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CIE AS Chemistry Your notes

22.2 Mass Spectrometry

Contents
Mass Spectrometry
Isotopic Abundance & Relative Atomic Mass
Molecular Ion Peak & Fragmentation
The M+1 & M+2 Peaks

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Mass Spectrometry
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Interpreting Mass Spectra
Mass spectroscopy is an analytical technique used to identify unknown compounds
The molecules in the small sample are bombarded with high energy electrons which can cause the
molecule to lose an electron
This results in the formation of a positively charged molecular ion with one unpaired electron
One of the electrons in the pair has been removed by the beam of electrons

Electron bombardment
MOLECULE ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ MOLECULE+• + e–
MOLECULE+• represents the molecular ion
The molecular ion can further fragment to form new ions, molecules, and radicals

Fragmentation of a molecule in mass spectroscopy

The same molecule can produce several different fragments in mass spectroscopy

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These fragmentation ions are accelerated by an electric field

Based on their mass (m) to charge (e) ratio, the fragments of ions are then separated by deflecting
them into the detector Your notes
For example, an ion with mass 16 and charge 2+ will have a m/e value of 8
The smaller and more positively charged fragment ions will be detected first as they will get deflected
the most and are more attracted to the negative pole of the magnet
Each fragment corresponds to a specific peak with a particular m/e value in the mass spectrum
The base peak is the peak corresponding to the most abundant ion

Isotopes
Isotopes are different atoms of the same element that contain the same number of protons and
electrons but a different number of neutrons.
These are atoms of the same elements but with different mass number
For example, Cl-35 and Cl-37 are isotopes as they are both atoms of the same element (chlorine,
Cl) but have a different mass number (35 and 37 respectively)
Mass spectroscopy can be used to find the relative abundance of the isotopes experimentally
The relative abundance of an isotope is the proportion of one particular isotope in a mixture of
isotopes found in nature
For example, the relative abundance of Cl-35 and Cl-37 is 75% and 25% respectively
This means that in nature, 75% of the chlorine atoms is the Cl-35 isotope and 25% is the Cl-37
isotope
The heights of the peaks in mass spectroscopy show the proportion of each isotope present
Example mass spectrum of boron

The peak heights show the relative abundance of the boron isotopes: boron-10 has a relative
abundance of 19.9% and boron-11 has a relative abundance of 80.1%

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Worked example
Your notes
In a sample of iron, the ions 54Fe2+ and 56Fe3+ are detected.
Calculate the m/e value ratio and determine which ion is deflected more inside the spectrometer.
Answer:
54
m/e (54Fe2+) = = 27
2
56
m/e (56Fe3+) = 3 = 18 . 7
= 19

Exam Tip
A small m/e value corresponds to fragments that are either small or have a high positive charge or a
combination of both

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Isotopic Abundance & Relative Atomic Mass

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Calculating Relative Atomic Mass
Isotopes are different atoms of the same element that contain the same number of protons and
electrons but a different number of neutrons.
These are atoms of the same elements but with different mass numbers
Because of this, the mass of an element is given as relative atomic mass (Ar) by using the average
mass of the isotopes
The relative atomic mass of an element can be calculated by using the relative abundance values
The relative abundance of an isotope is either given or can be read off the mass spectrum

( relative abundance isotope 1 mass isotope 1) + ( relative abundance isotope 2 mass isotope 2) etc .
Ar =
100

Worked example
Calculate the relative atomic mass, Ar, of oxygen to 2 d.p.

Isotope Percentage abundance

16O 99.76

17O 0.04

18O 0.20

Answer:

( 99 . 76 × 0. 04 ) + ( 0. 04 × 17 ) + ( 0. 20 × 18 )
Ar =
100
Ar = 16.0044
Ar = 16.00 (to 2 d.p)

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Worked example
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Calculate the relative atomic mass of boron using its mass spectrum, to 2 d.p.

