FU RT HER

MAS S
SPE CTR OME TR
Y
A guide for A level students

KNOCKHARDY PUBLISHING
 KNOCKHARDY PUBLISHING

MASS SPECTROMETRY
INTRODUCTION
This Powerpoint show is one of several produced to help students understand
selected topics at AS and A2 level Chemistry. It is based on the requirements of
the AQA and OCR specifications but is suitable for other examination boards.
Individual students may use the material at home for revision purposes or it may
be used for classroom teaching if an interactive white board is available.
Accompanying notes on this, and the full range of AS and A2 topics, are available
from the KNOCKHARDY SCIENCE WEBSITE at...

www.argonet.co.uk/users/hoptonj/sci.htm

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MASS SPECTROMETRY

CONTENTS
• Fragmentation of molecular ions - theory
• What a mass spectrum tells you
• Molecular ions
• Fragmentation
• Mass spectra of alkanes
• Mass spectra of halogenoalkanes
• Mass spectra of aldehydes and ketones
• Test questions
• Check list
 MASS SPECTROMETRY

Before you start it would be helpful to…

• recall the basic principles of a mass spectrometer

• know the different types of functional group in organic chemsitry
 MOLECULAR MASS DETERMINATION
USING MASS SPECTROMETRY

Nowadays, mass spectrometry is used

to identify unknown or new compounds.

IONISATION When a molecule is ionised it forms a

MOLECULAR ION which can also
MOLECULAR ION undergo FRAGMENTATION or RE-
ARRANGEMENT to produce particles of
FRAGMENTION smaller mass.

Only particles with a positive charge

will be deflected and detected.

RE-ARRANGEMENT FRAGMENTION The resulting spectrum has many peaks.

The final peak (M+) shows the molecular

ion (highest m/z value) and indicates the
molecular mass. The rest of the
spectrum provides information about
the structure.
 THE MASS SPECTRUM

Spectra obtained for organic molecules have many peaks. Each peak is due to a
particular fragment with a certain m/z value.

highest m/z value usually corresponds to the molecular ion

its position provides information about the molecular mass of a substance

the tallest peaks come from the most stable species

 THE MASS SPECTRUM

Spectra obtained for organic molecules have many peaks. Each peak is due to a
particular fragment with a certain m/z value.

highest m/z value usually corresponds to the molecular ion

its position provides information about the molecular mass of a substance

the tallest peaks come from the most stable species

Interpretation of thousands of spectra has shown that many classes of organic

compound show characteristic fragmentation patterns due to their functional groups.
It is possible to identify the type of compound from its spectrum by looking at the ...

position of peaks
differences between major peaks
 THE MASS SPECTRUM - THE MOLECULAR ION

In the spectrum of octane, a signal occurs at 114 due to the species C8H18+

The species due to the final signal is known as the molecular ion and is usually
corresponds to the molecular mass of the compound.
100
80
Abundance %
60

molecular ion
40

114
20

0
. m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 THE MASS SPECTRUM - THE MOLECULAR ION

The small peak (M+1) at 115 due to the natural abundance (about 1%) of carbon-13.
The height of this peak relative to that for the molecular ion depends on the number of
carbon atoms in the molecule. The more carbons present, the larger the M+1 peak.
100
80
Abundance %
60
40

114
20

0
. m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 THE MASS SPECTRUM - FRAGMENTATION

The rest of the spectrum provides additional information of the molecule’s structure.
Peaks appear due to characteristic fragments (e.g. 29 due to C2H5+) and differences
between two peaks also indicates the loss of certain units (18 for H2O, 28 for CO).
100

43
80
Abundance %
60

29
57 71 85
40

114
20

0
. m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 FRAGMENTATION PATTERNS

ALKANES
The mass spectra of simple hydrocarbons have peaks at m/z values corresponding to
the ions produced by breaking C-C bonds. Peaks can occur at ...

