Molecular absorption

spectroscopy
FTIR
IR spectral regions
REGION WAVELENGTHS
(), m
WAVENUMBERS
( ), cm
-1
FREQUENCY (v), Hz
Near 0.78 to 2.5 12800 to 4000 3.8 x 10
14
to 1.2 x 10
14
Middle 2.5 to 50 400 to 200 1.2 x 10
14
to 6.0 x 10
12
Far 50 to 1000 200 to 10 6.0 x 10
14
to 2.0 x 10
11
Most
used
2.5 to 15 4000 to 670 1.3 x 10
14
to 2.0 x 10
13
v
IR absorption spectrum of a
polystyrene film
IR spectra
Frequency is seldom used as the abscissa
Inconvenient size of unit
1.3 x 10
14
to 2.0 x 10
13
Hz or s
-1
This axis is often referred to frequency
The terminology is not correct



IR spectra
Plot of %T vs. cm
-1
Linear wavenumber scale is preferred
Direct proportionality between
wavenumber and both energy and
frequency

v =

= v = hc
c
h h E
Molecules
Are composed of atoms held toghether by
chemical bonds
The atoms in a molecule are always
moving or vibrating
The intensities of vibrations increase when
IR radiation is absorbed
Each chemical bond requires a precise amount
of energy to make it vibrate
Each frequency of IR radiation provides a precise
amount
Radiation is absorbed by a molecule only if the
frequency of the radiation provides energy in the
precise amount required by one of the bonds in
the molecule
Molecules can be large or small
The atoms they contain may be the same
or different
The bonds between them may vary from
weak to small
IR active
To absorb IR radiation
The molecule absorbs IR radiation that
corresponds to the energy difference for
the vibrational transition
Energy is quantized
A molecule must undergo a net change
in dipole moment as it vibrates or
rotates

Dipole moment
The charge distribution around a molecule
is not symmetric because one of the atom
has a higher electron density
Example HCl
Is determined by the magnitude of the
charge difference and the distance
between the two centers of charge
DIPOLE MOMENTS
Only bonds which have significant dipole moments will
absorb infrared radiation.
Bonds which do not absorb infrared include:
Symmetrically substituted alkenes and alkynes
C C R R
R
R R
R
Many types of C-C Bonds
Symmetric diatomic molecules
H-H Cl-Cl
C
O
The carbonyl group is one
of the strongest absorbers
O H C O
Also O-H and C-O bonds
o+
o-
STRONG ABSORBERS
+ +
- -
C
O
C
O
o+
o-
oscillating dipoles couple and
energy is transferred
infrared beam
Rotational transitions
Small energy is required to cause a change in
rotational level
s 100 cm
-1
or > 100m
Rotational levels are quantized
Absorption of gases in the FIR region is
characterized by discrete, well defined lines
In liquids and solids; intramolecular collisions
and interactions cause broadening of the lines
into a continuum


v
Vibrational-rotational
transitions
Vibrational energy levels are quantized
AE between quantum states correspond to MIR
region for most molecules
Spectrum of a gas
A series of closely spaced lines
There are several rotational energy levels for each
vibrational level
Spectra of solids and liquids
Broad vibrational bands
Rotation is restricted in solids and liquids

Depending on the number of ways the
bond can move (bend, stretch etc.), each
type of bond may absorb IR radiation at
one or more specific frequencies.

Types of molecular vibrations
Stretching
A continuous change in the interatomic distance
along the axis of the bands between the two atoms
Symmetrical
Asymmetrical
Bending
A change in the angle between two bonds
4 types
Scissoring
Rocking
Wagging
Twisting
Stretching vibrations
Linear molecule
Stretching vibrations

Bending vibrations
Hookes Law
=
1
2tc
v
K

larger K,
higher frequency
larger atom masses,
lower frequency
constants
2150 1650 1200
C=C > C=C > C-C
=
C-H > C-C > C-O > C-Cl > C-Br
3000 1200 1100 750 650
increasing K
increasing
1
m
=
2 1
2 1
m m
m m

+
+
=
Stretching vibrations of CO
2
Stretching vibrations of CO
2
The greater the change in dipole moment, the more
intense the absorption

When the bond stretches, the increasing distance between the
atoms increases the dipole moment

The intensity of an absorption band depends on the number of
bonds responsible for the absorption
Bond order affects bond strength, so bond order
affects the position of absorption bands

The approximate wavenumber of an absorption can be
calculated from Hookes law

is the wavenumber of the stretching vibration
f is the force constant
m
1
and m
2
are the masses of the atoms
2
1
2 1
2 1
) (
2
1
|
|
.
|

\
|
+
=
m m
m m f
c t
v
v

The exact position of the absorption band

depends on
electron delocalization
the electronic effect of neighboring substituents
hydrogen bonding
CH
3
CCH
2
CH
2
CH
3
O
O
O-
C O C O
at 1720 cm
1
at 1680 cm
1
Putting an atom other than carbon next to the carbonyl group
causes the position of the carbonyl absorption band to shift
The predominant effect of the nitrogen of an amide is electron
donation by resonance

The predominant effect of the oxygen of an ester is inductive
electron withdrawal

