IR Spectroscopy

Unit 2 Module 2
Section 6.1 6.5
Mellony S. Manning

Recall that...
A molecule of any substance has
an internal energy (U) which can
be considered as the sum of the
energy of its electrons, the energy
of vibration between its
constituent atoms and the energy
associated with rotation of the
molecule.
U Eelec + Erot + Evib

Types of Excitation

Recall that...
Eelec > Evib > Erot

Recall that...
Electronic energy levels are widely
separated the absorption of a high energy
photon (short wavelength) can excite a
molecule from one energy level to another
In complex molecules the energy levels
are more closely spaced than in simple
molecules; near ultraviolet and visible
light can cause electronic transitions
These substances will absorb light in some
areas of the near ultraviolet and visible
regions
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6.1 Explain the origin of

absorption in IR Spectroscopy
6

Electromagnetic
Spectrum

Infra-red Spectroscopy
The vibrational energy states of the
various parts of a molecule are much closer
together than the electronic energy levels
Radiation of lower energy (longer wavelength)
are sufficient to bring about vibrational
changes

Infra-red Spectroscopy
Light absorption which is due only to vibrational
changes occurs in the infrared region
Rotational energy states of molecules are so closely
spaced that light in the far infrared and microwave
regions of the electromagnetic spectrum has enough
energy to cause these small changes

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Infra-red Spectroscopy
Bonds are vibrating all the time, but if
you shine exactly the right amount of
energy on a bond, you can kick it into a
higher state of vibration
The amount of energy needed to do
this will vary from bond to bond; each
different bond will absorb a different
frequency (and hence energy) of infrared radiation
http://www.chemguide.co.uk/analysis/ir/background.html#top

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IR Spectroscopy Principle
Shine a range of infra-red frequencies
through an organic sample and some
frequencies get absorbed by the
compound
Some frequencies pass through the
compound with almost no loss, but other
frequencies are strongly absorbed
How much of a particular frequency gets
through the compound is measured as
percentage transmittance
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13

Infra-red Spectroscopy
The horizontal axis is in wavenumbers:

Energies in infra-red radiation correspond to

the energies involved in bond vibrations

***For a molecule to absorb IR, the

vibrations within a molecule must cause
a net change in the dipole moment of
the molecule
http://teaching.shu.ac.uk/hwb/chemistry/tutorials/molspec/irspec1.htm

15

Vibrations
For a molecule to absorb infrared radiation it must undergo a net
change in dipole moment as a result of vibrational or rotational
motion.
Vibrations can be subdivided into two classes, depending on
whether the bond length or angle is changing:
Stretching:
Change in inter-atomic distance along bond axis
Two types of stretch: Symmetric, Asymmetric
Bending:
Change in angle between two bonds.
There are four types of bend: Rocking, Scissoring,
Wagging, Twisting
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Vibrations - Bond
Stretching
The two nuclei can vibrate backwards and
forwards - towards and away from each other around an average position.
Insert animation

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Vibrations Stretching
(Cont'd)
The energy involved in this vibration
depends on the length of the bond
and the mass of the atoms at either
end
Smaller mass higher frequency of
vibration
Stronger bonds higher frequency of
vibration

What is the relationship

between bond length and

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Vibrations - Bending

Different bonds will

absorb a different
frequency of infra-red
radiation in order to
jump from one
vibration state to a
higher one

19

IR Active Molecules
The fundamental vibrational modes
(where n is # atoms) for a molecule is
given by:
Linear molecules = 3n 5
Non-linear molecules = 3n 6

Some modes are not IR active.

