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2. Purification/Separation 3. Analysis/Characterization
Recrystallization C,H,N,O,S etc. analysis (AAS, ICPAS,ICPMS etc)
Chromatography Mass spectrometry
NMR
Thin Layer Chromatography(TLC) IR
Column Chromatography UV-Vis
Gas Chromatography EPR, Mossbauer, XPS, Auger,Etc.
Spectroscopy/ Molecular Spectroscopy
Definition: The study of interaction of electromagnetic radiations
with matters or chemicals or molecules. ( Practical side of study of
spectra)
• Electromagnetic radiation/wave
• Molecules/Energy levels in molecules
• Wavelength
• Amplitude
• Intensity
• Frequency
• Phase
• Time period
Electromagnetic Spectrum
• Molecules/Energy levels in molecules
Symmetrical Asymmetrical
Stretching Stretching
Bending Bending
Scissoring
O=C=O Wagging
Quantum Mechanics : Discrete Energy Levels
Energy
1- 100 kJmol-1
0.01- 1 kJmol-1 < 0.01 kJmol-1
Insignificant
Types of Spectra
Absorption Spectra
• When molecule is exposed to electromagnetic
radiation, the energy of incident photons is transferred
• Raising from ground state to excited state
• Absorption and Absorption Spectrum
• Structural elucidation of molecule
Emission Spectra
• When molecule is subjected to Intense heat and electric discharge
• Returning to lower energy level may emit radiation
• Transition of molecule from excited state to ground state
• Corresponding frequency ν = (E2−E1)/h
• Emission and Emission spectrum
IR Spectroscopy or Vibrational Spectroscopy
You Know
IR radiation, Range, Types of Vibration, Vibrational Levels
IR energy : vibrational energy level change
O C O O C O
O O µ1 = 0 O O µ1 = 0
O C O O C O
O O µ2 = 0 O C O µ2 = some
value
Symmetric Stretching Asymmetric Stretching
No dipole-moment change (µ1 = µ2) Dipole-moment change (µ1 ≠ µ2 )
IR inactive IR active
Cl
O C O
O O µ1 = 0 µ1 = µ2= 0
C C
O O Cl
Cl
µ2 = some value Cl
B A B B A B B A B
Symmetric Stretching Asymmetric Stretching Bending
IR ? IR ? IR ?
According to Quantum Theory
Vibration Energy is quantized, so also the vibrational energy levels
Permitted vibrational energy E= h√(v+1/2)
∆E= E’-E = h√(v’+1/2) - h√(v+1/2) (Where, v= Vibrational Quantum Number)
Fundamental frequency (√0): Transition from v=0 to v=1
When the vibration of a Diatomic molecule is considered to be
Simple Harmonic Motion(SHM) and Diatomic molecule is considered to be Simple
Harmonic Oscillator
For SHM, selection rule for transition : ∆V= ±1
For Anharmonic, selection rule for transition : ∆V = ±1, ±2, ±3, ±4, ……………..
F = -kX
µ=(m1m2)/(m1+m2)
Or
E 1/µ=(1/m1)+ (1/m2)
Where µ= reduced mass
√=1/2∏(k/µ)1/2 s-1
r
Harmonic and Anharmonic vibration of Diatomic molecule
Harmonic Anharmonic
V=7
V=6 X
Energy (E)
V=7
V=5 X 11/2h√
V=6
V=4 9/2h√ V=5
V=3 X 7/2h√ V=4
V=3
V=2 5/2h√ V=2
V=1 3/2h√ V=1
V=0 1/2h√ V=0
Harmonic : ∆V = ±1
Selection rule : Anharmonic : ∆V = ±1, ±2, ±3, ±4, ……………..
H
O O O
H
O N O
N
O O HO N
O
J=3
V2 J=2
J=1
J=0
Transition V1
J=3
J=2
J=1
J=0
J=3
V0 J=2
E0 J=1
J=0
Characterization of UV spectra
C
H
C
C
H
3
3
Benzene Acetone
λmax=255nm λmax=279nm
So λmax gives the position of absorption ε gives the extent of absorption which depend
upon the concentration and structure of the molecule. Hence, regarded as characteristic
properties of spectra.
Origin of Absorption bands in UV-Vis Spectra
(On the basis of MOT-Molecular Orbital Theory)
σ* Anti-bonding MO
∏*
n Nonbonding
O
∏
C
Bonding BO H3C CH3 NH 2
σ
O
σ σ* > ∏ ∏ * >n σ* > n ∏*
H
C
3 N
H2
P
r
o
p
an
e
H
e
x
a
ne
Etc. Etc.
Chromophore
The part of the molecule having n- or ∏- electrons which is essentially responsible
for absorption of radiation (Sometimes show colour)
O Alkene Alkyne
N C C C C C N
O Cyano
Nitro
N N C O
Azo Carbonyl
Auxochrome
A functional group with one on more lone pair of electrons which when attached
to a chromophore alters both its wavelength (λ) and intensity(I or ε )
S
H
N
H
O
H
O
R
2 Chromophore
OH Auxochrome
Auxochrome
O O
C C
H
C
3C
H
3 C
H3
n ∏ * n ∏ *
λmax=255nm λmax=270nm λmax=279nm λmax=324nm
∏6
*
∏4
* *
∏5
* ∏4
*
∏3
∏ * ∏3
∏2
∏2
∏ ∏1 ∏1
H
C
C
2H
2H
2H
C
C
C
C
C
H
2
2CC
CC
CH
2
H H HH H H
λmax=170nm λmax=217nm λmax=240nm
Lycopene
N N C
H
3
ε = 2750 ε = 3560
λmax=255nm
N H 3 N H 2 O H N H 2
C
H3
ε = 19000 ε = 10250
Hypochromic Shift
Application of UV Spectroscopy
Detection of Impurities-Additional peaks comparison with pure compounds
(e. g. Cyclohexane-Benzene-255nm)
Detector
Detector
Laws of Photochemistry
1. Grothus-Draper Law It states that,
Only light which is absorbed can be effective in producing a chemical change.
Light of a particular wavelength or covering a small range of wavelength responsible for
photochemical change known as Effective light.
O
HO O UV
Cu2+ Cu2O
HO O
O
IR, orange, UV all three radiations are absorbed, but only UV light is responsible for
chemical change. So UV is effective light.
Absorbing substance
dl
Incident radiation Transmitted radiation
I0 I
Path length ‘l ’
If ‘I’ is the intensity of light and ‘l ’ is the thickness of absorbing material, then
∫ dI/I = -k ∫ dl
⇒ ln I = -kl + C
When l = 0 I = I0 So, C = ln I0
Then, ln I = -kl + ln I0
⇒ ln I/I0 = -kl
⇒ ln I/I0 = -k C l
Absorbance, A= ε C l
ε = k/2.303
ε = Molar extinction Co-efficient