100 Topic 7 — Modern Analytical Techniques I

Mass Spectrometry
This topic’s about some of the fancy techniques chemists use to work out what different unknown compounds are. Neat.

Mass Spectrometry Can Help to Identify Compounds

1) You saw on page 7 how you can use a mass spectrum showing the relative isotopic abundances of an
element to work out its relative atomic mass. You can also get mass spectra for molecular samples.
2) A mass spectrum is produced by a mass spectrometer. The molecules in the sample are bombarded with
electrons, which remove an electron from the molecule to form a molecular ion, M+(g).
3) To find the relative molecular mass of a compound you look at the | | | | | | | | | | | |
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Assuming the ion

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molecular ion peak (the M peak). This is the peak with the highest m/z value
has a +1 charge, which
(ignoring any small M+1 peaks that occur due to the isotope carbon-13). it normally will have.
The mass/charge value of the molecular ion peak is the molecular mass.
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The y-axis gives 100 CH3CH2CH2+ Pentane Here’s the mass spectrum of pentane.
relative abundance (%)

the abundance CH3CH2CH2CH2CH3 Its M peak is at 72 — so the

80
of ions, often as M peak — caused compound’s Mr is 72.
a percentage. 60 by molecular ion For most organic compounds the
CH3CH2CH2CH2CH3+ M peak is the one with the second
40 CH3CH2+
The x-axis units CH3CH2CH2CH2+ highest mass/charge ratio.
are given as a 20 CH3+ The smaller peak to the right of the
M+1 peak M peak is called the M+1 peak —
‘mass/charge’
ratio.
0 it’s caused by the presence of
10 20 30 40 50 60 70 the carbon isotope 13C.
mass/charge (m/z)

The Molecular Ion can be Broken into Smaller Fragments

1) The bombarding electrons make some of the molecular ions break up into fragments.
The fragments that are ions show up on the mass spectrum, making a fragmentation pattern. Fragmentation
patterns are actually pretty cool because you can use them to identify molecules and even their structure.
CH3CH2 + CH3+
For propane, the molecular ion is CH3CH2CH3+, and the fragments free radical ion
it breaks into include CH3+ (Mr = 15) and CH3CH2+ (Mr = 29). CH3CH2CH3+
Only the ions show up on the mass spectrum — the free radicals are ‘lost’. CH3CH2+ + CH3
ion free radical

2) To work out the structural formula, you’ve got to work out what ion could have
made each peak from its m/z value. (You assume that the m/z value of a peak Fragment Molecular Mass
matches the mass of the ion that made it.) Here are some common fragments: CH3+ 15
C2H5+ 29
relative abundance (%)

Example:  se this mass spectrum

U
to work out the structure CH3CH2CH2+
of the molecule: or 43
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It’s only the m/z values
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you’re interested in — ignore OH+ 17

the heights of the bars. 0 5 10 15 20 25 30 35 40 45 50
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mass/charge (m/z)

31 +
CH2OH
relative abundance (%)

1. Identify the fragments

+
This molecule’s got a peak at 15 m/z, + 29 CH2CH3
15 CH3
so it’s likely to have a CH3 group. + 46 M peak +
CH2 14 CH3CH2OH
It’s also got a peak at 17 m/z, 17 OH
+

so it’s likely to have an OH group.

Other ions are matched to the peaks here: 0 5 10 15 20 25 30 35 40 45 50
mass/charge (m/z)
2. Piece them together to form a molecule with the correct Mr
Ethanol has all the fragments on this spectrum. H H
Ethanol’s molecular mass is 46. H C C O H
This should be the same as the m/z value of the M peak — it is. H H

Topic 7 — Modern Analytical Techniques I

 101

1862_RG_MainHead
Mass Spectrometry
Mass Spectrometry is Used to Differentiate Between Similar Molecules
1) Even if two different compounds contain the same atoms, you can still tell them apart with
mass spectrometry because they won’t produce exactly the same set of fragments.
2) The formulae of propanal and propanone are shown below.

