CHEM F313: Instrumental Methods of Analysis

Lecture 05
UV-Vis Spectrometry (contd.)
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Outline
 Spectra-structure Relationship
 Use of electronic spectra
 Solvent Effect

Today’s Class
Example of Woodword Rule
, β unsaturated ketones/aldehydes
Benzenoid and Aromatic systems

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Empirical rules for calculation of
absorption positions
1. Homo-annular Conjugated double bonds

2. Hetero-annular Conjugated double bonds

3. Exocyclic and Endocyclic double bonds

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Empirical rules for calculation of
absorption positions

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 Examples

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,β-unsaturated ketones/
Aldehydes in EtOH
units l, nm
Base value for Acyclic ketones/ 6-member cyclic enones 215
5-member cyclic enones 202
Base value for Acyclic Aldehydes –C=C-CHO 207
Base value for ,β-unsaturated acid esters, -C=C-CO2R(H) 195
Additional conjugation, -C=C-C=C-CO- 30
Homoannular diene 39
Heteroannular 0
Alkyl, Ring Residue a=10, b=12, g … =18
Hydroxyl -OH a=35, b=30, g=30, d=50
Alkoxyl, -OR a=35, b=30, g=17, d=31
Alkyl mercapto, -SR a=0, b=85, g=0, d=0
Chloro, a=15, b=12, g=15, d=15
Bromo a=25, b=30, g=25, d=25
-NH2, -NHR, -NR2 a=0, b=95, g=0, d=0
-OCOR 6
Exocyclic double bond 5
Solvent shift
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Solvent effect
Add contribution from Solvent
The value of absorption maxima is shifted due to the change in the polarity of
the solvent. i.e., the absorption maxima is solvent dependent.

More polar solvents will experience hydrogen bonding with carbonyl group
and n-π* transition will experience blue shift.
Solvents Wavelength,
shift, nm
Water -8
After making the solvent
Methanol 0
corrections, the value of absorption
Chloroform -1
maxima is obtained in ethanol
Dioxan +7
Hexane +11
Cyclohexane +11

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 Examples

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Conclusions
Example of Woodword Rule
, β unsaturated ketones/aldehydes
Benzenoid and Aromatic system

 Next Class
 Instrumentation
 Re-emission of Energy
 Charge Transfer Spectra

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