Spectroscopy & Characterization of Polymers: Chain Microstructure

17/10/2014
19. Spectroscopy & Characterization

of Polymers
Chain microstructure
How do you know if a vinyl polymer is isotactic, atactic etc.?
Composition?
Sequence distribution, MW distribution in copolymer
Spectroscopic methods
Molecular
spectroscopy
IR
NMR
others
17/10/2014
Spectroscopy Fundamentals
General aspects of spectroscopy
Interaction of focussed EM radiation with the sample surface

Reflection, transmission, absorption and/or scattering (change in energy,
frequency)
Absorption occurs when energy of light corresponds to the atomic states of
the sample i.e. Light is only absorbed if its energy corresponds to the
energy difference between two quantum states of the sample
E E2 E1 hf
The speed of light, c (cm/sec), equals the
wavelength (cm), times the frequency,
c ,
Light can also be described in terms of circular motion, the time period
required to go one revolution (2 radians) is
period
*As frequency is no. of

cycles/unit time
is angular frequency in radians/sec. The period of a full revolution would

equal the reciprocal of frequency, so
period
or 2
2
17/10/2014
IR spectroscopy detects the molecular vibrations by the absorption of

infrared light or by the inelastic scattering of light by a molecule. It
characterizes the electromagnetic waves in terms of wavenumber which
is defined as the reciprocal of wavelength with unit cm1.
The photon energy can also be expressed in terms of wavenumber as,

E h ph
E hc
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Origin of Molecular Vibrations:

Simple Harmonic Motion
Molecules in solids are always in vibration at their equilibrium positions and

these vibrations can be simply modelled as massless springs connecting
nuclei in a molecule.
Consider a diatomic molecule vibration by stretching or compressing the
bond (a massless spring) between two nuclei.
The vibrational energy can be calculated using
the spring model. The force F due to linear

elastic deformation of the bond is proportional
to displacement x of two nuclei from its equilibrium
distance re.
F kx ma m
d 2x
dt 2
(1)
Where K is stiffness of the spring or force constant.
After solving the differential equation for frequency,
x cosot
d 2x
dt
o2 cosot o2 x
After substitution in eq. 1, we get
k
m
For sinusoidal function, the ois the circular frequency in radians/sec and
can be termed as the natural frequency of the oscillator.
To change the frequency into cycles/sec
1
2
k
m
17/10/2014
Here, o is directly proportional to the stiffness of the bond, and inversely

proportional to the mass of atoms, therefore a C-C covalent bond
stretching vibration would have lower frequency than a C-H vibration for
the same stiffness of the bond.
For a simple harmonic vibration after interaction with light
F kx k (r re )
The potential energy of the vibration for small
displacements
Evib
1 2 1
kx k (r re ) 2
2
2
This is called simple harmonic motion if there is no

energy loss by the system.
Potential energy (E) of diatomic molecule vibration is quantized
Potential energy of harmonic motion is a parabolic function of displacement

from the equilibrium position of nuclei.
17/10/2014
IR Spectroscopy
Infrared spectroscopy is based on the phenomenon of infrared absorption

by molecular vibrations.
When a molecule is irradiated by electromagnetic waves within the infrared
frequency range, one particular frequency may match the natural
vibrational frequency of the molecule (vib).
Consequently, the molecular vibration will be excited by waves with the
frequency ph=vib
Excited/high
E state
Ground
state
IR Spectroscopy
Energies associated with vibrations of atoms in a molecule with respect to

one another are quantized and absorption of IR radiation give rise to
transitions between these different states.
1
Evib h vib ( )
2
Where is the vibration quantum number with vibration levels (0, 1,2,3,).
vib is the vibrational frequency of a molecule. The ground state
corresponds to = 0.
Since vibrating atoms are linked by bonds, it is usual to refer to the
vibrations as bond deformations such as stretching and bending.
The vibrational frequency of molecules is in the range of middle infrared
(IR) frequencies (61012 1.21014 Hz). Commonly, the vibrational
spectroscopy covers a wavenumber range from 200 to 4000 cm1
17/10/2014
IR Spectroscopy
Infrared modes of Polymers
The basis of the IR spectroscopy is that for a particular type of bond

deformation E and hence , depends on the type of bond involved. (E
and arte higher for N-H than C-H stretching)
Resonance occurs when the frequency of the incident light corresponds to
one of the natural frequencies of vibration of a material.
X-H stretching region (4000-2500 cm-1)
Triple-bond region (2500-2000 cm-1)
Double-bond region (2000-1500 cm-1)
Fingerprint region (1500-600 cm-1)
17/10/2014
Typical IR spectrum
Finger print region
Infrared modes of Polymers
17/10/2014
Instrumentation
IR Instrumentation
Radiation source/ IR Lamp
Focusing optics
Dispersing elements, prism, gratings
Slit
Most modem instruments use interferometers that don't need slits
A range of frequencies/IR wavelengths is incident onto your sample,

separate the light according to wavelength and measure how much light
has been absorbed at each frequency (by comparing intensities to light
from the source that hasn't passed through the sample i.e. base line
reference).
17/10/2014
IR Instrumentation
1. Reference/background
run
IR, Io
I,
transmitted
1. Sample run
Io
10

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17/10/2014

19. Spectroscopy & Characterization

How do you know if a vinyl polymer is isotactic, atactic etc.?

Sequence distribution, MW distribution in copolymer

Interaction of focussed EM radiation with the sample surface

The speed of light, c (cm/sec), equals the

wavelength (cm), times the frequency,

*As frequency is no. of

is angular frequency in radians/sec. The period of a full revolution would

IR spectroscopy detects the molecular vibrations by the absorption of

The photon energy can also be expressed in terms of wavenumber as,

Origin of Molecular Vibrations:

Molecules in solids are always in vibration at their equilibrium positions and

the spring model. The force F due to linear

Where K is stiffness of the spring or force constant.

Simple Harmonic Motion

After solving the differential equation for frequency,

After substitution in eq. 1, we get

Simple Harmonic Motion

Here, o is directly proportional to the stiffness of the bond, and inversely

The potential energy of the vibration for small

This is called simple harmonic motion if there is no

Simple Harmonic Motion

Potential energy (E) of diatomic molecule vibration is quantized

Potential energy of harmonic motion is a parabolic function of displacement

Infrared spectroscopy is based on the phenomenon of infrared absorption

Energies associated with vibrations of atoms in a molecule with respect to

Infrared modes of Polymers

The basis of the IR spectroscopy is that for a particular type of bond

X-H stretching region (4000-2500 cm-1)

Triple-bond region (2500-2000 cm-1)

Double-bond region (2000-1500 cm-1)

Fingerprint region (1500-600 cm-1)

Infrared modes of Polymers

Radiation source/ IR Lamp

Dispersing elements, prism, gratings

Most modem instruments use interferometers that don't need slits

A range of frequencies/IR wavelengths is incident onto your sample,

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