MASS SPECTROMETER

OBJECTIVES:

To describe how the mass spectrometer works

Make use of mass spectra

MAKING SENSE… KEY WORDS:

Try to put what happens in a MASS SPECTRA

mass spectrometer into a logical
SPECTROMETER
sensible order
IONISATION
ABUNDANCE
 What is it?
• A device for finding the mass of atoms and
groups of atoms.
• The particles are charged, accelerated into
a magnetic field and deflected by their
mass/charge ratio.
• The resulting beams of ions are analysed
and the identities of the particles
discovered.
 MASS SPECTROMETER
WHAT IS A MASS SPECTROMETER

An instrument to accurately determine the relative

atomic mass
Separates atoms or molecules according to their charge and
mass.
This can be used to identify substances 

illegal drugs identification

drug testing and discovery
food contamination detection
pesticide residue analysis
isotope ratio determination
protein identification etc.
Atoms of the same element with different numbers of neutrons are called isotopes.
Isotopes of an element have: the same atomic number but different mass numbers

Three isotopes of hydrogen

All hydrogen atoms contain one proton (and one electron), but they can contain
different numbers of neutrons. Hydrogen-1 is the most abundant (most common)
isotope of hydrogen.

All three isotopes of hydrogen have identical chemical properties. This is because the
number of electrons determines chemical properties, and all three isotopes have one
electron in their atoms.

An isotope is named after the element and the mass number of its atoms. For example,
carbon-12 is an isotope of carbon with a mass number of 12.
Relative abundance (relative intensity): The y-axis of a mass
spectrum. Quantifies the amount of an ion produced in relation to
the amount of the most abundant ion (the base peak). In this
simulated mass spectrum, the ion of m/z = 30 has relative abundance of
100%, so it is the base peak.
 How it works
The sample is first
Vapourised.

Then it is Ionised by
having high energy
electrons fired at it.

M(g) + e- → M+(g) +
2e-

VIA These ions are then

Accelerated by a
How it works

A good vacuum is essential

in the whole of the
apparatus
 How it works
The accelerated ions are Deflected by the magnetic field, bigger ions are deflected less.

The ion beams

can be
focussed on
the Detector
 MASS SPECTROMETER
THE LAYOUT

4 key stages:

• Ionisation
• Acceleration
• Deflection
• Detection

---- = heavy ions

---- = ions reaching detector
---- = light ions
 MASS SPECTROMETER
SUMMARISING WHAT
HAPPENS:

1. Ionisation: Atoms are

converted to
ions
2. Acceleration: Ions are
accelerated
3. Deflected: Deflected
according to
their mass &
charge
4. Detection: They arrive at
a detector
 MASS SPECTROMETER
SUMMARISING WHAT HAPPENS:

1. Ionisation: Atoms are converted to ions

2. Acceleration: Ions are accelerated
3. Deflected: Deflected according to their mass & charge
4. Detection: They arrive at a detector

CONDITIONS:
a) Vacuum  so ions do not collide with air molecules
(might stop them reaching the detector)
b) Gaseous State  solids are vaporised before being
injected
 MASS SPECTROMETER
LOOK IN MORE DETAIL:

Stage 1: Ionisation

Beam of electrons knocks electrons from atoms or

molecules in the sample.

This is true even for things which you would normally

expect to form negative ions (chlorine, for
example) or never form ions at all (argon,
for example).

Nearly all lose just one electron (~5% will lose two)

Mass spectrometers always work with positive ions!!

 MASS SPECTROMETER
Stage 2: Acceleration

The ions are accelerated so that they all have the same
kinetic energy.

Stage 3: Deflection

The ions are then deflected by a magnetic field according

to the ratio of their mass to charge (m/z),
where z is the charge (usually +1)

Heavier ions are deflected less than light ones

2+ ions are deflected twice as much as 1+ ions

 MASS SPECTROMETER
Stage 4: Detection

Magnetic field is gradually increased  increases

deflection

This allows ions of increasing mass to enter the detector

On striking the detector ions accept electrons, lose their

charge and create a current

Current created is proportional to the abundance of each

ion
 MASS SPECTROMETER
MASS SPECTRA OF ELEMENTS

From the strength of the magnetic field at

which a particular ion hits the detector the
value of the mass to charge ratio (called m/z)
is calculated

A graph is produced
(mass spectra)
showing the relative
abundances of each
ion type
Mass spectra
of zirconium
 MASS SPECTROMETER
MASS SPECTRA OF ELEMENTS

We can use the mass spectrometer to identify the

different isotopes making up an element

Each isotope is detected separately because they have

different masses

To calculate an Zirconium has 5

elements relative isotopes!
atomic mass (which
is given in the periodic
table) you must take
account of the relative
abundances of each isotope
 MASS SPECTROMETER
CALCULATING RAM OF ELEMENTS

This is the mass spectra for chlorine

We have 2 isotopes with relative

isotopic masses of 35 and 37,
detected in a ratio of 3:1
(or 75%:25%)

To calculate the relative atomic

mass of chlorine:

(35 x 75) + (37 x 25)

100 Check the Ar of Chlorine
= 35.5 in your periodic table
 MASS SPECTROMETER
CALCULATING RAM OF ELEMENTS

RAM of Cl = 35.5

Notice there is no line at 35.5 on the

mass spectra. No atoms of Cl actually
have this mass. It is the average of all
the isotopes and their abundances!
STEPS:
1. Multiply the m/z value by the relative abundance %
for each peak
2. Add results for each peak together
3. Divide by total relative abundance
 MASS SPECTROMETER
CALCULATING RAM OF ELEMENTS

Calculate the RAM of the element from its mass spectra:

Boron Zirconium
100

51.5
23 17.1
17.4
11.2
2.8

Most abundant OR Use the percentage

assigned 100 detected
 MASS SPECTROMETER
CALCULATING RAM OF ELEMENTS

(10 x 23) + (100 x 11)

Boron 123
100

RAM = 10.8
23
 MASS SPECTROMETER
CALCULATING RAM OF ELEMENTS

(90 x 51.5) + (91 x 11.2) + (92 x 17.1) + (94 x 17.4) + (96 x 2.8)
100

RAM = 91.3

51.5
17.1
17.4
11.2
2.8
 MASS SPECTROMETER
DOUBLY CHARGED IONS:

It’s not always as simple as we’ve just made it

During ionisation a small number of ions with a 2+ charge

are created

These are deflected more than singly charged ions (behave

as if they have half the mass)

A closer look Cl shows peaks at m/z 17.5 and 18.5.

Because double ionisation is rare these peaks have very

small abundances
 MASS SPECTROMETER
CHLORINE GETS TRICKIER…

Chlorine can form a molecule  Cl2

This can also be ionised, creating molecular ions

Its spectra will therefore show 3 other peaks:

- At m/z 70, due to 35

Cl 35
Cl
- At m/z 72, due to 35
Cl 37
Cl
- At m/z 74, due to 37
Cl 37
Cl

Mass spectra can be used for complex molecules  you’ll

do this at A2!!
 MASS SPECTROMETER
SPECTROMETERS IN SPACE

Space probes will carry spectrometers to identify

elements in rocks

E.g. Giotto Space Probe passing close to Halley’s comet

Remember: we need a vacuum

for a mass spectrometer to
work. This is easy for a space
probe as space is a vacuum!!
 MASS SPECTROMETER
DATA FOR HALLEY’S COMET

Greenburg J. M (2002). Cosmic Dust and Our Origins.

Surface Science. 500: 793-822