Answer:

( 19 .9 × 10 ) + ( 80 .1 × 11 )
Ar =
100
Ar = 10.801
Ar = 10.80 (to 2 d.p)

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Molecular Ion Peak & Fragmentation

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Mass Spectrometry: Deducing Molecular Formula
Each peak in the mass spectrum corresponds to a certain fragment with a particular m/e value
The peak with the highest m/e value is the molecular ion (M+) peak which gives information about the
molecular mass of the compound
The molecular ion is the entire molecule that has lost one electron when bombarded with a beam of
electrons
Electron bombardment
MOLECULE ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ MOLECULE+• + e–
The [M+1] peak is a smaller peak which is due to the natural abundance of the isotope carbon-13
The height of the [M+1] peak for a particular ion depends on how many carbon atoms are present in that
molecule; the more carbon atoms, the larger the [M+1] peak is
For example, the height of the [M+1] peak for an hexane (containing six carbon atoms) ion will be
greater than the height of the [M+1] peak of an ethane (containing two carbon atoms) ion

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Worked example
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Determine whether the following mass spectrum corresponds to propanal or butanal.

Answer:
The mass spectrum corresponds to propanal as the molecular ion peak is at m/e = 58
Propanal arises from the CH3CH2CHO+ ion which has a molecular mass of 58
Butanal arises from the CH3CH2CH2CHO+ ion which has a molecular mass of 72

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Identifying Molecules using Fragmentation

The molecular ion peak can be used to identify the molecular mass of a compound Your notes
However, different compounds may have the same molecular mass
To further determine the structure of the unknown compound, fragmentation is used
Fragments may appear due to the formation of characteristic fragments or the loss of small
molecules
For example, a peak at 29 is due to the characteristic fragment C2H5+
Loss of small molecules gives rise to peaks at 18 (H2O), 28 (CO), and 44 (CO2)

Alkanes
Simple alkanes are fragmented in mass spectroscopy by breaking the C-C bonds
M/e values of some of the common alkane fragments are given in the table below
m/e values of fragments table

Fragment m/e

CH3+ 15

C2 H 5+ 29

C3H 7+ 43

C 4H 9+ 57

C5H11+ 71

C6H13+ 85

Mass spectrum showing fragmentation of alkanes

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Your notes

Straight chain alkanes show characteristic peaks

Halogenoalkanes
Halogenoalkanes often have multiple peaks around the molecular ion peak
This is caused by the fact that there are different isotopes of the halogens
Mass spectrum for a bromine containing species

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Your notes

Mass spectra show different halogen isotopes in the molecular ion

Alcohols
Alcohols often tend to lose a water molecule giving rise to a peak at 18 below the molecular ion
Another common peak is found at m/e value 31 which corresponds to the CH2OH+­fragment
For example, the mass spectrum of propan-1-ol shows that the compound has fragmented in four
different ways:
Loss of H• to form a C3H7O+ fragment with m/e = 59
Loss of a water molecule to form a C3H6+ fragment with m/e = 42
Loss of a •C2H5 to form a CH2OH+ fragment with m/e = 31
And the loss of •CH2OH to form a C2H5+ fragment with m/e = 29
Mass spectrum of propan-1-ol

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Mass spectrum showing the fragmentation patterns in propan-1-ol (alcohol)

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Worked example
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Which of the following statements about the mass spectrum of CH3Br is correct?
A. There is one peak for the molecular ion with an m/e value of 44
B. There is one peak for the molecular ion with an m/e value of 95
C. The last two peaks have abundances in the ratio 3:1 and occur at m/e values of 94 and 96
D. The last two peaks are of equal size and occur at m/e values of 94 and 96
Answer:
The correct answer is D as bromomethane (CH3Br) will fragment into 3 peaks
CH381Br → [CH381Br]+ + e− at m/e 96
CH379Br → [CH379Br]+ + e− at m/e 94
CH3Br → [CH3]+ + •Br at m/e 15
The last two peaks (which correspond to the molecular ion peak) therefore are equal in size and
occur at m/e values of 94 and 96

