Chem Factsheet

www.curriculum-press.co.uk Number 113

High Resolution NMR Spectroscopy
To succeed in this topic you need to understand:
• the structure of atoms
• the functional groups of the organic compounds studied at AS
and A2
• that chemists need to analyse compounds (for example through
mass spectrometry and infra-red)
After working through this Factsheet you will be able to:
• understand the importance of NMR as an analytical technique
• predict and interpret high resolution proton NMR spectra
What is NMR?
NMR stands for nuclear magnetic resonance. It is a powerful
technique which gives us detailed information about the structure
of compounds. NMR can be used to analyse a number of elements
in compounds provided they have an odd mass number; these
include 13 C, 19F and 31P, but is most commonly used to study
hydrogen atoms, 1H. Remember that the nucleus of a hydrogen
atom contains a single proton, so we often refer to hydrogen NMR
as proton NMR. NMR is always used in conjunction with other
techniques, like mass spectrometry and infra-red, but is arguably
the most powerful method of analysis available to organic chemists.
How does NMR work?
Hydrogen nuclei have a property called spin, which makes them
behave like tiny magnets. When you hold the nuclei in a magnetic
field, they align themselves with the field, like compass needles all
pointing north (Fig 1).
Fig 1 Hydrogen nuclei without and with a magnetic field applied
Direction of applied
The exact amount of energy required depends on the chemical
environment of the hydrogen nuclei. Nuclei with a high electron
density surrounding them are shielded from the effects of the
magnetic field, so require more energy, while nuclei near to an
electron-withdrawing group like chlorine or oxygen are deshielded
and need less energy. The NMR machine detects the amount of
energy needed and scans through a range of energies until all the
hydrogen nuclei have flipped.
How is an NMR carried out?
To carry out an NMR spectrum, the sample is first dissolved in a
solvent. The solvent must not contain any hydrogen atoms, since
these would interfere with the resonance of the sample. The solvents
normally used are tetrachloromethane (CCl4), or deuterated solvents
like CDCl 3, where the hydrogen atoms have been replaced by
deuterium atoms (the 2H isotope of hydrogen), which do not
interfere with the magnetic resonance.Spectra are calibrated using
tetramethylsilane (TMS) (Fig 3).
Fig 3 Tetramethylsilane
CH 3
H 3C Si CH 3
CH 3
All the hydrogen atoms in TMS are in the same, highly shielded,
environment and so will produce a single peak in the NMR spectrum.
The horizontal axis of the spectrum is called the chemical shift (δ),
which is measured in parts per million (ppm). It indicates the
difference in absorbed energy between the TMS protons and the
sample protons. The peak for TMS at 0 ppm does not always appear
in the spectra, since machines are often internally calibrated, but if

there is a peak at 0 ppm, it will be due to the TMS protons.

What does an NMR spectrum tell us?
Fig 4 shows the proton NMR spectrum of 1,2-dichloro-2-
magnetic field

methylpropane. In the spectrum there are two peaks, at 1.6 and 3.7
ppm. There are four pieces of information we can gather from these
peaks.
No magnetic field applied
Fig 4 The proton NMR spectrum of 1,2-dichloro-2-methylpropane
If exactly the right amount of energy is absorbed by the nuclei, they
will flip and point in the other direction (Fig 2). This is called nuclear
magnetic resonance. H

Fig 2 Hydrogen nuclei absorb energy and their spin flips H C H

H H
Direction of applied

H C C C H
Cl Cl H
magnetic field

10 9 8 7 6 5 4 3 2 1 0
δ (ppm)
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113 High Resolution NMR Spectroscopy Chem Factsheet

