IMA Lecture 04
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Siddharth JainIMA Lecture 04
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Siddharth JainCHEM F313: Instrumental Methods of Analysis
Lecture 04
UV-VIS Absorption Spectroscopy
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UV-VIS transitions: Features
• Excitation occurs in a very short times (10-15s)
• Frank Condon principle
• HOMO-LUMO transition
• Not all transitions from filled to unfilled is
allowed
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UV-VIS spectra: interpretation
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Transition in Carbonyl based Molecule
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Conjugated vs non-conjugated
napthyl
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List of Chromophores
Chromophore Wavelength,
nm, lmax Q:Which of the following substituents
C=C 175 will substantially change the
C≡C 175, 195, 223 benzene λmax in the electronic
spectrum?
C=O 160, 185, 280
R-NO2 200, 274 1. –CH=CH2
C≡N 165 2. -CO-Me
3. -CH2-CO-Me
C=C-C=C 217 4. -CH2-CH2-CH3
C=C-C=O 220, 315 5. -OH
C=C-C≡C 220, 230 6. -N=N-Me
C6H6 184, 204, 255
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Solvent Effects
• Dilute solutions are required, ~ 0.01 g/L (for weak signals). WHY??
Solvents LOWER
Wavelength, 1. Careful handling and sample preparation
limit, nm, lmax 2. Effect of solvent does not nullify
Water 205 completely even after using reference
beam – strongly absorbing solvents will
Ethanol 210
leave small cross-section available for
Hexane, 210 sample
Cyclohexane, 3. Fineness of spectrum is affected by
Methanol, Diethyl
solvent
ether, Acetonitrile
4. Variation of solvent polarity leads to
THF 220 differences in UV-Vis absorption
DCM 235
Chloroform 245
CCl4 265 • Conjugated dienes and aromatic hydrocarbons
C 6 H6 280
experience very little solvent shift
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Case Study:α,β -unsaturated ketones in
different solvents
• Stabilization of orbitals in the medium is crucial in understanding
the shift of the spectral band
Solvents Wavelength, In water,
shift, nm 1. n-π* moves to lower wavelength, ΔE
Water +8 non-bonding orbitals are better
Methanol 0
stabilised in H-bonding solvents
Chloroform -1 2. π-π* moves to higher wavelength, ΔE
Dioxan -5 π* orbitals better stabilized than π in
Diethyl ether -7 polar medium (shown in Table)
Hexane -11
Cyclohexane -11
Shift towards higher wavelength = red shift or bathochromic shift
Shift towards lower wavelength = blue shift or hypsochromic shift
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Solvent effect
