Experiment III

Mass Spectrometry

CHM120H5F
Teaching Assistant: Rima Rahmatullah
PRA9105
Date performed: 19-05-2021
Date submitted: 26-05-2021

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1. Introduction
Mass spectrometry is an analytical technique utilized in the identification and
confirmation of unknown chemical species through the measurement of their ions’
mass-to-charge (m/z) ratios. This methodology encompasses numerous chemical
applications as well as astronomical, biochemical, ecological, geological, medicinal,
and physical, such as ascertaining molecular masses and formulas, dissociation
lengths, and bond lengths [1]. The employed spectrometric instrumentation is labelled
mass spectrometer, which ionizes gaseous molecules through their exposition to an
electron beam, traverses molecules through different electric and magnetic fields until
a detector is contacted, separates the generated ions on the base of their mass-to-charge
proportion, and documents the diverse number of ionic compounds yielded. These ion
molecules’ relative intensities are plotted against their respective mass charge ratios in
order to derive a diagram designated mass spectrum, which illustrates peaks
corresponding to each ionization of the unknown molecule.

Following the deconstruction of the unidentified sample and the formation of ions,
the fragmented ions travel within an accelerated region and between two plates, which
possess a considerable difference in potential and are quantified through the equation:
1 2
m v =qV , where m is the ion mass, v is the velocity of particles per second, q is the
2
charge, and V is the potential of the ion accelerating plates. Subsequently, the
accelerated ions are exposed to a magnetic field, which aids in the ions’ travel along
mv
the circular path of the spectrometer and is calculated through: r = , where r is the
qB
radius of the circle and B is the magnetic field. The combination and rearrangement of
m r2 B 2
the aforementioned equations yield: = , which is further reorganized in order to
q 2V
generate m/z quantities. The analysis of the spectrum of these mass–to–charge
proportions enable the identification of the ion formations and the original unknown
molecule. In this experiment, a set of mass spectrometric quantities will be employed
and analyzed in the identification of unknown chemical species #13.

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 2. Results

Table 1. The tabulated mass spectrum of the unknown organic molecule #13
Mass Charge Relative Abundance
12 0.1
13 0.1
14 0.3
15 0.3
24 0.2
25 1.5
26 11.2
27 100.0
28 3.8
29 0.1
79 4.0
80 1.5
81 4.0
82 1.5
83 0.1
91 0.5
92 0.0
93 0.6
94 0.4
95 0.1
104 0.8
105 2.4
106 1.7
107 74.4
108 2.6
109 69.8
110 1.5
170 0.1
171 0.9
172 0.2
173 1.9
174 0.2
175 0.9
186 6.2
187 0.2
188 11.8
189 0.4
190 5.8
191 0.1

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 Mass Spectrum of Unknown #13
100
90
80
Relative Intensity

70
60
50
40
30
20
10
0
0 5 10 15 20 25 30 35 40 45

Mass–to–charge Ratio (amu/electron charge)

Figure 1 illustrates the mass spectrum of the unknown organic molecule #13 (C2H4Br2)

Table 2. The tabulated peaks of the unknown molecule’s mass spectrum

Mass Charge Relative Abundance
24 0.2
25 1.5
26 11.2
27 100.0
28 3.8
29 0.1
79 4.0
104 0.8
105 2.4
106 1.7
107 74.4
108 2.6
109 69.8
110 1.5
175 0.9
186 6.2
187 0.2
188 11.8
189 0.4
190 5.8
191 0.1

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 The molecule portrayed in the mass spectrum and its tabulated version is
dibromoethane, which possesses three ionic fragments ([C2H4Br2]+•, [C2H4Br]+, and
[C2H3]+, respectively) corresponding to three ionic peaks (at m/z values 188, 107, and 27,
respectively). The first peak at mass charge 188 and relative abundance 11.8 is the
molecular ion peak (parent ion) and pertains to the molecular formula of the unknown
compound dibromoethane [C2H4Br2]+•, the second peak pertaining to the fragment vinyl
bromide [C2H4Br]+, and the third peak pertaining to the fragment ethylenyl or vinyl radical
[C2H3]+.

The dibromoethane encompasses two possible structural configurations:

1,1–dibromoethane

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 1,2–dibromoethane

3. Discussion
The aforementioned catalogued data assisted in the identification of the unknown
molecule through the thorough analysis of the mass charge quantities; the utilization of
the nitrogen, halogen, and M+2 peak rules; and the employment of the trial and error
method of possible molecular arrangements. In order to establish the identity of the
molecular formula, the mass–to–charge ratios were scrutinized for their respective
relative intensity peaks, with the highest peaks being indicative of the possible ionic
fragments produced through the spectrometric ionization process and the mass
difference between these ions being suggestive of the substituents separated through
the same process. Subsequently, a portion of the ionic fragments’ intensity peaks were
classified as the base peak (peak with the highest relative abundance) and the
molecular ion peak (peak of the parent ion, which is the ion of the unknown molecule).
Upon classification, possible molecular formulas were derived for each of the ionic
fragments and the functional groups lost and were assessed based on the similarities
between the different ions and the coherence of the ionic fragments and the
substituents together.