1. The number of different chemical environments in the compound 4. How many neighbours each hydrogen atom has
Firstly, the NMR shows us that there are two different chemical Finally, the spectrum gives us information about the
environments for hydrogen atoms in this compound (Figure 5). neighbouring hydrogen atoms of the nuclei. This comes from
The six hydrogens in the methyl (CH3) groups are in the same the splitting pattern, where the peaks in the spectrum are split
environment since they are the same distance from the chlorine into groups of sub-peaks (Table 2). The splitting pattern depends
atoms and from the central carbon atom. The two hydrogens in on how many non-equivalent hydrogen nuclei are on the
Environment 2 are closer to one of the chlorine atoms and adjacent carbon atoms. Splitting occurs because the magnetic
therefore chemically different from Environment 1. fields of different hydrogen nuclei interact with each other, and
the number of sub-peaks is always one more (n+1) than the
Fig 5 The two hydrogen environments in 1,2-dichloro-2- number of hydrogens (n) on the adjacent carbon atom. You
methylpropane won’t need to explain how this happens, but you do need to
H understand its effects.
H C H environment 1
Table 2 Splitting patterns
H H
environment 2
H C C C H Number of Splitting How it looks Typical
Cl Cl H hydrogen atoms pattern structure
on the adjacent (n+1)
2. The relative number of hydrogens in each environment carbon atom (n)
The second piece of information comes from the integration
curve, the line above each peak. The height of this line
corresponds to the area under the curve and therefore tells us
the relative numbers of hydrogen atoms in the different 0 Singlet R3CCH
environments. If you measure the height of the two integration
curves in Fig 4 you will find that they are in a ratio of 1:3. This
matches the structure of the compound, with two hydrogen
nuclei in Environment 2 and six in Environment 1.
3. The electron density around the hydrogen atoms 1 Doublet R2CH-CH
The third piece of information is about the nature of each
environment. This information is given by the chemical shifts
(Table 1). In the exam, you will be given the chemical shifts that
you need, so don’t try to memorise them.
Looking at Fig 4 again, the peaks at 1.6 and 3.7 ppm correspond
respectively to the methyl hydrogens (Environment 1) and the
CH2Cl hydrogens (Environment 2), which are deshielded by the
closer electron-withdrawing chlorine atom. 2 Triplet RCH2-CH

Table 1 Typical chemical shifts of a range of hydrogen nuclei

Proton Chemical shift (ppm)
R-CH3 0.8-1.2
R2-CH2 1.1-1.5
R3-CH 1.5 3 Quartet CH3-CH
R3-OH 1.0-6.0

Note that the OH hydrogen

atom can appear almost In the NMR of 1,2-dichloro-2-methylpropane (Fig 4), both peaks are
anywhere along the chemical singlets. This means that none of the hydrogens are adjacent to
shift scale non-equivalent hydrogen nuclei (Fig 6).
O
1.0-6.0 Fig 6 No adjacent hydrogen atoms to either environment
C
R CH2R H
R-CH2-Cl 2.5-4.3 environment 1
H C H
R-CH2-OH 3.3-4.0 H H
R H environment 2
4.4-6.9 H C C C H
C C
R R Cl Cl H
O
C 9.2-9.8
R H This carbon atom is adjacent to both environments. It has no hydrogen
O atoms so both peaks are singlets
C 10.0-12.0
R OH
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113 High Resolution NMR Spectroscopy Chem Factsheet

Fig 7 shows the proton NMR spectrum of ethyl ethanoate. The Answer
three peaks show that there are three different environments for the The displayed formula and NMR spectrum of chloroethane are
hydrogen atoms. The integration curves give us a ratio of 2:1:3, shown in Fig 9. There are two hydrogen environments: the methyl
and analysis of the splitting patterns (Table 3) leads to a full hydrogens (a) and the CH2Cl hydrogens (b). Using Table 1 the
assignment of peaks (Fig 8). approximate chemical shifts are 1.1-1.5 and 2.5-4.3 ppm respectively.
The peak at about 1.4 ppm (corresponding to the CH3) is split into a
Fig 7 The proton NMR spectrum of ethyl ethanoate triplet by the neighbouring CH2Cl hydrogens, while the peak at 3.5
ppm (corresponding to the CH2Cl) is split into a quartet by the
H methyl group.
O
H H
H C C
Fig 9 Chloroethane and its NMR spectrum
O C C H
H
H H -CH3(a)
b
a H H

