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Uv-Vis Spectroscopy: CHM 3402 Dr. Mohd Rashidi Abdull Manap
Uv-Vis Spectroscopy: CHM 3402 Dr. Mohd Rashidi Abdull Manap
https://archives.library.illinois.edu/erec/University%20Archives
/1505050/Organic/Arenes/Chapter%205/sec5-14/5-14.htm
When red photons are
absorbed from white
lights, your eyes see green
color
https://www.rojakdaily.com/lifestyle/article/5705/batu-caves-g
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https://www.implen.de/wp-content/uploads/docs/UV-Vis_Nan
oPhotometer_for_authenticity_testing_of_spirits.pdf
https://www.researchgate.
net/figure/UV-VIS-spectra-
of-diverse-carotenoids-imp
ortant-for-photoprotection
-and-cosmetics_fig2_3331
54388
https://www.thehealthsite.com/
fitness/refined-oil-vs-filtered-oil-
which-is-healthier-k0115-25951
8/
•Experimental UV–Visible
absorption peaks arising due to
electronic transitions
•This is due to the presence of
chemical species in the sample
•The electronic transitions can be
understand by the means of
molecular orbitals
https://www.sciencedirect.com/topics/chemistry/uv-vis-absor
tion-spectrophotometry
The valence electrons are the only ones whose energies permit them to be
excited by near UV/visible radiation.
s* (anti-bonding)
p* (anti-bonding)
Four types of transitions
*
n (non-bonding) *
n*
p (bonding)
n*
s (bonding)
s s* transition in vacuum UV
n s* saturated compounds with non-bonding electrons
n ~ 150-250 nm
e ~ 100-3000 ( not strong)
n p*, p p* requires unsaturated functional groups (eq. double bonds)
most commonly used, energy good range for UV/Vis
n ~ 200 - 700 nm
n p* : e ~ 10-100
p p*: e ~ 1000 – 10,000
13
Chromophore Excitation lmax, nm Solvent
C=O
n→p* 290 hexane
p→p* 180 hexane
N=O
n→p* 275 ethanol
p→p* 200 ethanol
=>
18
s* s*
C C p* p*
hv
= hv
=hc/
p p
s s
Example: ethylene absorbs at max = 165 nm = 10,000
19
C O
s* s*
p* p*
n hv
n
p p
s s
n
The n to p* transition is at even longer wavelengths but is not as strong as p to p*
transitions. It is said to be “forbidden.”
Example:
Acetone: n max = 188 nm ; = 1860
n max = 279 nm ; = 15
20
Conjugated systems:
C C
LUMO
HOMO
O
O
22
Absorption Characteristics of Some Common Chromophores
Chromophore Example Solvent lmax (nm) emax Type of
transition
Alkene C6H13HC CH2 n-Heptane 177 13,000 pp*
Alkyne n-Heptane 178 10,000 pp*
C5H11C C CH3 196 2,000
_
225 160
_
Carbonyl O n-Hexane 186 1,000 ns*
280 16
np*
CH3CCH3
n-Hexane 180 Large
O ns*
293 12
CH3CH np*
Carboxyl O Ethanol 204 41 np*
CH3COH
Amido O Water 214 60 np*
CH3CNH2
Azo H3CN NCH3 Ethanol 339 5 np*
Nitro CH3NO2 Isooctane 280 22 np*
Nitroso C4H9NO Ethyl ether 300 100 _
665 20 np*
Nitrate C2H5ONO2 Dioxane 270 12 np* 23
Structure elucidation of organic
compounds
UV-Vis spectroscopy is useful in the
structure elucidation
• The presence or absence of unsaturation
• The presence of hetero atoms
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UV-Vis Spectroscopic Samples
Electronic Spectra
https://doi.org/10.1016/j.saa.2009.01.017
3-Application and Interpretation of a
UV-Vis spectrum
• How does UV-Vis method fit into this process?
UV-Vis
Wavelength(nm) Functional Groups
Shift in Molecular
wavelength environment
UV-Vis Spectra (300 to 900 nm) 𝝀𝒎𝒂𝒙 =? 𝒏𝒎
Beer’s Law in
UV-Vis
Spectroscopy
https://doi.org/10.1016/j.est.2019.101066
Quantitative Analysis with UV-Vis
Beer’s Law
A=ebc
e: the molar absorptivity (L mol-1 cm-1)
b: the path length of the sample
c :the concentration of the compound in
solution, expressed in mol L-1
Path
length / cm 0 0.2 0.4 0.6 0.8 1.0
https://doi.org/10.1016/j.molstruc.2018.04.005
Molecular structure determination with
UV-Vis
Blue spectrum
360 nm - π−π* transition
530 nm - n−π* transition
https://doi.org/10.1016/j.molstruc.2017.11.082
Molecular structure determination with
UV-Vis
Caffeine in DCM
Below 243 nm -solvent
274.7 nm n→π* transition of lone pair in caffeine C=O
https://doi.org/10.1016/j.foodchem.2007.10.024
http://www.chem.ucla.edu/~bacher/UV-vis/uv
e.html.html
Factors affecting absorption
• The solvent
• Degree of conjugation
50
UV Spectral Nomenclature
51
Red line shows the absorption peak intensities of caffeine are
reduced and blue shifted (360 nm) and a new (287 nm) peak is
formed.
https://doi.org/10.1016/j.molstruc.2017.11.082
- For Compounds with Multiple Chromophores:
53
- For Compounds with Multiple Chromophores:
54
Solvent Effects - Intensity
Solvents can induce significant changes in the intensity of peaks.
56
• If a polar solvent is used the dipole–dipole interaction reduces the energy
of the excited state more than the ground state, hence the absorption in a
polar solvent such as ethanol will be at a longer wavelength (lower energy,
hence lower frequency) than in a non-polar solvent such as hexane.
57
Solvent effects
• For n -> π* transition, the n state is much more easily
stabilized by polar solvent effects (H-bonds and
association), so in going from nonpolar to polar solvent
there is a blue shift or hypsochromic shift (decrease in
λmax, increase in ΔE).
58
O
methanol heptane
59
Solvent Effects
60
Thank you