UV Spectroscopy

1. Introduction
2. UV spectroscopy
3. Why UV?
4. Principle of UV spectroscopy
5. Beer-Lambert law
6. Spectroscopic process
7. Band structure
8. Electronic transition
9. Instrumentation
10. Woodward –Fieser rule
11. Terms used in UV spectroscopy
12. Absorption and intensity shifts
13. conclusion
 Introduction
 Spectrocopy : Branch of science that deals with interaction of
electromagnetic radiation with matter.
 Electromagnetic radiation: A radiation that has both magnetic and electric
field, vary simultaneously. Ray include Gamma ray, X-ray, UV ray , Visible
ray, Infrared ray, radio and all radiations.
• Here magnetic and electric field are perpendicular to each other.
 Principle of spectroscopy
•Principle
is to measure the spectrum of sample containing atom
or molecule.

Spectrum:
It is a graph between intensity oif absorbed or emitted radiation
by sample Vs frequency or wavelength.

Spectrometer:
Instrument design to measure spectrum of compound.
 There are two types of spectroscopy:
1.Absorption spectroscopy
2.Emission spectroscopy
Absorption spectroscopy: Technique which concerns
with the measurement of absorption of EMR. UV (185-
400nm), Visible(400-800nm), IR (0.76-15 μm).
Emission spectroscopy: Technique which concerns with
the emission of particle or radiation and accordingly
amount of dispersion is measured. e.g., mass
spectroscopy.
What happens when EMR intracts with
matter?
 UV-Vis Spectroscopy:
• It is a absorption spectroscopy.
• It is the measurement of
reduction of a beam of light
after it passes through light.
• In the spectrum beyond violet is
called Ultra Violet region and
before red is visible region (of
different colours).
• 200nm-400nm – UV region
• 400nm-800nm – Visible region
WHY UV?
UV help us for:
•Detection of functional group
•Detection of impurities
•Qualitative analysis
•Quantitative analysis
•To recognize simple compound without chromophore
•Useful to detect conjugation of compound
Principle of UV-Vis spectroscopy:
Spectroscopic process:
• Sample is irradiated with the broad spectrum of UV.
• If particular transition matches the energy of any band
of UV, it will be absorbed.
• UV passes through the sample and observed through
detector.
• From residual radiation the spectrum appears with
gaps with discrete energy it is called absorbed
spectrum.
Band structure:

• UV tends to give wide overlapping bands.

• For atomic spectra of pure sample quantized fine
discrete bands are observed.
• For molecules not all bands have same rotational and
vibrational energy states.
• As they have different energies, this impact their
wavelength transition observed.
• When energy levels are superimposed any transition
can take place.
Electronic transitions:
• Do not require more energy
for the transition.
• They are atoms attached
with double or triple bond
to form compound.
• These compounds are
mainly responsible for
absorption radiation.
• Exception-ethene (175nm)
all have 200nm-400nm
wavelength.
Instruments:

• Photometer : An instrument for measurement

of intensity of light or relative intensity of pair
of light. also called illuminometer.
• Spectrometer : an instrument measures the
ratio, or function of two, of the radiant power
of two EM beam over a large wavelength
region.
• Colorimeter: an instrument whuch is used for
measuring absorption in visible region is
generally called colorimeter.
Instrumentation of
spectrometer:
1. Source of radiant energy
2. Collimating system
3. Sample container
4. Filter and monochromator
5. Detector
6. Recorder or readout device
 Source of radiant energy:

Requirement for ideal source:

1.It should be stable and should not allow any fluctuation.
2.Itshould emit light of continuous spectrum of high & uniform
intensity over entire wavelength region in which it is used
3.Itshould provide incident light of sufficient intensity for
transmitted energy to be detected at the end of optic path.
4.It should not show fatigue on continued used.
Tungsten halogen lamp:

• Construction is similar to household lamp.

• The bulb contain filament of tungsten fixed in
evacuated condition and then filled with inert
gases.
• Filament can heated upto 3000k beyond it
starts sublimating.
• It is used when polychromatic light is required.

Demerits:
1.It emits major portion of its radiant energy in
near IR region of the spectrum.
Hydrogen discharge lamp:

• In hydrogen lamp pair of electrode is

enclosed in glass tube filled with
hydrogen gas.
• When current pass through these
electrodes maintained at high
voltage discharge of electron occurs
which excites the hydrogen
molecules which in turn produces
UV radiation near UV region.
• They are stable and robust.
Xenon discharge lamp:
• It possess two tungsten electrode situated at
some distance.
• These are enclosed in a glass tube with quartz
or fused silica and xenon gas is filled under
pressure.
• An intense arc is form between electrodes by
applying high voltage.
• This is a god source of continuous plus
additional intense radiation. Its intensity is
higher than hydrogen discharge lamp.

