Mass Spectrometry

Atoms

Mass spectrometry can be used to determine

eg

copper
%
abundance

1) how many isotopes an element has

2) the mass of each isotope
3) the proportion of each isotope

100
90
80
70
60
50
40
30
20
10
0
63

65

m/e

There are two peaks so two isotopes, one of mass 63 units and one of mass 65 units. The 63 amu is
the more abundant isotope at 75%.
Relative atomic mass of copper = (63 x 75) + (65 x 25) = 63.5 amu
100
Molecules:

1) elements

Mass spectrometry can be used to determine which atoms are bonded to which others, so can be used
to determine the structure of an unknown molecule.
eg chlorine: if an electron is removed in the mass spectrometer, there are two possibilities
1)

a non-bonding electron is removed so the whole molecule stays intact but has a positive
charge

Cl2+

which can be either

or
or

Cl 37
Cl 35
Cl 35

Cl+
37
Cl+
37
Cl+
35

electron removed
2)

a bonding electron is removed. This breaks the bond, and the molecule separates into
two fragments, one of the fragments having the positive charge.

electron removed
Which of the two fragments has the positive charge is random.

Cl+ ion
moves to
-ve plate

Cl atom
no charge so
not attracted
to ve plate

Five different particles can therefore be produced in the mass spectroscope, and there will be five
peaks in the mass spectrum:
35 = 35Cl+
37 = 37Cl+
70 = 35Cl - 35Cl+
72 = 35Cl - 37Cl+
74 = 37Cl - 37Cl+
Molecules:

2) compounds

eg ethanol

H
C

C2H5OH

If a non-bonding electron is removed, the particle produced is the whole molecule with a +ve charge:
C2H5OH+
This is called the molecular ion peak. It is not always present in the mass spectrum, but if it is there
it is the peak with the largest m/e
If a bonding electron is removed, the molecule will break into two fragments, either of which can have
the positive charge:

CH3+ and CH2OH

and

CH3 and CH2OH+

C2H5 and OH
+

and

C2H5 and OH+

H
H

H and C2H4OH
+

and

H and C2H4OH+

There are lots of different ways of breaking the molecule so there are lots of different fragments, all of
which can appear in the mass spectrum:
1 = H+
15 = CH3+
17 = OH+
29 = C2H5+
31 = CH2OH+
45 = C2H4OH+and C2H5O+
46 = C2H5OH+

%
abundance
31
15
45
17
1

29
46

10

20

30

40

50

m/e
Compounds containing carbon usually have a small peak after each carbon-containing fragment due to
the existence of the carbon-13 isotope.

Question: C4H10 has two isomers:

H
H
H
H
H

C C
H H
C H
C C

C
H

H
H

H
H

and

A compound of formula C4H10 is analysed and the mass spectrum obtained is:
43

29
%
abundance
15
58
10

20

30

40

50

60

m/e

a) Identify the species responsible for peaks at

29
43
58

15

b) Which of the two isomers was present in the sample? Give reasons.