Chapter 11: Measurement and Data Processing

Title: Lesson 3 Spectroscopic identification of

organic compounds (NMR) (SL and HL)
Learning Objectives:
– Describe how mass spectrometry (MS), proton nuclear
magnetic resonance spectroscopy (1H NMR), and infrared
spectroscopy (IR) are techniques that can be used to help
identify the structure of compounds
– Describe high resolution NMR spectroscopy (HL ONLY)
Nuclear magnetic resonance spectroscopy (NMR)
 Technique for finding the structure and
shape of molecules – a combo of
nuclear physics and chemistry

 The nuclei of atoms with an odd number

of protons or mass e.g. 1H, 13C, 19F, and
31P spin and behave like tiny bar
Planck’
magnets s
Equatio
 If placed in an external magnetic field, n
some of these nuclei will line up
with an applied field, and, if they have
sufficient energy, some will line up
against it

 This arrangement leads to two nuclear

energy levels

 The energy needed for the nuclei to

reverse their spin and change their
orientation in a magnetic field can be
provided by radio waves
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How does it work? NMR Spectroscopy Video - RSC

 A sample is placed in an
electromagnet

 Field strength is varied until

the radio waves have the
exact frequency to make the
nuclei flip over and spin
the opposite direction

 This is called resonance

and can be detected
electronically and recorded
in the form of a spectrum
NMR spectroscopy is non-invasive as the
sample can be recovered unchanged
after the experiment
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How does NMR spectroscopy work?

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Hydrogen nuclei in different chemical environments
have different chemical shifts…
 As electrons shield the nucleus from the full effects of the external
magnetic field, differences in electron distribution produce
different energy separations between two spin energy levels

 Nuclei in different chemical environments produce different

signals in the spectrum… 1H NMR is particularly useful (found in all
organic molecules)

 Signals are measured against a standard signal produced by 12

hydrogen nuclei in tetramethylsilane (TMS)

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 The position of the NMR signal relative to this standard is called the
chemical shift of the proton NMR Video - Part 1

 Hydrogen in particular environments have characteristic chemical shifts

E.g. Ethanol has 3 different

proton or hydrogen
environments (colour coded
in diagram)

Complete list is given in

section 27 of the IB data
booklet Main Menu
Proton NMR spectroscopy

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Interpreting 1H NMR spectra NMR Video - Integration
NMR Video - Chemical Shift

1
H NMR
spectrum for
ethanal

Spectrum trace shows:

 A peak at 9.7 for CHO
 A peak at 2.1 for CH3

 Note: Area under the CH3 peak is three times larger than that under the CHO peak, this tells us the
relative number of protons in each environment

 The integrated gives this information more directly, as it goes up in steps which are proportional to the number
of protons
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Integration and the number of hydrogens
The height of the peaks in an NMR spectrum does not give
us any useful information.
However, the area
under the peaks on
a 1H NMR spectrum
is proportional to the
number of hydrogen
atoms causing the 3
signal. The ratio of
2
the areas under the
peaks tells you the 1
ratio of 1H atoms in
each environment.

The spectrum can be integrated to find this information.

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Interpreting 1H NMR spectra activity – (Number of Environments)

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 Combining the information
(a) Empirical
 The analyst formula
may have to
use data from
other sources (b) Molecular
formula
along with
techniques
such as IR
spectroscopy in
order to give a
complete
structure of the
molecule… (c) Mass
Spectrometry
(d) Infrared
Spectroscopy

(e) NMR
Spectrometry

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Uses of NMR spectroscopy
NMR spectroscopy uses the same
technology as magnetic resonance
imaging (MRI). This is an important
non-invasive method of gaining
information about internal structures in
the body used in diagnostic medicine
and scientific research.

NMR spectroscopy is also used in

the pharmaceutical industry to
check the purity of compounds.

Often, a combination of mass spectrometry, infrared

spectroscopy and NMR spectroscopy is used in modern
analysis to elucidate the structure of organic molecules.
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 Spectroscopic identification of organic compounds -
Further NMR spectroscopy (HL)
 Tetramethylsilane (TMS) as the reference

 NMR signals are measured against a standard produced by the 12 hydrogen

nuclei in tetramethlysilane (TMS)

The absolute
 All the hydrogen nuclei are in the same environment, so one signal is recorded
frequency of the
signal depends on
 Because silicon has a lower electronegativity than carbon, TMS the strength of the
absorbs radio waves in a different region from that absorbed by magnetic field.
hydrogen nuclei attached only to carbon
However, the
chemical shift –
 The standard signal will not overlap with any signals under investigation
relative to the
TMS is inert and
standard – stays the
soluble in most
same.
organic solvents. Low
You won’t need to boiling point mean it
emical shift (δ) of a proton in a molecule is defined as:
use this in can easily be
calculations… removed from the
= frequency of radio waves absorbed by the protons in the sample sample.
= frequency of radio waves absorbed by the protons in the TMS
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 NMR Video - Spin-Spin Coupling
High resolution H NMR Spectroscopy NMR Video - Spin-Spin Coupling
1

Part 2
 NMR spectrum does not generally consist of a series of single peaks shown in the low
resolution spectra shown earlier

 High resolution NMR reveals that the single peaks are split or resolved into a group of
smaller parts
Splitting of peaks happens because the
effective magnetic field, experienced by
particular nuclei, is modified by the magnetic
field produced by neighbouring protons.