Demerits:
1.The lamp since operates at very high voltage
become very hot during operation since needs
thermal insulation.
Mercury arc lamp:
• In mercury lamp mercury vapor is
stored under high pressure and
excitation of mercury atoms are
done by electric discharge
Demerits:
1.Not suitable for continuous
spectral studies (because it
doesn’t provide continuous
spectra)
Collimating system:
The radiation emitted by source is collimated (made parallel) by
lenses, mirror and splits.
1.Lenses:

•ordinate silicate glass transmit between 350nm to 300nm and it is

suitable for visible and near IR region
•Quartzand fused silica are material which are used for lenses to
work below 300nm.
2.Mirror :
•theseare use to reflect, collimate or focus light beam in
spectrometer.
•To minimize light loss mirrors are aluminized on their front surface.
3. Slits:
•Slits
are important device to convert a polychromatic
beam into monochromatic radiation. To achieve this
entrance slit and exit slits are used.
•The width of slit plays an important role in resolution of
polychromatic radiation.

Lense Mirrors Slits

Monochromator :

It is a device used to isolate the radiation of desired

wavelength from continuous spectra. Following types of
monochromator devices are used:
•Filters

•Prisms

•Gratings
Filters:
The selection of filter is based on the peak transmittance
and band pass width. on the basis of that there are two
types of filters :
•Absorption filter: selective absorption of unwanted
radiation and transmit the radiation which is required.
ex. Glass and Gelatin filters.
Merits : cheaper, simple in construction, selection is
easy.
Demerits : less accurate.
• Interference filter: rejection of unwanted wavelength by
selective reflection.
Merits:
o provide greater transmittance and narrower bamd pass
as compare to absorption filter.
o inexpensive and additional filter can be used to cut of
unwanted wavelength.

Interference filter

Filter wheel
 Prism:
• Prism is made up of glass or
fused silica.
• When white light is passed
through glass prism, dispersion
of polychromatic light rainbow
occurs. On rotating prism
different wavelength of light can
be obtained which can be
distinguish with the help of slits
• The effective wavelength
depends upon dispersive power
of prism and optical angle.
Grating:

Grating is the most effective in converting a

polychromatic light to monochromatic light. They are
commonly used in spectrometer.
They are of two types:
1.Diffraction grating
2.Transmission grating
 Diffraction grating:
1. More refined dispersion of
light is obtained by diffraction
grating.
2. These consists large number
of parallel lines about 15000
to 30000 / inch is ruled on
highly polished surface of
aluminum.
3. To made surface reflective a
layer of aluminum is made on
surface, in order to minimize
greater amount of scattering
surface the gratings are
blazed to concentrate the
radiation into a single order.
Transmission grating:

• It is similar to diffraction grating but refraction takes

place in place of reflection.
• Refraction produces reinforcement.
Sample holder:

• The cells or cuvettes are used to

handle sample liquid.
• It can be either cylindrical or
rectangular in nature.
• For study in UV region cells are
prepared from quartz or fussed
silica whereas colour corrected
fused glass are used for visible
region.
Detectors :
• It is a device which convert light energy into electrical
signals.
• After light passed through the sample it enable us to
detect and measure the resulting light.
• These detector come in the form of liught that takes
energy in the form of light, and convert into electrical
signal that can be recorded, if necessary amplified.
Three common types of detectors are:
1.Barrier layer cells/ Photovoltaic cells
2.Photo emissive cell detector/ photoemissive tube
3.Photomultiplier
Photovoltaic cell or Barrier layer cell:

