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SPECTROSCOPY
Spectroscopy
• Study of the Interaction of Electromagnetic
Radiation (Energy) and Matter
• Electromagnetic Spectrum:-
Nuclear
Vibrational
Ultraviolet Visible magnetic
infrared
resonance
2.5 µ m 15 µ m 1m 5m
200 nm 400 nm 800 nm
BLUE RED
σ∗
Unoccupied levels
π∗
Occupied levels
π
σ
Molecular orbitals
UV-Spectroscopy
electrons are
UV Spectroscopy
σ∗
σ σ ∗ alkanes
π∗
σ π ∗ carbonyls
π π ∗ unsaturated cmpds.
Energy
n
n σ ∗ O, N, S, halogens
n π ∗ carbonyls
π
σ
UV transition type
• 1.σ→σ* transitions: for compounds with σ bond
only, high ΔE, short λ (< 200 nm).
Chromophores
A. Definition:-
I. Chromophores
A. Organic Chromophores
• Alkanes – only posses σ-bonds and no lone pairs of electrons,
so only the high energy σ σ* transition is observed in the far
UV
σ C C
UV Spectroscopy
I. Chromophores
A. Organic Chromophores
• Alcohols, ethers, amines and sulfur compounds – in the
cases of simple, aliphatic examples of these compounds the n
σ* is the most often observed transition; like the alkane σ σ* it
is most often at shorter λ than 200 nm
Note how this transition occurs from the HOMO to the LUMO
C N
σ∗ CN
C N
anitbonding
nN sp3
C N
orbital
σ CN C N
UV Spectroscopy
I. Chromophores
A. Organic Chromophores
• Alkenes and Alkynes – in the case of isolated examples of
these compounds the π π* is observed at 175 and 170 nm,
respectively
π∗
π
UV Spectroscopy
I. Chromophores
A. Organic Chromophores
• Carbonyls – n π* transitions (~285 nm); π π* (188 nm)
π∗
It has been
determined from
C O
n spectral studies, that
carbonyl oxygen
more approximates
sp rather than sp2 !
π O
C=C Ethene π __
> π* 171 15,000 hexane
C≡C 1-Hexyne π __
> π* 180 10,000 hexane
n __
> π* 290 15 hexane
C=O Ethanal
π __
> π* 180 10,000 hexane
Nitromethan n __
> π* 275 17 ethanol
N=O
e π __
> π* 200 5,000 ethanol
Methyl
C-X X=Br bromide n __
> σ* 205 200 hexane
X=I Methyl n __
> σ* 255 360 hexane
Iodide
UV Spectroscopy
I. Chromophore
A. Substituent Effects
Hyperchromic
ε
Hypsochromic Bathochromic
Hypochromic
200 nm 700 nm
UV Absorptions for some isolate chromophores
UV Spectroscopy
A. Instrumentation :-
1. The construction of a traditional UV-VIS spectrometer is very
similar to an IR, as similar functions – sample handling,
irradiation, detection and output are required
2. Here is a simple schematic that covers most modern UV
spectrometers:
log(I0/I) = A
UV-VIS sources I0 I
sample
200 700
detector
λ, nm
monochromator/
reference
14
Molecular 12
Extinction
10
Coefficient(w)
wavelength(mu)
APPLICATIONS OF UV AND
VISIBLE SPECTROSCOPY
• UV/Vis spectroscopy is routinely used in the
quantitative determination of solutions of
transition metal ions and highly conjugated
organic compounds.
• Organic compounds, especially those with a
high degree of conjugation, also absorb light in
the UV or visible regions of the
electromagnetic spectrum.
• Thus UV/VIS spectroscopy can be used to
determine the concentration of a solution.
• Applications
• Quantitative determination of
chromophores concentrations in solution
• Impurity determination by spectrum
subtraction
• Determination of reaction kinetics