This is known as spin-spin coupling.

Magnetic field experienced by

the proton in the methyl group
depends on the spin of the
proton attached to the carbon
atom of the carbonyl group
(CHO) Ethanal – low and hi res
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Magnetic field of the CH3 group ΔE
depends on the proton spin of the ‘With’
CHO group… a
field

 The local magnetic field is

increased when the magnetic
field of the CHO proton is
aligned with the external field
and decreased when aligned
against it

 As the energy separation

between the two spin states
ΔE
‘Against’
of a proton depends on the field
n
local magnetic field…

 There are two possible values

for energy difference between
the two nuclear energy
levels for the CH3 protons
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 Instead of one signal corresponding to one energy difference, ΔE, two
signals corresponding to ΔEa and ΔEn are produced

 Each line corresponds to a different spin on the neighbouring proton

2 peaks
(because
of 2
 Both equally likely, so lines are of equal intensity different
alignmen
ts of CHO
proton)

2 peaks for CH3 groups due to the

possible combinations of alignments for
the proton in CHO

‘With ‘Again
’ st’ Main Menu
 4 peaks
(because The low-resolution peak corresponding to the
of CHO proton is split due to the different
different magnetic fields produced by the
alignmen
ts of CH3
combinations of spin for the three
protons) protons of the neighbouring methyl
group

Possible alignments for 3 protons in CH3

group

Important Note: The lack of splitting with -OH groups

Unless the alcohol is absolutely free of any water, the 4 peaks in the signal for CHO due to the
hydrogen on the -OH group and any hydrogens on the next CH3 group
door carbon don't interact to produce any splitting. The -OH
peak is a singlet and you don't have to worry about its
• 2 possible orientations for each proton, so
effect on the next door hydrogens. total of 23 combos possible.
• Four different local magnetic fields
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Spin coupling

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 Splitting patterns produced from different numbers of neighbouring
protons can be deduced by Pascal’s triangle:

NOTE:

 Protons bonded to the same atom do not interact with one another (they behave as a
group)
 Protons on non-adjacent carbon atoms do not interact with one another
Nice Website About NMR Theory - Chem Guide

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Splitting pattern activity

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H NMR chemical shift assignment
1

The chemical shift values of peaks on an 1H NMR spectrum

give information about the likely types of proton environment
in a compound.
Type of
δ/ppm
proton

0.7–1.2

2.1–2.6

9.0–10.0

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 1
H NMR chemical shift assignment activity

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X-ray diffraction
 We see the world because light shines on objects and we observe the
light that is scattered from them

 We cannot examine individual atoms and molecules this way because

the wavelength of visible light is too long to interact effectively with
matter so small

 Inter-atomic distances are of the order of 10-9m which corresponds to

wavelengths of X-rays

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 When X rays pass through a
crystalline solid, they are scattered in
an orderly way by the electrons in
the substance

 Scattered waves interact with each

other to cause a diffraction pattern

 ‘In phase waves’:

 Peaks are still aligned

 Waves interfere constructively

 They reinforce each other,

producing a resultant wave
with larger amplitude than the
original

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 ‘Out of phase waves’:
 Peaks misaligned by 180o

 Waves interfere destructively

 Peak of one wave aligned with

the trough of another

 Cancel each other out

completely if the amplitude is
the same (complete
 When X rays shine on a crystal, they are reflected in consecutive planes
destructive interference)

 Scattered waves interfere as they travel different distances through a crystal

 The X rays may be at different phases (depending on wavelength) as they hit the
detector

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What affects the diffraction pattern? X Rays Diffraction Video

 Depends on the
relationship between:
 Angle of incidence (θ)
 The wavelength of the incident
X ray (λ)
 The distance between atoms
and their relative orientations
(d)

 X rays of a single or small range of wavelengths are used to ensure a simple

correspondence between the diffraction pattern and the crystal structure

 Sample must be in solid state to give ordered diffraction patterns that can be
interpreted

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The electron density map
 A map of electron density in a solid
can be determined directly from the
X ray diffraction pattern

 Contour lines connect points with the

same electron density

 Identity of the atoms can be

determined as the pattern in
electron densities are related to an
element’s electron configuration
Note: Hydrogen atoms
Anthracen
only have 1 electron, so
e
are not visible due to
low electron density!
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