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
Dr. Marc Collins
WORD Mass Spectrometry
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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
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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
