MASS SPECTROMETRY

UWI
CAPE WORKSHOP 2012
Dr. K.Wilson
CAPE Objectives
 Explain the principles of mass spectrometry.
 Use mass spectral data to:
 Determine relative isotopic masses and relative
isotopic abundance.
 Distinguish between molecules of similar relative
molecular mass.
 Predict possible identities of simple organic molecules
based on their fragmentation pattern.
 Explain the significance of the (M+1) peak in a
mass spectrum.
Introduction
 Mass spectrometry (MS) is an analytical
technique that separates components of a sample
based on their mass to charge (m/z) ratios.

 Mass Spectroscopy can be used to determine:

 Relative atomic mass of an element
 Molecular mass of a molecule
 Structure elucidation of organic compounds
Schematic of a Mass Spectrometer
Vapourisation
 Sample is vapourised after it is injected into the
mass spectrometer, by gentle heating.
Ionisation
 The next step in the operation of this instrument is
to IONISE the sample.
 A beam of the vapourised sample is subjected to an
electric discharge.
 This causes an electron to be dislodged from the
sample and so produce a positive ion.

M  g   M g   e 
Acceleration
 The positive ions are repelled away from the very
positive ionisation chamber.
 As the ions pass through the acceleration chamber,
they are made to accelerate with the same velocity.
 The ions are accelerated into a finely focused
beam.
Deflection
 At this stage, the ions with the same
mass/charge (m/z) ratio, travel in the
same path
 but in a different path to ions with a
different m/z ratio.

 The ions are deflected by a magnetic field

according to their masses. The lighter
they are, the more they are deflected.

 The strength of the magnetic field

increases until all the ions of interest get
detected.
Detection
 The beam of ions passing through the machine is
detected electrically.

 Ions with a particular mass reach the detector. Different

masses can be collected by changing the magnetic or
electric field.

 The electrometer measures the

charge carried by each beam,
which is then recorded graphically.
Review
 The following is a diagram of a mass spectrometer.

 Identify the parts labelled A, B, and C.

 State and explain which one of the following ions

will undergo the greatest deflection, under

the same conditions, in a mass spectrometer.
6
Li+ , 6Li2+ , 7Li+ , 7Li 2+
Isotopes and Relative Atomic Mass
 Isotopes
 Atoms of an element that have same atomic number but
different mass number.
 Examples: 1H, 2H, 3H & 12C, 13C
Mass Spectrum of Magnesium
 Based on the mass
spectrum results,
magnesium has 3
isotopes of atomic
masses 24, 25 and 26
amu.

 The relative abundances

of these isotopes are
78.9%, 10.1% and
11.3% respectively.
Isotopes and Relative Atomic Mass (RAM)

 Based on the mass spectra of magnesium, the

relative atomic mass of Mg can be calculated as:
 RAM =78.1 (24)  10.1 (25)  11.3 (26)  24.2 amu
100 100 100

 An element’s atomic weight is a weighted average of

the isotopic masses of the element’s naturally
occurring isotopes.
Mass spectra of organic compounds

 The mass spectrum of an organic sample is obtained

in the same way described earlier:
 Vapourisation, Ionisation, Acceleration, Deflection and
Detection. (V.I.A.D.D.)

 The positive organic ion of the molecule that is

formed is called the molecular ion – or the parent
ion.

 The molecular ion is often given the symbol M+.

Difference between mass spectrum of a compound
and that of an element.

 In the mass spectrum of an element, each line

represents a different isotope of that element.

 For a compound, each line represents a different

fragment produced when the molecular ion breaks
up.
Mass spectra of organic
compounds
 The vapourised organic molecules are energetically
unstable, and break up into smaller charged
fragments.

 The charged fragments will travel through the mass

spectrometer like any other positive ion until it gets
to the detector.
Typical Mass Spectrum
Base Peak
(Most Intense/stable
peak)

Molecular
Ion Peak..
M+ peak
Mass spectrum of pentane

m/z Fragment
72 +
CH3CH2CH2CH2CH3
57 +
CH2CH2CH2CH3
43 +
CH2CH2CH3
29 +
CH2CH3

[CH 3CH 2 CH 2 CH 2 CH 3 ]  CH 3CH 2 CH 2 CH 2    CH 3


 Some common fragments and their (m/z ratio)

m/z Fragment * C-C single bond

fragments with m/z
15 +
CH3
ratio of 43 depends
29 +
CH2CH3 or +CHO on the intensity of
this peak, since at
*43 * +CH2CH2CH3 or * or +
C CH3
this point, the
O
fragment can be
Difference in mass of fragment and Fragment lost isomeric.
mass of molecular ion
14 .
CH2
17 .
OH
26 .
CN
31 .
OCH3
35 .
Cl
45 .
OCH2CH3
Peak heights and the stability of ions

 The most intense peak on the mass spectrum is the

most stable ion formed.

 The positive fragments formed from organic

compounds are called “carbocations”

 A carbocation is a carbon atom with a +ve charge.

Carbocations
 Primary

 Secondary

 Tertiary
The (M+1) peak
 A complete (un-simplified) mass
spectrum, will most certainly have a
small line one (1) m/z unit to the right of
the main molecular ion peak.

 This small peak is called the M+1 peak.

 The (M+1) peak is caused by the

presence of the 13C isotope in the
molecule.
 13
C is a stable isotope of carbon and not
to be confused with the radioactive 14C.

 Carbon-13 accounts for

approximately1% of all carbon atoms.
Where are mass spectrometers used?
 Mass spectrometers are used in industry and academia for both routine and research
purposes. The following list is just a brief summary of some of the major mass
spectrometric applications:

 Biotechnology: The analysis of proteins, peptides, oligonucleotides

 Pharmaceutical: Drug discovery, combinatorial chemistry, pharmacokinetics, drug

metabolism

 Clinical: Haemoglobin analysis, drug testing

 Environmental: Water quality, food contamination

 Geological: Oil composition

 Forensic Science:
Question 1

 Compound Q has the molecular formula C4H7ClO and

does not produce misty fumes when added to water.
The mass spectrum of Q contains two molecular ion
peaks at m/z = 106 and m/z = 108. It also has a major
peak at m/z = 43.
 Suggest why there are two molecular ion peaks.
 A fragment ion produced from Q has m/z = 43 and
contains atoms of three different elements.
 Identify this fragment ion and write an equation showing
its formation from the molecular ion of Q.
Answer 1
 For a m/z = 43, three possible fragments should
come to mind.

 H3C CH2 or H3C CH

+
or H3C
+
C
+
CH2 CH3 O

 Can rule out the first two because the question told
you, the fragment has 3 different atoms….
Answer 1 cont’d
 Molecular ion is therefore:

or
Question 2
 A low resolution mass spectrum of
2-methybutan-2-ol shows peaks at m/z values of 73, 71 and 59.
The molecular ion peak is absent. Propose a structural formula
for EACH of the given peaks.
 m/z = 73
 m/z = 71
 m/z = 59.
 The mass spectrum of pentan-2-ol which is isomeric to 2-
methybutan-2-ol shows a molecular ion peak. Account for this
difference between the two isomers.
 Give TWO other uses of mass spectrometry as an analytical
tool.
Answer 2
CH3
H3C C CH2
 2-methybutan-2-ol
OH CH3
RMM =88

CH3
+
C CH2
 m/z = 73 or
OH CH3

CH3
+
H3C C CH2
 m/z = 71 CH3
CH3
+
H3C C
 m/z = 59 OH
The End
Questions????????

keneshawilson@gmail.co
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