• Detector has thin film metallic layer coated with silver

or gold.
• It also has a metal plate base which acts as anode.
• These two layers are separated with semiconductor
laye of selenium.
Method:
1.When light radiation fall on selenium electrons become
mobile and taken up by transparent metal layer.
2.It creates potential; difference across the terminals and
causes the flow of current.
• The flow of current is directly proportional to the
intensity and wavelength of light falling on it.
Photo emissive tube or Photo emissive cell
detector:
• It consists a evacuated glass tube with a
photocathode and collector anode.
• Surface of photocathode is coated with element like
cesium silver oxide or mixture of them.
Process:
1.When radiant energy falls on photo emissive cathode
electrons are emitted which then attracted to anode
causing flow of current.
2.More sensitive compare to barrier layer cell and
therefore widely used.
Photo emissive cell Schematic diagram
Photomultiplier tubes:
• The principle employed in this detector is multiplication
of photoelectron by secondary emission.
• In vacuum tube a primary photo cathode is fixed which
received radiations from sample.
• 8-10 dynodes are fixed each with increasing potential
of 75-100V higher than preceding one.
• Near last dynode an anode is fixed.
• Photomultiplier is extremely sensitive to light and best
suited where weaker or low radiations are received.
Comparison b/w single beam and double
beam spectrometer:
Single beam Double beam
spectrometer spectrometer
• Calibration should be done • Calibration is done only in
with blank every time before the beginning
measuring the absorbance
or transmittance of any
sample
• It permits a large degree
• Radiant energy intensity of inherent compensation
changes with fluctuation of for fluctuation in intensity
voltage. of radiant energy.
• It measures the total • It measures the % of light
amount of transmitted light absorbed by the sample.
reaching the detector
• In single beam it is not • In double beam it is possible
possible to compare blank to do direct one step
comparison of sample in one
and sample together.
path with a standard in other
• In single beam radiant path.
energy wavelength has to • In this scanning can be done
be adjusted every time. over a wide wavelength
region
• Working on single beam is
tedious and time • Double beam is fast and non-
consuming tedious.
Terms used in UV spectroscopy:
Absorption & intensity shifts:
• When absorption intensity of compound is increased it
is called hyperchromic shift.
• If auxochrome introduces to a compound its intensity
increases.

• When absorption intensity of a compound decreases it

is called hypochromic shift.
Shifts and effects:
Conclusion:
• Qualitative and Quantitative analysis:
It is used for characterizing aromatic compounds.
It can be used to find out molar concentration.
• Detection of impurities
It is one of the important method to determine the
impurities
• Detection of isomers are possible
• Determination of molecular weight using beer’s law.
Nanocomposites
Definitions:

✓Nanocomposites are broad range of materials consisting of two or more components, with at
least one component having dimensions in the nm regime (i.e. between 1 and 100 nm)

✓Nanocomposites consist of two phases (i.e nanocrystalline phase + matrix phase)

Phase may be
inorganic-inorganic, inorganic-organic or organic-organic

✓Nanocomposite means nanosized particles (i.e metals, semiconductors, dielectric materials,

etc) embedded in different matrix materials (ceramics, glass, polymers, etc).
General features of nanocomposites
Nanocomposites differ from traditional composites in the smaller size of the
particles in the matrix materials.

Small size may cause

a)Physical sensivity of bulk materials to physical or mechanical energy
b)Higher chemical reactivity of grain boundaries
Physical sensitivity Chemical reactivity

❑ Small size effect ❑ Higher gas absorption

❑ Quantum confinement effect ❑ Increased nonstoichiometry
❑ Regrowth
❑ Rotation and orientation
❑ Sub graining
❑ Assembly
Physical sensitivity
Small size effect:

When the particle sizes in composite materials approach lengths of physical interaction with energy,
such as light wave, electromagnetic waves, the periodic boundry conditions of coupling interaction
with energy would behave different from its microscopic counterparts,
which results in unusual properties

Quantum confinement effect:

When electrons are confined to a small domain, such as a nanoparticles, the electrons behave like
“particles in a box” and their resulting new energy levels are determined by quantum confinement
effect. These new energy levels give rise to the modification of
optoelectronic properties such as “blue shift” light emitting diode
Chemical reactivity
Higher gas absorption:
large specific area of nanopartilces can easily absorb gaseous species

Increased nonstoichiometry phases:

Nanomaterials easily form chemically unsaturated bonds and nonstoichiometry compounds

Regrowth:
Nanomaterials are probably easier to recrystallise and regrow in processing and service conditions than
traditional materials

Rotation and orientation:

Crystallographic rotation and orientation of nanoparticles have been found in processing of nanocomposites

Sub-grain:
Nanoparticles enveloped into larger particles act as dispersed pinholes to divide the large particles into
several parts.