H H O H O H
H C C C H C C C H
H H H H H
propanal
propanal propanone
propanone A massage spectrum

They’ve got the same Mr , but different structures, so they produce some different fragments.
For example, propanal will have a C2H5+ fragment but propanone won’t.
3) Every compound produces a different mass spectrum — so the spectrum’s like a fingerprint for the compound.
Large computer databases of mass spectra can be used to identify a compound from its spectrum.

Practice Questions
Q1 What is meant by the molecular ion?
Q2 What is the M peak?
Q3 What causes the presence of an M+1 peak on the mass spectra of most organic compounds?
Exam Questions

Q1 Below is the mass spectrum of an organic compound, Q.

Y
a) What is the Mr of compound Q? [1 mark]
relative abundance

b) What fragments are the peaks marked

X and Y most likely to correspond to? [2 marks]

X c) Suggest a structure for this compound. [1 mark]

d) Why is it unlikely that this

0 5 10 15 20 25 30 35 40 45 compound is an alcohol? [1 mark]
mass/charge (m/z)

Q2 Mass spectrometry is run on a sample of but-2-ene (CH3CHCHCH3) and a mass spectrum is produced.
For the following questions, assume that all ions form with a +1 charge.

a) At what m/z value would you expect the M peak of but-2-ene to appear? [1 mark]

b) A peak appears on the spectrum at m/z = 41. Suggest which fragment is responsible for this peak. [1 mark]

c) Apart from the M peak and the peak at m/z = 41, suggest one other peak that you would expect
to be present on the mass spectrum of but-2-ene. What fragment does it correspond to? [2 marks]

Q3 An unknown alcohol has the chemical formula C3H8O.

A sample of the compound was inserted into a mass spectrometer and a mass spectrum was produced.
A peak appears on the mass spectrum at m/z = 31.
Name the unknown alcohol and draw its structure. Explain your answer. [4 marks]

Use the clues, identify a molecule — mass spectrometry my dear Watson...

I hate break ups — even if it is to make some lovely ions and a fragmentation pattern. But remember — mass
spectrometry only records fragments that have a charge. So, when drawing or writing the fragments that a peak could be
responsible for, remember to put that little positive sign next to them — you’ll lose marks in the exam if you don’t show it.

Topic 7 — Modern Analytical Techniques I

102

Infrared Spectroscopy
If you’ve got some stuff and don’t know what it is, don’t taste it. You can stick it in an infrared spectrometer.
You’ll wind up with some scary looking graphs. But just learn the basics, and you’ll be fine.

Infrared Radiation Makes Some Bonds Vibrate More

1) In infrared (IR) spectroscopy, a beam of IR radiation is passed through a sample of a chemical.
2) The IR radiation is absorbed by the covalent bonds in the molecules, increasing their vibrational energy.
3) Bonds between different atoms absorb different frequencies of IR radiation. Bonds in different places in a
molecule absorb different frequencies too — so the O–H group in an alcohol and the O–H in a carboxylic acid
absorb different frequencies. This table shows what frequencies different bonds absorb:

Group Where it’s found Wavenumber (cm–1)

Alkanes 2962-2853
C–H stretching Alkenes 3095-3010
Aldehydes 2900-2820 and 2775-2700
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C–H bending Alkanes 1485-1365 Bending is just

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another sort of
N–H stretching Amines 3500-3300 vibration.

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Alcohols 3750-3200
O–H stretching
Carboxylic Acids 3300-2500 (broad)
C=C stretching Alkenes 1669-1645
Aldehydes 1740-1720
C=O stretching Ketones 1720-1700 ||
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You don’t need to

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Carboxylic Acids 1725-1700 learn this data,

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but you do need
4) You’ll be given all the infrared spectroscopy data you need in the exams. to understand
It may be presented a bit differently to the table above and it might contain different || | | | ||
how to use it.
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information. Don’t worry though — just use it in the same way as the stuff above.

