Uv Seminar

UV-Visible Spectrophotometer Thrirumugam.
S Instrumentation
Introduction Principle & Working Specications of the Instrument
Ultra-Violet Visible Spectrophotometer

Instrumentation and Analysis
Analysis
Spectrograph Results
Summary
Thrirumugam.S
Pondicherry University, Dept. Of Physics.
Advanced Laboratory - Presentation, 2011
UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Outline
Analysis
1 Instrumentation
Summary
2 Analysis

Introduction
Analysis
What is Spectrophotometer?
It is an instrument used to record the spectrum.
Summary
What is the Range? Wavelength = 180nm - 800nm How it is recording the Spectrum? Digitally Working of the Instrument. Source Sample Detector

Figure: Energy Levels of a molecule
Analysis
Summary

Figure: Electronic Structure
Analysis
Summary

A molecules internal energy = Energy of (electrons + vibration + rotation) The electronic energy levels of Simple molecules are widely separated .
Absorption of a high energy photon, excite the
Analysis
Summary
molecule. Complex molecules are more closely spaced. Photons of near UV and Visible light can effect the transition.

Figure: Idealized absorption spectrum
Analysis
Summary

Principle
Analysis
Radiation = matter:
Absorbtion Transmission Scattering Reection Fluorescence.
Summary

Figure: Interaction of light and matter
Analysis
Summary

Interaction of light and matter
Scattering - almost instantaneously completely
Analysis
Summary
re-emitted uniformly in all directions (OR) unchanged. Fluorescence - excites the molecule to a higher energy state;
the molecule then drops back to an intermediate energy
level by re-emitting a photon.

the energy of the incident photon is retained in the
molecule or is lost by a non-radiative process such as collision Radiation is emitted uniformly in all directions

Figure: Working of UV/Vis spectrometer
Analysis
Summary

Components Present
There are many components present in the Instrument.
Necessary Components
Source Sample Compartment Detector
Analysis
Summary
Other Components
Monochromator Setup Filters Interface

Figure: Schematic diagram of a spectrophotometer
Analysis
Summary

Multichannel Spectrometer
No monochromator, but disperses transmitted light and measures "all wavelengths at once"
Analysis
Summary
No scanning - simple and fast More expensive Limited resolution

Figure: Carry 5000
Analysis
Summary

Source
Analysis
No single lamp provides radiation across the whole of the range required, so two are used.
UV Lamp(Deuterium)[ = 180 350nm] Halogen Lamp[ = 300 1200nm]
Summary
The radiation is separated according to its wavelength by a diffraction grating followed by a narrow slit.

Sample
Usually examined in solution(Slovent + Solute).
The most commonly used solvents are water, 95%
Analysis
ethanol, and n-hexane.
Summary
Cuvettes
Must be transparent to the radiation Quartz or fused silica in UV region Silicate Glass in range 350 - 2000 nm.
Solid samples can also be used Thin foil coated over quartz

Detectors
Analysis
Summary
For Detecting the radiations of wavelength range 180nm-800nm Photo Multiplier Tube(PMT) is used. For the wavelengh range 700nm-2500nm PbSmart(PbSe) Semiconductor Detector is used. Detectors has its own limitations.

Beam & Path Length
Analysis
Beam Length
The total length traversed by the radiation between the Source and the Detector is 1.25m
Summary
Path Length
The total length traversed by the radiation through the sample is 1cm

Scan Rate
Analysis
The rate of change of wavelength() w.r.t time

minimum = 20 maximum = 600
Summary
For scan range 200-800nm with scan rate 20 takes 30min

Interface
Analysis
Old
General Purpose Interface Bus(GPIB) 8 bit electrically parallel bus. Lacks command protocols.
Summary
New
USB or Ethernet are also used

Software Utilities
Analysis
Background Correction Base line Correction Peak nder Scan Analysis Signal-to-noise Mode
Summary

Accessories
Analysis
Filters
Two lters are used: 1 below 600nm and other above 600nm
Summary
Sample Compartment
Purging is available in our Instrument Vaccum mechanism can also be used.

Analysis
Analysis
The processes concerned here are absorption and
Summary
transmission.
Reection, scatter and uorescence are kept to a
minimum
The UV/Vis spectrum gives us a pattern which
represents a unique behaviour pattern of our sample.

Analysis
Analysis
Identication of an unknown sample - not possible. Although this data may be used to conrm its nature
Summary
deduced from its infrared spectrum or by other techniques.

If we knew the structure beforehand we could calculate
the theoretical appearance of the samples spectrum using the Fieser-Woodward Rules.

Beer-Lambarts Law
The Beer Lambarts Law: I = I0 exp(L) Where, L - Path Length Absorption Co-effecient = n1 B Einstein co-effecient, B= 1 | < 2|0 |1 > |2 6 0 h2 (3) h c (2) (1)
Analysis
Summary
Absorbance A = constant x concentration x cell length

Terminology
Chromophore Any group of atoms that absorbs light
Analysis
whether or not a color is thereby produced.

Auxochrome A group which extends the conjugation of
Summary
a chromophore by sharing of nonbonding electrons.

Bathochromic shift The shift of absorption to a longer
wavelength.
Hypsochromic shift The shift of absorption to a shorter
wavelength.
Hyperchromic effect An increase in absorption intensity. Hypochromic effect A decrease in absorption intensity.

