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Characterization of Polymers, Elastomers and Composites

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Prof. Santanu Chattopadhyay
Rubber Technology Centre, IIT Kharagpur
Week 04 Lecture 02 : Introduction of UV-Vis and infrared spectroscopy for polymers,
elastomers and composites

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CONCEPTS COVERED

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 What is UV-Visible spectroscopy?
 The electronic transitions
 Hypsochromic and bathochromic shift

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 Hyperchromic & hypochromic effect
 Solvatochromism
 Chromophore, auxochrome
 Woodward Fieser rule
 UV curing and applications
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 Advantages and limitations

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 What is UV-Visible spectroscopy?
UV-Vis spectroscopy is an analytical technique that measures the amount of discrete wavelengths of UV or visible light that are
absorbed by or transmitted through a sample in comparison to a reference or blank sample.

Radio wave

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Microwave
Electromagnetic wave

Infrared

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Visible wavelength: 400-700 nm
Ultraviolet
wavelength: 100-400 nm
 UV A (315-400 nm)
X-ray

Gamma Rays
N UV B (280-315 nm)
 UV C (100-280 nm)

[Link]
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Transitions involved in UV-Visible spectroscopy:

σ*
Possible types of interactions or transitions can be
(Anti bonding orbitals)
π* observed. They are
 σ–σ*

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 π–π*
 n–π*
 n–σ*
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n (Non bonding orbital)  σ–π* (Forbidden transitions)

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 π–σ*
The order of the interaction according to the energy is
as follows: σ–σ* > n–σ* > π–π* > n–π*.
π
(Bonding orbitals)
σ

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Transitions involved in UV-Visible spectroscopy:
 During excitation, the atoms in the bond of molecules merge to form molecular orbitals, which are
occupied by electrons of different energy levels. The electrons get excited from the highest
σ*
occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). The
π* resulting spot is called the excited state or antibonding state.

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 σ–σ* transition is a transition that needs larger energy to take place. E.g. methane (CH4)

 n–σ* transition requires lesser energy than the σ–σ* transition. Absorption peaks occur
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n below 200 nm, Saturated compounds having atoms with unshared electrons undergo

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this transition. Examples are water and ethanol.

 π–π* and n–π* transitions require unsaturated functional groups to occur.

π Alkene and alkynes are examples of π–π* transition and carbonyl
compounds are examples of n–π* transition.
σ

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 Hypsochromic and bathochromic shift :
 Blue Shift or Hypsochromic Shift:
Bathochromic Shift Hypsochromic Shift
Blue shift or hypsochromic shift is defined as the decrease in wavelength, with a
corresponding increase in frequency, of an electromagnetic wave.

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λmax

 Red Shift or Bathochromic Shift:

Red shift or Bathochromic shift is defined as the displacement

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of spectral lines towards longer wavelengths (the red end of the
spectrum).

700 600
wavelength (nm)
500 N 400

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Hyperchromic & hypochromic effect :
Hypochromic Effect:
Hypochromicity describes a material’s decreasing ability to absorb
light.

Hypochromic
Hyperchromic Effect :
Hyperchromicity describes the material’s increasing ability to absorb

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Absorbance

light.

Why does it happen?

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Hyperchromic This can occur because of a change in environmental conditions: for
example, a change in solvent polarity will result in solvatochromism.

Wavelength (nm)

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[Link]
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 Reichardt's dye dissolved in different solvents
Solvatochromism :
In chemistry, solvatochromism is the phenomenon observed when the colour due to
a solute is different when that solute is dissolved in different solvents. It is a
reversible change of the absorption or emission spectrum of a material that is
induced by the action of solvents.

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 Positive solvatochromism corresponds to a bathochromic shift (or red shift)
with increasing solvent polarity.
 Negative solvatochromism corresponds to a hypsochromic shift (or blue
shift) with increasing solvent polarity.

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Reichardt's dye
Electric field

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Increasing solvent polarity

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[Link]
What is Chromophore?
A chromophore is the part of a molecule responsible for its color.

 The functional groups containing multiple bonds capable of absorbing radiations above 200 nm due to π–π*, n–π* transitions.
 Examples: N=O, C=O, C=C etc.

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What is Auxochrome?
An auxochrome is a functional group of atoms attached to the chromophore which modifies the ability of the chromophore to absorb
light, altering the wavelength or intensity of the absorption.

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 The functional group with non bonding electrons that does not absorb radiation in near UV region but when attached to a
chromophore alters the wavelength and intensity of absorption.


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Examples: Benzene λmax=255 nm, Phenol λmax =270 nm, Aniline λmax=280 nm

[Link]
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Woodward Fieser rule for UV spectroscopy and calculation of λmax of organic compounds:
1. Woodward Fieser rule for conjugated diene and polyenes :-

A. Homo annular diene :– cyclic diene having conjugated double bond in same ring.
B. Hetero annular diene :– cyclic diene having conjugated double bond in different ring.
C. Endo cyclic double bond :– double bond present in a ring.

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D. Exocyclic double bond :- double bond in which one of the double bonds atom is a part of a ring.
E. Double bond extending :– when more double bond are present other than conjugated.

Different base value :-

 Acyclic conjugated diene or Hetero annular conjugated diene has 215 nm wavelength.

