Application of Infrared

Spectroscopy Chapter 17
Dr. Nizam M. El-Ashgar
Chemistry Department
Islamic University of Gaza

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• Infrared spectrometry is applied to the qualitative and
quantitative determination of molecular species of all
types.
• The most widely used region is the mid-infrared that
extends from about 400 to 4000 cm-1 (2.5 to 25 m).
(Absorption, reflection and emission spectra are
employed)
• The near-infrared region from 4000 to 14,000 cm-1 (0.75
to 2.5 m) also finds considerable use for the routine
quantitative determination. (water, CO2, low conc.
Hydrocarbons, amine nitrogen, many other compounds)
• The far-infrared region has been for the determination of
the structures of inorganic and metal-organic species.
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 MID-INFRARED ABSORPTION
SPECTROMETRY

Sample Handling
• No good solvents exist that are transparent throughout
the region of interest.
• As a consequence, sample handling is frequently the
most difficult and time-consuming part of an infrared
spectrometric analysis.
• Gases: The spectrum of a low-boiling liquid or gas can
be obtained by permitting the sample to expand into an
evacuated cylindrical cell equipped with suitable
windows.
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 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 path length (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.

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• Solutions:
• A convenient way of obtaining infrared spectra is on
solutions prepared to contain a known concentration
of sample.
• This technique is somewhat limited in its
applications, however, by the availability of solvents
that are transparent over significant regions in the
infrared.
Solvents:
• No single solvents is transparent throughout the
entire mid-infrared region.
• Water and alcohols are seldom employed, not only
because they absorb strongly, but also because they
attack alkali-metal halides, the most common
materials used for cell windows.

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 Cells:
• Sodium chloride windows are most commonly employed; even
with care, however, their surfaces eventually become fogged due
to absorption of moisture.
• Polishing with a buffing powder returns them to their original
condition.
Liquids:
• When the amount of liquid sample is small or when a suitable
solvent is unavailable, it is common practice to obtain spectra on
the pure (neat) liquid.
• A drop of the neat liquid is squeezed between two rock-salt plated
to give a layer that has a thickness of 0.01 mm or less.
• The two plates, held together are then mounted in the beam path.
Such a technique does not give reproducible transmittance data,
but the resulting spectra are usually satisfactory for qualitative
investigations. 8
Preparing a “Neat” IR Liquid
Sample

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IR solution Cell (Quantitative analysis)

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IR Liquid Sample Cell

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Carbon Tetrachloride

no C-H!

Cl

Cl C Cl

Cl
C-Cl stretch

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 Solids:
• Most organic compounds exhibit numerous absorption peaks
throughout the mid-infrared region, and finding a solvent that does
not have overlapping peaks is often impossible.
• As a consequence, spectra are often obtained on dispersions of the
solid in a liquid or solid matrix.
Pelleting:
• One of the most popular techniques for handling solid samples has
been KBr pelleting.
• A milligram or less of the finely ground sample is mixed with
about 100 mg of dried potassium bromide powder.
• The mixture is then pressed in a die at 10,000 to 15,000 pounds
per square inch to yield a transparent disk.
• The disk is then held in the instrument beam for spectroscopic
examination.
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Preparing a KBr Disk

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 Mulls (suspension):
• Infrared spectra of solids that are not soluble in an
infrared-transparent solvent or are not conveniently
pelleted in KBr are often obtained by dispersing the
analyte in a mineral oil or fluorinated hydrocarbon
mull.
• Mulls are formed by grinding 2 to 5 mg of the finely
powdered sample in the presence of one or two drops
of a heavy hydrocarbon oil (Nujol).
• If hydrocarbon bands interfere, Fluorolube, a
halogenated polymer, can be used.
• The resulting mull is then examined as a film between
flat salt plates.

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 Determination of cell thickness
• Determination of thickness (b) : Pathlength of thin IR sample
holder can be determined by observation of the interference
patterns associated with constructive interference from
reflection of light from the two internal surfaces of cell:
– Insertion of empty cell in the light path (reference beam
passed unobstructed to monochromator).
– Interference fringe (maxima and minima) occurs.
– Maxima: internal reflection of radiation by cell surfaces at
distance of multiple N of wavelength of radiation.
– 2b = N  2b/N =  N = 2b/ 
– Number if interference fringes N between two known
wavelengths
– N = 2b/  1 – 2b/  2 N
b=
2(  2  1) 19
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 Qualitative Analysis
• Used for identifying organic, inorganic, and biological species.
• The time required to perform a structural determination was
reduced by a factor of ten, one hundred, or even one thousand (by
FTIR modern instruments).
Identification of an organic compound is a two-step process.

• The first step involves determining what functional groups are

most likely present by examining the group frequency region.

