Proton Nuclear Magnetic

Resonance – H1 NMR

Presented by: Amey Deshpande

Chapter 13
 Overview
1. Introduction
2. Relaxation process
3. NMR signals
4. Number of signals
5. Positions of signals (Chemical Shift)
6. Factors affecting chemical shift
7. Solvents used
8. Peak area and proton counting
9. Splitting of signals/ spin-spin coupling
10. Coupling constant – “J”
11. Important tips for Interpreting an NMR Spectra
12. Applications of NMR
13. Limitations of NMR
14. Conclusion
Chapter 13
1. Introduction

Nucleus is Resonance – two

involved Magnetic fields oscillating things
are involved (EM wave +
precessing
protons)

Chapter 13
1. Introduction
• A nucleus with an odd atomic number or
an odd mass number has a nuclear spin
• The spinning charged nucleus generates
a magnetic field

Chapter 13
1. Introduction
• Precessional Motion  spinning axis revolves
around vertical axis
• Precessional Frequency (ν) number of
revolutions

Chapter 13
 1. Introduction
• Little Physics!
Where, ω= angular Precessional velocity
ω = γH0 1
γ  gyro-magnetic ratio/ Nuclear const.
2πμ
And γ= H0 applied magnetic field (Gauss)
hI 2 μ magnetic moment of spinning
bar magnet
But γH0= 2πv 3
h Plank’s constant
Hence, from 1,2 & 3 I spin quantum number
angular Precessional v  EM radiation frequency
velocity, ω = 2πv
Chapter 13
1. Introduction- A proton in magnetic field
Excited
Excitedstate
state= =
High energy
High
energy
N
N N
N SS S
S

Add
Add Energy
Energy
Energy Released

N
N S
S N
N S
S N S N S

Aligned
Aligned= =
Low Energy
Low Back to low energy ground state
Energy
• When the spin falls back into line with the magnetic field it
releases energy. We detect this energy and it provides
information on:

• The environment of the hydrogen in the molecule

• How many hydrogen atoms are 13

Chapter in that environment.
 1. Introduction
• Precessional Frequency – some more Physics!!

γH0 For a proton, γ= 26750

v=
2π
When H0=14092 Gauss, energy required to cause flipping
is calculated as…..
26750 X 14092
v= =60,025,636 ≈60 million cycles per sec
2 X 3.14 = 60 MHz
= RADIO FREQUENCY!!
Chapter 13
 1. Introduction- NMR spectrum

• Different sets of proton  different precessional frequency

 absorb at different radio frequencies
• Practically, It is convenient to keep radiofrequency constant
& vary magnetic field strength

Chapter 13
 2. Relaxation process
(non-radiational transitions)
Spin-spin relaxation Spin-Lattice Relaxation
(Longitudinal relaxation)
• Mutual exchange of • transfer of energy from the
spin nucleus in its higher energy
• Transfer of energy state to the molecular lattice
• energy is transferred as
from one nucleus to vibrational, transitional &
other rotational
• No loss of energy •Less effective in solids
• causes broadening
• COUSES LINE •KEEPS EXCESS OF NUCLEI
BROADENING (solids) IN THE LOWER ENERGY
STATE
Chapter 13
3. NMR signals
• The number of signals shows how
many different kinds of protons are
present.
• Magnetically equivalent protons are
also chemically equivalent protons

Chapter 13
4.No of signals
Equivalent H’s
• Two H’s that are in identical environments
(homotopic) have the same NMR signal
• Test by replacing each with X
 if they give the identical result, they are equivalent
 Protons are considered homotopic

Chapter 13
4.No of signals
Nonequivalent H’s
• Replacement of each H with “X” gives a
different constitutional isomer
• Then the H’s are in constitutionally
heterotopic environments and will have
different chemical shifts – they are
nonequivalent under all circumstances

Chapter 13
4.No of signals
Enantiotopic Distinctions
• If H’s are in environments that are mirror images of
each other, they are enantiotopic
• Replacement of each H with X produces a set of
enantiomers
• The H’s have the same NMR signal (in the absence
of chiral materials)

Chapter 13
5. Position of Signals (Chemical Shift)
Magnetic Shielding
• If all protons absorbed the same amount of
energy in a given magnetic field, not much
information could be obtained
• But protons are surrounded by electrons
that shield them from the external field
• Circulating electrons create an induced
magnetic field that opposes the external
magnetic field
Effective magnetic field

Chapter 13
5. Position of Signals (Chemical Shift)
Shielded Protons
• Magnetic field strength must be increased for a
shielded proton to flip at the same frequency
• Differences detected by machine, cause
differences in signals (chemical shift, δ )

Chapter 13
5. Position of Signals (Chemical Shift)
Scale of NMR Spectra : “Tetramethyl silane” as Reference

τ=10 - δ
δ τ

Chapter 13
5. Position of Signals (Chemical Shift)
“Tetramethyl silane” as Reference
• miscible with almost all organic substances

• highly volatile – readily removed from the

system
• does not interact with sample
• Since silicon is less electronegative than carbon,
TMS protons are highly shielded. Signal defined as
zero.

