NMR Spectroscopy: Koradiya Ketan N. Inorganic Chemistry, Reg. Roll No-5, Bhavnagar University, Bhavnagar-05

NMR SPECTROSCOPY
Koradiya Ketan N.
Inorganic Chemistry, Reg. roll No-5,
Bhavnagar University, Bhavnagar-05
Introduction
 Nuclear magnetic resonance, or NMR

involves the study of what occurs when
the nuclei of certain atoms are placed in
a static magnetic field and exposed to a
second changing magnetic field.
Spin States
A nucleus with an odd atomic number or an odd mass
number has a nuclear spin
The number of allowed spin states is quantized, and

is determined by its spin quantum number, I
There are 2I+1 allowed spin states

Nuclei with I = 0 have only one spin state and are
NMR inactive. These include 12C and 16O, two of
nic compounds.
the most common nuclei in organic compounds.
Nuclei with odd mass numbers have half-integer spin

quantum numbers.
i.e. 13C, 1H, 31P are spin I = 1/2
17O is spin I = 5/2
A spinning nucleus with a spin quantum number of ½

has 2 possible spin states.
2I+1 = 2 (1/2) + 1 = 2
+ +
+ 1/2 - 1/2
TWO SPIN STATES
The Most Interesting Elements (to us) All Have 2
Allowed Spin States
These are
•1H
•13C
•19F
•31P
Deuterium 2H is spin active with I = 1!
2 (1) + 1 = 3 spin states for

deuterium
The spinning of the nuclei causes them to
behave like magnets
These nuclear magnets are influenced by other magnetic

fields. These other magnetic fields may be externally
applied or they can be generated by other nearby nuclei or
electrons in the molecule.
Externally applied magnetic fields may result from the

magnet that the sample is placed in or from irradiation
by radio frequency light.
External Magnetic Field
When placed in an external field, spinning protons act
like bar magnets.
In an Applied Magnetic
Nuclei with 2 allowed Field
spin states can align
either with or against
the field, with slight
excess of nuclei
aligned with the field
The nuclei precess

about an axis parallel
to the applied
magnetic field, with a
frequency called the
Larmor Frequency (w)
Two Energy States
The magnetic fields
of the spinning
nuclei will align
either with the
external field, or
against the field
A photon with the

right amount of
energy can be
absorbed and cause
the spinning proton
to flip.
In an applied magnetic field the spin states have
different energies and therefore different
populations.
quantized
Opposed
-1/2 -1/2
DE = hn
Radiofrequency
+1/2
+1/2
E and Magnet Strength
Energy difference is proportional to the magnetic field
strength.
E = h =  h B0
2
Gyromagnetic ratio, , is a constant for each nucleus

(26,753 s-1gauss-1 for H).
In a 14,092 gauss field, a 60 MHz photon is required to

flip a proton.
Low energy, radio frequency.

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.
Shielded Protons
Magnetic field strength must be increased for a
shielded proton to flip at the same frequency.
=>
Protons in a Molecule
Depending on their chemical environment, protons in a
molecule are shielded by different amounts.
=>
NMR Signals
The number of signals shows how many different kinds of
protons are present.
The location of the signals shows how shielded or

deshielded the proton is.
The intensity of the signal shows the number of protons

of that type.
Signal splitting shows the number of protons on adjacent

atoms.
The NMR Spectrometer
NMR Spectrometer
RF (60 MHz) hn
Oscillator absorption RF
Recorder
signal Detector
Transmitter
Receiver
MAGNET MAGNET
N S
Probe
How does our NMR observe the
signals?
1) The sample tube is placed in a strong magnetic field to
produce the primary splitting of the energy levels and
create the necessary population imbalance.
2) The sample is irradiated with a range of radio frequency
light to transfer nuclei from the lower to the higher
energy state.
3) The oscillating magnetic fields produced by the nuclei
are observed using the same coil that was used for the
irradiation. A complex, decaying signal is observed that
contains all of the information about the nuclei. This is
called the free induction decay (FID)
4) A Fourier transform is performed on the FID to
produce an NMR spectrum with each signal represented
by a peak at its relative Larmar frequency which is the
frequency with which it wobbles as it spins.
This is actually done several times and the results are
added to increase the signal to noise ratio.
Tetramethylsilane
CH3
H3C Si CH3
CH3
TMS is added to the 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.
Chemical Shift
Measured in parts per million.
Ratio of shift downfield from TMS (Hz) to total

spectrometer frequency (Hz).
Same value for 60, 100, or 300 MHz machine.
Called the delta scale.

Delta Scale
Location of Signals
More electronegative
atoms deshield more and
give larger shift values.
Effect decreases with
distance.
Additional
electronegative atoms
cause increase in chemical
shift.
=>
Aromatic Protons, 7-8
Vinyl Protons, 5-6
Acetylenic Protons, 2.5
Aldehyde Proton, 9-10
Electronegative
oxygen atom
O-H and N-H Signals
Chemical shift depends on concentration.
Hydrogen bonding in concentrated solutions

deshield the protons, so signal is around 3.5
for N-H and 4.5 for O-H.
Proton exchanges between the molecules

broaden the peak.
Carboxylic Acid
Proton, 10+
Number of Signals
Equivalent hydrogen's have the same chemical shift.
Intensity of Signals
The area under each peak is proportional to the number of
protons.
Shown by integral trace.
Spin-Spin Splitting
Nonequivalent protons on adjacent carbons have
magnetic fields that may align with or oppose
the external field.
This magnetic coupling causes the proton to

absorb slightly downfield when the external
field is reinforced and slightly upfield when the
external field is opposed.
All possibilities exist, so signal is split.

1,1,2-Tribromoethane
Nonequivalent protons on adjacent carbons.
Doublet: 1 Adjacent Proton
Triplet: 2 Adjacent Protons
The N + 1 Rule
If a signal is split by N equivalent
protons,
it is split into N + 1 peaks.
Range of Magnetic
Coupling
Equivalent protons do not split each other.
Protons bonded to the same carbon will split each

other only if they are not equivalent.
Protons on adjacent carbons normally will couple.
Protons separated by four or more bonds will not

couple.
Splitting for Ethyl Groups
Splitting for
Isopropyl Groups
Thank you

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NMR SPECTROSCOPY

 Nuclear magnetic resonance, or NMR

The number of allowed spin states is quantized, and

There are 2I+1 allowed spin states

the most common nuclei in organic compounds.

Nuclei with odd mass numbers have half-integer spin

A spinning nucleus with a spin quantum number of ½

2 (1) + 1 = 3 spin states for

These nuclear magnets are influenced by other magnetic

Externally applied magnetic fields may result from the

The nuclei precess

A photon with the

Gyromagnetic ratio, , is a constant for each nucleus

In a 14,092 gauss field, a 60 MHz photon is required to

Low energy, radio frequency.

But protons are surrounded by electrons that shield them

Circulating electrons create an induced magnetic field

The location of the signals shows how shielded or

The intensity of the signal shows the number of protons

Signal splitting shows the number of protons on adjacent

TMS is added to the sample.

Since silicon is less electronegative than carbon, TMS

Organic protons absorb downfield (to the left) of the

Ratio of shift downfield from TMS (Hz) to total

Same value for 60, 100, or 300 MHz machine.

Called the delta scale.

Hydrogen bonding in concentrated solutions

Proton exchanges between the molecules

This magnetic coupling causes the proton to

All possibilities exist, so signal is split.

Protons bonded to the same carbon will split each

Protons on adjacent carbons normally will couple.

Protons separated by four or more bonds will not

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