Topic 15E:

Nuclear
Magnetic
Resonance (NMR)
NMR stands for Nuclear Magnetic Resonance

NMR is a technique that can be used to tell us about the number of atoms of an
element in a compound and about their relative positions in the molecule.

Only atoms with an odd number of nucleons can be visualised. So 13C is one of
the atoms that can be observed.
3. be able to use data from 13C NMR spectroscopy to:
a. predict the different environments for carbon atoms present in a molecule, given values
of chemical shift, δ
b. justify the number of peaks present in a 13C NMR spectrum because of carbon atoms in
different environments

Each different carbon environment will produce a different peak, however the
height of the peak is not necessarily linked to the number of carbon atoms in
that environment.
Isopropyl proanoate would have 5 13C peaks

The more electrons are withdrawn from the carbon atom, the greater the
chemical shift.
3.
4.

Nuclear Magnetic Resonance (N.M.R)

If a nucleus of an atom has an odd number of protons or neutrons, it will
produce a tiny magnetic field as it spins.

The nucleus of a Hydrogen atom is one atom that does this. 1

1 H
SN NS

Radio wave radiation causes the spin of the nucleus to change direction
Which in turn changes the polarity of the tiny magnetic field.

The exact wavelength of radio wave which can cause this change in spin depends
on the “environment” a hydrogen atom is in.

Which means what the hydrogen atom is bonded to etc.

4. & 5

N S This
Radio
If hydrogen
This
radiation
wave
emitted
field
radiation
the nucleus
they
atoms
is then
it returns
SN

radiation
are
re-radiated
willtospin
to
can
spin
placed
the
NS

isprovide
measured
within
from
ininalignment
lower
theathe
the opposite
energy
by
energy
large
anucleus
withspin
detector
magnetic
to cause
direction
that field
when
4. & 5 The chemical shift will be in particular regions depending on the
type of hydrogen which can help us analyse unknown compounds.
4. & 5

Nuclear Magnetic Resonance (N.M.R)

This energy
Energy

corresponds to the
energy of specific
radio waves.
4. & 5

Basic principles of N.M.R.

N S SN
N
S ADD ENERGY
The energy required to change the spin of the smaller magnet (hydrogen nuclei)
corresponds to a specific wavelength of radiation found in the radio wave part of
the spectrum.

This will be slightly different due to the “environment” of the Hydrogen. E.g:

H H Ethanol: How many “Hydrogen

environments” are there?
H C C O H
1 2 3 4 5 6
H H
4. & 5

YES! 3 
H H
Each of these 3 “different
types” of Hydrogen will require
H C C O H a slightly different energy
(therefore wavelength) of
H H radiation to cause it to change
its spin in the magnetic field.

The area under each peak

corresponds to the number
of hydrogen atoms in that
environment

Chemical shift d
4. & 5
How many peaks would be found on an NMR trace for the
following compounds? Give the relative intensities of each peak.

O O O
1 3 5
CH3 C CH3 C H C
O CH3 CH3 O CH2 CH3

Methyl ethanoate Propanone Ethyl methanoate

O O CH3 O
2 4 6
CH3 CH2 C CH3 CH2 C CH3 C CH2 C
OH H CH3 OH

Propanoic acid Propanal 3,3-dimethylbutanoic acid

Use page 7 from the data book to sketch an NMR trace for all 6 of the compounds

d Chemical Shift
4. & 5

O
1
CH3 C
2 Peaks Relative intensities: 3:3 (1:1)
O CH3

Methyl ethanoate
Sketch of trace:

d Chemical Shift
4. & 5

O
2
CH3 CH2 C
3 Peaks Relative intensities: 3:2:1
OH

Propanoic acid

Sketch of trace:

d Chemical Shift
4. & 5

O
3
CH3 C
1 Peak Relative intensity: 6 (1)
CH3

Propanone
Sketch of trace:

d Chemical Shift
4. & 5

O
4
CH3 CH2 C
3 Peaks Relative intensities: 3:2:1
H

Propanal

Sketch of trace:

d Chemical Shift
4. & 5

O
5
H C
3 Peaks Relative intensities: 1:2:3
O CH2 CH3

Ethyl methanoate
Sketch of trace:

d Chemical Shift
4. & 5

CH3 O
6
CH3 C CH2 C
3 Peaks Relative intensities: 9:2:1
CH3 OH

3,3-dimethylbutanoic acid

Sketch of trace:

d Chemical Shift
4. & 5

All peaks are relative to a peak produced by Tetramethylsilane (TMS) as a

reference point set at 0 on the trace

Why is it used? CH3

CH3 Si CH3
Unreactive

It is non toxic CH3

Has 12 hydrogens in the same environment (that’s a big peak!)