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 In this experiment, the mass spectrum of the unidentified molecule #13 was
provided, which is representative of an organic molecule (denoting the presence of
carbon (C) and hydrogen (H) atoms and C–H bonding). Reviewing the tabulated mass
charge proportions and their relative abundances disclosed that the base peak of this
molecule is located at the m/z value 27 as its relative intensity is 100%, which is the
highest achievable value. Additionally, this m/z value is considered the molecular
mass of the unknown molecule’s base (without the emitted, attached substituents) as
the charge quantity (z, the denominator quantity) is almost always +1. Since the base
peak possesses a relatively small molecular mass in comparison to the extent of the
mass spectrum values, which range from 12 to 191, the base peak is not considered the
molecular ion peak in this case (which occurs either at the end of the spectrum or near
end of the spectrum). Furthermore, two more ionic fragments were established at m/z
values of 107 and 188 with respective relative intensity peaks at 74.4 and 11.8. The
identification of the molecular ion peak is usually attributed to the highest molecular
m/z (mass) value within the spectrum; however, the great differences between each of
the ionic fragments coupled with the height (percent) approximation of the relative
abundance peaks at a distance of 2 m/z are indicative of the presence of a halogen
atom within the unknown molecule. The molecular incorporation of the halogen(s)
shifted the molecular ion peak from the highest m/z value to the ionic fragment closest
to the highest m/z value. Moreover, this modification has ruled out the mandated
incorporation of nitrogen atoms within the unknown compound as only odd molecular
weights mandate the presence of nitrogen atoms, whereas now the even mass reveals
only a possibility of nitrogen appearing in the unidentified molecule.

As such, the molecular ion peak (M+) of the halogenated unknown molecule is
located at the m/z quantity 188 with a relative intensity peak of 11.8. Since this is a
halogen-incorporating molecule, a M+2 peak is present at the m/z value 190 with a
relative intensity of 5.8. Although the ratio of 11.8 : 5.8, simplified to 2 : 1, is not
suggestive of any isotope ratio of halogen atoms, this ratio is closest to the ratio of the
bromine isotopes 79Br and 81Br (1 : 1) in comparison with the ratio of the chlorine
isotopes (3 : 1). Furthermore, the mass difference between the parent ion and the first
ionic fragment, which is 81, and between the first fragment and the second fragment,
which is 80, alongside the approximation of those subtracted quantities disclosed the
identity of the substituents emitted through the ionization process, which denotes the

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loss of the same functional group (twice) from the unidentified molecule. From Table
2 in the lab manual [1], the identity of the emitted substituents was revealed to be the
bromine atom, which possesses two different atomic masses (79 and 81) in
correspondence with the two isotopic forms of bromine. The additional unit of mass in
80 corresponds to a hydrogen atom (with a mass of 1) accompanying the bromine
isotope (mass of 79), which causes the first substituent lost to be 81Br and the second
substituent HBr. To further validate the incorporation of the bromine atom within the
unidentified molecule, the mass charge proportions 79 and 81 (equivalent to the atomic
masses of the bromine isotopes), which correspond to relative abundance peaks at 4.0
and 4.0, respectively, possess a perfect 1 : 1 ratio representative of a molecule
containing a bromine atom. Moreover, the mass–to–charge ratios 107 and 109,
corresponding to relative intensities at 74.4 and 69.8, retain a similar 1 : 1 ratio
illustrative of a bromine-containing compound.

Possible identifications for the base were the compounds hydrogen cyanide,
molecular formula HCN (with H = 1, C = 12, and N = 14 for a total of HCN = 27) and
ethylenyl, molecular formula C2H3 (with C2 = 24 and H3 = 3 for a total of C 2H3 = 27).
As the incorporation of dibromo in the hydrogen cyanide molecule is highly
improbable (if not impossible as the presence of the bromine atom has no impact on
HCN and cannot bond with HCN) and does not exist within nature (thus possessing no
relative abundance), the only possible molecular formula of the base peak is C 2H3.
Additionally, HCN has an odd number of nitrogen atoms, which is impossible with a
molecular ion peak corresponding to an even mass. As this unknown organic molecule
encompasses two substituents (an 81Br atom and an HBr functional group) with a base
of C2H3, the unknown molecule has been ascertained with the molecular formula of
C2H4Br2, which is chemically designated dibromoethane, and a molecular weight of
188.