• The second step then involves a detailed comparison of the

spectrum of the unknown with the spectra of pure compounds that
contain all of the functional groups found in the first step.
The fingerprint region, from 1200 to 600 cm -1 is particularly useful
because small differences in the structure and constitution of a
molecule result in significant changes in the appearance and
distribution of absorption peaks in this region.
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 IR Spectrum

Baseline

Absorbance/
Peak

• No two molecules will give exactly the same IR spectrum

(except enantiomers)
• Group frequency region (Simple stretching): 1200-3500 cm-1
• Fingerprint region (Complex vibrations): 400-1200 cm-1,
 Group Frequencies:
• The approximate frequency (or wavenumber) at which an organic
functional group, such as C=O, C=C, C—H, CC, or O—H
absorbs infrared radiation can be calculated from the masses of
the atoms and the force constant of the bond between them.
• These frequencies, called group frequencies, are seldom totally
invariant ‫ غير ثابتة القيمة‬because of interactions with other
vibrations associated with one or both of the atoms composing the
group.
• A range of frequencies can be assigned within which it is highly
probable that the absorption peak for a given functional group
will be found.
• Are usually due to stretching vibrations of
diatomic units 23
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 The “Fingerprint” Region:
• Small differences in the structure and constitution of a
molecule result in significant changes in the
distribution of absorption peaks in this region of the
spectrum that extends from about 1200 to 700 cm-1.
• As a consequence, a close match between two spectra
in this fingerprint region constitutes strong evidence for
the identity of compounds yielding the spectra.
• Exact interpretation of spectra in this region is seldom
possible because of the complexity of the spectra.

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Correlation chart: General regions of an infrared spectrum

Note that the blue coloured sections above the dashed line
refer to stretching vibrations, and the green coloured band
below the line encompasses bending vibrations. 29
Summary of IR Absorptions

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 Computer Search Systems:
• Virtually all infrared instrument manufactures now offer
computer search systems to assist chemist in identifying
compounds from stored infrared spectral data.
• The position and relative magnitudes of peaks in the spectrum
of the analyte are determined and stored in memory to give a
peak profile, which can then be compared with profiles of pure
compounds stored.
• The computer then matches profiles and prints a list of
compounds having spectra similar to that of the analyte.
• Usually the spectrum of the analyte and that of each potential
match can then be shown simultaneously on the computer
display for comparison. 31
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 Infrared interpretation

• Step 1
– Look first for the carbonyl C=O band.
– Look for a strong band at 1820-1660 cm-1.
This band is usually the most intense absorption band in a
spectrum. It will have a medium width. If you see the
carbonyl band, look for other bands associated with
functional groups that contain the carbonyl by going to step 2.
– If no C=O band is present, check for alcohols and go to step
3.
• Step 2
– If a C=O is present you want to determine if it is part of an
acid, an ester, or an aldehyde or ketone. At this time you may
not be able to distinguish aldehyde from ketone.
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• ACID
– Look for indications that an O-H is also present.
– It has a broad absorption near 3300-2500 cm-1.
– This actually will overlap the C-H stretch. There will also be
a C-O single bond band near 1100-1300 cm-1.
– Look for the carbonyl band near 1725-1700 cm-1.
• ESTER
– Look for C-O absorption of medium intensity near 1300-1000
cm-1.
– There will be no O-H band.

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• ALDEHYDE
– Look for aldehyde type C-H absorption bands. These are
two weak absorptions to the right of the C-H stretch near
2850 cm-1 and 2750 cm-1 and are caused by the C-H bond
that is part of the CHO aldehyde functional group.
– Look for the carbonyl band around 1740-1720 cm-1.
• KETONE
– The weak aldehyde CH absorption bands will be absent.
Look for the carbonyl CO band around 1725-1705 cm-1.
• Step 3
– If no carbonyl band appears in the spectrum, look for an
alcohol O-H band.
• ALCOHOL
– Look for the broad OH band near 3600-3300 cm-1 and a C-
O absorption band near 1300-1000 cm-1. 35
• Step 4
– If no carbonyl bands and no O-H bands are in the spectrum,
check for double bonds, C=C, from an aromatic or an
alkene.
• ALKENE
– Look for weak absorption near 1650 cm-1 for a double bond.
There will be a CH stretch band near 3000 cm-1.
• AROMATIC
– Look for the benzene, C=C, double bonds which appear as
medium to strong absorptions in the region 1650-1450 cm-1.
The CH stretch band is much weaker than in alkenes.

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C-H stretching region
• Alkanes C-H sp3 stretch < 3000 cm-1
• Alkenes C-H sp2 stretch > 3000 cm-1
• Alkynes C-H sp stretch ~ 3300 cm-1
• C-H Bending region
• CH2 bending ~ 1460 cm-1
• CH3 bending (asym) appears near the same value
• CH3 bending (sym) ~ 1380 cm-1

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• Step 5
– If none of the previous groups can be identified, you may
have an alkane.
• ALKANE
– The main absorption will be the C-H stretch near 3000 cm-1.
The spectrum will be simple with another band near 1450
cm-1.
• Step 6
– If the spectrum still cannot be assigned you may have an
alkyl halide.
• ALKYL BROMIDE
– Look for the C-H stretch and a relatively simple spectrum
with an absorption to the right of 667 cm-1.