Assembly
Nanoparticles are easy to aggregate and assemble in liquid or gaseous media
Nanocomposites
materials

Nanocomposites can be formed by blending inorganic nanoclusters, fullerenes,

clays, metals, oxides or semiconductors with numerous organic polymers or
organic and organometallic compounds, biological molecules, enzymes, and sol-
gel derived polymers

Layered silicates

Latex Dispersed nanocomposites

 Continued…
 Resulting nanocomposite may
exhibit drastically different (often
enhanced) properties than the
individual components
Lycurgus Cup

 Electrical, magnetic,
electrochemical, catalytic,
Lycurgus Cup is
optical, structural, and made of glass.
mechanical properties Roman ~400 AD,
Myth of King Lycurgus

Appears green in
reflected light and
red in transmitted
light
Classification of nanocomposites
Ceramic based nanocomposites
• Increase in the strength, hardness, and abression by refining particle size Enhance ductility, touchness,
• formability, superplasticity by nanophase
• Change electrical conduction and magnetic properties by increasing the disordered
grain boundry interface
Metallic based nanocomposites
• • Increased hardness, strength and superplasticity; Lowered melting point;
• • Increased electrical resistivity due to increased disordered grain surfaces;
• • Increased miscibility of the non-equilibrium components in alloying and solid solution;
• • Improved magnetic properties such as coercivity, superparamagnetsation, saturation
magnetization and magnetocolatic properties

Polymer based nanocomposites.

•electrical, optical, magnetic and catalytic properties arising from the inorganic materials, and enhanced
thermal and mechanical stability originating from the polymeric matrix
Advantages and limitations of ceramic nanocomposite processing methods .

Methods Advantages Limitations

Powder process Simple Low formation rate, high
temperature, agglomeration, poor
phase dispersion, formation of
secondary phases in the product.
Greater shrinkage and lower amount
Sol-Gel Process Simple, low processing temperature; versatile; of voids, compared to the mixing
high chemical homogeneity; rigorous method
stoichiometry control; high purity products;
formation of three dimensional polymers
containing metal-oxygen bonds. Single or multiple
matrices. Applicable specifically for the production
of composite materials with liquids or with
viscous fluids that are derived from alkoxides.

Polymer Possibility of preparing finer particles; better Inhomogeneous and phase- segregated
Precursor reinforcement dispersion materials due to agglomeration and
Process dispersion of ultra-fine particles
Advantages and limitations of processing methods for metal-based
nanocomposites.
Methods Advantages Limitations
Spray Pyrolysis Effective preparation of ultra fine, spherical and homogeneous High cost associated with producing
powders in multicomponent systems, reproductive size and quality. large quantities of uniform,
nanosized particles.
Short contact times between matrix and reinforcements; moulding into
Liquid Infiltration different and near net shapes of different stiffness and enhanced wear Use of high temperature;
resistance; rapid solidification; both lab scale and industrial scale segregation of reinforcements;
production. formation of undesired products
during processing.
Simple; effective.

Rapid Solidification Process Only metal-metal nanocomposites;

(RSP) induced agglomeration and non-
homogeneous distribution of fine
particles.

RSP with ultrasonics Good distribution without agglomeration, even with fine particles.

Homogeneous mixing and uniform distribution.

High Energy Ball Milling
Chemical Processes (Sol-Gel,
Colloidal) Simple; low processing temperature; versatile; high chemical Weak bonding, low wear-
homogeneity; rigorous stoichiometry control; high purity products. resistance, high permeability and
difficult control of porosity.
Optimization of many
CVD/PVD Capability to produce highly dense and pure materials; uniform parameters; cost; relative
thick films; adhesion at high deposition rates; good reproducibility complexity.
Advantages and limitations of polymer-based nanocomposite
processing methods

Methods Advantages Limitations

Intercalation / Synthesis of intercalated nanocomposites based on polymers Industrial use of large amounts of
Prepolymer from with low or even no polarity. Preparation of homogeneous solvents.
dispersions of the filler.
Solution
Easy procedure, based on the dispersion of the filler in the
In-situ Intercalative polymer precursors. Difficult control of intragallery
Polymerization polymerization. Limited applications.

Melt Intercalation Limited applications to polyolefins,

Environmentally benign; use of polymers not suited for other who represent the majority of used
processes; compatible with industrial polymer processes. polymers.
Large scale production; easy procedure. Limited applications; based mainly in
Template water soluble polymers, contaminated
Synthesis by side products
Greater shrinkage and lower amount of
voids, compared to the mixing method
Sol-Gel Process Simple, low processing temperature; versatile; high chemical
homogeneity; rigorous stoichiometry control; high purity
products; formation of three dimensional polymers containing
metal-oxygen bonds. Single or multiple matrices. Applicable
specifically for the production of composite materials with liquids
or with viscous fluids that are derived from alkoxides.
Thank you