CHAPTER 2.

4
IR Spectroscopy
CHM 260
CONTENT

 2.4.1 Molecular species that absorb IR

 2.4.2 Sample handling techniques
 2.4.3 Stretching and bending vibrations
 2.4.4 Qualitative applications
 2.4.5 Structural analysis
• The applications of IR spectrometry fall into three major
categories based on the three IR spectral regions:
1. INTRODUCTION
Mid-IR (670 - 4,000 cm )
-1

• Is of concerned and greatest practical use.

• Fundamental molecular vibrations.
• Strong absorbance.
2. Near-IR (4,000 – 14,000cm-1)
• Overtones and combinations.
• Weaker, overlapping absorbance.
3. Far-IR region(15 – 1000 μm)
THE ELECTROMAGNETIC
SPECTRUM
Increasing Wavelength

50,000 12,820 4000 400 cm-1

Gamma X-ray UV NIR IR FIR Micro Radio

200 380 780 2500 25 000 nm

Increasing Energy

K-shell Outer-shell Molecular Molecular

electrons electrons vibrations Rotation
THE ELECTROMAGNETIC
SPECTRUM
 FTIR
 Isone of the measurement techniques for
collecting IR spectra.
 Instead of recording the amount of energy
absorbed when frequency of the IR light passes
through a monochromator, the IR light is guided
through an interferometer.
 The IR light passes through the sample to
produce the interferogram (measured signal) .
 Background correction is carried out - to
eliminate the effect of IR active gases such as
CO2 and water vapor from the spectrum
 FTIR - Advantage
 FourierTransform Infra Red (FT-IR)
spectroscopy is an extremely powerful
technique for identifying the molecular
composition of many organic and inorganic
materials.
 Time saving (the entire radiation is passed
through the sample simultaneously since no
monochromator is used).
 When analysed by infrared spectroscopy,
materials produce a spectrum or fingerprint.
2.4.1 Molecular species that
absorb IR
 IR radiation of less then about 100 cm-1 is absorbed and
converted into molecular rotation energy by organic
molecule.
 IR radiation of 10,000-100 cm-1 is absorbed and
converted into molecular vibration energy by organic
molecule.
 IR radiation is not energetic enough to bring about the
kinds of electronic transitions as of UV-Vis.
 Thus IR radiation is confined largely to molecular species
that have small energy differences between various
vibrational and rotational states.
 IR absorption spectra for molecular species arise from
various changes in energy brought about by transitions
of molecules from one vibrational or rotational energy
state to another.
Dipole Moment
 To absorb IR radiation, a molecule must
undergo a net change in dipole moment as it
vibrates or rotates.
 Nearly all molecules containing covalent
bonds will show some degree of IR absorption
except the diatomic molecules such as H2, N2
and O2 in which there is no net change in
dipole moment when they vibrate or rotate.
 The dipole moment (μ) is determined by
 The magnitude of the charge difference (δ)
 The distance between the two centres of
charge (d)
Dipole Moment
Example: Vibration of HCl molecule

 A regular fluctuation in its dipole moment occurs.

 A field is established that can interact with the electric
fields associated with radiation.
 If the frequency of the radiation exactly matches a natural
vibrational frequency the radiation of the molecule,
absorption of the radiation takes place that produces a
change in the amplitude of the molecular vibration.
 Similarly, the rotation of asymmetric molecules around
their centres of mass results in periodic dipole moment
fluctuations that allow interaction with the radiation field.
LEARNING CHECK…
1. Briefly explain why symmetrical stretching C=C in
CH2=CH2 is infrared (IR) inactive. (2m – Mac 2016)
2. Briefly describe the characteristic of an IR active
molecule. (2m – Mac 2015)
3. Briefly explain why C≡C stretching vibration in
CH3CH2C≡CCH2CH3 is IR inactive. (2m - Sep 2014)
4. Symmetric C≡C alkynes stretching normally absent
in IR spectrum. Explain this phenomenon. (1m –
Mac 2014)
5. What are the requirements for an organic
molecule to be IR active ? (2m – Sep 2014)
6. Explain briefly why homonuclear molecules such as
O2, N2, and Cl2 do not absorb IR radiation. (2m –
Nov&Mac 2013)
2.4.3 Vibrations – Stretching
and Bending
 There are 2 fundamental types of vibration [page 433,
(Skoog et.al., 2004)].