H C C Cl -CH2Cl(b)

H H

11 10 9 8 7 6 5 4 3 2 1 0
δ (ppm)

Table 3 Assigning the peaks in the NMR of ethyl ethanoate

10 9 8 7 6 5 4 3 2 1 0
Chemical Relative Splitting Number of Assigned δ (ppm)
shift number pattern adjacent to proton
of hydrogen hydrogens group An unusual case: Alcohol OH groups
atoms The hydrogen atom in alcohol OH groups is unusual in two ways.
4.1 2 Quartet 3 b Firstly, as it says in Table 1, this proton can have almost any chemical
shift. The actual shift depends on, among other things, the solvent
2.0 3 Singlet 0 a that the compound is dissolved in. Secondly, at room temperature
OH proton peaks do not get split like others, no matter how many
1.2 3 Triplet 2 c
adjacent hydrogen nuclei there are. This helps you, therefore, to
identify them in the spectra since they are always singlet peaks.
Fig 8 Assigned peaks in ethyl ethanoate
Practice Questions
a H 1. For each of the following compounds, draw the displayed
b c
O formula, label the different hydrogen environments and predict
H H
H C C
approximate chemical shifts for each peak in the proton NMR
spectrum:
O C C H
(a) 2-chloropropane
H
(b) 1-chloropropane
H H (c) ethanol
(d) ethanoic acid
(e) 2-chloropentane
Worked example (f) 3-chloropentane
1. Draw the displayed formula of chloroethane.
2. State the number of different hydrogen environments found 2. Sketch the proton NMR spectra you would expect for the
in chloroethane. following compounds:
3. Predict approximate chemical shifts for the different (a) ethanoic acid
environments. (b) propanone
4. Predict the splitting pattern of the NMR peaks. (c) ethanal
5. Sketch the NMR spectrum of chloroethane, including (d) ethanol
integration curves to show the relative numbers of hydrogen
atoms in each environment.

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113 High Resolution NMR Spectroscopy Chem Factsheet

(b)
Answers

Question 1 O
(a) Environment 2 C
Cl H3C CH3
Environment 1 = 2.5-4.3 ppm
H 3C C CH3 Environment 2 = 0.8-1.2 ppm
H
Environment 1

H H
(b) Environment 1 = 0.8-1.2 ppm
H 3C C C Cl
Environment 2 = 1.1-1.5 ppm
1 H H Environment 3 = 2.5-4.3 ppm
2 3
10 9 8 7 6 5 4 3 2 1 0
H H
(c) Environment 1 = 0.8-1.2 ppm δ (ppm)
H C C O Environment 2 = 3.3-4.0 ppm
H H H Environment 3 = 1.0-6.0 ppm (c)
1 2 3
O

O C
(d) H H 3C H
H C C O Environment 1 = 2.0-3.0 ppm
H H Environment 2 = 10.0-12.0 ppm
1 2

Cl H H Environment 1 = 0.8-1.2 ppm

Environment 2 = 2.5-4.3 ppm
(e) H 3C C C C CH3
Environment 3 = 1.1-1.5 ppm
1 H H H 5 Environment 4 = 1.1-1.5 ppm
2 3 4 Environment 5 = 0.8-1.2 ppm

(f) Environment 1 = 0.8-1.2 ppm 10 9 8 7 6 5 4 3 2 1 0

H Cl H Environment 2 = 1.1-1.5 ppm δ (ppm)
H3C C C C CH 3 Environment 3 = 2.5-4.3 ppm
1 Note that this molecule is (d)
H H H 1
symmetrical so has only three
2 3 2
different hydrogen environments H H
H C C O
H
Question 2 H H
(a)

O
C
H 3C OH

11 10 9 8 7 6 5 4 3 2 1 0
δ (ppm)
Acknowledgements: This Factsheet was researched and written by Emily Perry.
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