1 of 30

Boardworks Ltd 2009

2 of 30

Boardworks Ltd 2007

Detecting elements and compounds

Mass spectrometry is a highly sensitive technique that can
be used to help identify compounds. Samples of only a few
milligrams are required.
Mass spectrometry is useful in the identification of unknown
materials, because the mass spectrum of an unknown
sample can be compared with a database of known spectra.
This makes it useful
in forensic science.
Spectra of samples
could be compared,
for example, to link a
suspect to a weapon
that has been fired.
3 of 30

Boardworks Ltd 2009

Mass spectroscopy in space

Mass spectrometers have been included onboard several
space probes.
In 2005, the Huygens probe landed on the surface of Titan,
the largest moon of Saturn.
During the descent towards
the surface of Titan, the mass
spectrometer analyzed the
atmospheric composition at
various heights. It was found
that the atmosphere consists
mainly of nitrogen and
methane. The presence of
argon-40 was also detected.
4 of 30

Boardworks Ltd 2009

Molecular ions
When a compound is analyzed in a mass spectrometer,
gaseous molecules are bombarded with high-speed
electrons from an electron gun.
These knock out an
electron from some of
the molecules, creating
molecular ions, which
travel to the detector
plates:
M(g) + e- M+(g) + 2eThe peak with the highest mass-to-charge ratio (m/z) is
formed by the molecular ion, and the value of m/z is equal to
the relative molecular mass of the compound.
5 of 30

Boardworks Ltd 2009

Molecular ions and peaks

abundance (%)

The peak at the highest m/z on the mass spectrum is formed

by the heaviest ion that passes through the spectrometer.
Unless all molecules of the original substance break up, this
corresponds to the molecular ion of the sample substance.
100
molecular ion peak
mass spectrum
80
of paracetamol
60
40
20
0
6 of 30

40

80

120

160

m/z

Boardworks Ltd 2009

High resolution mass spectroscopy

High resolution mass spectrometry can determine the m/z
of a peak to several decimal places. This can distinguish
between compounds that have very similar relative
molecular masses (Mr) but different empirical formulae.
To integer values, hexane (C6H14) and pentanal (C5H10O)
both have a Mr of 86. However, using atomic masses to four
decimal places, the Mr of hexane is 86.1106, while the Mr of
pentanal is 86.0739.
With a high enough resolution, it is
therefore possible to distinguish
between hexane and pentanal,
which are both colourless liquids.
7 of 30

Boardworks Ltd 2009

Determining molecular formulae

8 of 30

Boardworks Ltd 2009

What is fragmentation?

9 of 30

Boardworks Ltd 2009

Interpreting mass spectra

10 of 30

Boardworks Ltd 2009

Mass spectroscopy

11 of 30

Boardworks Ltd 2009

12 of 30

Boardworks Ltd 2007

IR energy and molecular vibrations

13 of 30

Boardworks Ltd 2009

IR energy and dipoles

14 of 30

Boardworks Ltd 2009

The infrared spectrometer

15 of 30

Boardworks Ltd 2009

Interpreting infrared spectra

For instance, CH
bonds absorb
radiation at a
wavenumber of
2950 cm-1, which
produces a peak in
an infrared
spectrum as shown
on the right.

16 of 30

transmission (%)

An infrared spectrum is a plot of transmission of infrared

radiation against wavenumber (1 / wavelength). Any
wavelength that is absorbed by the sample will transmit less
than the others, forming a dip or peak in the graph.
100
80
60
40
20
0
3000

2000

1000

wavenumber (cm-1)
Boardworks Ltd 2009

IR radiation and greenhouse gases

Nitrogen and oxygen, the most abundant gases in the
atmosphere, do not absorb infrared energy. This is because
the vibrations caused would not change the dipole of the
molecules.
However, methane, water
and carbon dioxide do
absorb strongly in the
infrared region.
These gases absorb
infrared radiation in the
atmosphere, stopping it
escaping into space: they
are greenhouse gases.
17 of 30

Boardworks Ltd 2009

Greenhouse gases

18 of 30

Boardworks Ltd 2009

Using infrared spectroscopy

When breathalyzed by
police, motorists blow into a
handheld device, which
gives an indication of the
amount of alcohol in their
breath. However, the result
is not accurate enough to
be used as evidence.
At the police station, the motorist blows into a more
accurate breathalyzer, containing an IR spectrometer.
The breathalyzer calculates the percentage of alcohol in
the breath by looking at the size of the absorption due to
the CH bond stretch in the alcohol.
19 of 30

Boardworks Ltd 2009

Infrared spectroscopy: summary

20 of 30

Boardworks Ltd 2009

21 of 30

Boardworks Ltd 2007

Identifying CH and CC bonds

Most organic compounds contain CH and CC bonds.
These are therefore often visible in an infrared spectrum.

The peak due to

CH is the
stronger of the
two because
there are many
more CH bonds
than CC bonds
in the compound.

transmission (%)

In the spectrum of an alkane, such as butane shown here,

there is a peak at 2950 cm-1 (due to CH) and a peak below
1500 cm-1 (due to CC).
100
80

CC

60

CH

40
20
0

3000

2000

1000

wavenumber (cm-1)
22 of 30

Boardworks Ltd 2009

Using the fingerprint region

The region below 1500 cm-1, usually called the fingerprint
region, has many peaks that are difficult to assign. The
pattern of these peaks is unique to a particular compound.

An exact match in
the fingerprint region
identifies a compound.
23 of 30

100

transmission (%)

A substance may
be identified by
comparing the IR
spectrum to a
database of
reference spectra.

fingerprint region

80
60
40
20
0

3000

2000

1000

wavenumber (cm-1)
Boardworks Ltd 2009

Identifying chemical groups

24 of 30

Boardworks Ltd 2009

Spotting characteristic bonds

25 of 30

Boardworks Ltd 2009

Interpreting IR spectra

26 of 30

Boardworks Ltd 2009

27 of 30

Boardworks Ltd 2007

Glossary

28 of 30

Boardworks Ltd 2009

Whats the keyword?

29 of 30

Boardworks Ltd 2009

Multiple-choice quiz

30 of 30

Boardworks Ltd 2009