Chem Factsheet

April 2003 Number 54

Organic Analysis I : Infrared Spectroscopy

Before working through this Factsheet you should: The amount of IR radiation absorbed at different wavelengths by the sample
• Have a good knowledge of the organic chemistry covered at AS and A2 level. chemical is compared with a blank sample cell and quoted as a percentage.
• Understand covalent bonding.
• Be able to recognise functional groups within organic structures. If a sample absorbs IR at a certain frequency and wavelength, the IR will
not pass through the compound to the detector, so a low transmittance %
After working through this Factsheet you will: will be recorded.
• Be able to interpret simple Infrared spectra.
• Have a basic understanding of how an infrared spectrometer works.
Spectra
The A2 syllabus requires candidates to be able to interpret simple infrared An example of an IR spectrum is shown below (fig 3).
spectra. At first glance this can appear to be a daunting task - the spectra
themselves look complex, and background reading about how the spectra Fig 3. Example of an IR spectrum
are produced can sometimes be confusing.
transmittance /%
Do not fear infrared spectra - they are a tool to help chemists determine the 100
structure of organic chemicals. With a little experience and use of any data
supplied in an exam paper, scoring marks on questions involving IR spectra
is not as difficult as it may seem. 80

In this Factsheet the workings of the infrared spectrometer will be briefly

outlined - look to a textbook for a more detailed description if you are 60
interested. The main focus of the Factsheet is to give candidates the
necessary experience of IR spectra, and the expertise to pick up some
40
valuable exam marks.

Introduction 20
Infra-red spectroscopy depends on the fact that infrared radiation is
absorbed by certain molecular bonds and causes them to vibrate vigorously.
These vibrations involve stretching or bending (Fig 1). 4000 3500 3000 2500 2000 1500 1000 500
wave number / cm-1
Fig 1. Symmetrical, asymmetrical, bending effects Note the axis labels:
• wavenumber (cm-1) (x-axis)
H H H H H H • transmittance (a percentage) (y-axis)
C C C
The wavenumber is related to the wavelength of the IR absorbed:

symmetrical asymmetrical bending or 1

Wavenumber =
stretching stretching scissoring Wavelength

The transmittance shows the percentage of the IR that passes through the
Different bonds absorb IR of different wavelengths and frequencies, e.g. sample cell - so the lower it is, the more is absorbed.
C=O absorbs IR of a different wavelength to O-H.
Here is a data table showing some different IR absorption ranges of different
By looking at the frequencies at which a substance absorbs IR radiation, bonds:
we can therefore gain an idea of the bonds in it.
Bond Wavenumber Range (cm-1)
The apparatus used in this form of analysis, an infrared spectrometer, is C-O 1000 - 1300
based on a split-beam mechanism (Fig 2). C=O 1650 - 1750
Fig 2. Infrared spectrometer C-H (alkanes) 2850 - 3000
C-H (alkenes) 3000 - 3100
Sample cell O-H 2500 - 3500 broad peaks due
N-H 3300 - 3500 to H-bonding
Light
source Such data was compiled by comparing the IR spectra of related compounds.
Beam split Note that bonds (such as C-H) will absorb slightly different wavelengths
Prism Control cell Detector for
beam comparison depending on the surrounding atoms. This means that it is impossible to
assign a precise wavenumber to a bond. Nevertheless, we can identify
bands or ranges corresponding to specific bonds, as shown in the data
table.
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Organic Analysis I : Infrared Spectroscopy Chem Factsheet

For the following IR spectrum of an ‘unknown’ organic compound, we can Peak Assigned Bond
assign different absorption peaks to particular bonds (using the data table)
and gain some information about the content and structure of the sample 2500 - 3500 cm-1 Broad O-H peak, characteristic shape
compound (Fig 4). 1700 - 1750 C=O
1250 - 1300 C-O
Fig 4. IR spectrum of unknown organic compound
The spectrum is in fact that of ethanoic acid, so the above bonds are
transmittance /% present:
H
100 O
H C C
O H
80 H

Remember that assigning peaks in IR spectra is not an ‘exact science’,

60 instead careful use of a data table and common sense is required.

40 Exam Hint: Ignore ‘interference peaks’, or ‘weak absorption peaks’,

and focus on strong peaks where transmittance drops to below 70%.

20
Assign peaks for the following spectrum (Fig 7):
4000 3500 3000 2500 2000 1500 1000 500
Fig 7.
wave number / cm-1
transmittance /%
100
Peak Assigned Bond
3100 - 3500 cm-1 O-H
2800 - 3000 cm-1 C-H 80
1050 - 1100 cm-1 C-O
60
Note that this information alone does not tell us what the unknown chemical
is, but helps to build a picture. We now know the following about the
sample: 40
• Not a carbonyl or carboxylic acid (no C=O).
• Not an amine, amide or amino acid (no N-H). 20
• O-H, C-O and C-H bonds are present.

The spectrum is actually that of ethanol, so all of the above-deduced 4000 3500 3000 2500 2000 1500 1000 500
information is correct. wave number / cm-1

Exam Hint: Look at the shape of the broad O-H absorption peak - it is
very distinctive and easy to spot (now you know what you are looking for!). Peak Assigned bond
3300 - 3500 cm-1 Broad N-H peak, ‘double pronged’ shape
The peaks given by O-H and N-H are usually broad owing to 2800 - 3000 cm-1 C-H
hydrogen bonding.
There are no other significant peaks that correlate with the data table.

The spectrum is that of propyl amine

Now look at this next spectrum and ‘assign’ the major peaks:
H H H
H
transmittance /%
H C C C N
100 H
H H H

80 As mentioned above, the shapes of N-H peaks and O-H peaks are different,
so usually can be told apart despite them being in the same region of the
spectra. The O-H peaks are broader, whilst the N-H peaks are often
60
‘double-pronged’ in shape.

40 Exam Hint: IR spectra are commonly used in conjunction with other

organic analysis techniques, such as UV spectrometry, mass
spectrometry and NMR, to identify unknown compounds.
20
The interpretation of simple IR spectra often forms part of an exam
question, as knowledge of these other forms of organic analysis are
also required - see later Factsheets.
4000 3500 3000 2500 2000 1500 1000 500
wave number / cm-1

2
Organic Analysis I : Infrared Spectroscopy Chem Factsheet

Questions Answers
Assign the peaks to bonds in the following spectra. In the answers you
will simply be given the structure of the compound from which the spectrum 1.
was generated, but with a little thought you can check to see if you have H H
O
assigned the correct bonds!
H C C C
1. H H H
transmittance /%
2.
100 H
O
H C C
80
N H
H
60 H

3.
40 H H
H
H C C O
20 C C
H H H

4000 3500 3000 2500 2000 1500 1000 500 O H

-1
wave number / cm

2.
transmittance /%

100

80

60

40

20

4000 3500 3000 2500 2000 1500 1000 500

wave number / cm-1

3.
transmittance /%
100

80

60

40

Acknowledgements:
20 This Factsheet was researched and written by Kieron Heath
Curriculum Press, Unit 305B, The Big Peg, 120 Vyse Street, Birmingham,
4000 3500 3000 2500 2000 1500 1000 500 B18 6NF
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