STRETCHING:
 involves a continuous change in interatomic distance
along the axis of the bond between the two atoms:
 Symmetric
 Asymmetric

BENDING:
 Characterized by a change in the angle between two
bonds
 Rocking (in-plane)
 Scissoring (in-plane)
 Wagging (out-of-plane)
 Twisting (out-of-plane)
The IR spectra
 The spectra of polyatomic covalent compounds are
often exceedingly complex, consisting of many of many
absorption bands
 The relative positions of atoms in a molecule are not
exactly fixed
 The positions fluctuate continuously as a consequence
of different types of vibrational motion of molecule
 The bond in a molecule act like tiny springs and like
springs, vibrate with a characteristic frequency
 These frequencies fall in the IR region of the EM
spectrum
 By passing IR radiation through a sample and observing
what frequencies are absorbed, it is possible to deduce
what types of chemical bonds are present in the
molecule.
Absorption in Different
Regions of the IR spectrum
 Regions of the IR spectrum
 Diagnostic region
 Region above 1500 cm-1
 Functional groups

 Fingerprint region
 Region below 1500 cm-1
 Harder to interpret
 Much more complicated
 But unique to molecules
 No other chemical species will have similar IR
spectrum
 Can be match and use to identify molecule
Bonds strength
 In general, triple bonds are stronger than
double or single bonds between the
same two atoms and have higher
frequencies of vibration (higher
wavenumbers)


C≡C C=C C-C

2150 cm-1 1650 cm-1 1200 cm-1
 Background
 The IR energy beam not only passes through
sample but also through a length of air.
 Air contains CO2 and water vapor
 FTIR determines the background spectrum (no
sample in the path) and stores it in the
computer memory.
 After a sample spectrum is determine, the
computer subtracts the background spectrum
from the sample, effectively removing the air
peaks.
2.4.2 Sample Handling Techniques
 Sample preparation for IR analysis

1. The KBr Method (Refer Lab manual

CHM260)
2. The Nujol Mull Method
3. Liquid Samples (Neat liquid) using a Salt
Plate
Solid- KBr disk sampling
Nujol Mull Method
 Mull is a pressed disk of solid sample.
 Mulls are prepared by thoroughly grinding
2-5 mg of solid in a smooth agate mortar.
 Grinding is continued after addition of 1-2
drops of mulling oil.
 The mull is examined as a thin film
between salt plates.
 Nujol (a high boiling petroleum oil/heavy
hydrocarbon oil) is commonly used as a
mulling agent.
 Liquid Samples -
Neat liquid using a Salt Plate
 Liquid samples may be examined neat (pure) or in solution.
 Neat liquids are examined between salt plates usually without a
spacer.
 Aqueous solution cannot be used for salt plates because it will
dissolve the salt plates.
 Pressing a neat liquid sample between flat plates produce a film
of 0.01 mm or less in thickness, the plate being held together by
capillary action.
 Samples of 1-10 mg are required.
 Thick samples of neat liquids usually absorb too strongly to
produce a satisfactory spectrum.
 Volatile liquids are examined in sealed cells with very thin
spacers,
 Silver chloride plates may be used for samples that dissolve
sodium chloride plates.
 LEARNING CHECK…
1. Explain the preparation of an IR sample by KBr method.
(3m – Mac 2016)
2. Explain the preparation of solid sample for IR analysis by
Nujol Mull Method (3m – Mac 2015).
3. In an IR analysis, the solid compound you want to analyze
is found to be insoluble in all the common IR solvents.
Discuss any one (1) alternative sample preparation
method to be used. (3m – Sep 2014)
4. Define the meaning of ‘neat liquid’ used in IR
spectroscopy (2 m – Mac 2014)
5. Briefly describe two (2) method of preparing a solid
sample for analysis using IR spectroscopy (3m – Mac 2014)
2.4.4 Qualitative Applications
Transmission

