MASS

SPECTROMETRY
Tutorial III

S Rusdi
Dept of Chemical Engineering
The Islamic University of Indonesia
MASS SPECTROMETRY
 What is mass?
1. Gravitational mass. Newtons law of gravitation:

Fg = GmM/r2 - gravitational force m

r
G gravitational constant;
m, M masses of spherical bodies;
r center-of-mass distance.
M
2. Inertial mass. Newtons second law of mechanics:

Fi = mdv/dt, - external force

v - velocity.

Mass equivalency principle. Gravitational and inertial masses are

equivalent.
Confirmed experimentally to the accuracy of 10-12 (1971).

Mass and energy equivalency. Einsteins law:

E = mc2, - total energy

c speed of light, 3108 m/s.

Example: 1 eV = 1.0710-9 u (Da).

MASS SPECTROMETRY
Sample Data
Introduction Output

Inlet Data
System

Ion Mass Ion

Source Analyzer Detector

Vacuum
Pumps
 MOLECULAR MASS DETERMINATION
USING MASS SPECTROMETRY

mass spectrometry is used to identify

unknown or new compounds.

IONISATION When a molecule is ionised it forms a

MOLECULAR ION which can also
MOLECULAR ION undergo FRAGMENTATION or
RE-ARRANGEMENT to produce
FRAGMENTION particles of smaller mass.

Only particles with a positive charge

(cation) will be deflected and detected.

RE-ARRANGEMENT FRAGMENTION The resulting spectrum has many peaks.

The final peak (M+) shows the molecular

ion (highest m/z value) and indicates the
molecular mass.
The rest of the spectrum provides
information about the structure.
 MASS SPECTROMETRY
Magnetic-Sector Instruments
Bonds in cation radicals
begin to break (fragment)

Sample
vaporized &
subjected to
bombardmen
t by electrons
that remove
an electron Mass to charge (m/z)
creating a ratio is measured
cation radical
Molecular ion (M+)
shows molecular weight

6
THE MASS SPECTROMETRY
Molecular ion (colored red).

Residual energy from the

collision may cause the
molecular ion to fragment into
Neutral pieces (colored green)
and smaller fragment ions
(colored pink and orange).

The molecular ion is a radical

cation, but the fragment ions
may either be radical cations
(pink) or carbocations (orange),
depending on the nature of the
neutral fragment.
 THE MASS SPECTROMETRY

(M) -
+ e (M )
+ . + 2e-

(M+. ) m 1 + + m .2
or
(M+. ) m 1 +. + m 2
Chemical ionisation
Methane:

CH4 + e -----> CH4+. + 2e ------> CH3+ + H.

CH4+. + CH4 -----> CH5+ +CH3.

CH4+. + CH4 -----> C2H5+ + H2 + H.

Isobutane:

i-C4H10 + e -----> i-C4H10+. + 2e

i-C4H10+. + i-C4H10 ------> i-C4H9+ + C4H9 +H2

Ammonia:

NH3 + e -----> NH3+. + 2e

NH3+. + NH3 ------> NH4+ + NH2.

NH4+ + NH3 --------->N2H7+

 FRAGMENTATION (Example)
The mass spectrum of Methane

The mass spectrum of CH4 consists of more peaks than just the M
peak.
Since the molecular ion is unstable, it fragments into other cations
and radical cations containing one, two, three, or four fewer
hydrogen atoms than methane itself.
Thus, the peaks at m/z 15, 14, 13 and 12 are due to these lower
molecular weight fragments as follow:

