Nuclear Magnetic Resonance

WHAT IS NUCLEAR MAGNETIC
RESONANCE (NMR)?
This page describes what a proton NMR spectrum is and how it
tells you useful things about the hydrogen atoms in organic
molecules.
The background to NMR spectroscopy

Nuclear magnetic resonance is concerned with the magnetic
properties of certain nuclei. On this page we are focussing on the
magnetic behaviour of hydrogen nuclei - hence the termproton
NMR or 1H-NMR.
Hydrogen atoms as little magnets
If you have a compass needle, it normally lines up with the Earth's
magnetic field with the north-seeking end pointing north. Provided it
isn't sealed in some sort of container, you could twist the needle
around with your fingers so that it pointed south - lining it up
opposed to the Earth's magnetic field.
It is very unstable opposed to the Earth's field, and as soon as you
let it go again, it will flip back to its more stable state.
Hydrogen nuclei also behave as little magnets and a hydrogen

nucleus can also be aligned with an external magnetic field or
opposed to it. Again, the alignment where it is opposed to the field
MD. KAMRUL ALAM KHAN, B.Sc Honors in Chemistry (SUST), M.Sc in Chemistry (SUST), CCNAE (All through first class), CELL: 01557704046
Kamrulclassroom.blogspot.com
is less stable (at a higher energy). It is possible to make it flip from

the more stable alignment to the less stable one by supplying
exactly the right amount of energy.
The energy needed to make this flip depends on the strength of the
external magnetic field used, but is usually in the range of energies
found in radio waves - at frequencies of about 60 - 100 MHz. (BBC
Radio 4 is found between 92 - 95 MHz!)
It's possible to detect this interaction between the radio waves of
just the right frequency and the proton as it flips from one
orientation to the other as a peak on a graph. This flipping of the
proton from one magnetic alignment to the other by the radio waves
is known as the resonance condition.
The importance of the hydrogen atom's environment

What we've said so far would apply to an isolated proton, but real
protons have other things around them - especially electrons. The
effect of the electrons is to cut down the size of the external
magnetic field felt by the hydrogen nucleus.
Suppose you were using a radio frequency of 90 MHz, and you

adjusted the size of the magnetic field so that an isolated proton

was in the resonance condition.
If you replaced the isolated proton with one that was attached to
something, it wouldn't be feeling the full effect of the external field
any more and so would stop resonating (flipping from one magnetic
alignment to the other). The resonance condition depends on
having exactly the right combination of external magnetic field and
radio frequency.
How would you bring it back into the resonance condition again?
You would have to increase the external magnetic field slightly to
compensate for the effect of the electrons.
Now suppose that you attached the hydrogen to something more
electronegative. The electrons in the bond would be further away
from the hydrogen nucleus, and so would have less effect on the
magnetic field around the hydrogen.
Note: Electronegativity is a measure of the ability of an

atom to attract a bonding pair of electrons. If you aren't
happy about electronegativity, you could follow this link at
some point in the future, but it probably isn't worth doing it
now!
The external magnetic field needed to bring the hydrogen into

resonance will be smaller if it is attached to a more electronegative
element, because the hydrogen nucleus feels more of the field.
Even small differences in the electronegativities of the attached
atom or groups of atoms will make a difference to the magnetic field
needed to achieve resonance.
Summary
For a given radio frequency (say, 90 MHz) each hydrogen atom will
need a slightly different magnetic field applied to it to bring it into
the resonance condition depending on what exactly it is attached to
- in other words the magnetic field needed is a useful guide to the
hydrogen atom's environment in the molecule.
Features of an NMR spectrum

A simple NMR spectrum looks like this:
Note: The nmr spectra on this page have been produced

from graphs taken from the Spectral Data Base System
for Organic Compounds (SDBS) at the National Institute of
Materials and Chemical Research in Japan.
It is possible that small errors may have been introduced
during the process of converting them for use on this site,
but these won't affect the argument in any way.
The peaks
There are two peaks because there are two different environments
for the hydrogens - in the CH3 group and attached to the oxygen in
the COOH group. They are in different places in the spectrum
because they need slightly different external magnetic fields to
bring them in to resonance at a particular radio frequency.
The sizes of the two peaks gives important information about the
numbers of hydrogen atoms in each environment. It isn't the height
of the peaks that matters, but the ratio of the areas under the
peaks. If you could measure the areas under the peaks in the
diagram above, you would find that they were in the ratio of 3 (for
the larger peak) to 1 (for the smaller one).
That shows a ratio of 3:1 in the number of hydrogen atoms in the
two environments - which is exactly what you would expect for
CH3COOH.
The need for a standard for comparison - TMS