m/z 15 29 43 57 71 85 etc.
CH3+ C2H5+ C3H7+ C4H9+ C5H11+ C6H13+

• the stability of the carbocation formed affects its abundance

• the more stable the cation the higher the peak

• the more alkyl groups attached to the carbocation the more stable it is

most stable tertiary 3° > secondary 2° > primary 1° least stable

alkyl groups are electron releasing and stabilise the cation
 FRAGMENTATION PATTERNS

HALOGENOALKANES
Multiple peaks occur in the molecular ion region due to different halogen isotopes.
There are two peaks for the molecular ion of C2H5Br, one for the molecule containing the
isotope 79Br and the other for the one with the 81Br isotope. Because the two isotopes
are of similar abundance, the peaks are of similar height.
100

molecular ion contains...79Br 81

Br
80
Abundance %
60
40
20

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 FRAGMENTATION PATTERNS

ALDEHYDES AND KETONES

Cleavage of bonds next to the carbonyl group (C=O) is a characteristic fragmentation
of aldehydes and ketones. A common fragment is carbon monoxide (CO) but as it is a
molecule and thus uncharged it will not produce a peak of its own. However, it will
produce an m/z drop of 28 somewhere in the spectrum.

The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group

the more stable the acylium ion RCO+, the more abundant it will be and
the more abundant the species the taller its peak in the mass spectrum
 FRAGMENTATION PATTERNS

Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
MOLECULAR ION
CH3 C C4H9 has m/z = 100
•+
 FRAGMENTATION PATTERNS

Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
MOLECULAR ION
CH3 C C4H9 has m/z = 100
•+

C4H9 C+ CH3• Breaking the bond between the methyl

group and the carbonyl group
m/z = 85 produces two possible ions,
depending on how the bond breaks.
O
Two peaks at m/z values 15 and 85 will
C4H9 C• CH3+ appear in the mass spectrum.
m/z = 15
 FRAGMENTATION PATTERNS

Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
MOLECULAR ION
CH3 C C4H9 has m/z = 100
•+

O
Breaking the bond between the butyl
group and the carbonyl group CH3 C+ C4H9•
produces two further ions, depending m/z = 43
on how the bond breaks.

Two peaks at m/z values 43 and 57 will O

appear in the mass spectrum.
CH3 C• C4H9+
m/z = 57
 FRAGMENTATION PATTERNS

Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
Example; MOLECULAR ION
CH3 C C4H9 has m/z = 100
•+

O O

C4H9 C+ CH3• CH3 C+ C4H9•

m/z = 85 m/z = 43

O O
C4H9 C• CH3+ CH3 C• C4H9+
m/z = 15 m/z = 57

A further peak occurs at m/z = 72 (100-28) due to loss of CO

IDENTIFY THE
COMPOUNDS
 IDENTIFY THE COMPOUND

43
100
Abundance %
80

29
60

122 124
40
20

79 81

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 IDENTIFY THE COMPOUND

43
100
Abundance %
80

29
60

122 124
40
20

79 81

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C3H7Br
 IDENTIFY THE COMPOUND

105
100
Abundance %
80

77
51
60

120
43
40

28
20

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 IDENTIFY THE COMPOUND

105
100
Abundance %
80

77
51
60

120
43
40

28
20

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C6H5COCH3
 IDENTIFY THE COMPOUND
100
Abundance %

105 106
80
60

51 77

57
40

43
20

28

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 IDENTIFY THE COMPOUND
100
Abundance %

105 106
80
60

51 77

57
40

43
20

28

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C6H5CHO
 IDENTIFY THE COMPOUND
100

56 57
113
43
Abundance %
80
60

71
40

142
20

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 IDENTIFY THE COMPOUND
100

56 57
113
43
Abundance %
80
60

71
40

142
20

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C10H22
 REVISION CHECK
What should you be able to do?

Understand how mass spectrometry can be used to calculate molecular mass

Recall the term molecular ion and understand what information it provides
Interpret simple mass spectra

CAN YOU DO ALL OF THESE? YES NO

You need to go over the
relevant topic(s) again
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WELL DONE!
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FU RH ER MA SS
SPE CTR OME TR
Y
The End

© 2004 JONATHAN HOPTON & KNOCKHARDY PUBLISHING