Module 2

Regions of Electromagnetic Radiation

)
Frequency (

Wavelength ()
(

Radio-waves Microwaves Infra-red Visible Ultra-violet X-ray Region -ray

Region Region Region Region Region
(HZ) 106 - 1010 1010 - 1012 1012 - 1014 1014 - 1015 1015 - 1016 1016 - 1018 1018-

h 10m – 1 cm 1 cm – 100µm 100µm – 1µm 700 – 400 nm 400-10 nm 10nm – 100p

100pm 1 pm
NMR, ESR Rotational Vibrational Electronic Electronic
Spectroscopy spectroscopy Spectroscopy Spec.

0.001 – 10 J/mole Order of some 100 Some 104 J/mole Some 100 Some 100s 107- 109 109- 1
J/mole kJ/mole kJ/mole J/mole J/mol

UHF TV, cellular, telephones. Table lamp,

(300 MHz and 3 GHz) Tube light (400 nm -800
nm or 400–790 THz)

dio, VHF TV. Microwave ovens, Sun Lamp X-ray

dio Police radar, satellite stations-- (3 to
30 GHz)
Electromagnetic Radiation
Electromagnetic Wave
 E2 Higher Energy State E2
hϒ hϒ

E1 Lower Energy State E1

Absorption Spectrum Emission Spectrum

ar energy levels:

ic energy (E): It is associated with the electrons present in a molecule, which can occupy
ar energy levels. The molecular orbitals can be bonding or antibonding. The energy gaps b
ic energy levels falls in UV-visible region.

nal energy(Eyib): Atoms in a molecule can vibrate by keeping the position of center
, the energy associated is called vibrational energy.
energy For example HCl molecule can under
ng vibration. The energy gaps between vibrational energy levels falls in the Infrared region

nal energy (Erot): If a molecule rotate in space about an axis passing through its centre of
o possess rotational energy. Rotational energy is possessed only by molecules of a gas or
rgy gaps between rotational energy levels falls in the microwave region.

ional energy(Etrans): If the position of centre of mass changes with time the molecule i
the translational energy. Translational energy of a molecule is usually not quantised.
his is the law which governs the absorption of light by a molecule.

he law states that “When a beam of monochromatic radiation is pas

hrough an absorbing solution of given concentration (c), the rate

decrease in intensity (-dI) of radiation with thickness of the solution

s proportional to the intensity of incident radiation (I) and also to

oncentration (c) of the solution.”

mbert’s Law

beam of monochromatic electromagnetic radiation is passed through an absorbing sol

ncentration (c), the rate of decrease in intensity (-dI) of radiation with thickness of the
roportional to the intensity of incident radiation (I) at that point and also to the concentra
olution

n of Beer Lambert’s law

 Limitations of Beer-Lambert’s
Lambert’s Law

This law is not valid, if the radiation used is not monochromatic

Law is valid only for dilute solutions, not applicable to highly concentrated
solutions (linear relationship exist only in the case of dilute solutions.)

Absorbance of Turbid solutions cannot be measured

Not valid where fluorescence or phosphorescence in the sample is present

ciple

e range of UV-Vis radiation is 200-800

800 nm. (UV region is 200-400
200 nm an
gion is 400-800 nm.)

V-Vis
Vis spectroscopy corresponds to the transition of valence electrons fr
nding molecular orbtital (BMO) to anti-bonding
anti molecular orbital (ABM

e most probable transition is from HOMO (Hihgest occupied MO) to LU

east unoccupied MO)
Presentation of the λ max
spectrum
 Feasible transitions in UV-Visible
UV Spectroscopy

possible electronic transitions are;

 Therefore, the order for the energy required for various transitions is
σ → σ* > n → σ* > π → π* > n → π*

1.

e saturated hydrocarbons can give only σ - σ* transitions of C-C σ bond and C-H σ
is type of transition occurs below 150nm..
ey involve very high energy. Eg: Methane shows λmax at 125 nm.

max of saturated hydrocarbons (corresponds to σ - σ*) cannot be detected usin

sible spectrometer. Because, the ordinary UV machines take spectra from 200-700
 Why Absorption maximum of methane is not observed in UV-Vis
UV spectroscop

• Methane is a saturated hydrocarbon and σ - σ* transition occurs below 150nm.