10
FRAGMENTATION (Example)
The mass spectrum of Methane

The tallest peak in the mass spectrum is called the base peak.
The base peak is also the M peak, although this may not always be
the case.
Though most C atoms have an atomic mass of 12, 1.1% have a mass
of 13. Thus, 13CH4 is responsible for the peak at m/z = 17. This is
called the M + 1 peak. 11
FRAGMENTATION
m/z values (mass/charge ratio)

ion relative mass (m) positive ion charge (z) m/z ratio

[14N]+ 14 1 14/1 = 1

[56Fe]+ 56 1 56/1 = 56

[56Fe]2+ 56 2 56/2 = 28

[35Cl]+ 37 1 35/1 = 35

[35Cl2]+ 70 1 70/1 = 70

[35Cl2]2+ 70 2 70/2 = 35

[CH3]+ 15 1 15/1 = 15
12
 What is Molecular Mass?
Mass: M = mene,
Isotope Mass Abundance Chemical Deviation from the
mass whole number

1H 1.00782510 99.9852% 1.00794 +0.0079

2H (D) 2.01410222 0.0148%

12C 12.0(0) 98.892% 12.011 +0.011

13C 13.0033544 1.108%
14N 14.00307439 99.635% 14.00674 +0.007
15N 15.0001077 0.365%
16O 15.99491502 99.759% 15.9994 -0.0006
17O 16.9991329 0.037%
18O 17.99916002 0.204%
31P 30.9737647 100% 30.9737647 -0.0262
32S 31.9720737 95.0% 32.066 +0.066
33S 32.9714619 0.76%
34S 33.9678646 4.22%
36S 35.967090 0.014%
What is Molecular Mass?
Mass: M = mene,

81Br
 M elements (Mono-isotopic)
(fluorine, phosphorus, cesium,
sodium, iodine)

M+1 elements
(carbon, nitrogen, hydrogen)

M+2 elements
(oxygen, chlorine, bromine, silicon,
sulfur)
 M+2 elements
(oxygen, chlorine, bromine, silicon,
sulfur)
Relative Abundance = Relative Peak High

Zirconium: 90Zr 51.5% 91Zr 11.2%

92Zr 17.1 % 94Zr 17.4% 96Zr 2.8%

Zr (m) = (51.5x90 + 11.2x91 + 17.1x92 + 2.8x96)/100

= 91.22
 Relative Abundance = Relative Peak High

Bromine: 50.50% 79Br and 49.50% 81Br

 Relative Abundance = Relative Peak High

In Br2 , the possible combinations of isotopes are:

79Br79Br:m/z 158
79Br81Br:m/z 160
81Br79Br:m/z 160
81Br81Br:m/z 162

Br 's isotopic distribution is essentially a 50:50 ratio of mass 79 and mass 81.
That means that there's a 25% chance of m/z 158 (0.50.5=0.25) arising from
79Br79Br.

There's a 50% chance of m/z 160 since there are two combinations
(79Br81Br and 81Br79Br) that give that mass (0.50.5+0.50.5=0.25).

There's a 25% chance of m/z 162 (0.50.5=0.25) arising from 81Br81Br

.
 Relative Abundance = Relative Peak High

the ionic fragment CH2Cl+ can be calculated, taking into

consideration the isotopic abundance for C, H and Cl
(75.77% 35Cl - 24.23% 35Cl) is shown follow :
Relative Abundance = Relative Peak High
Relative Abundance = Relative Peak High

Chlorine: 75.77% 35Cl and 24.23% 37Cl

How to calculate the isotopic distribution?

N! i
P
(
i) p(
1p
)Ni

i
!(N
i!
)
N= number of atoms
i = ith isotope
p = probability of being heavy isotope (e.g. 13C)
Note: the total isotopic distribution is the convolution of the
individual isotopic distributions for each possible isotope.

atomic weight =(relative abundanceatomic mass)

Yergey, J. A. Int. J. Mass Spectrom. Ion Physics,

1983, 52, 337-349.
Rockwood, A. L.; Van Orden, S. L.; Smith, R. D.
Anal. Chem. 1995, 67, 2699-2704.
 Abundance of Atoms
Element Most Abundant Isotope Secondary Isotope Abundance/100 atoms of Primary Isotope