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 Homo annular conjugated diene :-253 nm
 Acyclic trienes :- 245 nm.
 Each alkyl substitution , ring residue or ring residue :- 5 nm
 Double bond extending conjugation :- 30 nm

Auxochrome base value :-

 – OR = 6 nm
 – SR = 30 nm
 – CL,-Br = 5 nm
 -OCOCH3 = 0nm
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[Link]
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Woodward Fieser rule for UV spectroscopy and calculation of λmax of organic compounds:
II) α, β unsaturated carbonyl compounds or ketones: 8. Polar groups:
a) –OH in α position = 35 nm
1. Base value: a) Acyclic α, β unsaturated ketones = 214 nm
–OH in β position = 30 nm
b) 6 membered cyclic α, β unsaturated ketones = 215 nm
–OH in δ position = 50 nm
c) 5 membered cyclic α, β unsaturated ketones = 202 nm

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d) α, β unsaturated aldehydes = 210 nm b) –OAc in α, β, γ, δ positions = 6 nm

e) α, β unsaturated carboxylic acids & esters = 195 nm c) –OMe in α position = 35 nm

–OMe in β position = 30 nm

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2. Alkyl substituent or Ring residue in α position = 10 nm –OMe in γ position = 17 nm

3. Alkyl substituent or Ring residue in β position = 12 nm –OMe in δ position = 31 nm

d) –Cl in α position = 15 nm

5. Double bond extending conjugation = 30 nm

6. Exocyclic double bonds = 5 nm

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4. Alkyl substituent or Ring residue in γ and higher positions = 18 nm
–Cl in β position = 12 nm
e) –Br in α position = 25 nm
–Br in β position = 30 nm
f) –NR2 in β position = 95 nm
7. Homodiene compound = 39 nm

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Woodward Fieser rule for UV spectroscopy and calculation of λmax of organic compounds:
III) Aromatic Compounds:
1) Base value: for a) ArCOR = 246 nm

b) ArCHO = 250 nm
f) –Cl in o, m position = 0 nm

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c) ArCO2H = 230 nm g) –Cl in p position = 10 nm

d) ArCO2R = 230 nm h) –Br in o, m position = 2 nm

i) –Br in p position = 15 nm

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2) Alkyl group or ring residue in ortho and meta position = 3 nm
j) –NH2 in o, m position = 13 nm
3) Alkyl group or ring residue in para position =10 nm k) –NH2 in p position = 58 nm
4) Polar groups: a) –OH, –OCH3, –OAlkyl in o, m position = 7 nm l) –NHCOCH3 in o, m position = 20 nm
b) –OH, –OCH3, –OAlkyl p position = 25 nm
c) –O (oxonium) in o position = 11 nm
d) –O (oxonium) in m position = 20 nm
e) –O (oxonium) in p position = 78 nm
N m) –NHCOCH3 in p position = 45 nm
n) –NHCH3 in p position = 73 nm
o) –N(CH3)2 in o, m position = 20 nm
p) –N(CH3)2 in p position = 85 nm

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Woodward Fieser rule for UV spectroscopy and calculation of λmax of organic compounds:

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[Link]
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 The detailed demonstration on this will be covered in the upcoming practical classes.

UV instrumentation:
 Source of radiation
 Collimating system
 Monochromator

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 Sample holder
 Detector

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 Amplifier
 Read out Device

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 UV curing:
 UV curing is the process by which ultraviolet light is used to initiate a photochemical reaction that
generates a crosslinked network of polymers. UV curing is adaptable to printing, coating, decorating,
stereolithography, and in the assembly of a variety of products and materials.

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 UV curing is used in applications where there is a need for converting or curing inks, adhesives UV curable paint
and coatings. UV-cured adhesive has become a high speed replacement for two-part adhesives,
eliminating the need for solvent removal, ratio mixing, and potential life concern.

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 Advantages of UV curing:
 A primary advantage of curing with ultraviolet light is the speed at which a material can be
processed. Speeding up the curing or drying step in a process can reduce flaws and errors by

Step 1:
Photo initiator(PI)
Step 2:
Activation of
Photo initiator
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decreasing time that an ink or coating spends wet.

Step 3:
Chemical reaction
between
Step 4:
Propagation to
crosslinked
Step 5:
Termination of
polymerization to
light absorption
(PI) monomers & PI coating finished pdt.

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Applications :

Ultraviolet-visible (UV-Vis) spectroscopy is a widely used technique in many areas of science ranging from

 bacterial culturing,

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 drug identification

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 checking of nucleic acid purity

 to quality control in the beverage industry

 chemical research.
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UV-Visible spectroscopy:
Advantages:
 UV-VIS spectrometers are easy to use.

Limitations:

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 The main disadvantage of using a UV-VIS spectrometer is the time it takes to prepare to use one. With UV-VIS
spectrometers, setup is key. You must clear the area of any outside light, electronic noise, or other outside

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contaminants that could interfere with the spectrometer's reading.

 A small bit of outside light or vibration from a small electronic device could interfere with the results you are

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hoping to achieve in using a UV-VIS spectrometer.

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REFERENCES

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⮚ Fundamentals of molecular spectroscopy : C.N. Banwell

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⮚ Organic Spectroscopy: William Kemp

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 CONCLUSION

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Here we briefly cover-

 What is UV-Visible spectroscopy?

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 The electronic transitions , Hypsochromic and bathochromic shift Hyperchromic &
hypochromic effect, solvatochromism

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 Chromophore, auxochrome, Woodward Fieser rule and calculation of λmax of
organic compounds UV curing and applications and lastly advantages and
limitations of uv spectroscopy.

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