Spectroscopy
by
Dr. Anil Kumar
Department of Applied Sciences,
University Institute of Engineering and Technology,
Panjab University, Chandigarh-160014
Ultimate source of energy ?
True or False
Sun rises in the East. False
Spectroscopy
Interaction of Radiation with Matter
Electromagnetic Radiations
Radiation Matter
C=λv
λ = wavelength, nm (10-9 m)
v = no. of wave cycles, Hertz/cps or s-1
C = velocity of light, 3 x 108 m/s
h (Plank’s constant) = 6.6242 x 10-27 erg sec
= 6.63 x 10-37 k Js or 1.58 x 10-37 kcal sec
E= hv = hc/λ Each molecule/compound has
fixed energy gap between the
UV-Visible = 200-800 nm (143-36 kcal/mol) ground state and excited state
Energy is quantized Energy is quantized
Spectroscopy
Why to study Spectroscopy?
What kind of information we can get from the Spectroscopy?
Radiation + unknown Matter = Electromagnetic Spectrum
Electromagnetic spectrum will give useful information about the
structure of that matter such as atoms, no. of atoms, type of bond
between atoms, conjugation, functional groups etc.
Spectroscopy
UV-Visible Spectroscopy : Gives only some basic information
about the unknown matter such as type of bond, conjugation, hetero
atom etc.
Infrared Spectroscopy : Very important technique, gives
information about the presence of functional groups in the unknown
matter
NMR Spectroscopy : Very useful spectroscopy. Gives no. of
hydrogens and carbons (other nuclei also) present in a molecule and
their environment and overall structure.
Mass Spectroscopy : Gives exact mass of the unknown matter.
UV-Visible Spectroscopy
Interaction of UV-Visible Radiation with Matter
UV Radiation λ = 200-400 nm
Visible Radiation λ = 400-800 nm
Matter
Matter
Matter
Matter
Matter
Matter
Matter
Matter
Matter
Matter
Matter
Matter
Matter
Matter
Interaction between Radiation and Matter
RADIATION
MATTER SPECTRUM
Simplified schematic diagram of an absorption spectrophotometer
Lambert-Beer’s Law for UV-Visible Spectroscopy
Lambert Law : It states that when a monochromatic beam of light passes through a
solution, rate of decrease of intensity with respect to the thickness of the medium is
directly proportional to the intensity of incident light.
- dI/dl = kI
Beer Law : It states that when a monochromatic beam of light passes through a
solution, rate of decrease of intensity with respect to the thickness of the medium is
directly proportional to the incident light and concentration of the solution.
Lambert-Beer Law:
- dI/dl = kʹ IC
Lambert-Beer Law :
-dI/dl = kʹ IC
-dI/I = kʹ C dl
After integration (Io to I and l = 0 to l = l)
-Log I / Io = kʹ/2.303 C l
Log Io / I = ϵCl
A = ϵCl A = Absorbance
ϵ = Molar extinction coefficient
C = Concentration
l = path length
Types of electronic Transition:
1. σ – σ* : Electron gets excited from sigma bonding
molecular orbital to sigma anti-bonding molecular orbital.
It is high energy process. Absorption will occur at lower
wavelength.
Generally such transitions do not absorb in the region 200-400
nm.
Examples: methane ethane etc. absorb below 200 nm
Types of electronic Transition:
2. n – σ* : Electron gets excited from non-bonding molecular
orbital to sigma anti-bonding molecular orbital. These
transitions require less energy than σ – σ* transitions.
Such transitions generally take place in saturated compounds
having at least one hetero atom.
Examples: Halide, alcohol, ether etc
H2O λmax = 167 nm , CH3OH λmax = 174 nm
CH3Cl λmax = 175 nm, CH3I λmax = 258 nm
Types of electronic Transition:
3. π – π* : Electron gets excited from pi-bonding molecular
orbital to pi-antibonding molecular orbital.
Such transitions occur in unsaturated compounds such as alkene,
alkyne etc.
Examples: ethene, 1,3-butadiene
For unconjugated system λmax = 170 - 190 nm
For conjugated system λmax = 215 - 250 nm
Types of electronic Transition:
4. n – π* : Electron gets excited from non-bonding molecular
orbital to pi-antibonding molecular orbital.
Such transitions occur in unsaturated compounds such as
aldehyde, ketones, acid, ester etc.
H3C
Examples: For acetone C O , two peaks
H3C
λ = 190 nm
λ = 275 nm
Selection Rules
1. Spin selection rule: DS = 0
allowed transitions: singlet singlet or triplet triplet
forbidden transitions: singlet triplet or triplet singlet
Changes in spin multiplicity are forbidden
2. Laporte (orbital ) selection rule: Dl = ±1
allowed transitions: s p or p d
forbidden transitions: s s or p p
Chromophore:
A functional group that absorbs in UV-visible region i.e. 200-800 nm.
e.g. >C=O, -NO2, N=N , C=C etc.
max = 255 nm
Auxochromes
A functional group that enhances the absorbing properties of chromophore,
e.g. –OR, -NH2, -NR2 etc
NH2
max = 280 nm
a) Effect of conjugation on λmax
H2C CH2 H2C C C CH2
H H
max = 190 nm max = 217 nm
The energy gap between HOMO to LUMO decreases due to conjugation.
Therefore, transition in 1,3-butadiene occur at higher wavelength as
compared to ethene. The max value is at about 217 nm, a significant
difference from the value of 190 nm in ethene.
Which of the isomers of pentadiene a) or b) will show the longest
wavelength of the UV absorption
a) CH2=CH-CH=CH-CH3
b) CH2=CH-CH2-CH=CH2
Isomer a), Since conjugated dienes have longer wavelength of
absorption than nonconjugated
The following are pairs of isomers, and one member of each pair absorbs
ultraviolet/visible light at longer wavelength than the other: In each case state
whether it is first or second member
a) 1,3-hexadiene and 1,4-hexadiene
b) 1,2-dihydronaphthalene and 1,4-dihydronaphthalene
a) 1,3-hexadiene
b) 1,2-dihydronaphthalene
Given that extending a chromophore involves additional conjugation or the
involvement of non bonding electrons, which of the following as a substituent in
benzene will substantially increase the maximum wavelength of absorption in
the electronic spectrum
a) –CH=CH2 b) –OH c) –N=N-Me d) –NO2 e) –CH3
All except e)
Woodward rules to calculate λmax in the case of Dienes
All values of λ are in nm (nanometer)
Examples
THANK YOU