Hydrogen 1H 2H 0.015

Carbon 12C 13C 1.080

Nitrogen 14N 15N 0.370

Oxygen 16O 17O 0.040

18O 0.200

Sulfur 32S 33S 0.800

34S 4.400

Chlorine 35Cl 37Cl 32.50

Bromine 79Br 81Br 98.00

Silicon 28Si 29Si 5.100

30Si 3.400
 Abundance of Atoms
Quantitative Peak Analysis
C4Br1O2H5
4C * 1.08 = 4.32 = molecules with a 13C atom per 100 molecules
5H * 0.015 = 0.075 = molecules with a 2H atom per 100 molecules
2O * 0.04 = 0.08 = molecules with a 17O atom per 100 molecules
Any of the three isotopes, 13C, 2H, or 17O occurring in our molecule would result in an
(M+1)+ peak.
To get the ratio of (M+1)+/M+, we need to add all three probabilities:
4.32 + 0.075 + 0.08 = 4.475 = (M+ 1)+ molecules per 100 M+ molecules
We can say then that the (M+1)+ peak is 4.475% as high as the M+ peak.
A similar analysis can be easily repeated for (M+2)+:
1Br * 98 = 98 = molecules with an 81Br molecule per 100 molecules
2O * 0.2 = 0.4 = molecules with an 18O molecule per 100 molecules
98 + 0.4 = 98.4 = (M+2)+ molecules per 100 M+ molecules
The (M + 2)+ peak is therefore 98.4% as tall as the M+ peak.
 THE MASS SPECTRUM
Spectra obtained for organic molecules have many peaks.
Each peak is due to a particular fragment with a certain m/z value.

highest m/z value usually corresponds to the molecular ion

its position provides information about the molecular mass of a

substance

the tallest peaks come from the most stable species

Interpretation of thousands of spectra has shown that many classes of organic

compound show characteristic fragmentation patterns due to their functional groups.
It is possible to identify the type of compound from its spectrum by looking at the ...

position of peaks differences between major peaks

THE MASS SPECTRUM - THE MOLECULAR ION
In the spectrum of octane, a signal occurs at 114 due to the species C8H18+

The species due to the final signal is known as the molecular ion and is usually
corresponds to the molecular mass of the compound.
100
80
Abundance %
60

molecular ion
40

114
20

0
. m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 THE MASS SPECTRUM - THE MOLECULAR ION
The small peak (M+1) at 115 due to the natural abundance (about 1%) of carbon-13.
The height of this peak relative to that for the molecular ion depends on the number
of carbon atoms in the molecule.
The more carbons present, the larger the M+1 peak.
100
80
Abundance %
60
40

114
20

0
. m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
THE MASS SPECTRUM
The molecular ion peak & the base peak
For example, the mass spectrum of pentane looks like this:

It's important to realise that the pattern of

lines in the mass spectrum of an organic
compound tells you something quite
different from the pattern of lines in the
mass spectrum of an element. With an
element, each line represents a different
isotope of that element. With a compound,
each line represents a different fragment
produced when the molecular ion breaks up.

In the stick diagram showing the mass spectrum of pentane, the line
produced by the heaviest ion passing through the machine (at m/z = 72) is
due to the molecular ion.
 THE MASS SPECTRUM
The molecular ion peak and the base peak

The tallest line in the stick diagram (in this case at m/z = 43) is called the
base peak.
This is usually given an arbitrary height of 100, and the height of everything
else is measured relative to this.
The base peak is the tallest peak because it represents the commonest
fragment ion to be formed - either because there are several ways in which
it could be produced during fragmentation of the parent ion, or because it is
a particularly stable ion.
 THE MASS SPECTRUM
Base Peak, Parent Peak=MI Peak

Base Peak, The largest peak in the spectrum. Parent Peak =MI Peak, The
peak corresponding to the unfragmented molecular cation. (m/z), The
mass/charge ratio. The charge is usually, but not always, +1.
THE MASS SPECTRUM
Base Peak, Parent Peak=MI Peak
 M+2 and M+1 Peaks
The most common elements giving rise to significant M + 2
peaks are chlorine and bromine.
Chlorine in nature is 75.77% 35Cl and 24.23% 37Cl.
A ratio of M to M + 2 of approximately 3:1 indicates the
presence of a single chlorine in a compound, as seen in
the MS of chloroethane.