Infrared Spectroscopy Helps You Identify Organic Molecules

1) An infrared spectrometer produces a graph that shows you what frequencies of radiation the molecules are
absorbing. So you can use it to identify the functional groups in a molecule. All you have to do is use the
infrared data table to match up the peaks on the spectrum with the functional groups that made them.
2) The peaks show you where radiation is being absorbed
(the peaks on IR spectra are upside-down — they point downwards).
3) Transmittance is always plotted on the y-axis, and wavenumber on the x-axis.
Wavenumber is the measure used for the frequency (it’s just 1/wavelength in cm).

100
Infrared spectrum of ethanal
The absorption at about
3000 cm–1 is caused
%
Transmittance %

by the C–H groups.

Transmittance

50

This strong, sharp

absorption at about
1700 cm–1 shows you 0
there’s an C=O group. 4000 3000 2000 1500 1000 500 The toe toucher was
-1
Wavenumber
Wavenumber (cm
(cm ) –1) Carol’s favourite stretch.

Topic 7 — Modern Analytical Techniques I

 103

Infrared Spectroscopy
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Infrared Spectroscopy Can Show if a Reaction’s Happened See pages 96‑97

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for more on
Infrared spectroscopy is great for telling if a functional group has changed during a reaction. the oxidation of
For example, if you oxidise an alcohol to an aldehyde you’ll see the O–H absorption disappear || |
alcohols.
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from the spectrum, and a C=O absorption appear. If you then oxidise it further to a carboxylic acid
an O–H peak at a slightly lower frequency than before will appear, alongside the C=O peak.

Example: A chemical was suspected to be a pure sample of an unknown aldehyde.

When the chemical was tested using infrared spectroscopy, the spectrum below was obtained.
Is the chemical an aldehyde? Explain your answer.
Infra-red Spectrum of Ethanol
1) If the chemical was an aldehyde, it would contain 100
a carbonyl group (a C=O functional group — see page 96).

Transmittance %
2) In infrared spectroscopy, a carbonyl group would show a
strong, sharp peak at about 1700-1750 cm–1.
50
3) The spectrum on the right doesn’t have a strong
peak at this frequency, and so is not an aldehyde
(or a ketone, a carboxylic acid or an ester).
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0
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Actually, this is the infrared spectrum of ethanol. 4000 3000 2000 1500 1000 500
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–1
Wavenumber (cm )

Practice Questions
Q1 What happens to a covalent bond when it absorbs infrared radiation?
Q2 Why do most infrared spectra of organic molecules have a strong, sharp peak at around 3000 cm–1?
Q3 What functional group would be responsible for a peak on an infrared spectrum at around 1740-1720 cm–1?
Exam Questions

Q1 The IR spectrum of an organic molecule is shown on the right.

a) Which of the following compounds
could be responsible for the spectrum? 100
Transmittance (%)

Use the infrared data on page 102.

A butanoic acid
B butanal 50

C 1-aminobutane
D butanol [1 mark] 0
4000 3500 3000 2500 1500 1000 500
2000
–1
b) Explain your answer to a). [2 marks] Wavenumber (cm )

Q2 The molecule that produces the IR spectrum shown

on the right has the molecular formula C3H6O2.
A B
Transmittance (%)

100
Use the infrared data on page 102.

a) Which functional groups are 50

responsible for peaks A and B? [2 marks]
0
b) Give the structural formula and name 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600
of this molecule. Explain your answer. [2 marks] –1
Wavenumber (cm )

To analyse my sleep patterns, I use into-bed spectroscopy...

Infrared spectra may just appear to be big, squiggly messes — but they’re actually dead handy at telling you what sort of
molecule an unknown compound is. Luckily you don’t have to remember where any of the infrared peaks are, but you do
need to be able to identify them using your data sheet. So get some practice in now and do those exam questions above.

Topic 7 — Modern Analytical Techniques I