According to the previously conducted procedure and analysis of the unidentified

molecule #13, the comprehensible application of mass spectrometry is the
identification of undetermined chemical species through mass–to–charge ratios and
fluctuating relative intensities and the determination of the exact or approximate
molecular weight of the anonymous species. Although this utilization is familiarized
and fundamental to chemical instrumentation, mass spectrometry explores numerous

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 scientific biospheres including forensic investigations, which encompass the swabbing
of unknown substances (trace evidence) and the determination of their molecular
components through the spectrometer analysis. Furthermore, a similar analytical
technique that ascertains the identity of anonymous molecules is nuclear magnetic
resonance (NMR) spectroscopy, which characterizes molecules through the
identification of their hydrogen and carbon structures. NMR spectroscopy transpires
through the placement of the unknown sample within a powerful magnetic field in
order to perturb the natural axial spin of the 1H and 13C nuclei with the aid of radio
waves. Lastly, possible sources of error would be the high-voltage bombardment of the
unknown molecule with the electron beam, which would fragment the molecule;
however, the fragmentation would be too broken to be identified properly by the
detector at the end of the spectrometer, and/or the detected fragments would not be
representative of the correct mass spectrum for the molecule. Improvements on this
failed spectrometric analysis would be to conduct numerous trials of the same
unknown molecular sample in order to establish the correct mass spectrum and
fragmented ions corresponding to the undetermined compound.

4. Summary
In conclusion, through the extensive analysis of the mass–to–charge
proportions and their respective relative intensities, the tabulated mass spectrum of the
anonymous organic molecule #13 illustrates the compound dibromoethane (C2H4Br2).
Moreover, the employment of the isotopic varieties and the cross examination of their
relative abundance peaks revealed the presence and identity of the halogenated
substituent bromine, which facilitated the discovery of the unknown molecule.

5. References
[1] Thottakad, R. Experiment 3 – Mass Spectrometry (CHM110H5S),
University of Toronto Mississauga, 2021
[2] Clark, J. Mass Spectra – The M+2 Peak,
https://www.chemguide.co.uk/analysis/masspec/mplus2.html#top (accessed May 28,
2021), 2014
[3] Beauchamp, J. Mass Spectroscopy Material (Chem 319, 422, 424),
https://www.cpp.edu/~psbeauchamp/pdf/MS_basic_notes,12-31-09.pdf (accessed
May 30, 2021)

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 [4] Dunnivant, F. and Ginsbach, J. Identifying the Molecular Ion Peak
http://people.whitman.edu/~dunnivfm/C_MS_Ebook/CH6/6_3.html (accessed May
31, 2021)

6. Learning Objectives
- Understanding the function fundamentals of mass spectrometry and the
spectrometer
- Understanding how to read and analyze mass spectra and apply chemical and
physical principles and rules
- Deriving molecular formulas from the ionic fragmentations and assessing the
possibilities of molecular formula assignments
- Recognizing the impact of isotopic forms on the relative intensity peaks

7. Appendix
Data Sheet
Data Sheet

Name: Malak Mahmoud Student No.: 1006825170

Lab Section No.: PRA9105 Date: 19-05-2021

Mass Charge Relative Abundance

12 0.1
13 0.1
14 0.3
15 0.3
24 0.2
25 1.5
26 11.2
27 100.0
28 3.8
29 0.1
79 4.0
80 1.5
81 4.0
82 1.5
83 0.1
91 0.5
92 0.0
93 0.6

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 94 0.4
95 0.1
104 0.8
105 2.4
106 1.7
107 74.4
108 2.6
109 69.8
110 1.5
170 0.1
171 0.9
172 0.2
173 1.9
174 0.2
175 0.9
186 6.2
187 0.2
188 11.8
189 0.4
190 5.8
191 0.1

Parent Ion:
Mass Charge: 188 – Relative Abundance: 11.8

Fragments:

1- Mass Charge: 107 – Relative Abundance: 74.4

2- Mass Charge: 27 – Relative Abundance: 100.0

Base Peak:
Mass Charge: 27 – Relative Abundance: 100.0

Molecular Ion Peak:

Mass Charge: 188 – Relative Abundance: 11.8

Academic Integrity Checklist

Report Name: Experiment II – The Synthesis and Analysis of a Chromium Salt

Course Name: CHM120H5F
TA’s Name: Rima Rahmatullah
I, Malak Mahmoud, affirm that this assignment represents entirely my own efforts. I
confirm that:

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 - I have acknowledged the use of another’s ideas with accurate citations.
- If I used the words of another (e.g., author, instructor, information source), I have
acknowledged this with quotation marks and proper citation.
- When paraphrasing the work of others, I used my own words (not merely using
synonyms or rearranging the sentence structure). I have also appropriately cited the
source(s) of the idea(s).
- I have checked my work against my notes to be sure I have correctly referenced all
direct quotes or borrowed ideas.
- My bibliography includes only the sources used to complete this assignment.
- This is the first time I have submitted this assignment (in whole or in part) for
academic credit in any year and/or at any institution.
- Any proofreading by another was limited to indicating areas of concern which I then
corrected myself. All changes (including grammar correction) were entirely my own.
- This is the final version of my assignment and not a draft. I have kept and will
continue to keep my work to myself and did not/will not share answers or content
with others, unless otherwise directed by my instructor.
- I understand the consequences of violating the University of Toronto’ academic
integrity policies as outlined in the Code of Behaviour on Academic Matters.
By signing this form, I agree that the statements above are true. If I do not agree with the
statements above, I will not submit my assignment and will consult the course instructor
immediately.
Student name: Malak Mahmoud
Signature: M.M.
Date: 26-05-2021

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