CO 2
SO 2
Why?
o f m o le c u le
lin e a r
N o n -lin e a r

Type
P o la r v s n o n -p o la r
V ib ra tio n a l m o d e (s y m m e tric s tre tc h )
V ib ra tio n a l m o d e (a s y m m e tric s tre tc h )
V ib ra tio n a l m o d e
(b e n d in g )

N o n -p o la r
N o n IR a c tiv e
IR a c tiv e
IR a c tiv e

p o la r
IR a c tiv e
IR a c tiv e
IR a c tiv e
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Vibrational Modes
Consider water:

http://chemwiki.ucdavis.edu/Physical_Chemistry/Spectroscopy/Vibrational_Spectroscopy/Vibrational_Modes#Degr
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ee_of_Freedom

Vibrational Modes
Consider carbon dioxide:

http://chemwiki.ucdavis.edu/Physical_Chemistry/Spectroscopy/Vibrational_Spectroscopy/Vibrational_Modes#Degr
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ee_of_Freedom

Vibrational Modes
Consider the methylene group:

http://chemwiki.ucdavis.edu/Physical_Chemistry/Spectroscopy/Vibrational_Spectroscopy/Vibrational_Modes#Degr
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ee_of_Freedom

Spectrum of propan-1-ol (CH3CH2CH2OH)

24

6.2 Describe the basic steps involved in analysing samples

by IR spectroscopy
25

The Infrared
Spectrometer

26

 Infrared radiation is produced by electrically

heating a filament which is divided by mirrors into 2
beams, a reference beam and a sample beam.
In the sampling area, a segmented rotating disk
allows each beam to pass through alternately.
The reference beam and the sample beam are
combined into a beam of alternating segments.
The detector measures the heat energy and the
recorder records the results as a plot of percent
absorption (or transmittance) as a function of
wavenumber (cm-1) or wavelength (m).
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Liquid Samples
Samples sandwiched between two plates of a
high purity salt (eg. KBr, CaF2)
The plates are transparent to the infrared light
and will not introduce any lines onto the spectra
Some salt plates are highly soluble in water, so
the sample and washing reagents must be
without water.

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Solid Samples
Solid samples can be prepared in four major
ways:
1) Crush the sample with a mulling agent (eg.
Nujol). A thin film of the mull is applied onto salt
plates and measured
2)Grind a quantity of the sample with a specially
purified salt (eg. KBr) finely (to remove scattering
effects from large crystals). This powder mixture is
then crushed in a mechanical to form a translucent
pellet through which the beam of the spectrometer
can pass
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Solid Samples
(Cont'd)
(3) Sample is first dissolved in a suitable, nonhygroscopic solvent. A drop of this solution is
deposited on surface of KBr or NaCl cell
(4) Microtomy - cut a thin film from a solid
sample. The integrity of the solid is preserved

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Gaseous Samples
Gaseous samples require little preparation
beyond purification, but a sample cell with a
long path length (typically 5-10cm) is
normally needed, as gases show relatively
weak absorbances

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6.3 Comment on the limitations associated

with the use of IR Spectroscopy
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Limitations of IR
Spectroscopy
IR Spectroscopy can only determine the
functional groups present (Qualitative
test)
IR does not tell you the way the groups
are attached
IR does not tell you the amounts of each
groups present
In order to fully elucidate the structure,
other techniques are required such as:Mass Spectroscopy and NMR (Nuclear
Magnetic Resonance) Spectroscopy
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6.4. Deduce the functional groups present in

Organic Compounds from IR spectra
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C H A R A C T E R IS T IC IN F R A R E D A B S O R P T IO N F R E Q U E N C IE S
B ond
C om pound Type
F r e q u e n c y r a n g e , c m -1
C -H
A lk a n e s
2 9 6 0 -2 8 5 0 (s ) s tre tc h
1 4 7 0 -1 3 5 0 (v ) s c is s o rin g a n d
b e n d in g
C H 3 U m b re lla D e fo r m a tio n
1 3 8 0 (m -w ) - D o u b le t is o p ro p y l, t-b u ty l
C -H
A lk e n e s
3 0 8 0 -3 0 2 0 (m ) s tre tc h
1 0 0 0 -6 7 5 (s) b e n d
C -H
A ro m a tic R in g s
3 1 0 0 -3 0 0 0 (m ) s tre tc h
P h e n y l R in g S u b s titu tio n B a n d s
8 7 0 -6 7 5 (s) b e n d
P h e n y l R in g S u b s titu tio n O v e rto n e s 2 0 0 0 -1 6 0 0 (w ) - fin g e rp rin t
re g io n
C -H
A lk y n e s
3 3 3 3 -3 2 6 7 (s ) s tre tc h
7 0 0 -6 1 0 (b ) b e n d