The position of a CO absorption varies because
CH
3
CH
2
OH
CH
3
CH
2
O CH
2
CH
3
C
O
H
3
C OH
C
O-
H
3
C OH
C
O
H
3
C O CH
3
C
O-
H
3
C O CH
3
~1050 cm
1
~1050 cm
1
~1250 cm
1
~1250 cm
1
and 1050 cm
1
FTIR spectrometer
The main optical components are
The IR source
The interferometer
The beamsplitter
The laser
The IR detector
IR source
The IR source produces IR radiation beam
that travels through the spectrometer
passing through the sample and to the
detector
Interferometer
Beamsplitter
Two mirrors
fixed
movable
Beamsplitter
Separates the IR beam into two beams of
nearly equal energy
One beam is reflected from the beam splitter
to a fixed mirror
The other beam is transmitted to a moving
mirror and back to the beam splitter where
the beams recombine
Laser
Used as an internal calibrator
control the moving mirrors position
signals the capture of data
IR transducer
After being absorbed at specific
frequencies by the sample,
the remainder of the IR beam is focused onto
the detector
The detector produces signal to the
amount of IR radiation striking it and sends
the signal to the computer for processing
FTIR spectrometer
FTIR spectrometer

Emits IR radiation across the region of
interest
IR beam is deflected off a mirror
Directs the IR beam into the interferogram
Where the spectral encoding takes place
Interferometer
IR source
Beamsplitter
Moving
mirror
Fixed
mirror
Detector
Sample
He-Ne Laser

The computer reads the interferogram and
uses Fourier transformation to decode the
intensity information for each frequency
and presents a spectrum
The spectrometer measures the intensity
of a speciallyencoded IR beam after it has
passed through the sample
The resulting signal, interferogram
Contains infromation about all frequencies
present in the beam
The IR beam exits the interferometer
Is deflected by a couple of mirrors before it
reaches the detector
Produces electrical signalin response to the
encoded radiation striking it.
Laser
Produces a single frequency of red light
that follows the same path as the IR beam
Calibrates the instrment internally

FOURIER TRANSFORMATION
Advantages of FTIR
All frequencies are measured simultaneously. Typical
scan times are only a few seconds.
The energy throughput is higher for any resolution,
giving a higher signal:noise ratio.
The laser wavelength is used as a reference for the
calculation of band positions, and is precise.
Stray light can be prevented.
Resolution is constant for the whole spectral range
Robustness as the FT instruments only have one
moving part

Applications of IR spectrometry
Major application (MIR region)
Structural investigations of molecular
compounds particularly organic
compounds

Major applications of IR
spectrometry
NIR and FIR regions
NIR region (4000 to 14,000 cm
-1
)
Quantitative determination of low MW
hydrocarbons, H
2
O, CO
2
, S
FIR region (15 to 100 m)
Structural determination of inorganic and
metal-organic species

What produces the IR spectrum
Materials that contain C (organic
compounds)
Many compounds; natural and synthetic
inorganic materials

Sample handling
No solvent is transparent throughout the
region of interest
Sample handling
Most difficult
Time-consuming
part of IR spectrometric analysis

Gases
Sample expands into an evacuated
cylindrical cells with suitable windows (Fig
16.3)
Variable lengths
A few cm to 10 m or longer
Measuring gases
Placed in a sealed cell
Specified T and P can be maintained
Gases are often present at low
concentrations
Mirrors are used to deflect the IR beam back
and forth before the beam is allowed to exit
Increased the interaction between gas sample and
IR beam
To acquire more spectral information
This gas cell provides a fixed
pathlength that is 2 m long
Solutions
Water and alcohols are not suitable
solvents
SOLVENTS FOR IR
SPECTROMETRY

No solvent is transparent throughout the region of interest
Liquids
Pure (neat) liquid
Very thin film, a short pathlength
A drop of neat liquid is squeezed between
two salt plates
Held together by capillary action
Placed in the beam of IR radiation
Non reproducible transmittance data
Satisfactory for qualitative analysis
Measuring liquids
Liquid cells
Holds the liquid between two crystal made
from materials that completely transmit IR
radiation

Cells
Liquid cells
(compared to UV/Vis spectroscopy)
Narrow pathlengths
0.01 to 1 mm
Relatively high sample concentrations
0.1% to 10%
Short pathlengths
Low molar absorbtivity

Liquid cells
Designed for easy assembly/disassembly
Use Teflon spacers
Allow variations in path lengths
Fixed path-length cells
Use a syringe to fill or empty

Demountable IR cell for liquid
sample

Common IR window materials
Selection of window materials
Cost
Range of transparency
Solubility in solvent
Reactivity with sample or solvent
Most common NaCl and KBr

Solids
Mulls
Pellets
Solids
Solid in a liquid or solid matrix
Samples are ground to fine powder
To avoid effects of scattered radiation


Pelleting
Most common technique; KBr pelleting
Halide salts have a property of cold flow
Translucent property when pressure is
applied to finely powdered salts
~1 mg (or less) sample is mixed with ~
100 mg dried KBr
Mix and grind in a mortar and pestle
Apply 10,000 to 15,000 psi in a die
Produce a transparent disk or pellet
Pelleting
Best done in vacuum or store the pellet in
a dessicator before measurement
Bands at 3450 and 1640 cm
-1
due to
absorbed moisture
Mulls
Solids
Not soluble in an IR transparent solvent
KBr pelleting is not convenient
Grind ~ 2 5 mg fine powder in a drop of
mulling agents
Heavy hydrocarbon (Nujol)
Fluorolube (halogenated polymer)
Examine as thin film between two salt
discs
Qualitative analysis
FTIR, NMR and MS
Indentify
Organic
Inorganic species
Biological
Limitations to the use of
correlation charts
To determine the identity or structure
Not possible using the correlation charts
alone (only as a guide).
Overlapping of group frequencies
Instrumental limitations
Spectral variations as a function of physical
states
Neat liquid
Solution
Pellet
Mull
Table of group frequencies for
organic functional groups


Group frequency region of MIR
Group frequency region of MIR
Active or inactive vibrations in
IR spectrum?
Quantitative analysis
Limitations
Complex spectra
Overlapping of absorption bands
Narrow absorption bands and
Stray radiation
Deviation from Beers law
Narrow pathlengths
Inconvenient
Lead to significant uncertainties