2 Spectroscopic Techniques

and Applications

UNIT SPECIFIC

RATIONALE

PRE-REQUISITES

LEARNING OUTCOMES

MAPPING OF UNIT WISE LEARNING OUTCOMES WITH THE COURSE OUTCOMES

EXPECTED MAPPING WITH COURSE OUTCOMES
Outcome (1- Weak Correlation; 2- Medium correlation; 3- Strong Correlation)
CO-1 CO-2 CO-3 CO-4 CO-5
U2-O1 3
U2-O2 3
36 | Chemistry - I

EXPECTED MAPPING WITH COURSE OUTCOMES

Outcome (1- Weak Correlation; 2- Medium correlation; 3- Strong Correlation)
CO-1 CO-2 CO-3 CO-4 CO-5
U2-O3 2 1
U2-O4 3
U2-O5 2

INTRODUCTION

Fig. 2.1: Region of Electromagnetic radiations

HISTORICAL TIME LINES

S. No. Period Name Discovery
1. 1814 Joseph von Fraunhofer. first spectroscope was invented
Robert Bunsen and The systematic attribution of spectra to chemical
2 1860
Gustav Kirchhoff elements began
Otto Heimstaedt and First fluorescence microscopes as an outgrowth
3. 1911-1913
Heinrich Lehmann of the UV microscope
4 1941 Arnold Beckman Introduced DU UV-vis spectrophotometer.
Discovery of NMR and got Nobel Prize in
5. 1944 Isidor Isaac Rabi
Physics
 Spectroscopic Techniques and Applications | 37
2.1 BASIC PRINCIPLES OF SPECTROSCOPY

2.1.1 Born Oppenheimer Approximation

Table 2.1 Energy in diatomic molecules

S. Type of energy Arises in molecule Electromagnetic
No. spectrum.
1. Translational When its center of gravity changes as a –
energy consequence of motion
2. Rotational energy When a molecule undergoes rotation about Microwave region
an axis perpendicular to the inter nuclear
axis and passing through the center of
gravity of the molecule.
3. Vibrational energy Because of to and fromotion of the nuclei Infrared region
of the molecule in such a way that center of
gravity does not change
4. Electronic energy Associated with the transition of an electron UV and visible region
from the ground state energy level to an
excited state energy level of the molecule
because of the absorption of a photon of a
suitable frequency.

2.1.2 Franck–Condon principle

38 | Chemistry - I

2.1.3 Jablonski Diagram: Relaxation Mechanism for Excited State

Molecules

Fig. 2.2: Jablonski diagram

Flow Chart. 2.1: Tabular information of modes of decay of electromagnetic radiations

 Spectroscopic Techniques and Applications | 39

2.2 ELECTRONIC SPECTROSCOPY

Fig. 2.3: Transition of spectrum in various energy levels

E R < EV < EE
40 | Chemistry - I

2.2.1 Types of Electronic Transitions

* * * *
*

Fig. 2.4: Electronic energy levels and Electronic

Transitions

* *
*

2.2.2 Applications of Electronic Spectroscopy

 Spectroscopic Techniques and Applications | 41

1. Extent of conjugation is
more in anthracene as
compare to Naphthalene
Benzene Naphthalene Anthracene and benzene.
Structures of Benzene, Naphthalene and, 2. The molar absorption
coefficient is a
Anthracene
measurement of how
3.0 strongly a substance
absorbs light. The larger
its value, the greater the
2.0 absorption.
Benzene
Naptalene 3. The peak wavelengths
Na

Anthracene tend to be shifted toward

1.0 the long wavelength
region as the conjugated
system gets larger.
0.0 4. max shifted from 256nm
200.0 300.0 400.0 500.0 600.0 700.0
nm benzene to 375 nm in
anthracene
Fig. 2.5: Absorption Spectra of
Benzene,Naphthalene and Anthracene
42 | Chemistry - I

2.2.3 Selection Rules For Electronic Transition

2.3 FLUORESCENCE SPECTROSCOPY

2.3.1 Principle

2.3.2 Applications
 Spectroscopic Techniques and Applications | 43

CH2 CH
H

N H
N HO N

O O CH3O H

N
POPOP Quinine
HO O O

CH3N N NCH3
CO2H
CH3 CH3

Fluorescein Acridine Orange

+
(C2H5)2 N O N(C2H5)2

+
N (CH CH)2 N(CH3)2
CO2H
C2H5 ClO4–

Rhodamine B Pyridine 1

POPOP Quinine Fluprescein Acridine Rhodamine B Pyridine 1

Sulphate Orange

Fig. 2.6 : Fluorescence spectrum of organic molecules

44 | Chemistry - I

Interesting Facts

2.4 ROTATIONAL AND VIBRATIONAL SPECTROSCOPY

2.4.1 Energy of Rotational Transitions

E = 6B

B E = 4B

E = 2B

Fig. 2.7: Rotational Energy

Levels
 Spectroscopic Techniques and Applications | 45

2.4.2 Selection Rule for A Rotational Transition is,

2.4.3 Vibrational Transitions (Infrared Spectroscopy)

2.4.4 Principle of Infra Red Spectroscopy

Wavelength ( m)
2.5 3 4 5 6 7 8 9 10 11 12 13 14 15 16

C N
Stretching
O–H, N–H –H C C vibrations
–H
C–H C O

– (C–C, C–O, C–N)