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C H A R A C T E R IS T IC IN F R A R E D A B S O
B ond
C om pound Type
C = C A lk e n e s
C C A lk y n e s
C = C A ro m a tic R in g s
C -O
A lc o h o ls , E th e r s , C a rb o x y lic a c id s ,
E s te rs
C = O A ld e h y d e s , K e to n e s , C a rb o x y lic
a c id s , E s te rs
O -H
M o n o m e ric -- A lc o h o ls , P h e n o ls
H y d ro g e n -b o n d e d -- A lc o h o ls ,
P h e n o ls
C a rb o x y lic a c id s

R P T IO N F R E Q U E N C IE S
F r e q u e n c y r a n g e , c m -1
1 6 8 0 -1 6 4 0 (m ,w )) s tre tc h
2 2 6 0 -2 1 0 0 ( w ,s h ) s tr e tc h
1 6 0 0 , 1 5 0 0 (w ) s tre tc h
1 2 6 0 -1 0 0 0 (s ) s tre tc h
1 7 6 0 -1 6 7 0 (s ) s tre tc h
3 6 4 0 -3 1 6 0 ( s ,b r) s tre tc h
3 6 0 0 -3 2 0 0 (b ) s tre tc h
3 0 0 0 -2 5 0 0 (b ) s tre tc h

v - v a ria b le , m - m e d iu m , s - s tro n g , b r - b ro a d , w - w e a k
36

C H A R A C T E R IS T IC IN F R A R E D A B S O R P T IO N F R E Q U E N C IE S
B ond
C om pound Type
F r e q u e n c y r a n g e , c m -1
N -H
A m in e s
3 5 0 0 -3 3 0 0 (m ) s tre tc h
1 6 5 0 -1 5 8 0 (m ) b e n d
C -N
A m in e s
1 3 4 0 -1 0 2 0 (m ) s tre tc h
N itrile s
2 2 6 0 -2 2 2 0 (v ) s tre tc h
C N
NO2
N itro C o m p o u n d s
1 6 6 0 -1 5 0 0 (s ) a s y m m e tric a l
s tre tc h
1 3 9 0 -1 2 6 0 (s ) s y m m e tric a l
s tre tc h

v - v a ria b le , m - m e d iu m , s - s tro n g , b r - b ro a d , w - w e a k
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The Fingerprint Region

This is the region to the right-hand side of
the diagram (~ 1500 to 500 cm-1) usually
contains a very complicated series of
absorptions
These are mainly due to all manner of
bending vibrations within the molecule

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IR Spectrum for
CH3CH2CH2CH2CH2CH3

Peaks: C-H stretches (2850-3300 cm-1)

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IR Spectrum for
H2C=CHCH2CH2CH2CH3

Peaks: C-H stretches (2850-3300 cm-1)

C=C stretches (1610-1680 cm-1)

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Ethanol - IR Spectrum

Peaks: C-H stretches (2850-3300 cm-1)

O-H (alcohol) stretches (3200-3550 cm-1)

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Octanal - IR Spectrum

Peaks: C-H stretches (2850-3300 cm-1

C=O stretches (1670-1750 cm-1)

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2-pentanone - IR
Spectrum

Peaks: C-H stretches (2850-3300 cm-1

C=O stretches (1670-1750 cm-1)

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Homework
6.5. Cite examples of the use of
IR spectroscopy in the monitoring
of air pollutants
***Use SO2 and CO2 as
examples***
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