Before we can explain what the horizontal scale means, we need to
explain the fact that it has a zero point - at the right-hand end of the
scale. The zero is where you would find a peak due to the
hydrogen atoms in tetramethylsilane - usually
calledTMS. Everything else is compared with this.
You will find that some NMR spectra show the peak due to TMS (at
zero), and others leave it out. Essentially, if you have to analyse a
spectrum which has a peak at zero, you can ignore it because
that's the TMS peak.
TMS is chosen as the standard for several reasons. The most
important are:
It has 12 hydrogen atoms all of which are in exactly the
same environment. They are joined to exactly the same

things in exactly the same way. That produces a single peak,
but it's also a strong peak (because there are lots of
hydrogen atoms).
The electrons in the C-H bonds are closer to the hydrogens

in this compound than in almost any other one. That means
that these hydrogen nuclei are the most shielded from the
external magnetic field, and so you would have to increase
the magnetic field by the greatest amount to bring the
hydrogens back into resonance.
The net effect of this is that TMS produces a peak on the
spectrum at the extreme right-hand side. Almost everything
else produces peaks to the left of it.
The chemical shift

The horizontal scale is shown as (ppm). is called thechemical
shift and is measured in parts per million - ppm.
A peak at a chemical shift of, say, 2.0 means that the hydrogen
atoms which caused that peak need a magnetic field two
millionths less than the field needed by TMS to produce
resonance.
A peak at a chemical shift of 2.0 is said to be downfield of TMS.
The further to the left a peak is, the more downfield it is.
Solvents for NMR spectroscopy

NMR spectra are usually measured using solutions of the
substance being investigated. It is important that the solvent itself
doesn't contain any simple hydrogen atoms, because they would
produce confusing peaks in the spectrum.
There are two ways of avoiding this. You can use a solvent such as
tetrachloromethane, CCl4, which doesn't contain any hydrogen, or
you can use a solvent in which any ordinary hydrogen atoms are
replaced by its isotope, deuterium - for example, CDCl 3 instead of

CHCl3. All the NMR spectra used on this site involve CDCl 3 as the
solvent.
Deuterium atoms have sufficiently different magnetic properties
from ordinary hydrogen that they don't produce peaks in the area of
the spectrum that we are looking at.
Note: Several text books say that deuterium atoms don't
have a magnetic field. It isn't true - they do have a field but
it is less than an ordinary hydrogen atom.
LOW RESOLUTION NMR SPECTRA

This page describes how you interpret simple low resolution
nuclear magnetic resonance (NMR) spectra. It assumes that you
have already read the background page on NMR so that you
understand what an NMR spectrum looks like and the use of the
term "chemical shift".
The difference between high and low resolution spectra
Note: This high resolution nmr spectrum has been produced

from a graph taken from the Spectral Data Base System for
Organic Compounds (SDBS) at the National Institute of Materials
and Chemical Research in Japan.
A low resolution spectrum looks much simpler because it can't

distinguish between the individual peaks in the various groups of
peaks.
Note: I haven't been able to find a reliable source of low

resolution NMR spectra. The low resolution spectra on this page
are my best guess at what the low resolution spectra would look
like, based on the high resolution ones.
The numbers against the peaks represent the relative areas under
each peak. That information is extremely important in interpreting