Factors affecting Absorption
Analysis
Summary
The Solvent Degree of Conjugation Acid - Base Indicators

Choice of Solvents
Table: Some solvents used in ultraviolet spectroscopy
Analysis
Solvent Acetonitrile Water Cyclohexane Hexane Methanol Ethanol Ether Methylene dichloride Chloroform Carbon tetrachloride
Summary
Minimum wavelength for 1 cm cell, nm 190 191 195 201 203 204 215 220 237 257

Figure: Spectra of Phenol in Iso-octane and in Ethanol
Analysis
Summary

Effect of Conjugation
Analysis
The longer the conjugated carbon chain in the
Summary
absorbing system, the greater the intensity of the absorption.

Conjugation does not have to be restricted to atoms of
the same type.

Increased conjugation moves the absorption band
towards a longer wavelength.

Analysis
Summary

Acid-Base Indicators
A small change in the chemical structure of the indicator molecule can cause a change in the chromophore and it will absorb in different parts of the visible spectrum.
Analysis
Summary

Our Spectrograph
Figure: NiSO4 ; C=0.2M
Analysis
Summary
Wavelength (nm) 721.000 500.000 394.000 269.000
Abs 0.440 0.010 1.046 0.005
Type P V P V

Results - Qualitative
Analysis
Summary
The bands observed are usually not specic enough to
allow a positive identication of an unknown sample

Results - Quantitative
Analysis
The estimation of the amount of a compound known to
Summary
be present in the sample. The energy separation, E, between the d orbitals E = h = 3.15 eV Crystal Field splitting energy (10Dq)

Figure: Scan Analysis Report
Analysis
Summary
Concentration 0.1 0.2 0.3 0.4
Absorbance 0.557 1.046 1.523 1.884

Figure: (a) %T vs concentration (b) Absorbance vs concentration
Analysis
Summary

Racah parameters
To describe the effects of electron-electron repulsion
within the metal complexes.

The Racah parameters are A, B and C.
Analysis
Summary
Tanabe-Sugano diagrams
each electron conguration split has an energy that can
be related by the B value.

A is ignored because it is roughly the same for any
metal center and C generally approximated as being 1/4B.

B represents is an approximation of the bond strength
between the ligand and metal.

Tanabe-Sugano Diagrams
Analysis
Summary

Analysis
Summary
comparisons between free ion B and B of a coordination complex is called the nephelauxetic ratio (the effect of reducing electron-electron repulsion via ligands).

How to use the Diagrams

the d-conguration of the metal ion known. Choose the appropriate Tanabe-Sugano diagram. Take a spectrum of the complex and identify Imax for
Analysis
Summary
spin-allowed (strong intensity) and spin forbidden (weak intensity) transitions.

Convert Imax to wavenumbers and generate energy
ratios relative to the lowest allowed transition. (i.e. E2/E1 and E3/E1)
Using a ruler, slide it across the printed diagram until
the E/B ratios between lines is equivalent to the ratios found in step 4.
Solve for B using the E/B values (y-axis, step 4) and
oct /B (x-axis, step 5) to yield the ligand eld splitting energy 10Dq.

Summary
Analysis
A knowledge on Instrumentation will be useful for the
Summary
acurate and fast measurements.
The Analysis of the Spectrograph gives the details
about the molecules.

UV - Vis Spectrophotometer
Advantages
Can be used to determine the Absorption of a
Analysis
Summary
molecule.
Give details about the color of the transition metal.
Disadvantages
Identication of an unknown sample - not possible.
UV-Visible Spectrophotometer Thrirumugam.S Appendix

References
References I
H.A.O. Hill, P. Day. Physical Methods in Advanced Inorganic Chemistry. John Wiley & Sons, Inc. 1968. C.-P. Sherman Hsu, Handbook of Instrumental Techniques for Analytical Chemistry. Tony Owen Fundamentals of modern UV-visible spectroscopy. Copyright Agilent Technologies, 2000. Prof. Greenlief CH 4200, 2004. Cary5000 Brochure Varian: UV VIS NIR Spectrophotometer

References
References II
Thermo Spectronic Basic UV-Vis Theory, Concepts and Applications Adam R. Riordan, et-al Pepperdine University, Malibu Chem. Educator, 10: 115119, 2005.

References
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UV-Visible Spectrophotometer Thrirumugam.

Ultra-Violet Visible Spectrophotometer

Advanced Laboratory - Presentation, 2011

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Introduction Principle & Working Specications of the Instrument

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Figure: Energy Levels of a molecule

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Figure: Electronic Structure

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Figure: Idealized absorption spectrum

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Figure: Interaction of light and matter

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Interaction of light and matter

Scattering - almost instantaneously completely

level by re-emitting a photon.

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Figure: Working of UV/Vis spectrometer

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Figure: Schematic diagram of a spectrophotometer

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

No scanning - simple and fast More expensive Limited resolution

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Figure: Carry 5000

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

ethanol, and n-hexane.

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Beam & Path Length

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

The rate of change of wavelength() w.r.t time

For scan range 200-800nm with scan rate 20 takes 30min

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

The processes concerned here are absorption and

represents a unique behaviour pattern of our sample.

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

deduced from its infrared spectrum or by other techniques.

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Absorbance A = constant x concentration x cell length

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Chromophore Any group of atoms that absorbs light

whether or not a color is thereby produced.

a chromophore by sharing of nonbonding electrons.

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Factors affecting Absorption

The Solvent Degree of Conjugation Acid - Base Indicators

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

Figure: Spectra of Phenol in Iso-octane and in Ethanol

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation

The longer the conjugated carbon chain in the

absorbing system, the greater the intensity of the absorption.

the same type.

towards a longer wavelength.

UV-Visible Spectrophotometer Thrirumugam.S Instrumentation