BIRD’S EYE-VIEW

Chemical Synthesis Separation/Purification Analysis/Characterization

 Research labs in Academic institutions

Chemicals
 R &D labs (Company, Private sectors)
1. Synthesis
 Needs experience and expertise
 Reaction conditions (Temp, Pressure, Concentration, reactants and products)
 Nature of reactants (Stable/Unstable, Hygroscopic, Oxidising/Reducing )
 Handling hazardous chemicals
 Precautions

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

Seeing a matter (e. g. Water)

By a common man By Student, Teacher, Researcher, scientist

 How We see Molecules!
Types of energy/energy levels present in molecule
• Translation (Overall movement of molecules)
• Vibration (Bonds as springs: Elongation-Compression, Bending)
• Rotation ( Rotation of centre of gravity of molecule around axes)
• Electronic (Electronic distribution)

Types of motion in molecule

 Types of Vibration in a molecule

Symmetrical Stretching Asymmetrical Stretching

Scissoring Rocking Wagging Twisting

 O
H H

Symmetrical Bending Asymmetrical

Stretching Scissoring Stretching

Symmetrical Asymmetrical
Stretching Stretching

Bending Bending
Scissoring
O=C=O Wagging
 Quantum Mechanics : Discrete Energy Levels

Energy

Electronic Vibrational Rotational Translational

Representation of Different Energy Levels in molecule

Discret Rotational, Vibrational and Electronic Energy Levels
∆Eelectronic > ∆Evib > ∆Erot > ∆Etrans

100- 104 kJmol-1

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

Requisite or requirements to be IR active

 All types of molecules are not IR active
 Molecules which exhibit a change in the dipole-moment
during vibration are only IR active

H-H O=O N N Not IR active (X)

CHCl3, CCl4, CO2, H2O, SO2 IR active (√)

 H H
H H µ1 = 0
H H
H H µ2 = 0
No dipole-moment change (µ1 = µ2)
IR inactive
O O
O O µ1 = 0
O O
O O µ2 = 0
No dipole-moment change (µ1 = µ2)
IR inactive

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

Bending (scissoring) Symmetric Stretching

Dipole-moment change (µ1 ≠ µ2 ) No dipole-moment change (µ1 = µ2)
IR active IR inactive

Find out yourself whether stretching/bending vibration is

IR active or inactive for these molecules
CH2Cl2, SO2, H2O, NH3, CH4

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

Inter-nuclear distance (r)

Harmonic : ∆V = ±1
Selection rule : Anharmonic : ∆V = ±1, ±2, ±3, ±4, ……………..

Selection Rule: A restriction in the transition between quantum states

of atoms, molecules
 IR spectra of diatomic molecules are simple: Due to only a bond between two atoms
 IR spectra of polyatomic molecules are complex : (Many bonds)
 In polyatomic molecule the bonds can vibrate in several ways, known as vibrational modes
 Each vibration is associated with an fundamental frequency

For Linear molecule : N= number of atoms

3N-5 = Number of vibrational modes or number of fundamental vibration
Linear CO2 HCN
No. of Vibration 4 4

For Non-Linear molecule : N= number of atoms

3N-6 = Number of vibrational modes or number of fundamental vibration
Nonlinear CH2Cl2 SO2 H2O CH4 NH3
No. of Vibration 9 3 3 9 6

Note: Actual number of observed bands for a molecule is generally different

Reason: Due to Overtone (v=0 to v=2) and Combination bands (Two or more fundamental
vibration are excited simultaneously)
Hence IR spectra is very complex
 Difficulties/Problem
 IR spectra of polyatomic molecule is quite complex
 Due to overtones and combination bands
 Not easy to assign mode for every vibration

Solution Group Frequency

To a certain extent, we can associate/relate some absorptions with

stretching or bending vibrations characteristic of particular
functional group in any molecule. Such frequencies are known as
Group Frequencies
 Functional Group & Fingerprint Region in IR

Stretching: Requires more energy Bending: Requires less energy

 Application of IR Spectroscopy
mixture compounds, pollution detection, milk analysis, forensic etc.