the spectra.
Interpreting a low resolution spectrum

Using the total number of peaks
Each peak represents a different environment for hydrogen atoms
in the molecule. In the methyl propanoate spectrum above, there
are three peaks because there are three different environments for
the hydrogens.
Remember that methyl propanoate is CH3CH2COOCH3. The
hydrogens in the CH2 group are obviously in a different
environment from those in the CH3 groups. The two CH3 groups
aren't in the same environment either. One is attached to a
CH2group, the other to an oxygen.
Using the areas under the peaks
The ratio of the areas under the peaks tell you the ratio of the
numbers of hydrogens in the various environments. In the methyl
propanoate case, the areas were in the ratio of 3:2:3, which is
exactly what you want for the two differently placed CH 3groups and
the CH2 group.
You will probably be told the relative areas under the peaks especially if you are only looking at low resolution spectra, but it is
just possible that you might have to work them out. NMR
spectrometers have a device which draws another line on the
spectrum called an integrator trace (or integration trace). You can
measure the relative areas from this trace.
Note: You need to find out whether your examiners expect you
to know how to interpret an integrator trace. Check your syllabus
and, particularly, past papers to see whether they ask it. If you
are doing a UK-based exam and haven't got copies of
your syllabus and past papers, follow this link to find out how to
get them.
If you do need to be able to interpret integrator traces, you can
find out how by following this link. You can also find it from the
NMR menu.
Using chemical shifts

The position of the peaks tells you useful things about what groups
the various hydrogen atoms are in. In any exam, you will be given a
table of chemical shifts if you need them. The important shifts for
the groups present in methyl propanoate are:
Notes: "R" represents an alkyl group (like methyl, ethyl, etc)

which in this case may have other things substituted in it.
The shifts are shown as ranges of values. The exact position
varies depending on what else is near that particular group in the
molecule.
Showing these groups on the low resolution spectrum gives:
Some sample questions

Example 1
An organic compound was known to be one of the following. Use
its low resolution NMR spectrum to decide which it is.
Notice that there are three peaks showing three different

environments for the hydrogens. That eliminates methyl ethanoate
as a possibility because that would only give two peaks - due to the
two differently situated CH3 group hydrogens.
Does the ratio of the areas under the peaks help? Not in this case both the other compounds would have three peaks in the ratio of
1:2:3.
Now you need to look at the chemical shifts:
Checking the positions of the various hydrogens in the two possible

compounds against the chemical shift table gives you this pattern
of shifts:
Comparing these with the actual spectrum means that the

substance was propanoic acid, CH3CH2COOH.
Example 2
How would you use low resolution NMR to distinguish between the
isomers propanone and propanal?
The propanone would only give one peak in its NMR spectrum
because both CH3 groups are in an identical environment - both are
attached to -COCH3.
The propanal would give three peaks with the areas underneath in
the ratio 3:2:1.
You could refer to the chemical shift table above to decide where
the peaks are likely to be found, but it isn't really necessary.
Example 3
How many peaks would there be in the low resolution NMR
spectrum of the following compound, and what would be the ratio of
the areas under the peaks?
All the CH3 groups are exactly equivalent so would only produce 1
peak. There would also be peaks for the hydrogens in the
CH2group and the COOH group.
There would be three peaks in total with areas in the ratio 9:2:1.
HIGH RESOLUTION NMR SPECTRA

This page describes how you interpret simple high resolution
nuclear magnetic resonance (NMR) spectra. It assumes that you
have already read the background page on NMR so that you
understand what an NMR spectrum looks like and the use of the
term "chemical shift". It also assumes that you know how to
interpret simple low resolution spectra.
The difference between high and low resolution spectra

What a low resolution NMR spectrum tells you
Remember:
The number of peaks tells you the numbers of different

environments the hydrogen atoms are in.
The ratio of the areas under the peaks tells you the ratio of
the numbers of hydrogen atoms in each of these
environments.
The chemical shifts give you important information about the

sort of environment the hydrogen atoms are in.
High resolution NMR spectra

In a high resolution spectrum, you find that many of what looked
like single peaks in the low resolution spectrum is split into clusters
of peaks.
For A'level purposes, you will only need to consider these
possibilities:
1 peak
a singlet
2 peaks in the cluster
a doublet
a triplet
a quartet
You can get exactly the same information from a high resolution
spectrum as from a low resolution one - you simply treat
eachcluster of peaks as if it were a single one in a low resolution
spectrum.
But in addition, the amount of splitting of the peaks gives you
important extra information.
Interpreting a high resolution spectrum

The n+1 rule
The amount of splitting tells you about the number of hydrogens
attached to the carbon atom or atoms next door to the one you are
currently interested in.
The number of sub-peaks in a cluster is one more than the number
of hydrogens attached to the next door carbon(s).
So - on the assumption that there is only one carbon atom with
hydrogens on next door to the carbon we're interested in (usually
true at A'level!):
singlet
next door to carbon with no hydrogens attached
doublet
next door to a CH group
triplet
next door to a CH2 group
quartet
next door to a CH3 group
Using the n+1 rule