• λmax of saturated hydrocarbons cannot be detected using UV-Visible
UV spectrometer. Becau
the ordinary UV machines take spectra from 200-700
200 nm.

.
he unsaturated hydrocarbons containing double or triple bonds shows this type of transi

π → π* transitions need lower energy than σ → σ* and n → σ* transition.

or example, C=C of ethylene molecule gives an absorption maxima at 169 nm and that
onjugated double bond of butadiene gives λmax at 217 nm.
.
aturated compounds containing non bonding electrons (lone
( pair of electrons
hows these types of transition. [O, N, S, X (halogen) contain ‘n’ electrons]
n → σ* transitions need lower energy than σ → σ*.
 Occur in low intensity.

Example, CH3-OH (methanol), CH3-CH2-Cl

Cl (ethyl chloride)

4.

Unsaturated compounds containing non bonding electrons (lone

( pair of electro
hows these types of transition.
Usually occurred in aldehydes and ketones.
hese transitions are generally observed with low intensity when compared w
σ→σ* and π→ π* transitions
 Applications of UV
Extent of Conjugation : The extent of conjugation can be estimated by UV spectroscopy.
As the extent of conjugation increases, absorption maximum (λ
( max ) of the compound will
shifts to a longer wavelength region.
Eg: I. Eg: II.

Comparing, a, b, c and d, the extent of conjugation increases as a< b <c < d. As the extent of
conjugation increases, absorption maximum (λmax ) of the compound will shifts to a longer
wavelength region. d shows the highest λmax
 Applications of UV
Detection of Impurities : Additional peaks can be observed due to impurities in the
mple

V-Vis spectroscopy can be used to detect benzene as a common impurity in cyclohex

nzene has a characteristic UV absorption peak due to its conjugated π-electron system. Speci

nzene absorbs strongly at wavelengths around 254 nm, corresponding to its π → π* elec

nsitions. Cyclohexane, being a saturated hydrocarbon, lacks conjugated π systems and does not

nificant absorption in the same UV region. Hence, the absorption spectrum of benzene stands out

en present as an impurity in cyclohexane.

 Applications of UV

3. Quantitative Analysis

4. Qualitative Analysis

5. Kinetics of Reactions

6. Environmental Monitoring

7. Food and Beverage Industry

8. Material Science

9. Biological Applications
 IR spectroscopy Involves
transition between vibratio
energy levels of a molecule,
absorbing IR radiation.
(IR Spectroscopy)

• IR Region, 400-4000 cm-1

R Region, 400-4000 cm-1 is between visible and microwave region of the
ectromagnetic spectrum
Who are IR active?
Selection Rule for IR activity
y those molecules which have a dipole moment change,
change during vibrat
IR ACTIVE or vibrationally active.

Homonuclear diatomic molecules (O2, N2, H2, Cl2) – IR Inactive. Because, they ha
no dipole moment.
Heteronuclear diatomic molecules (HF, HCl) – IR Active. Because, they possess
dipole moment change during vibration.
(Refer examples on note book)
IR SPECTRUM
ow many fundamental vibrations are possible

For ‘N’ atoms in a molecule,

Total degrees of freedom = 3N

Vibrational degrees of freedom for a linear molecule = 3N

3N--5

Vibrational degrees of freedom for a non-linear

non molecule = 3N
3N--6

? Calculate the number of vibrational modes of (a) H2O (b) HF (c) CO2 (d) CH4

(For examples, refer note book)

 Applications of Infrared spectroscopy

1. Determination of force constant of a diatomic molecule

2. Identification of functional groups in a molecule.

For example IR range of >C=0 group in ketones is 1700-1725 cm-l
-OH group in alcohol is at 3300-3500 cm-l

3. Identification of unknown compounds

compounds.. (This is generally done by comparison of
spectrum of an unknown compound with that of a known compound
compound..)

4. Determination of purity
 The Indian scientist C. V. Raman won Nobel prize for physics in this work.

rinciple
 Raman Spectroscopy is based on scattering of light.
light

 When the sample is irradiated with a coherent source of light (typically a

laser), the light get scattered.

