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Dr. B. Sateesh Kumar
M.Sc., CSIR-JRF, Ph.D
Assistant Professor in Chemistry
GDC TKL
UV Visible
Spectroscopy
Useful to B.Sc /M.Sc
Chemistry students
Spectroscopy
• Spectroscopy is the branch of science which deals with the study
of interaction of electromagnetic radiation with matter. During
this interaction energy is absorbed or emitted by the matter
@DrBSK
Atomic spectroscopy deals with the interaction of electromagnetic radiation
with atom.
Molecular spectroscopy deals with the interaction ofelectromagnetic
radiation with molecule.
What are the Spectroscopic Methods ?????
4 methods widely used in Organic Chemistry
UV-Visible
Infrared
Nuclear magnetic resonance
Mass spectroscopy
@DrBSK
Rotational spectroscopy
• Electromagnetic radiation is a form of energy that is transmitted
through space.
• Electromagnetic radiation is a mixture of the electrical and
magnetic component which are perpendicular To each other and
also perpendicular to propagation line as a shown in the figure.
@DrBSK
EMR Spectrum
@DrBSK
Introduction UV-Visible
• Ultraviolet and visible spectroscopy is also known as
electronic spectroscopy. Generally, it can be used to
determine the degree of unsaturation within the molecules.
The ultraviolet spectrum: Generally, an electronic transition occurs due to the
absorption of EMR in the range of 10 nm to 780 nm. So this region is known
as a ultra-violet visible region which is further divided into the following
region.
Far UV (vacuum) region (10-200 nm): The absorption below 200 nm
(atomic absorption) appeared in this region
@DrBSK
Near UV region (200-380): The atmosphere is transparent in this
region.
The absorption due to p & d electronic transition appears in the range
of the ultraviolet spectrum
@DrBSK
Visible region (380-780): If enough no. of π bond in
conjugation, absorption takes place in this region
HOMO
LUMO
hv
Electronic Transitition
UV-Visible Light
Principle of U.V Spectroscopy
@DrBSK
• The most favourable transition of an electron from higher
occupied molecular orbital (HOMO) to the lowest
unoccupied molecular orbital (LUMO).
@DrBSK
Electronic Transitions
@DrBSK
Major Electronic Transitions
@DrBSK
Electronic Transitions of molecules
@DrBSK
•A transition of an electron from bonding sigma orbital to
higher energy antibonding sigma orbital is designated
σ → σ∗ .
σ → σ∗ transition
Example: CH4, CH3CH2CH3, C6H12 etc
@DrBSK
H3C CH3
  *
CH3 CH3
•Methane shows an absorbance maximum at 125 nm.
•It is observed in saturated hydrocarbons
Transitions are not seen in typical UV-Vis. spectra (200 - 700 nm)
n → σ∗ transition
• Transition of electron from nonbonding to antibonding sigma orbital
(n → σ∗) .
•This transition observed in saturated compounds with one hetero atom
like oxygen, nitrogen, fluorine, chlorine, etc.
• Normally, saturated alkylhalides, alcohols, ethers, aldehyde, ketones and
amines participate in this type of transition.
@DrBSK
• These transitions require comparatively less energy than the
σ → σ∗ transition.
@DrBSK
R X
[Alkyl halide]
n *
R X
Represent
• Transition of electrons from pi bonding orbital to anti bonding
pi orbital (π → π∗)
•UV-Vis spectroscopy is available in compounds with
unsaturated hydrocarbons and carbonyl compounds, aromatic
compounds..etc.
• It transition requires lesser energy than n → σ∗ transition.
π → π∗ transition
@DrBSK
H2C CH2 H2C CH2
alkene
Represent
π → π∗ transition
Conjugation increases W.L
increases
@DrBSK
• Transition of electrons from nonbonding orbital (n)to antibonding pi
orbital (n → π∗).
•Non bonding electrons in unshared pair on a hetero atom is excited to
π∗ antibonding orbital.
• It involves the least amount of energy(means higher wave elngth)
than all types of transition in ultraviolet visible spectroscopy.
n → π∗ transition
@DrBSK
In saturated ketones, n → π∗ transitions around 280 nm are
the lowest energy transition.
n → π∗ is forbidden by symmetry consideration.
Thus the intensity of the band due to this transition is low,
although the wavelength is long.