Also note the drop of 35/37

(64-29 = 35; 66-29 = 35)
Halogens can fragment readily
 M+2 and M+1 Peaks
Bromine in nature is 50.7% 79Br and 49.3% 81Br.
A ratio of M to M + 2 of approximately 1:1
indicates the presence of a single bromine atom in
a compound, as seen in the MS of 1-
bromopropane.
 M+2 and M+1 Peaks

Sulfur is the only other element common to

organic compounds that gives a significant M
+ 2 peak
32S = 95.02% and 34S = 4.21%
Because M + 1 peaks are relatively low in
intensity compared to the molecular ion and
often difficult to measure with any precision,
they are generally not useful for accurate
determinations of molecular weight.
 M+ peak :
Peaks above the molecular weight appear as a result
of naturally occurring heavier isotopes in the sample
(M+1) from 1.1% 13C in nature
(M and M+2) in 75.8%/24.2% ratio = 35Cl and 37Cl
(M and M+2) in 50.7%/49.3% ratio = 79Br and 81Br

Propane H H H
MW = M+ = 44 H C C C H
H H H

M+1 = 45
From 1.1% 13C

36
Click on image to enlarge

M+ peak: Halides

M+ and M+2 in
75.8%:24.2% (~ CH3C
3:1) ratio l
= 35Cl and 37Cl

M+ and M+2 in Br
50.7%:49.3% (~
1:1) ratio
= 79Br and 81Br

37
FRAGMENTATION PATTERNS

The formation of molecular ions

When the vaporised organic sample passes into the ionisation chamber of a
mass spectrometer, it is bombarded by a stream of electrons.
These electrons have a high enough energy to knock an electron off an
organic molecule to form a positive ion. This ion is called the molecular ion
- or sometimes the parent ion.
The molecular ion is often given the symbol M+ or
the dot in this second version represents the fact that somewhere in the
ion there will be a single unpaired electron. That's one half of what was
originally a pair of electrons - the other half is the electron which was
removed in the ionisation process.
The molecular ions are energetically unstable, and some of them will break
up into smaller pieces.
The simplest case is that a molecular ion breaks into two parts - one of
which is another positive ion, and the other is an uncharged free radical.

Note: A free radical is an atom or group of atoms which contains a single unpaired electron.
FRAGMENTATION PATTERNS
The uncharged free radical won't produce a line on the mass spectrum.
Only charged particles will be accelerated, deflected and detected by the
mass spectrometer.
These uncharged particles will simply get lost in the machine - eventually,
they get removed by the vacuum pump.
The ion, X+, will travel through the mass spectrometer just like any other
positive ion - and will produce a line on the stick diagram.
All sorts of fragmentations of the original molecular ion are possible - and
that means that you will get a whole host of lines in the mass spectrum.
The other lines in the mass spectrum are more difficult to explain.
For example, lines with m/z values 1 or 2 less than one of the easy lines are
often due to loss of one or more hydrogen atoms during the fragmentation
process.
You are very unlikely to have to explain any but the most obvious cases in
an A'level exam.
FRAGMENTATION PATTERNS
Using fragmentation patterns
This section will ignore the information you can get from the
molecular ion (or ions). That is covered in three other pages which
you can get at via the mass spectrometry menu. You will find a
link at the bottom of the page.

Working out which ion produces which line

This is generally the simplest thing you can be asked to do.
FRAGMENTATION (Example)
The mass spectrum of pentane
C4H9+ would be [CH3CH2CH2CH2]+, and this would be produced
by the following fragmentation:

The methyl radical produced will simply get lost in the machine.

The line at m/z = 43 can be worked out similarly. If you play

around with the numbers, you will find that this corresponds to
a break producing a 3-carbon ion:

The line at m/z = 29 is typical of an ethyl ion, [CH3CH2]+:

FRAGMENTATION (Example)
The mass spectrum of pentane
Let's have another look at the mass spectrum for pentane:

What causes the line at m/z = 57?