The peak it produces is to an extreme compared to other hydrogen environments,

and we can set the relative intensity for all other environments

d Chemical Shift
4. & 5

High Resolution N.M.R.

All of the traces we have looked at so far are for “low resolution NMR” where
each hydrogen environment produces a peak.
However, imagine the NMR traces for these two isomers:
OH
Hexan-2-ol
CH3 CH CH2 CH2 CH2 CH3
OH
Hexan-3-ol
CH3 CH2 CH CH2 CH2 CH3

d Chemical Shift

Both of these compounds would produce traces with 7 peaks with a ratio of
1:1:2:2:2:3:3
So it would be very hard to tell them apart using NMR.
Chemists can use High Resolution NMR to tell these two compounds apart.
4. & 5

High Resolution N.M.R.

In High Resolution NMR peaks can be split into sub peaks:

doublet
singlet

quintet
triplet

The peaks are “split”. This is known as “spin-spin coupling”

4. & 5
The signal produced by a specific “type” of hydrogen will be split up into subpeaks
depending on how many hydrogen atoms are bonded to the carbon atom “next
door”. These are called adjacent Hydrogens.
The n+1 Rule
H H
The number of Hydrogen atoms
H C C O H on the atom “next door” + 1 =
Number of sub-peaks in a peak.
H H
Carbon atom next
door has 2 H-atoms
2 + 1 = 3 Triplet (t)
Carbon atom next
door has 3 H-atoms
3 + 1 = 4 Quartet (q)
OH Hydrogens dont
get split
0 + 1 = 1 Singlet (s)
Chemical shift d
4. & 5
Pascal's Rule
The ratio of the sub-peaks within a peak are determined by Pascal's Rule (Pascal's
Triangle):
1
1 1 Multiplicity Intensity Ratio
1 2 1 Singlet (s) 1
1 3 3 1 Doublet (d) 1:1
Triplet (t) 1:2:1
1 4 6 4 1
Quartet (q) 1:3:3:1
1 5 10 10 5 1
1 6 15 20 15 6 1
1 7 21 35 35 21 7 1
1 8 28 56 70 56 28 8 1

Multiplicity Neighbouring H’s Neighbouring group*

Singlet (s) 0 C

Doublet (d) 1 CH

Triplet (t) 2 CH2

Quartet (q) 3 CH3

4. & 5
High Resolution NMR
If we go back to our low resolution problem of hexan-2-ol and hexan-3-ol we can
easily tell which one produced which of these high resolution traces:
Hexan-2-ol Hexan-3-ol
OH OH
CH3 CH CH2 CH2 CH2 CH3 CH3 CH2 CH CH2 CH2 CH3

Peak ratio: 3:1:1:2:2:2:3 3:2:1:1:2:2:3

Subpeaks: 2:1:6:4:5:6:3 3:5:5:1:4:6:3

Hexan-3-ol

d Chemical Shift

Hexan-2-ol

d Chemical Shift
4. & 5
Piecing it all together: An example
The N.M.R. Trace for a compound C4H8O2
• 3 hydrogen environments
• No OHs

Quartet
So adjacent Hs = 3
CH2 next to a CH3

CH3 -CH2 Singlet Triplet

From the chemical shift we So adjacent Hs = 0 3 adjacent Hs =2
can tell that it is a H-C-O CH3 next to no H’s CH3 next to a CH2

CH3 -CH2-O CH3-C CH3-CH 2

So we know: This covers all the hydrogen and carbon

atoms, where can the oxygen go?
Its ethyl
CH3-CH2-O-C-CH3
ethanoate!