What information can you get from this NMR spectrum?
Note: The nmr spectra on this page have been produced from
data taken from the Spectral Data Base System for Organic
Compounds (SDBS) at the National Institute of Materials and
Chemical Research in Japan.
Any small errors that I've introduced during the process of
converting them for use on this site won't affect the argument in
any way.
Assume that you know that the compound above has the molecular
formula C4H8O2.
Treating this as a low resolution spectrum to start with, there are
three clusters of peaks and so three different environments for the
hydrogens. The hydrogens in those three environments are in the
ratio 2:3:3. Since there are 8 hydrogens altogether, this represents
a CH2 group and two CH3 groups.
What about the splitting?
The CH2 group at about 4.1 ppm is a quartet. That tells you that it is
next door to a carbon with three hydrogens attached - a CH 3group.
The CH3 group at about 1.3 ppm is a triplet. That must be next door
to a CH2 group.
This combination of these two clusters of peaks - one a quartet and
the other a triplet - is typical of an ethyl group, CH 3CH2. It is very
common. Get to recognise it!
Finally, the CH3 group at about 2.0 ppm is a singlet. That means
that the carbon next door doesn't have any hydrogens attached.
So what is this compound? You would also use chemical shift data
to help to identify the environment each group was in, and
eventually you would come up with:
Note: You now know how to get the information you need from
NMR spectra, but it often isn't easy to fit all that information
together into a final formula. You simply need to practise! Go
through all the examples in past papers from your Exam Board.
How complicated they are will vary markedly from Board to
Board. Some of the compounds you will come across may be
very unfamiliar. Don't forget to use the information in chemical
shift tables - if your examiners include some obscure group, it's
almost certain you will need to use it. Take all the hints that are
going!
Two special cases

Alcohols
Where is the -O-H peak?
This is very confusing! Different sources quote totally different
chemical shifts for the hydrogen atom in the -OH group in alcohols often inconsistently. For example:
The Nuffield Data Book quotes 2.0 - 4.0, but the Nuffield text
book shows a peak at about 5.4.
The OCR Data Sheet for use in their exams quotes 3.5 - 5.5.
A reliable degree level organic chemistry text book

quotes1.0 - 5.0, but then shows an NMR spectrum for
ethanol with a peak at about 6.1.
The SDBS database (used throughout this site) gives the

-OH peak in ethanol at about 2.6.
The problem seems to be that the position of the -OH peak varies
dramatically depending on the conditions - for example, what
solvent is used, the concentration, and the purity of the alcohol especially on whether or not it is totally dry.
Help! Do you need to worry about this? Not really - you can
assume that in an exam question, any NMR spectrum will be
consistent with the chemical shift data you are given.
A clever way of picking out the -OH peak

If you measure an NMR spectrum for an alcohol like ethanol, and
then add a few drops of deuterium oxide, D 2O, to the solution, allow
it to settle and then re-measure the spectrum, the -OH peak
disappears! By comparing the two spectra, you can tell immediately
which peak was due to the -OH group.
Note: Deuterium oxide (sometimes called "heavy water") is
simply water in which all the normal hydrogen-1 atoms are
replaced by its isotope, hydrogen-2 (or deuterium).
The reason for the loss of the peak lies in the interaction between
the deuterium oxide and the alcohol. All alcohols, such as ethanol,
are very, very slightly acidic. The hydrogen on the -OH group
transfers to one of the lone pairs on the oxygen of the water
molecule. The fact that here we've got "heavy water" makes no
difference to that.
The negative ion formed is most likely to bump into a simple

deuterium oxide molecule to regenerate the alcohol - except that
now the -OH group has turned into an -OD group.
Deuterium atoms don't produce peaks in the same region of an

NMR spectrum as ordinary hydrogen atoms, and so the peak
disappears.
You might wonder what happens to the positive ion in the first
equation and the OD- in the second one. These get lost into the
normal equilibrium which exists wherever you have water
molecules - heavy or otherwise.
The lack of splitting with -OH groups