C, N, O

+– +–
vibrations
Bending

5000 4000 3600 3400 3200 3000 2800 2600 2400 2200 2000 1900 1800 1700 1600 1500 1400 1300 1200 1150 1100 1050 1000 950 900 850 800 750 700 650
Frequency (cm–1)
Group frequency region Fingerprint region

Fig. 2.8: Functional Group region and Finger print region in IR spectra
46 | Chemistry - I

2.4.5 SELECTION RULE FOR VIBRATIONAL TRANSITION

2.4.6 Applications of IR Spectroscopy

 Spectroscopic Techniques and Applications | 47

4000 cm–1 3000 cm–1 2000 cm–1 1500 cm–1 1000 cm–1 500 cm–1

Fig. 2.9: Finger print region in IR spectrum

100

50

H H
1102
C–H stretch
H O C C H
3391
2961 C–O 1055
O–H stretch ethanol H H stretches
0
4000 3000 2000 1500 1000 500

Fig. 2.10: IR spectrum of Ethanol

48 | Chemistry - I

2.5 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY (NMR)

2.5.1 Rules for determining net spin (I) of a nucleus

2.5.2 Theory of NMR Spectroscopy

2.5.3 Chemical Shift

 Spectroscopic Techniques and Applications | 49

2.5.4 Application of NMR Spectroscopy

50 | Chemistry - I

1H NMR Spectrum of ethanol

3
CH3
quartet
triplet
1 2

CH2 singlet
OH
TMS

9 8 7 6 5 4 3 2 1 0 6 4 2 / ppm

Fig. 2.11 : 1H NMR Spectrum of ethanol

image adapted from https://sdbs.db.aist.go.jp Theoretical splitting

1.53 a
H-1 NMR spectrum of butan-1-ol assuming OH proton 0.94
(2)
CH3 – CH2 – CH2 – CH2 – O – H has no splitting effect (3)
d (2) quintet
and is not split itself triplet
a b c e 3.63 plus
d
0.94 1.39 1.53 2.24 1H proton shift ppm triplet e sextet
3.63
(3) (2) (2) (1) (proton ration) 2.24 1.39
(2)
(1) (2)
singlet c
low resolution spectrum T
(2) (2) (2) (3) M
(1) b S
Intensity

4.0 3.0 2.0 1.0 9.0

H-1 NMR chemical shift ppm

11 10 9 8 7 6 5 4 3 2 1 0

Fig. 2.12 : NMR spectrum of butan-1-ol

 Spectroscopic Techniques and Applications | 51

image adapted from https://sdbs.db.aist.go.jp H-1 NMR spectrum of butanone a (3)

(National Institute of Advanced CH3 – C – CH2 – CH3
Industrial Science and Technology)
(proton ratio) O
Intensity

a b c 1:2:1 triplet
1H proton shift ppm 2.14 2.45 1.06 (3) c CH2
splits
CH3
low
(2) (3) (3) resolution T
spectrum 1:3:3:1 quartet
M
CH3 (2) b
S
3.0 ppm 0.0 splits
2.0 1.0
CH2

H-1 NMR chemical shift ppm

11 10 9 8 7 6 5 4 3 2 1 0

Fig. 2.13 : NMR spectrum of butanone

52 | Chemistry - I

2.6 MAGNETIC RESONANCE IMAGING (MRI)

 Spectroscopic Techniques and Applications | 53

Fig 2.14 : MRI Image of Brain Fig. 2. 15: MRI Image of Cardiac Fig. 2. 16: MRI Image of
Abdomen

2.6.1 Applications of MRI

2.7 X- RAY DIFFRACTION (XRD ANALYSIS)

2.7.1 Principles of X-Ray Powder Diffraction (XRD)

54 | Chemistry - I

2.7.2 APPLICATIONS

* Sugar Ag nanocomposites
(111)

Ag nanocrystals
Intensity (a.u.)

(200)

(311)
(200)

* **
*
30 45 60 75
2 (degree)

Fig. 2.17: Silver nanocomposites and silver

nanocrystals through X-ray diffraction pattern
 Spectroscopic Techniques and Applications | 55
SUMMARY