NMR part 2

3. Look at the peak ratios

the peak ratio tells you how many protons are in a region relative to another peak

Some students refer to the peak ratios as peak heights. This is dangerous! Sometimes you can look at a
peak and say it is twice the height of another peak but it can be very misleading.

the peak ratios integrate the area under each peak number of hydrogens

So a tall sharp peak versus a broad short peak will be very different heights but they might actually have
the same number of hydrogens.

The peak ratios will usually be given as a number written above the peak. You can more or less assume
that this is the number of hydrogens corresponding to that peak. This is extremely useful.

occasionally they might give you the values as numbers such as 1.6 and 0.8 etc. This is just to test you
to see if you know it is a ratio. Divide them all by the small number number of hydrogens.

4. The splitting pattern....the n+1 rule

This part is the most difficult and most useful but usually causes students the most problems, so dont
worry if it doesnt make much sense first time round. Stick with it.

In part 1 we looked at identifying different environments in a spectrum, describing them as different

groups of peaks. We looked at a simplified spectrum where one peak corresponded to a single region.

This is a good starting point but a peak can be "split" into multiple peaks, which is due to the interaction
of electron clouds of protons on adjacent carbons. The splitting is known as spin-spin coupling.
The spectrum on the left is what we looked at in part 1, where each peak corresponds to a different
environment. This was a simplified spectrum, the peaks were actually split to give the spectrum on the
right.

You dont really need to worry about how this works, just how to apply it.

splitting only happens between hydrogen atoms on adjacent carbons.

The hydrogens must be no more than 3 bonds apart. If they are any further apart then no splitting
occurs.

No splitting occurs between hydrogens on the same carbon i.e. the Hs in a CH3 group dont split each
other.

Example

In the left hand molecule above, the hydrogens on the CH3 (carbon 1) will split the hydrogens on carbon 2
and vice-versa.

With the molecule on the right, no splitting occurs. The introduction of the oxygen atom means the
hydrogens on carbon 1 and 2 are 4 bonds apart (too far apart).
How many peaks?
From the structure

To work out how many peaks we will see in the spectrum we need to use the simple (ish) n+1 rule. Using
ethanol as an example:

Ethanol has 3 regions in its NMR spectrum (CH3, CH2 and OH). To work out how many peaks the CH3 peak
is split into, we simply:

look what it is next to and add 1 on to the number of hydrogens on that carbon.

CH3 next to a CH2, which has 2 hydrogens, we add 1 on to the 2 to give 3. Therefore, the CH3 peak is split
into 3 peaks.

Similarly for the CH2.....look at what it is next to and add 1 on....it is next to a CH3, so 3 + 1 = 4...the CH2
peak is split into 4 peaks...

the OH is NOT split and they dont split anything else...it's just the way they are!! Similarly for NHs
and NH2s. So always single peaks.

From the spectrum

You also need to do the above process in reverse, which is more common.

For example, if you have a peak split into 3, then you can work out what is next to it i.e. what is causing it
to be split into 3.

this is the confusing part. You only get information on what it is next to, not the actual group itself.

Id look at this as the n-1 rule. If you have a peak split into 3 you need to do 3-1, so it must have been split
by something with 2 hydrogens i.e. a CH2. We know there is a CH2 in the spectrum but that is all.

Some nomenclature...
if a peak is NOT split it is called a singlet

if a peak is split into 2 it is a doublet

if a peak is split into 3 it is a triplet

if a peak is split into 4 it is a quartet

more than 4 peaks = a multiplet

Patterns

Having done a lot of past papers, there are common fragments that appear in NMR spectra. I have listed
the most common fragments below and put in bold the group we are looking at:

CH3-CH2 1 ppm triplet

CH3-CH2 2 ppm quartet

CH3C=O 2 ppm singlet

CH3- CH 1 ppm doublet

(CH3)3C- 1 ppm singlet

CH2-CH2 2-4 ppm 2 x triplet in different environments (no Hs on the other sides of the CH2s)

OH 1-5 ppm singlet

CHs often multiple peaks as can fit a lot of groups around them.

CH3s cannot get higher than a triplet.

All this splitting information is useful for working towards the final structure. Draw all the fragments, this
is what the marks are for. Once you have the fragments the structure often presents itself.

Solvents
They often ask about the solvents used in NMR. The vital point is that the solvent must NOT contain
hydrogen as it will add extra peaks to the spectrum and complicate things.

To get round this, deuterium, D, (an isotope of hydrogen) is used instead of hydrogen.

Suitable solvents include:

CCl4 (although I dont think anyone uses this now in labs as it is carcinogenic!)

CDCl3

D2O (this is H2O with the D replacing the H)

Reference peak
At 0 ppm there is always a small peak, which is a reference peak. The compound responsible for this is
TMS (tetramethylsilane).Si(CH3)4. They may ask you to draw the structure or ask what it is for.

It is used as it is non-toxic, inert and can be removed easily.