DR. K.S.

DUBEY
HEAD OF CHEMISTRY DEPT.

GUIDANCE BY SUBMITTED BY
DR. ARUN AKANSHA SHARMA
KAKKAR [Link]. IIIrd SEM.
ROLL NO. :-01
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 OUTLINES
 Spectroscopy
 Introduction of NMR
 Importance of NMR
 Applications of NMR
 Requirements of NMR
 Types of NMR
 Principle of NMR
 Theory of NMR

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Instrumentation
Reference standard
Solvent use
Chemical shift

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Spectroscopy is the branch of science that
deals with the interaction of EMR with
matter except MS.

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INTRODUCTION

NMR is s spectroscopy which is based on

the absorption of in the RF reason 4 to
900 MHz by nuclei of the atoms

Proton nuclear magnetic resonance

spectroscopy is one the most powerful tool
for explaining the number of hydrogen or
proton in the compound.
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It is used to study a wide
variety of nuclei.
•H
1

• F
19

• P
31

• N
15

• C
13
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 BASIC THEORY OF NMR

A moving
perpendicular An electric current
external magnetic in a closed loop will
field will induce an create a
electric current in a perpendicular
closed loop magnetic field

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 THEORY OF NMR
 The NMR is mostly consult with
nucleus spin quantum no. (I)= ½ .
The proton having a I = ½ when A Spinning Gyroscope
place in EMF. (Ho) it’s start to spin in a Gravity Field

around the nuclear axis and

generate a another m.f..
According to quantum mechanics
there are( 2I + 1) so two spin stage +
½ and - ½ for the proton.

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When a charge particle place in magnetic
field. It’s start to revel and therefore it’s pusses
angular movement due to generation of
another magnetic field.
 The charge particle with nucleus spin has
magnitude and direction. Both this property is
describe by the factor called as magnetic
movement (µ).
 when the proton take place in magnetic field
. It has two spin steps + ½ and - ½ so, there
are two energy level for spin steps + ½ & -½.

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If the sum of protons and neutrons is even, I is zero
or integral (0,1,2,3 …..).

If the sum of proton and neutrons is odd, I is a half

integral (1/2, 3/2, 5/2….).

If the both protons and neutrons are even

numbered, I is zero.

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 EFFECT OF MAGNETIC FIELD
= g h / 4p

Bo

In the absence of external field, Add a strong external field (Bo) and the nuclear
each nuclei is energetically degenerate magnetic moment: aligns with (low energy)
against (high-energy)

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Magnetic properties of nuclei
 The net spin associated with the proton and
neutron.
 The distribution of positive charge.
 Nuclei are made of proton and neutron both have
spin value of ½ proton give charge.

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Energy Levels of proton
Transition from the low energy to high energy spin state occurs through an
absorption of a photon of radio-frequency (RF) energy

RF

Frequency of absorption: n = g Bo / 2p

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Spins Orientation in a Magnetic Field
(Energy Levels)
• Magnetic moments are oriented in one of two directions in magnetic
field (for I =1/2)

• Difference in energy between the two states is given by

DE = g h Bo / 2p:

where:
Bo – external magnetic field
h – Planck’s constant
g – gyromagnetic ratio
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Requirements of NMR
 Compound must be having proton.
 Spin associated with proton and neutron.
 Nuclei is generated magnetic dipole.
 Magnetic moment generated by nuclei.

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NMR Instrumentation diagram

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SAMPLE USE IN NMR
 Both liquid and solid type of samples can be used in NMR
spectroscopy.

 For liquid sample, conventional solution-state NMR

spectroscopy is used for analysing where as for solid type
sample, solid-state spectroscopy NMR is used.

 In solid-phase media, samples like crystals, microcrystalline

powders, gels, anisotropic solutions, proteins, protein fibrils or
all kinds of polymers etc.

 In liquid phase, different types of liquid solutions, nucleic

acid, protein, carbohydrates etc. 18
Reference standard IN NMR
 The sample is dissolved in a solvent, usually CDCl3
(deutero-chloroform), and placed in a M.F.
 A RF generator then irradiates the sample with a
short pulse of radiation, causing resonance.
 When the nuclei fall back to their lower energy
state, the detector measures the energy released
and a spectrum is recorded.
Types of Ref. strd

internal External
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CHARACTERISTICS:
 Chemical inertness
 Magnetically neutral
 Gives single sharp peak
 Easily recognizable peak
 Miscible with wide range of solvents
 Volatility –to facilitate recovery from valuable samples

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1 TMS(Tetra Methyl Silan)
 TMS at 0.5% con. is used normally
 It is chemically inert and miscible with large range of
solvents
 Highly volatile and easily removed to get back the
sample

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2 . Sodium salts of 3(tri
methylsilyl)propane
 It is a water soluble compound.
 It is used as internal standard for running PMR
spectra of water soluble subs. in the deuterium oxide
solvent.

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PROPERTIES OF
SOLVENT
 chemically inert
 inexpensive
 it should contain no proton
 magnetically isotopic
 Highly volatile
 low boiling point

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commonly solvent use
CCl4
CdCl3
DMSO
CS2

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SHIELDING
 Shielding of protons – High electron density
around a nucleus shields the nucleus from external
magnetic field and signals are upfiled in NMR
spectrum .

