Infrared Spectroscopy

“Sample Handling & Applications”

“5”

Dr. M. Abbas Bhatti

Ph.D (Scholar-BZU), M.Phil (PU), B.Pharm (PU)
Pharmaceutical Chemistry
Dr.M.Abbas Bhatti Islam College of Pharmacy, Sialkot. 1
 Sampling system of infrared
spectroscopy
 1- Gases:
 A gas sample is introduced into evacuated gas
cell, which is made of cylindrical glass body
about 10cm in length.
 For trace analysis at ppm level (air-pollution &
breathe analysis) very long path length (upto
30m) can be obtained by using multiple-
reflection cells.

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Gas cells

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 2- Liquids & Solutions:
 A neat sample may be examined as a thin film
(0.1mm thickness) squeezed between two
optically polished circular flat plates (5mm
thickness & 25mm diameter) of rock salt
(NaCl, KBr).
 The plates held together by capillary action &
mounted in the sample beam.

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 Plates must be cleaned immediately after use
by rinsing with suitable solvent (chloroform),
kept dry, store in well closed desiccator &
should be handled by their edges.

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 3- Solids:
 Two common techniques for solid sample,
mulls & pellets.
a) Mulls:
The finely ground solid sample (2-10mg)
mixed with Nujol (mineral oil) to make a thick
paste, which is spread b/w 2 plates (alkali halides).
 Then mounted in a path of infrared beam & the
spectrum is run.

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Dr.M.Abbas Bhatti 7
 b) Pellet:
 Finely ground sample is thoroughly mixed
with same wt of powdered KBr.
 The mixture is then pass under high pressure
(8000-20,000 psi) in a press (13mm diameter) to
form a small pellet (transparent).
 An evacuable, heated (40°c) metal desiccator
is useful for storing die components & KBr.

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Dr.M.Abbas Bhatti 9
FTIR sampling compartment

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 Qualitative Analyses, Structural Determination &
Interpretation

 Before trying to interpret an IR spectrum, there

are some things should remember:
 The method of collecting the spectra should be
stated- mull, thin film, KBr pellet & solution
etc.
 The analyst should compare the reference &
sample spectra under the same conditions.

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 Conti..

 Older spectra displayed λ (wavelength) on the

x-axis but modern grating & FTIR spectra are
generally plotted wavenumber linearly.
 The y-axis units should also be noted.
 Recently, the y-axis for IR absorption spectra
is “Transmittance” or “% Transmittance”, with
100%T at the top of the spectrum.

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 Conti..

 Transmittance is the ratio of radiant power

transmitted by the sample to the radiant power
incident on the sample.
 Transmittance range from 0 to 1.0 (multiplied
by 100) = %T from 0 to 100.
 The absorption peaks are pointing toward the
bottom of the spectrum.

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 Conti..

 The y-axis could be given in A, where A is

defined as = - log T.

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 Conti..

 The IR spectrum of each compound is unique,

matching the IR spectrum of an unknown peak
to a reference spectrum of a known material is
good way to identify the unknown.
 This is often done with the aid of computerized
spectral libraries & search routines.
 A number of companies, instrument
manufacturers & government agencies publish
collections of reference spectra in electronic
format & in hardcopy.
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 Conti..

 These spectral databases may contain spectra

of more than 200,000 compounds, for specific
fields such as environmental chemistry,
pharmaceuticals, polymers & forensic science.

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 Interpretation of IR Spectra
 The 1st region to look at is the 4000–1300 cm-1
region, called the functional group region.
 This is the region where strong absorptions
due to stretching from the hydroxyl, amine,
carbonyl & CHx groups occur.
 This region also has areas of weak absorptions
-1
that are very informative. The 2000–1660 cm
region will show a set of weak overtone if an
aromatic ring is present.
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 Conti..

 The intensity pattern of these weak bands can

identify how the ring is substituted i.e., ortho,
meta, or para.
 _
In this region, alkynes (C=C), cyano groups
_
(C=N) _
& diazonium salts (N=N) identified. In
addition, S – H, Si – H & P – H also
recognized.
-1
 The region 1300–910 cm is called fingerprint
region, because of the complex absorption
patterns & make spectrum unique.
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 Conti..

 There are some important bands in this region,

especially the C – C – O band of alcohols &
the C – O – C of esters. These should be
confirmed in conjunction with the appropriate
bands (OH or C=O) in the functional group
region.
 The low frequency end of the spectrum, 910–
650 cm,-1 is sometimes called the aromatic
region. If there are no strong absorptions in
this region, means no aromatic group.
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 Conti..

 Below 800 cm,-1 absorption due to C–Cl & C–

Br bonds occurs.
 Examples such as:
 Hydrocarbons

-1

Hexane, C6H14, a normal alkane

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 Conti..

 Aromatic Hydrocarbons:
 Benzene C6H6 an aromatic hydrocarbon.

-1

 Organic compounds with C – O Bonds ????

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 Applications of Infrared Spectroscopy:
 1- Structure determination:
Structure of organic compound determined by
correlation & interpretation of spectra.
 2- Identification of compounds:
By comparison of infrared spectrum of sample
with an authenticated peak.
 3- Detection of impurities:
The presence of absorption bands at position
where the compound is not expected, indicate
the presence of impurities.
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 Conti..
For example; cyclohexanone is readily
detected in cycolohexanol by intense carbonyl
band.
 4- Progress of a reaction:
Can be determined by examining IR spectra of
sample drawn from the reaction medium.
For example: oxidation of secondary alcohol
to ketone determined by disappearance of O-H
band near 3600cm‾¹ & appearance of C=O
band near 1715cm‾¹.
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 Conti..

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 Conti..
 5- Percentage composition of a mixture:
If Beer’s law is obeyed, the spectrum of
mixture resulting from the known composition
of pure components is determined (multiple
standard).
Then measure the spectra of unknown sample
& by graphic method (% age purity find).
 6- Study of atmospheric contaminants:
Infrared spectroscopy has been employed for
variety of compounds for which limits of
exposure have been set by health
administration.
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 7- Determination of total amine contents:
The total primary & secondary amine content
of aliphatic amines can be determined easily &
rapidly by functional group analysis in the
near-infrared.
 8- Analysis of petroleum, hydrocarbons, oil
& grease contents by EPA:
Semi quantitative determination of petroleum,
hydrocarbons, oils & grease can be done by
comparison of IR spectra of sample with
standards.

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 The most common use of IR spectroscopies
are for qualitative identification & structure
determination of organic compounds.

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 Quantitative analysis:
 IR spectroscopy was considered to provide
only qualitative & semi quantitative analysis of
common samples, particularly when data were
acquired by use of conventional dispersive
instrument.
 However, the development of FT-IR
instrumentation & computerized data-
processing capabilities have highly improved
the performance of quantitative IR work.

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 The basis for quantitative analysis of
absorption spectrometry is the Beer’s law.
 A = αbc
 α = molar absorptivity
 b = path length
 c = concentration
 Instead of transmittance scale, absorbance is
used in quantitative analysis, absorbance “A”

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