The mass spectrometer:

1. Ionisation:
• First the ions are vaporised (turned into a gas).
The atom or molecule is ionised by knocking one or more
electrons off to give a positive ion. This is done by
bombarding it with electrons.
• The positive ions are brought together to form a narrow
beam.
2. Acceleration:
• The ions are accelerated so that they all have the same
kinetic energy.
• This is done using a negatively charged accelerating
plate.
3. Deflection:
• The ions are then deflected by a magnetic field according to
their mass/charge ratio. The lighter they are, the more they are
deflected. The more charged, the more deflection.
• The amount of deflection also depends on the number of
positive charges on the ion - in other words, on how many
electrons were knocked off in the first stage. The more the ion is
charged, the more it gets deflected.
4. Detection:
• The beam of ions passing through the machine is detected
electrically.
• The signal is amplified and recorded.

This is a mass spectrum

Mass spectrum of magnesium:
This spectrum shows the three
isotopes of magnesium:
Finding out the relative atomic mass:

• Relative atomic mass

m
𝒎𝒂𝒔𝒔 𝒊𝒔𝒐𝒕𝒐𝒑𝒆𝒔=the top   number ∨the value ¿the graph .
z

𝒓𝒆𝒍𝒂𝒕𝒊𝒗𝒆 𝒂𝒃𝒖𝒏𝒅𝒂𝒏𝒄𝒆= 𝒇𝒓𝒐𝒎𝒕𝒉𝒆𝒎𝒂𝒔𝒔 𝒔𝒑𝒆𝒄𝒕𝒓𝒖𝒎 𝒐𝒓 𝒅𝒂𝒕𝒂 𝒈𝒊𝒗𝒆𝒏.

Questions…
• The mass spectrum of lithium showed two peaks.
• The ​first peak was at m/z=6 and had an abundance of ​7.4%;
• the second peak was at m/z=7 and had an ​abundance of 92.6%.​
Q1. Calculate the relative atomic mass of the lithium ​sample to three
significant figures.

Q2. A mass spectrum of a sample of hydrogen showed that it contained:

1
H 99.20% and 2H 0.8000% Calculate the relative atomic mass of the hydrogen
sample. You should give your answer to 4 significant figures.
 Mass spectrum of Chlorine:

Although chlorine contains Cl2 molecules only, we observe peaks for chlorine atoms because
Cl2+ isn’t a stable ion. It will split to give the a chlorine atom and a Cl+ ion: this is known as
fragmentation.
What about the ratio 3:1?
• The isotope 35Cl is 3 times more
common that the isotope 37Cl.

• Its peak is 3 times the height of the

other. The ratio is 3:1.
• The 35Cl isotope has the abundance of
75% .
37
Cl has 75/3 = 25% abundance.
Atomic region / molecular region:
• The atomic region shows the peaks for the Chlorine atoms.
• The molecular region shows the peaks for the molecules Cl2.

The molecular region shows three peaks because the chlorine isotopes can
combine in three different ways:

(35Cl- 35Cl) + where m/z is 70

(35Cl- 37Cl) + OR (37Cl- 35Cl) + where m/z is 72
(37Cl- 37Cl) + where m/z is 74
Molecule/atoms
responsible for a
peak is always
charged.
• Probabilities allows us to confirm the peak ratio for the Cl2+
molecules.
Why do we get the peak ratio 9:6:1?
• We simply multiply the probability of the
atoms joined together:
• 35Cl- 35Cl is so
•
35
Cl- 37Cl is so These will be on
the same peak.
• 37Cl- 35Cl is so We add them to
give
• 37Cl- 37Cl is

• Hence the ratio 9:6:1

 Calculating the formula of a compound:
• Two types of formula to know:
Empirical: That’s the simplest ratio of atoms present within a
compound.

Molecular: That’s the actual number of atoms present in a

compound.
Calculating the empirical formula:

element Na Cl O

% by mass
Empirical formula:
Ar

%mass/Ar

Ratio
Other example:

Remember you can only have

whole numbers
Calculating the molecular formula:
• You can easily do that using the empirical formula and
the molecular mass of a compound.
Let’s use a new example:
Benzene, a hydrocarbon (atom made of carbon and
hydrogen only), has a relative molecular mass of 78 and
contains 92.3 % carbon.
1) What is its empirical formula?
2) What is the mass of the empirical formula?
3) What is the molecular formula?
Answers:
• 1) What is its empirical formula?

CH

2) What is the mass of the empirical formula?

12+1=13

3) What is the molecular formula? 78/13=6 so C6H6

Further question:
• A compound of carbon, hydrogen and oxygen has a
relative molecular mass of 60. The percentage
composition by mass is C 40.0%, H 6.70%, O 53.3%.
1. Find the empirical formula of the compound.
2. Find its molecular formula.
 Determining compounds’ structures

Stater: what is
this? What can
we use for?
Using the mass spectrometer to predict the chemical
structure of a compound.
The mass spectrum of a compound:
(recalling)
• When a compound is placed in the spectrometer, electrons
are bombarded onto it to knock off electrons and produce a
positive ion. The ion is then accelerated before being
deflected by the electromagnet according to their
mass/charge ratio.

• For example:
CH3CH2CH3 will show the ion CH3CH2CH3+

• The ion of a molecule if often called M+

Not so simple!
• As well as giving off the molecular ion M+, the
compound is fragmented. That means it breaks up or
splits to give different ions that will give us ideas
about its structure.
• For example: (propane)
CH3CH2CH3 can be fragmented into these:
• CH3CH2+ and CH3 radical
• CH3+ and CH3CH2 radical

• The radicals are not detected, only the ions are!

What shows on the spectrum?
REMEMBER:
m/z essentially tells you
the molecular mass of
the ion.

The vertical axis tells you

the abundance of the
ion
The peak on the far right
has the largest m/z, so the
The other peaks give you an idea of the fragments largest Mr. This is the
obtained from the molecule. molecular mass of the
i.e: m/z= 29 could be CH3CH2+ compound you are testing.
Some good tips to remember:
• If you have a peak at m/z= 29, this is the CH3CH2+ ion.

• If there is a peak at m/z= Mr-15 , that’s because you lost a CH3

radical. It does not always appear on m/z= 15!

• Look at the spectrum of propane:

Mr propane = 44
There is a peak at m/z= 44-15=29 because this happened:

CH3CH2CH3  CH3CH2+ and CH3 radical

Traps not to fall in:
• When you look at the mass spectra of a compound,
you are looking at a molecule and its fragments.

• When you look at the mass spectra of an element

(i.e. chlorine), you are looking at isotopes.

• A halogenoalkane will show two peaks for the

molecule, because of the halogen isotopes.
Complete the examples on your worksheet to see if you understand the idea!