1. Establishing the identity of compound and structure elucidation

 Particular group absorbs at characteristic wavelength range, no matter to which
compound it belongs
2. For detecting impure sample
 Detecting impurities in sample
 Spectra of impure sample contains more peaks than pure sample

3. Provide valuable information of molecular symmetry,

dipole moment, bond length and bond strength
√=1/2∏(k/µ)1/2 s-1

Force constant k: Bond strength and bond length

4. Distinguish two types of H-bonding
On dilution inter H-bonding diminishes, but intra H-bonding remains intact

H
O O O
H
O N O
N
O O HO N
O

5. Distinguishing Positional Isomers

 Diagram of IR Spectrophotometer

Source: Nerst Glower (Rare earth oxide), SiC, Tungsten Filament

 UV-Vis Spectroscopy or Electronic Spectroscopy
J=3
J=2
V1 J=1
J=0
λ Range: 200nm-400nm (UV)
400nm-780nm (Vis)
J=3
V0 J=2
E2 J=1
J=0
Energy gap or change: 100-104 kJmol-1
J=3
J=2
V2 J=1
J=0
Transition J=3
J=2
V1 J=1
J=0 Acetone
J=3
J=2
V0 J=1
E1 J=0

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

UV spectra data are expressed in λmax and A or ε

 λmax :The wavelength at which maximum absorption occurs

 λmax is different for different compound

C
H
C
C
H
3
3

Benzene Acetone
λmax=255nm λmax=279nm

 ε (Molar extinction coefficient): The extent of absorption for a given concentration of

compound at any given wavelength

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

Examples having σ , ∏ , n electrons Etc.

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

λmax=443, 471, 502nm

 Hyperchromic Shift

N N C
H
3
ε = 2750 ε = 3560

λmax=255nm
N H 3 N H 2 O H N H 2

265nm 280nm 270nm 280nm

Hypsochromic Bathochromic
Blue Shift Red Shift

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)

 Structure elucidation of organic compounds-presence or absence of unsaturation,

presence of hetero atoms and Similar structure-Similar spectra

 Quantitative analysis-By Beer-Lambert’s Law

 Qualitative analysis-identification is done by comparing with known sample,

especially aromatic compounds and aromatic olefins

 Dissociation constant of acids and bases

 Chemical Kinetics-rate of reaction

 Qualitative analysis of pharmaceutical substances (e.g. vitamins)

 Dissociation energy determination from the absorbed wavelength(λ)

 Molecular weight determination

Diagram of UV Spectrophotometer

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.

2. Stark-Einstein Law (Einstein’s law of photochemical equivalence) It states that,

 In the primary process, each reacting molecule is activated by
one quantum of effective light
 1: 1 relationship = Number of reacting molecule: Number of quanta absorbed
One Einstein is the energy of one mole of photon E = Nh√=Nhc/λ
N=Avogadro’s Number h=Plank’s constant
3. Lambert’s Law

“Equal fractions of incident radiation are absorbed by successive layers of equal

thickness of absorbing substance.”

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 ∝ dl or -dI/I = k dl or dI/I = -k dl

Where, k=proportionality constant
 On integration we get

∫ 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

⇒ I0/I = exp(-kl) or I = I0 exp (-kl)

* Beer - Lambert’s Law or Beer’s Law It states that,

“Equal fractions of incident radiation are absorbed by successive layers of

solution with equal concentration and equal thickness of absorbing substance.”

So, -dI/I ∝ C dl or dI/I = -k C dl

C = concentration of solution
 On integration we get,

∫ dI/I = -k C ∫ dl Limitations of Beer-Lambert’s Law

 Only valid for monochromatic radiation
⇒ ln I = -k C l + Const  Not valid if Temperature changes during
measurement
When l = 0 I = I0 So, Const = ln I0  Only applicable to dilute solutions (<0.01M)
Then, ln I = -k C l + ln I0 High concentration(refractive index alters)

⇒ ln I/I0 = -k C l

⇒ ln I0/I = k C l or log I0/I = (k/2.303) C l

log I0/I = (k/2.303) C l = ε C l

Absorbance, A= ε C l

ε = k/2.303
ε = Molar extinction Co-efficient