Unless the alcohol is absolutely free of any water, the hydrogen on
the -OH group and any hydrogens on the next door carbon don't
interact to produce any splitting. The -OH peak is a singlet and you
don't have to worry about its effect on the next door hydrogens.
The left-hand cluster of peaks is due to the CH 2 group. It is a

quartet because of the 3 hydrogens on the next door CH 3 group.
You can ignore the effect of the -OH hydrogen.
Similarly, the -OH peak in the middle of the spectrum is a singlet. It
hasn't turned into a triplet because of the influence of the
CH2 group.
Note: The reason for this is quite complex, and certainly goes
beyond A'level. It lies in the very rapid interchange that occurs
between the hydrogen atoms on the -OH group and either
water molecules or other alcohol molecules. To find out about it
you will have to read either a degree level organic chemistry
book or one specifically about NMR.
For A'level purposes just accept the fact that -OH produces a
singlet and has no effect on neighbouring groups!
Equivalent hydrogen atoms

Hydrogen atoms attached to the same carbon atom are said to
be equivalent. Equivalent hydrogen atoms have no effect on each
other - so that one hydrogen atom in a CH2 group doesn't cause
any splitting in the spectrum of the other one.
But hydrogen atoms on neighbouring carbon atoms can also be

equivalent if they are in exactly the same environment. For
example:
These four hydrogens are all exactly equivalent. You would get a
single peak with no splitting at all.
You only have to change the molecule very slightly for this no
longer to be true.
Because the molecule now contains different atoms at each end,

the hydrogens are no longer all in the same environment. This
compound would give two separate peaks on a low resolution NMR
spectrum. The high resolution spectrum would show that both
peaks subdivided into triplets - because each is next door to a
differently placed CH2 group.

Nuclear Magnetic Resonance

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WHAT IS NUCLEAR MAGNETIC

The background to NMR spectroscopy

Hydrogen nuclei also behave as little magnets and a hydrogen

is less stable (at a higher energy). It is possible to make it flip from

The importance of the hydrogen atom's environment

Suppose you were using a radio frequency of 90 MHz, and you

adjusted the size of the magnetic field so that an isolated proton

Note: Electronegativity is a measure of the ability of an

The external magnetic field needed to bring the hydrogen into

Features of an NMR spectrum

Note: The nmr spectra on this page have been produced

The need for a standard for comparison - TMS

It has 12 hydrogen atoms all of which are in exactly the

same environment. They are joined to exactly the same

The electrons in the C-H bonds are closer to the hydrogens

The chemical shift

Solvents for NMR spectroscopy

replaced by its isotope, deuterium - for example, CDCl 3 instead of

LOW RESOLUTION NMR SPECTRA

The difference between high and low resolution spectra

Note: This high resolution nmr spectrum has been produced

A low resolution spectrum looks much simpler because it can't

Note: I haven't been able to find a reliable source of low

each peak. That information is extremely important in interpreting

Interpreting a low resolution spectrum

Using chemical shifts

Notes: "R" represents an alkyl group (like methyl, ethyl, etc)

Showing these groups on the low resolution spectrum gives:

Some sample questions

Notice that there are three peaks showing three different

Now you need to look at the chemical shifts:

Checking the positions of the various hydrogens in the two possible

Comparing these with the actual spectrum means that the

HIGH RESOLUTION NMR SPECTRA

interpret simple low resolution spectra.

The difference between high and low resolution spectra

The number of peaks tells you the numbers of different

The chemical shifts give you important information about the

High resolution NMR spectra

2 peaks in the cluster

3 peaks in the cluster

4 peaks in the cluster

important extra information.

Interpreting a high resolution spectrum

next door to carbon with no hydrogens attached

next door to a CH group

next door to a CH2 group

next door to a CH3 group

Using the n+1 rule

Two special cases

A reliable degree level organic chemistry text book

The SDBS database (used throughout this site) gives the

A clever way of picking out the -OH peak

The negative ion formed is most likely to bump into a simple

Deuterium atoms don't produce peaks in the same region of an

The lack of splitting with -OH groups

The left-hand cluster of peaks is due to the CH 2 group. It is a

Equivalent hydrogen atoms

But hydrogen atoms on neighbouring carbon atoms can also be

Because the molecule now contains different atoms at each end,

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