 Most of the light undergoes elastic scattering and a small portion undergoes
inelastic scattering.
When the molecule, excited from v=0 (ground vibrational state) to higher unsta
brational state, returns to the original vibrational state (v=0), we get Rayle
attering

When the molecule, excited from v=0 (ground vibrational state) to higher unstable
brational state, returns to the first excited vibrational state (v=1), we get Stokes
nes.

When the molecule, initially in the first excited vibrational state (v=1), is promoted
gher unstable vibrational state and returns to ground vibrational state v=0, we g
nti-Stokes lines.
he Rayleigh line is far more intense than the stoke lines which, have greater intensity than the an
okes line.
nti-Stokes
Stokes lines are difficult to observe since there are very few molecules in the first excited
brational state.

Mutual Exclusion Principle

r centrosymmetric molecules (molecules that possess a center of symmetry), the vib

hich is active in IR is inactive in Raman and the vibration which is inactive in IR is act
aman spectra.

Eg; Vibrations of homonuclear diatomic molecules (such as H2, O2, N2, X2 (halogens like Cl2)
which are inactive in IR are observed in Raman spectra.
C2H4 , CS2 are other good examples of centre of symmetric molecules.
Applications of Raman Spectroscopy
 NMR (Nuclear Magnetic Resonance) spectroscopy is based on
absorption of radiowaves of frequency 60-500 mHz, by the nucleus o
atom.

Absorption of radiofrequency induce transitions from lower energy s

state to higher energy spin state of an atom, when they placed in
external magnetic field.
election Rule
NMR active , Spin Quantum No; I ≠ 0 ( I

NMR Inactive, Spin Quantum No. I=0

Atomic Mass Value of I NMR activity Examples

no. no.
Odd Odd I>0 NMR active 1H1
(half integer value 1/2,
3/2….)

Even Odd I>0 NMR active 6C 13

(half integer value 1/2,
3/2….)
Odd Even I>0 NMR active 1H2
(integer value 1,2,3….)

Even Even I=0 NMR Inactive 2He 4

inciple
ubatomic particles (electrons, protons and neutrons) spin on its own axis
ll produce a magnetic field.
ccording to quantum mechanics, a nucleus of spin ‘I’ will have (
entations.
or protons, spin I = ½ will have (2 x ½ + 1) = 2 orientations. They are - ½ a

the absence of an external magnetic field, these orientations are of

ergy.
a magnetic field is applied, then the energy levels splits and + ½ aligned
wer energy.
β spin state

α spin state
e energy difference (ΔE) between the magnetic energy levels is almost equal t
ergy of the radio waves.

hen proton nuclei absorb energy from the radio frequency region, the lower energ
te (α spin state) will get excited to the higher energy state (β spin state). This is fli
Resonance of spin state.

hen the radio frequency is removed, the nuclei will come back to the lower energy
spin state) by releasing energy.

is absorption of released energy is recorded as a spectrum, which will give inform

out nuclei of an atom.
No. of nmr signals = No. of equivalent protons

(Refer note book and practice examples)

 Applications of NMR Spectroscopy
MRI (Magnetic Resonance Imaging)

RI is a medical imaging technique to visualize

ernal structures of body base on the principle of
MR.
RI machine use a strong superconducting
agnetic field (1-3 Tesla) around the patient.
RI make use the fact that body tissue contain a
s of water, and hence protons (1H1 nuclei) are
udied.
hen the person is inside a powerful magnetic field, average magnetic moment of proton
comes aligned with the direction of the field.
When radiowaves producing resonance frequency is given, which flip the proton sp
om lower energy state to higher.
When radiowaves are cut off, spin of protons returned, called relaxation.
uring relaxation, a radiowave signal is generated from the human body, w
measured, recorded and converted to 3-D image of internal body parts.
he relaxation time for different tissues ( for diseased and normal tissues ) are diffe
ication of MRI
Determine brain, central nervous system and liver disorders.
Determine major forms of cancer including breast cancer
Generates the pictures of arteries
Measures signal changes in the brain
Determine gastro-intestinal, pancreas and kidney disorders.
Applications of NMR Spectroscopy

1. Identification of structural isomers

2. MRI Scanning

3. Identification of cis –trans

trans isomers.

4. Detection of H-bonding
bonding

5. Quantitative Analysis