• Solids – films, powders –organics and

inorganics but not metals
• Liquids – pure liquids, mixtures ,solutions,
viscous liquids eg.
lube oil
 Important to consider the thickness,
particle size and refractive index when
doing sampling in transmission
Environment
(for FTIR instrumentation)
 Dust free
 Vibration free
 Away from direct sunlight
 Ambient temperature: 15 C to 35 C
 Ambient relative humidity: 60-65% maximum
(non-condensing)
Nitrogen gas purging
 To remove water and carbon dioxide
 Required when power failure is more than
1 day
 When open the main cover of instrument
 Purge for 20 minutes at pressure < 6.9 Kpa
2.4.5 Structural Analysis

Also Refer to :
• Table 17-3, page 461 (Skoog et.al., 2007)
• Example of spectra , page 461-462 (Skoog et.al., 2007)
 Example: Alcohol

Source:http://orgchem.colorado.edu/Spectroscopy/irtutor/tutorial.html
 Example: Carboxylic acid

 Source:http://orgchem.colorado.edu/Spectroscopy/irtutor/tutorial.html
 Example: Aromatic compound

 Source:http://orgchem.colorado.edu/Spectroscopy/irtutor/tutorial.html
 LEARNING CHECK…
1. Provide two (2) most obvious absorption bands and
approximate wave number for the IR spectrum of propanoic
acid (2m – Mac 2015)
2. In IR spectroscopy, indicate why a C=O stretching vibration
occurs at 1750 cm-1 while the C-O stretch occurs at about
1100 cm-1 (2m – Sep 2014)
3. In an organic synthesis, sodium borohydride reagent is used
to reduce the starting material, cyclohexanone to the
product cyclohexanol. If you use IR spectroscopy to monitor
this reaction, show the characteristic absorption frequencies
to distinguish between the IR spectra of the reactant and the
product (3 m – Sep 2014).
4. Explain how it would be possible to distinguish the butanone
and buten-1-ol based on FTIR spectrum (4m – Mac 2014)
5. How would you use IR spectroscopy to distinguish between a
pair of constitutional isomers; H2C=CHOCH3 and CH3CH2CHO
? (4m – Sep 2013)
 LEARNING CHECK…
6. Discuss briefly the purpose of running a ‘background’
spectrum at the beginning of an IR analysis. (2m – Nov & Mac
2013)
7. A compound with the molecular formula C6H10 has two (2)
isomers; cyclohexene and 2-hexyne. Using appendix (1),
choose any one (1) relevent absorption peak and the
corresponding bond for each compound which help you
distinguish the isomers from each other (2m – Nov & Mac 2013)
8. Bottles of isomeric compounds, acetone and allyl alcohol
were incorrectly labelled. Use the following IR information to
help you determine which compound is in which bottle (2m –
Nov & Mac 2013)
Bottle No. IR absorption peak (cm-1) Compound

1 3333 (broad), 1030 (medium) ?

2 1720 (sharp) ?
LEARNING CHECK…
9. Without doing any calculations, which
member of each pair do you expect to
occur at the higher frequency ? (2m –
Nov 2013)
a) C=C or C=O
b) C=O or C-O

1. Justify the strong absorption at 1450-

1600 cm-1 in the IR spectrum of
methylbenzene. (2m –Mar 2016)
REFERENCES
 Skoog et. al., 2004. Fundamental of Analytical
Chemistry, 8th ed.
 Skoog et. al., 2007. Principles of Instrumental
Analysis, 6th ed.
 Lab Manual CHM260
 Past semesters exam papers.
 http://orgchem.colorado.edu/Spectroscopy/i
rtutor/tutorial.html
 Pavia, Donald L. Introduction to
Spectroscopy, 5th Edition. Cengage Learning,
2015. VitalSource Bookshelf Online.