@DrBSK
O
R
R
O
R
R
?
See this color due
to
See you in next
Part-3
Chromophore concept
and shifts of UV
Spectroscopy

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Spectroscopy Part-2.pptx

  • 1. Dr. B. Sateesh Kumar M.Sc., CSIR-JRF, Ph.D Assistant Professor in Chemistry GDC TKL UV Visible Spectroscopy Useful to B.Sc /M.Sc Chemistry students
  • 2. Spectroscopy • Spectroscopy is the branch of science which deals with the study of interaction of electromagnetic radiation with matter. During this interaction energy is absorbed or emitted by the matter @DrBSK Atomic spectroscopy deals with the interaction of electromagnetic radiation with atom. Molecular spectroscopy deals with the interaction ofelectromagnetic radiation with molecule.
  • 3. What are the Spectroscopic Methods ????? 4 methods widely used in Organic Chemistry UV-Visible Infrared Nuclear magnetic resonance Mass spectroscopy @DrBSK Rotational spectroscopy
  • 4. • Electromagnetic radiation is a form of energy that is transmitted through space. • Electromagnetic radiation is a mixture of the electrical and magnetic component which are perpendicular To each other and also perpendicular to propagation line as a shown in the figure. @DrBSK
  • 6. Introduction UV-Visible • Ultraviolet and visible spectroscopy is also known as electronic spectroscopy. Generally, it can be used to determine the degree of unsaturation within the molecules.
  • 7. The ultraviolet spectrum: Generally, an electronic transition occurs due to the absorption of EMR in the range of 10 nm to 780 nm. So this region is known as a ultra-violet visible region which is further divided into the following region. Far UV (vacuum) region (10-200 nm): The absorption below 200 nm (atomic absorption) appeared in this region @DrBSK
  • 8. Near UV region (200-380): The atmosphere is transparent in this region. The absorption due to p & d electronic transition appears in the range of the ultraviolet spectrum @DrBSK Visible region (380-780): If enough no. of π bond in conjugation, absorption takes place in this region
  • 10. • The most favourable transition of an electron from higher occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). @DrBSK
  • 13. Electronic Transitions of molecules @DrBSK
  • 14. •A transition of an electron from bonding sigma orbital to higher energy antibonding sigma orbital is designated σ → σ∗ . σ → σ∗ transition Example: CH4, CH3CH2CH3, C6H12 etc @DrBSK H3C CH3   * CH3 CH3 •Methane shows an absorbance maximum at 125 nm. •It is observed in saturated hydrocarbons Transitions are not seen in typical UV-Vis. spectra (200 - 700 nm)
  • 15. n → σ∗ transition • Transition of electron from nonbonding to antibonding sigma orbital (n → σ∗) . •This transition observed in saturated compounds with one hetero atom like oxygen, nitrogen, fluorine, chlorine, etc. • Normally, saturated alkylhalides, alcohols, ethers, aldehyde, ketones and amines participate in this type of transition. @DrBSK • These transitions require comparatively less energy than the σ → σ∗ transition.
  • 16. @DrBSK R X [Alkyl halide] n * R X Represent
  • 17. • Transition of electrons from pi bonding orbital to anti bonding pi orbital (π → π∗) •UV-Vis spectroscopy is available in compounds with unsaturated hydrocarbons and carbonyl compounds, aromatic compounds..etc. • It transition requires lesser energy than n → σ∗ transition. π → π∗ transition @DrBSK
  • 18. H2C CH2 H2C CH2 alkene Represent π → π∗ transition Conjugation increases W.L increases @DrBSK
  • 19. • Transition of electrons from nonbonding orbital (n)to antibonding pi orbital (n → π∗). •Non bonding electrons in unshared pair on a hetero atom is excited to π∗ antibonding orbital. • It involves the least amount of energy(means higher wave elngth) than all types of transition in ultraviolet visible spectroscopy. n → π∗ transition @DrBSK
  • 20. In saturated ketones, n → π∗ transitions around 280 nm are the lowest energy transition. n → π∗ is forbidden by symmetry consideration. Thus the intensity of the band due to this transition is low, although the wavelength is long. @DrBSK O R R O R R
  • 21. ? See this color due to See you in next Part-3 Chromophore concept and shifts of UV Spectroscopy