How many carbon atoms are there in this ion? There can't be 5
because 5 x 12 = 60. What about 4? 4 x 12 = 48. That leaves 9 to
make up a total of 57.
How about C4H9+ then?
 FRAGMENTATION PATTERNS
The mass spectrum of Hexane
Hexane (m/z = 86 for parent) has peaks at
m/z = 71, 57, 43, 29

71=Loss of CH3 (15)

57=Loss of CH3CH2 (29)

43
 FRAGMENTATION PATTERNS
The mass spectrum of 2-methylbutane.
2-methylbutane is an isomer of pentane (isomers are molecules with the same
molecular formula, but a different spatial arrangement of the atoms).

Look first at the very strong peak at m/z = 43.

This is caused by a different ion than the corresponding peak in the pentane
mass spectrum. This peak in 2-methylbutane is caused by:
FRAGMENTATION PATTERNS
The mass spectrum of 2-methylbutane.
The ion formed is a secondary carbocation - it has two alkyl groups attached to
the carbon with the positive charge. As such, it is relatively stable.
The peak at m/z = 57 is much taller than the corresponding line in pentane.
Again a secondary carbocation is formed - this time, by:

You would get the same ion, of course, if the left-hand CH3 group broke off
instead of the bottom one as we've drawn it.
In these two spectra, this is probably the most dramatic example of the extra
stability of a secondary carbocation.
 FRAGMENTATION PATTERNS
The mass spectrum of Neopentane

Molecular ions break into characteristic fragments that can be

identifed
Serves as a fingerprint for comparison with known materials in
analysis (used in forensics)
Positive charge goes to fragments that best can stabilize it

46
FRAGMENTATION PATTERNS
The mass spectrum of Neopentane

M -15 = 57

CH3=15
MW=72;
M+ peak not seen
47
 FRAGMENTATION PATTERNS

The mass spectrum of pentan-3-one

This time the base peak (the tallest peak - and so the commonest fragment
ion) is at m/z = 57. But this isn't produced by the same ion as the same m/z
value peak in pentane.
FRAGMENTATION PATTERNS
The mass spectrum of pentan-3-one
If you remember, the m/z = 57 peak in pentane was produced by
[CH3CH2CH2CH2]+. If you look at the structure of pentan-3-one, it's impossible
to get that particular fragment from it.
Work along the molecule mentally chopping bits off until you come up with
something that adds up to 57. With a small amount of patience, you'll
eventually find [CH3CH2CO]+ - which is produced by this fragmentation:

You would get exactly the same products whichever side of the CO group
you split the molecular ion.
The m/z = 29 peak is produced by the ethyl ion - which once again could be
formed by splitting the molecular ion either side of the CO group.
 FRAGMENTATION PATTERNS

Peak heights and the stability of ions

The more stable an ion is, the more likely it is to form. The more of a particular
sort of ion that's formed, the higher its peak height will be. We'll look at two
common examples of this.

Examples involving carbocations (carbonium ions)

Summarizing the most important conclusion from the page on carbocations:

Order of Stability of Carbocation :

Primary< Secondary<Tertiary
Applying the logic of this to fragmentation patterns, it means that a split which
produces a secondary carbocation is going to be more successful than one
producing a primary one. A split producing a tertiary carbocation will be more
successful still.
Let's look at the mass spectrum of 2-methylbutane. 2-methylbutane is an
isomer of pentane - isomers are molecules with the same molecular formula,
but a different spatial arrangement of the atoms.
FRAGMENTATION PATTERNS
Examples involving acylium ions, [RCO]+
Ions with the positive charge on the carbon of a carbonyl group, C=O, are also
relatively stable.
This is fairly clearly seen in the mass spectra of ketones like pentan-3-one.

The base peak, at m/z=57, is due to the [CH3CH2CO]+ ion.

We've already discussed the fragmentation that produces this.