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DESHIELDING
 Deshielding of protons – Lower electron
density around a nucleus deshield the nucleus from
the external magnetic field and the signals are
downfield in the NMR spectrum.
.

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Chemical Shift
 The chemical shift of a nucleus is the difference
b/w the resonance frequency of the nucleus and a
standard, relative to the standard.
 This quantity is reported in ppm and given the
symbol delta, d.
 Chemical shift is measure in three major spectra.

1Delta(δ) 2Tau scale(τ) 3 Hertz (Hz)

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FACTORS INFLUENCING
CHEMICAL SHIFT

 Electronegativity Effects
 Van der Waal’s Deshielding
 Hydrogen Bonding
 Magnetic anisotropy
 Concentration
 Temperature
 Solvent Effect

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 HYDROGEN BONDING

H atom exhibit property of H bonding in a

compound which absorbs at a low field in
comparison to the one which does not shows
H bonding.
H bonded proton being attached to a highly
electronegative atom will have smaller
electron density around it less shielded .

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IMPORTANTANCE OF NMR
 NMR is the use to study physical , chemical,
biological properties of matter.
 NMR finds applications in several areas of
science.
 To study chemical structure using simple one-
dimensional techniques.
Two-dimensional techniques are used stru. Of
more complicated molecules

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 How to identify structure of molecules

1. Number of signals: How many different types of H

present in the molecule.
2. Position of signals (chemical shift): Which types of
protons are present.
3. Relative areas under signals (integration): How many
H of each type.
4. Splitting pattern: How many neighboring H.

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[Link] of signals: How many
different types of hydrogen in the
molecule.

• Magnetically equivalent H resonate at the

same applied field.

• Magnetically equivalent H are also chemically

equivalent.

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 number of signals
H3C CH3
C
C
H3C CH3
one
one

CH3

CH3
one
two 35
36
2. Position of signals (chemical shift):
which types of protons are present
Ranges of different functional groups

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[Link] (relative areas under each
signal): how many protons of each types.

a b c
CH3CH2CH2Br a 3H [Link]=[Link]
b 2H
c 2H

a b a
CH3CHCH3 a 6H a:b=6:1
Cl b 1H

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integration
H3C CH3
C
a C a
H3C CH3

a 12 H a 12 H

CH3 a

a b

CH3
a 6H a
a 6H
b 4H
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 c b a

Integration: measure the height of each “step” in the integration and

then calculate the lowest whole number ratio: [Link] = 24 mm : 16 mm
: 32 mm = 1.5 : 1.0 : 2.0  3H : 2H : 4H

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4. Splitting pattern: how many neighboring
hydrogen
In general, n-equivalent neighboring hydrogen will split a 1H
signal into an ( n + 1 ) Pascal pattern.

“neighboring” – no more than three bonds away

n n+1 Pascal pattern:
0 1 1 singlet
1 2 1 1 doublet
2 3 1 2 1 triplet
3 4 1 3 3 1 quartet
4 5 1 4 6 4 1 quintet
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1,2-Tribromoethane
Nonequivalent protons on adjacent carbons.

=>

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 isopropyl chloride

a b a

a doublet 6H
b septet 1H

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2-bromobutane
b d c a
CH3CHCH2CH3
Br

a triplet 3H
b doublet 3H
c complex 2H
d complex 1H

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1-BROMOPROPANE

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 of NMR

 Structure determination – A large

number of principles are known
which will decide about the structure
of unknown compound from its PMR
spectrum.

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 DETECTION OF AROMATICITY
 protons attached to benzyl , heterocyclic or
polynuclear compounds ( whose follow Huckel
rule) are extremely deshielded due to the
circulating sextet of π electrons.

 Thus the signal for the aromatic protons appear

at a very low field than that observed even for
benzene.

 Compound. Chemical shift (δ)

 Benzene 7.37
 Cyclohexane. 5.57
 Toluene. 2.32
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 Hydrogen Bonding – The amount of deshielding is
proportional to the strength of the hydrogen bond.
The shifts arises associated with hydrogen bonding
arises from three terms.

1. The electrostatic effect of donor atom ( dominant of strong

H – bond)

2. Dimagneric anisotropy of the donor atom

( dominant in weak H- bond)

3. Change in long range shielding of the acceptor group (

operating in intermolecular H- bond)

Compound ROH RSH RCOOH RCONH2

δ (ppm) 0.5-4.5 1-2 9-13 5-13

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Determination of Rate – The rate constant for
the exchange of proton affects the resolution
of proton signals as follows

Position of proton during reaction

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 Structural (three-dimensional) studies
 Proteins, Protein-ligand complexes
 DNA, RNA, Protein/DNA complexes
 Polysaccharides
 Metabolomics
 Drug Design
Structure Activity Relationships by NMR
 Medicine -MRI

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MRI images of the Human Brain
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Detection of electronegative group.
Qualitative analysis(detection of
functional group).
Quantitative analysis.
 Determination of molecular weight.
Detection of seeds in agriculture.
 Identification of structural isomers.
Distinguish b/w cis and trans isomers.

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