• Organic protons absorb downfield (to the left) of the

TMS signal
Chapter 13
 6. Factors influencing Chemical Shift
1. Inductive effect
w does electronegativity influence chemical shift?
hemical shift related to magnetic field strength at nucleus
ectron cloud shields nucleus from effects of Bo

H X H X H X H X

Increasing EN of X
Decreasing electron density around H
Deshielding
Downfield chemical shift

Chapter 13
6. Factors influencing Chemical Shift
2. Anisotropic effect Alkenes/ vinyl protons

Chapter 13
6. Factors influencing Chemical Shift
2. Anisotropic effect Alkynes/ Acetylenic Protons

Chapter 13
6. Factors influencing Chemical Shift
2. Anisotropic effect
Aromatic Protons

Chapter 13
6. Factors influencing Chemical Shift
3. Van der Waal’s Deshielding

• Observed in overcrowded molecule, with

sterically hindered protons
• Adjacent bulky group repels the cloud of
e- around H+
• Causes Deshielding – Downfield Shift

CF3
Chapter 13
 6. Factors influencing Chemical
Shift
4. Hydrogen bonding
• hydrogen bonded proton is bound to highly EN group/
atom
•EN group pulls the e- cloud of proton  deshielding
downfield chemical shift

Chapter 13
Typical Values

Chapter 13
7. Solvents Used
• Important characteristics for solvents
1. Chemically inert and magnetically isotropic
2. Devoid of hydrogen atom
3. Should dissolve the sample to a reasonable
extent
•Examples
Carbon tetra chloride (CCl4), Carbon disulphide (CS2),
Duteriochloroform (CDCl3),
Hexachloroacetone((CCl3)2C=O)
Some other solvents require corrections of the order 0.5 ppm or more in tau value
e.g. Pyridine, Dioxane, acetonitrile, Trichloro acetonitrile

Chapter 13
 8. Splitting of the signals (Spin-
spin coupling)

Some Useful Terms

-spin coupling: one nuclear spin influences spin of another nucleus

ting: effect on NMR signal caused by spin-spin coupling J

pling constant (J): spacing between lines in a splitting pattern

Chapter 13
 9. Splitting of the signals (Spin-
spin coupling)
Rules and Restrictions
General rule: the signal for a proton with n neighbors
is split into n+1 lines

es and Restrictions for Proton-Proton Spin-Spin Coupling

Only nonequivalent protons couple

X
•Hb couples with Hc
X Hb Hc Hd H

Ha C C C
•HbHand Ha do not couple because they are equivale
C

H H H • Hc
H and Hd do not couple because they are equivale
Chapter 13
 9. Splitting of the signals (Spin-
spin coupling)
Rules and Restrictions

ons separated by more than three single bonds usually do not couple
Hb Hd •Ha couples with Hb

Ha C
XC C •Ha couples with Hc
•Ha does not couple with Hd
Hc

ds do not count toward this bond limit, but J may be too small to observe
free spacer
Hb Hc •Ha couples with Hb
C C •Ha couples with Hc
Ha C •Ha couples with Hd but J may be very small

Hd
Chapter 13
 9. Splitting of the signals (Spin-
spin coupling)
Rules and Restrictions
ons separated by more than three single bonds usually do not couple
Hd
•Benzene ring = one big free spacer
Hc F
•All benzene ring protons may couple with each other but J may be s

Hb
•Ha, HbCl
, Hc, and Hd all couple with each other

•JHaad may be too small to observe

zene ring blocks some coupling that we expect to observe

H X
CH3

X
CH2CH3

Chapter 13
 9. Splitting of the signals (Spin-
spin coupling)
Signal Splitting
Rules and Restrictions

3. Signals for O-H and N-H are usually singlets

H H

singlet H2N C C OH singlet

H H

triplet triplet

itting of O-H or N-H protons may be observed in rare circumstances

Chapter 13
10. Coupling constant – ‘J’

• Distance between the peaks of a split signal

• Measured in Hz (usually 0-18)
• Not dependent on strength of the external field
• Gives info on type of H
 Multiplets with the same coupling constants may come
from adjacent groups of protons that split each other
 Structural features

Chapter 13
11. Important tips Interpreting an
NMR Spectra
1. regarding chemical shift values
i. tau values of :- methyle> methylene >methine
ii. tau value depends upon – nature of substituent on
carbon aton bearing proton i.e. greater EN of
substituent lower is tau value
iii. tau value depends on type of hybrid orbital holding
proton :- sp3 > sp > sp2
iv. tau value of aromatic proton is always < 4 ppm
the value depends on the degree & nature of
substitution
Chapter 13
11. Important tips Interpreting an
NMR Spectra
1. regarding chemical shift values
v. tau value of aldehydic proton are usually lower, i.e. 0.8
ppm or lower
vi. Tau value in cyclic compound is always higher than
that of any other proton. Protons in cyclopropane has
maximum tau value
vii. tau for –OH an –NH proton depends on temp, solvent,
conc. and neighboring group…e.g- for alcoholic –OH
its 4.5 - 9 τ and for phenolic –OH its -2 to 6 τ
viii. for –COOH tau is -0.5 to -2.0
Chapter 13
11. Important tips Interpreting an
NMR Spectra
2. The number of signals in an NMR spectrum
tells the number of sets of different the
protons in different chemical environments
3. It also tells the number of equivalent protons
causing the splitting of signals

Chapter 13
12.

Chapter 13
13. Limitations of NMR

1. Lack of sensitivity – abt 1 ml sample of at least

1% conc.
2. Overlapping of spectra in some compounds –
difficult to interpret
3. NO information about molecular weight is given
but RELATIVE number of different protons
present are only known
4. Mostly ONLY LIQUIDS can be studied (solid
polymers are preheated with solvents)

Chapter 13
14. Conclusion

• NMR uses magnetic property of nucleus

for obtaining Spectra
• Phenomenon like chemical shift, spin-spin
coupling and signal splitting help to
analyze the sample by interpreting the
spectra
• Although it has wide range of applications,
it has got few limitations also
Chapter 13
THANK YOU

Chapter 13