N 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.

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Table: Abbreviated table of group frequencies of organic groups

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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.

Solution:

Functional Group Absorptions

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terminal alkyne 3300 cm-1 (C–H stretch) Z1

2260–2000 cm-1 (C≡C stretch) Z3

aromatic ring 3100–3000 cm-1 (sp2 C–H stretch) Z2

~1600 cm-1 and 1500–1450 cm-1 (benzene ring stretch) Z5

aldehyde ~2900 and ~2700 cm-1 (C–H stretch) Z2

1740–1720 cm-1 (C=O stretch) Z4

carboxylic acid 3000–2500 cm-1 (O–H stretch) Z1

1725–1700 cm-1 (C=O stretch) Z4

aryl ketone 1700–1680 cm-1 (C=O stretch) Z4

~1600 cm-1 and 1500–1450 cm-1 (benzene ring stretch) Z5

enone 1685–1665 cm-1 (C=O stretch) Z4

1680–1620 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 ≡C–H stretch, but not a zone 3 C≡C stretch, due to the symmetry of the
triple bond. A benzene ring in which all six ring hydrogens have been substituted (e.g.,
hexamethyl benzene) has zone 5 peaks but not zone 2 sp2 C–H stretches. A tertiary amide (one
without an N–H bond) has a C=O stretch in zone 4 but no N–H stretch in zone 1.

2. What is the effect of conjugation on the energy of an infrared absorption band?

Ans: Conjugation shifts a band to lower energy. For example, a ketone typically absorbs in the region of
1750–1705 cm-1, whereas an enone (alkene-carbonyl conjugation O=C–C=C; also called an α,β-
unsaturated ketone) absorbs at 1685–1665 cm -1, and an aryl ketone (ketone conjugated with a benzene

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ring) absorbs at 1700–1680 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.

Ans: 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 O–H No N–
H: no nitrogen in formula No terminal alkyne: no zone 3 absorption
Zone 2: > 3000 cm-1: vinyl or aryl C–H
< 3000 cm-1: alkane C–H
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

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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:

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Solution

Solution:

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Solution:

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Solution:

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Solution:

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6.4 Factors affecting group frequencies

6.5 Instrumentation

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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 source, knowing that the energy of the photons in this region is insufficient to
break the chemical bonds and to degrade the sample; (c) Fourier transform single beam model.

 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.
 Non-dispersive instruments: use filters for wavelength selection or an infrared-absorbing
gas in the detection system for the analysis of gas at specific wavelength.

Quantitative Applications

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Quantitative analyses based on the absorption of infrared radiation, although important, are less
frequently encountered than those for UV/Vis absorption. One reason is the greater tendency for
instrumental deviations from Beer’s law when using infrared radiation. Since infrared absorption
bands are relatively narrow, deviations due to the lack of monochromatic radiation are more
pronounced. In addition, infrared sources are less intense than sources of UV/Vis radiation,
making stray radiation more of a problem. Differences in path-length for samples and standards
when using thin liquid films or KBr pellets are a problem, although an internal standard can be
used to correct for any difference in path-length. Finally, establishing a 100% T (A = 0) baseline
is often difficult since the optical properties of NaCl sample cells may change significantly with
wavelength due to contamination and degradation. This problem can be minimized by
determining absorbance relative to a baseline established for the absorption band.

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