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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
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
Spectra obtained for organic molecules have many peaks. Each peak is due to a
particular fragment with a certain m/z value.
Spectra obtained for organic molecules have many peaks. Each peak is due to a
particular fragment with a certain m/z value.
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 more alkyl groups attached to the carbocation the more stable it is
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
0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
FRAGMENTATION PATTERNS
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
O
MOLECULAR ION
CH3 C C4H9 has m/z = 100
•+
FRAGMENTATION PATTERNS
O
MOLECULAR ION
CH3 C C4H9 has m/z = 100
•+
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.
O
Example; MOLECULAR ION
CH3 C C4H9 has m/z = 100
•+
O O
O O
C4H9 C• CH3+ CH3 C• C4H9+
m/z = 15 m/z = 57
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?