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Worked example
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Which alcohol is not likely to have a fragment ion at m/e at 43 in its mass spectrum?
A. (CH3)2CHCH2OH
B. CH3CH(OH)CH2CH2CH3
C. CH3CH2CH2CH2OH
D. CH3CH2CH(OH)CH3
Answer:
The correct answer is D because a line at m/e = 43 corresponds to an ion with a mass of 43 for
example:
[CH3CH2CH2]+
[(CH3)2CH]+
2-butanol is not likely to have a fragment at m/e = 43 as it does not have either of these fragments
in its structure

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The M+1 & M+2 Peaks

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Determine Number of Carbon Atoms Using M+1 Peak
The [M+1] peak is caused by the presence of the carbon-13 (13C) isotope in the molecule
Carbon-13 makes up approximately 1.1% of all carbon atoms
Therefore, the [M+1] peak is much smaller than the M peak as the isotope is less common
The ratio of 13C to 12C is approximately 1:99
Thus, the greater the number of carbon atoms present in a molecule the greater the height of the [M+1]
peak
The number of carbon atoms, n, in a compound can be deduced using the [M+1] peak and the following
formula:
100 × abundance of ⎡⎢⎣M+ 1 ⎤⎥⎦
n=
1.1 × abundace of M+ ion

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Worked example
Your notes
Determine the number of carbon atoms of compound X with the following mass spectrum:

Answer:
The M+ ion peak is at m/e 58 with a relative abundance of around 85
The [M+1] peak is at m/e 59 with a relative abundance of 3
Therefore, the number of carbon atoms (n) is:
100 × 3
n = = 3. 21
1. 1 × 85
There are therefore 3 carbon atoms present in compound X

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Detecting Bromine & Chlorine Atoms Using M+2 Peak

The presence of bromine or chlorine atoms in a compound gives rise to a [M+2] and possibly [M+4] Your notes
peak

Chlorine
Chlorine exists as two isotopes, 35Cl and 37Cl
A compound containing one chlorine atom will therefore have two molecular ion peaks due to the two
different isotopes it can contain
35Cl = M+ peak
37Cl = [M+2] peak
The ratio of the peak heights is 3:1 (as the relative abundance of 35Cl is 3x greater than that of 37Cl)
A compound containing two chlorine atoms will have three molecular ion peaks due to the different
combinations of chlorine isotopes they can contain
35Cl + 35Cl = M+ peak
35Cl + 37Cl = [M+2] peak
37Cl + 37Cl = [M+4] peak
The ratio of the peak heights is 9:6:1
Mass spectra of chlorine containing compounds

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Your notes

Mass spectrum of compounds containing one chlorine atom (1) and two chlorine atoms (2)
Bromine
Bromine too exists as two isotopes, 79Br and 81Br
A compound containing one bromine atom will have two molecular ion peaks
79Br = M+ peak
81Br = [M+2] peak
The ratio of the peak heights is 1:1 (they are of similar heights as their relative abundance is the
same!)

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A compound containing two bromine atoms will have three molecular ion peaks
79Br + 79Br= M+ peak
79Br+ 81Br = [M+2] peak Your notes
81Br + 81Br= [M+4] peak
The ratio of the peak heights is 1:2:1
Mass spectra of bromine containing compounds

Mass spectrum of compounds containing one bromine atom (1) and two bromine atoms (2)

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Worked example
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Two stable isotope of bromine have relative masses of 79 and 81
Which is the correct pattern of peaks in the mass spectrum of molecular bromine?

Answer:
The correct answer is D
Bromine is a diatomic molecule there will be 5 peaks on the mass spectrum of bromine
Bromine consists of molecules, not individual atoms
When bromine is passed through the mass spectrometer, an electron is given off to give the
molecular ion, Br2+
Some of these will fragment to make Br + Br+
Br2+ → Br + Br+
The Br atom passes through the machine, and the Br+ ions will give lines at 79 and 81
There will also be a line for the unfragmented Br2+ ion
This will give 3 molecular ion peaks
Br2+ ion containing the isotopes 79 + 79 = 158
Br2+ containing the isotopes 79 + 81 = 160

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Br2+ containing the isotopes 81 + 81 = 162

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