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 1-Hexene

sp2
C-H
C=C
stretch
out of plane
sp3 bendings (oops)
C-H stretch CH2 CH CH2 CH2 CH2 CH3

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 Toluene

sp2 sp3
C-H C-H CH3 aromatic
C=C

aromatic oops

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 Cyclohexanol

OH bending
O-H
stretch C-O
stretch
sp3 C-H stretch

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 1-Butanamine

N-H
bend CH2
N-H
stretch CH3
doublet bend

sp3 C-H stretch CH3 CH2 CH2 CH2 NH2

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 4-Methyl-2-pentanone
C-H < 3000, C=O @ 1715 cm-1

CH3 O

CH3 CH CH2 C CH3

C-H stretch C=O stretch

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 Acetophenone

C-H stretch

C CH3 aromatic C=C

conj C=O

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Strengths and Limitations

• IR alone cannot determine a structure

• Some signals may be ambiguous
• The functional group is usually indicated
• The absence of a signal is definite proof that the
functional group is absent
• Correspondence with a known sample’s IR
spectrum confirms the identity of the compound

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 Quantitative Applications

• Quantitative infrared absorption methods differ

somewhat from ultraviolet/visible molecular
spectroscopic methods because of the greater complexity
of the spectra, the narrowness of the absorption bands,
and the instrumental limitations of infrared instruments.
• Quantitative data obtained with infrared instruments are
generally significantly inferior in quality to data obtained
with ultraviolet/visible spectrophotometers.

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Quantitative Analysis
• IR more difficult than UV-Vis because
– narrow bands (variation in e)
– complex spectra
– weak incident beam
– low transducer sensitivity
– solvent absorption
• IR mostly used for rapid qualitative but not quantitative
analysis
– Beer’s law failure
– Long optical path-length required
– Regular FT-IR is worse than UV-VIS
– Exception - Tunable IR laser, quantum cascade laser,
optical parametric oscillator, OPO. 47
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• Absorbance measurements:
– In UV/Vis: matched absorption cells for solvent
and solution are employed and so
A = log (I solvent /I solution)
– Blank cancel out the effects of:
• Radiation losses due to reflection
• Scattering and absorption by solvent
• Absorption by container windows
– In IR: Reference cell (blank) seldom employed
because:
• Difficulty in obtaining identical cells.
• IR cells have short bathlengths (difficult to
duplicate)
• Cell windows rapidly attacked (atmosphere &
solvent).
• Deviations from Beer’s law
– More common than in UV/Vis
– IR absorption bands are relatively narrow
• Dispersive instruments: low intensity sources
and low sensitivity detectors require the use
of relatively wide monochromator slit widths.
• Non linear relationship between absorbance
and concentration.
• Quantitative data from dispersive IR Instruments
are less precise and accurate than those from
UV/Vis instruments.
• FT instruments are better than dispersive ones
Empirical calibration curves are often required
for IR quantitative work.
• Correction for scattering and absorption by
solvent an cell
• Two methods:
1. Cell-in/cell-out:
– spectra of pure solvent and analyte solution obtained
successively.
– The same cell is used for both measurements.
T0 = P0/Pr & Ts = P/Pr
– If Pr remains constant during the two measurements, then
the transmittance of the sample with respect to solvent is
obtained by
T = Ts/T0 = P/P0
2. Baseline method:
– Solvent transmittance assumed to be constant
between the shoulders of the absorption peak
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.
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• Typical Applications:
– All organic and inorganic molecular species
absorb in IR region (except homonuclear
molecules).
– Uniqueness of IR spectrum
– Specificity: application to analysis of mixtures
of closely related organic compounds
Example: Analysis of mixture of aromatic
hydrocarbon
Resolution of C8H10 isomers in a mixture
includes:
o-xylene, m-xylene, p-xylene and ethyl
benzene. Need to set up the correct number of
simultaneous equations.
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• Determination of Air Contaminants
– Sensitive, rapid and highly specific
methods are required.
.

– Table 17-3. analysis of mixtures of

gases by computerized instrument
Fig.16-14.
– 20m sample cell was employed
– Data obtained within 1 or 2 min after
injection.

– Table 17-4 application of IR filter

photometer.
– Determination of various chemicals in
the atmosphere
• Disadvantages and Limitations to
Quantitative IR methods:
– Frequent non-adherence to Beer’s law
– Complexity of spectra
• Enhances the probability of absorption peaks
overlapping
– Narrowness of peaks and effects of stray
radiation
• Makes abs measurements dependent on slit width & λ
setting
– Narrow cells: lead to significant analytical
uncertainty

So, errors associated to IR quantitative analysis

often cannot be reduced to the level associated
with UV/Vis
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