NMR part 1

NMR stands for Nuclear Magnetic Resonance.

There are two types of NMR at A-level: hydrogen NMR (or proton NMR) and carbon-13 NMR. Proton
NMR can be referred to as 1H NMR and carbon-13 as 13C.

It is the most useful and difficult of the spectroscopic techniques that you will encounter at A2.

This discussion will be on proton NMR as it is more difficult than carbon-13. If you can get to grips with
the proton stuff, then the carbon NMR will be a breeze (see part 4).

NMR theory
You only need to have a basic understanding of how NMR works. The theory questions are very rare but
it is worth having a few marks up your sleeve just incase.

All hydrogen atoms (protons) in a molecule have their own magnetic field and are spinning in random
directions. When the sample is put in the NMR machine (a big magnet), all the protons become
ordered/aligned with or against the magnetic field of the machine.

The molecule/sample is then irradiated with radio waves. The protons absorb the radiation giving them
extra energy. They change their spin and jump between energy levels. NMR measures the strength of
this absorption.

Protons in different environments in a molecule will absorb slightly different frequencies resulting in
different signals in the NMR spectrum.

Interpreting 1H NMR spectra

The questions normally ask you to work out a structure from a spectrum. This can be quite daunting at
first so you need to do it step by step and forget the final structure.

You must show the examiner that you can do NMR. The final structure might only be worth 1 mark.
Therefore you should aim to go through a checklist of things to look for every time you do an NMR
question.

I would recommend breaking the spectrum down into 4 areas:

 1.number of environments
2.chemical shift
3.peak ratios
4.splitting pattern

1.Number of environments

It is important to understand that different protons have different environments. This means that they
absorb slightly different frequencies of the radiation and each group of protons e.g. CH3, CH2 etc. are
shown by different peaks in the spectrum.

Note that the hydrogens in, for example, a CH3 group are all in the same environment, hence why we
group things as CH3, CH2 etc.

How to identify the number of environments

To keep things simple at this stage, you can tell the number of regions by counting the number of peaks
in the spectrum (see part 2 for what a spectrum really looks like).

For example, in the spectrum below there are 5 peaks, which means there are 5 different proton
environments. Dont worry about the spectrum just now, there is plenty more on this coming.

5 different
environments

You also have to be able to look at a structure and work out how many regions there are. How many
regions does pentane have?
 the easiest way to do this is to look at what each group is next to and look for similarities

If two groups have the same group(s) next to them, then we can say that they are in the same
environment. For example:

The CH3 on the left (number 1) and the CH3 on the right (number 5) are the same. Both have a CH2 next
to them and nothing else. Those CH3s are said to be in the same environment and will be shown in the
same part of the spectrum.

We can use the same theory for the rest of the molecule and look for groups that are the same:

Number 1: CH3 next to a CH2

We can see that numbers 2 and 4 are the same and give a
Number 2: CH2 next to a CH2 and a CH3
2nd region in the spectrum. Number 3 is on its own and gives
a 3rd region.
Number 3: CH2 next to 2 x CH2
There are therefore 3 regions in total for this molecule so the
Number 4: CH2 next to a CH2 and a CH3
spectrum would have 3 groups of peaks.
Number 5: CH3 next to a CH2

Another quick example:

CH3CH2-OH: how many regions?

The answer is 3...one for the CH3, one for the CH2 and one for the OH. They are all different from each
other.

2. Chemical Shift

The chemical shift is simply a scale from 0 to around 12 in ppm (parts per million) on the x-axis of the
spectrum. They use the symbol to represent chemical shift.

From the chemical shift you can get a rough idea of what group a peak may correspond to. You can use
your data booklet/sheet, which has a list (you will be mostly looking at CH3, CH2 and CH groups).

you cannot rely upon the data booklet like you might do for IR spectroscopy. It is very useful to have
a rough idea what comes where on the scale and then use the data booklet to confirm it.

Below is a very basic NMR spectrum. It is just to show the chemical shift on the x-axis.
My guide to chemical shift

We are looking mainly at CH3, CH2 and CH groups.

CH3s usually the lowest then CH2 then CH. The problem is that if you put a C=O group or an O next to an
alkyl group it will be shifted to the left.

This is the basic data sheet that I use:

Chemical shift (ppm) Group

1 ppm CH3
2 ppm CH3C=O
3 ppm CH3-O
1-5 ppm OH
7-8 ppm benzene
9-11 ppm aldehyde
11-12 ppm carboxylic acid

1 ppm: if anything comes at around 1 ppm then it is definitely a CH3 group.

2-3 ppm: this is to show the CH3 group being shifted left. The C=O shifts it by around 1 ppm and the O
shifts by around 2 ppm.

I used CH3 to demonstrate the point but the same theory applies to CH2s and CHs. They will start a
bit higher than 1.

CH2s and CHs: its not as easy to identify these as a CH3 at 1 ppm. A CH2 might be around 2-3 ppm and a
CH a bit higher again.
 but as things can be shifted left, a CH3 could end up higher than a CH2 for example. This is why is is
not a good idea to rely upon the data sheet.

1-5 ppm: OH peaks move around and could come anywhere in this region.

> 7 ppm: very useful as it is easy to identify groups as benzene, aldehydes or carboxylic acids.

Like any question Id start somewhere easy. So look for anything above 7ppm or around 1ppm.

dont expect to solve the whole structure by looking at ppm only. This is just a starting point. Treat it
like a jigsaw puzzle.