An introduction

to
Mass Spectrometry
(CAPE WORKSHOP)

Prepared by: Dr. Marc Collins

Date: Tuesday, January 9-12, 2023.
 • This content is authorized solely for the personal, non-commercial use
of participants (teachers and students) in the UWI CAPE Chemistry
Workshop 2023. The content may NOT be copied, shared or displayed
(posted/uploaded) whether in part or in its entirety without the written
permission of the Department of Chemistry, UWI Mona, Kingston
Jamaica.

• The Department of Chemistry, UWI Mona thanks the following persons

for their contribution to this resource:
• Dr. Marc Collins
• Dr. Novelette Sadler-McKnight

2
QUICK BRAIN
TEASER!!!
 Objectives of this Presentation
• OBJECTIVE #1: Explain the basic principles of Mass Spectrometry and the function
of the mass spectrometer.

• OBJECTIVE #2: Be able to interpret and use mass spectral data to:
a) distinguish between molecules of similar relative
molecular mass
b) predict the possible identities of simple organic molecules
based on their fragmentation pattern

• OBJECTIVE #3: Explain the significance of isotopic peaks (M+1, M+2) peaks in mass
spectra;

Dr. Marc Collins

 Overview
• Mass Spectrometry (MS) is an analytical chemistry technique that helps to identify the amount and type of
chemicals present in a given sample by measuring the mass-to-charge ratio (m/z) and abundance of gas-
phase ions.

• Uses
1. Determine Molecular Weights (Relative molecular mass)
2. Structurally Characterize Unknown compounds
3. Identify Components in a Mixture
4. Study gas Phase reactions.
• Applications

1. Forensic science and drug testing (identifying components in a mixture)

2. Research and Drug Discovery(Structurally characterize unknowns, determine molecular weights)
3. Industry (Chemical, Petroleum and Pharmaceutical)
4. Dating of geological samples (isotope ratio mass spectrometry)
5. Use by Geologists to test the quality of petroleum reserves.
6. Used by environmental scientists to monitor water and air quality.

Dr. Marc Collins

 The Mass Spectrometer
The three main components of the Mass spectrometer are:

1. The Ion source - Receives the sample and produces ions.

2. The mass analyzer - sorts these ions based on their
mass to charge ratio m/z
3. The detector - an electron multiplier produces
a signal proportional to the number of ions striking it. 2

All components of the system are controlled

by a computer.(The data system). It has software 1 3
includes programs to calibrate the MS, acquire
the data and process the data to produce the
final spectrum. Schematic diagram of the mass spectrometer
Dr. Marc Collins
 The Gas Chromatograph-Mass Spectrometer
(GC-MS)

Dr. Marc Collins

 Components of the Mass Spectrometer

Dr. Marc Collins

 Components of the Mass Spectrometer
Ionization: Many types Electron Impact ionization
is the most common

Acceleration: Ion are shunted into the mass analyzer

Mass Analyzer: Most important part of the

mass spec, (Separation of the ions based on
their masses takes place here). Many types

Detector: receives and amplifies the signal and sends

output to a computer that generates a spectrum of
relative intensity vs mass-to-charge

Dr. Marc Collins

 What does a sample mass spectrum looks like?
Y
Fragment Ions

Sample Mass
spectrum
of 2- Butanone

M+ / Molecular Ion

Dr. Marc Collins

 Word Mass Spectrometry
• Source:
• A model of mass spectrometry
• Royal Society of Chemistry, Education Resource
• “Use this modelling activity to explore your students’ understanding of
the process of fragmentation in mass spectrometry”.
• https://edu.rsc.org/resources/a-model-of-mass-
spectrometry/2390.article

Dr. Marc Collins

 WORD Mass Spectrometry - #1

A word was analysed by the spectrometer and it produced 5 fragments.

Determine what the word is using the Mass-to-charge ratios of the fragments
and the table above. Hint: It’s a Three-Letter-Word
m/z: 1; 3; 4; 67; 68; 71
Dr. Marc Collins
 WORD Mass Spectrometry
Y
71 is the mass of the
“Wordecular” ion

71

X
Dr. Marc Collins
 WORD Mass Spectrometry
X
71 is the mass of the
“Wordecular” ion

C
A AT
71 ?
AC or CA T
(m/z) Y
Dr. Marc Collins
 WORD Mass Spectrometry

Dr. Marc Collins

 WORD Mass Spectrometry - #2

A word was analysed by the spectrometer and it produced 9 fragments.

Determine what the word is using the Mass-to-charge ratios of the fragments
and the table above. Hint: It’s a Four-Letter-Word
m/z: 1; 7 ; 8 ; 37; 38; 45; 67; 74; 75
Dr. Marc Collins
 WORD Mass Spectrometry

Dr. Marc Collins

 WORD Mass Spectrometry

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 WORD Mass Spectrometry

Dr. Marc Collins

 What does a sample mass spectrum looks like?
Y

Sample Mass
spectrum
of 2- Butanone

Dr. Marc Collins

 What useful information can we get from a mass spectrum?
• We can identify the M+ peak: The ion obtained by
Y the loss of an electron from the molecule. The
molecular ion peak is the peak that represents the
heaviest ion. This peak has the highest m/z ratio on
the mass spectrum but it does not necessarily
represent the most abundant ion

• We can identify the base peak: The base peak is

always the tallest peak in the spectrum, assigned
X 100% intensity. The base peak represents the most
common and most abundant ion.

• Other useful terms

Radical cation: +Ve Charged species with an odd
number of electrons

• Fragment ions: Lighter Cations formed by

Decomposition of the molecular ions. These often
correspond to stable carbocations.
Dr. Marc Collins
16

Interpretation
of Spectra

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 17

Interpretation
of Spectra

109

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 18
Isotopic abundances

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 19
Isotopic
abundances

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 20
Isotope
patterns

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 21
Isotope
patterns

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 22
Isotope
patterns

Dr. Marc Collins

Dr. Marc Collins
EXERCISES

Rel. Abundance

15 (6.6%)
words

worrds
29 (30%)

m/z
MASS SPECTRUM

wordsp
31 (100%)

45 (32%)
46 (21%)
47 (0.5%)
Dr. Marc Collins
EXERCISES

Rel. Abundance

Ethanol
15 (6.6%)
words

worrds
29 (30%)
m/z
MASS SPECTRUM

wordsp
31 (100%)

45 (32%)
46 (21%)
47 (0.5%)
Dr. Marc Collins
EXERCISES

Rel. Abundance
100

60
80

20
40

0
0
15 (1.4%)

20
29(38%)
31 (44%)

41 (51%)
40

43 (21%)
45 (4.8%)
m/z
m/z
42 (100%)

55 (65%)
57 (21%)
60
MASS SPECTRUM

70 (51%)
71 (4.1%)
88 (0.3%)
80

88 (0.5%)
100
Dr. Marc Collins
EXERCISES
Rel. Abundance
0
10

0
6
0
8

0
2
0
4

0
0
15 (1.4%)
20

29(38%)
31 (44%)

41 (51%)
40

43 (21%)
42

45 (4.8%)
(100%)

m/z

55 (65%)
57 (21%)
60
MASS SPECTRUM

70 (51%)
71 (4.1%)
88 (0.3%)
80

88 (0.5%)
M+

0
10
EXERCISES

Dr. Marc Collins

EXERCISES
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 W X

Y Z

EXERCISES
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EXERCISES
Dr. Marc Collins