Note: There are lots of other examples of positive ions with extra stability and
which are produced in large numbers in a mass spectrometer as a result.
 FRAGMENTATION PATTERNS
Using mass spectra to distinguish between compounds
Suppose you had to suggest a way of distinguishing between pentan-2-one
and pentan-3-one using their mass spectra.
Pentan-2-one
CH3COCH2CH2CH3

Pentan-3-one
CH3CH2COCH2CH3
Each of these is likely to split to produce ions with a positive charge on the
CO group.
In the pentan-2-one case, there are two different ions like this:
[CH3CO]+
[COCH2CH2CH3]+
That would give you strong lines at m/z = 43 and 71.
 FRAGMENTATION PATTERNS
With pentan-3-one, you would only get one ion of this kind:
[CH3CH2CO]+
In that case, you would get a strong line at 57.

We don't need to worry about the other lines in the spectra - the 43, 57 and
71 lines give you plenty of difference between the two.
The 43 and 71 lines are missing from the pentan-3-one spectrum, and the
57 line is missing from the pentan-2-one one.

Note: Don't confuse the line at m/z = 58

in the pentan-2-one spectrum. That's due
to a complicated rearrangement which you
couldn't possibly predict at A'level
FRAGMENTATION PATTERNS
The two spectra look like this:
 FRAGMENTATION PATTERNS
ALKANES
The mass spectra of simple hydrocarbons have peaks at m/z values corresponding to
the ions produced by breaking C-C bonds. Peaks can occur at ...

m/z 15 29 43 57 71 85 etc.
CH3+ C2H5+ C3H7+ C4H9+ C5H11+ C6H13+

o the stability of the carbocation formed affects its abundance

o the more stable the cation the higher the peak

o the more alkyl groups attached to the carbocation the more stable it is

most stable tertiary 3 > secondary 2 > primary 1 least stable

alkyl groups are electron releasing and stabilise the cation
 FRAGMENTATION PATTERNS
HALOGENOALKANES
Multiple peaks occur in the molecular ion region due to different halogen isotopes.
There are two peaks for the molecular ion of C2H5Br, one for the molecule containing
the isotope 79Br and the other for the one with the 81Br isotope. Because the two
isotopes are of similar abundance, the peaks are of similar height.
100

molecular ion contains...79Br 81Br

80
Abundance %
60
40
20

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 FRAGMENTATION PATTERNS
ALDEHYDES AND KETONES
Cleavage of bonds next to the carbonyl group (C=O) is a characteristic fragmentation
of aldehydes and ketones. A common fragment is carbon monoxide (CO) but as it is
a molecule and thus uncharged it will not produce a peak of its own. However, it will
produce an m/z drop of 28 somewhere in the spectrum.

The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group

the more stable the acylium ion RCO+, the more abundant it will be and
the more abundant the species the taller its peak in the mass spectrum
 FRAGMENTATION PATTERNS
Aldehydes and ketones
The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
MOLECULAR ION
CH3 C C4H9 has m/z = 100
+
 FRAGMENTATION PATTERNS
Aldehydes and ketones
The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
MOLECULAR ION
CH3 C C4H9 has m/z = 100
+

O
C4H9 C+ CH3 Breaking the bond between the methyl
group and the carbonyl group
m/z = 85 produces two possible ions,
depending on how the bond breaks.
O
Two peaks at m/z values 15 and 85 will
C4H9 C CH3+ appear in the mass spectrum.
m/z = 15
 FRAGMENTATION PATTERNS
Aldehydes and ketones
The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
MOLECULAR ION
CH3 C C4H9 has m/z = 100
+

O
Breaking the bond between the butyl
group and the carbonyl group CH3 C+ C4H9
produces two further ions, depending m/z = 43
on how the bond breaks.

Two peaks at m/z values 43 and 57 will O

appear in the mass spectrum.
CH3 C C4H9+
m/z = 57
 FRAGMENTATION PATTERNS
Aldehydes and ketones
The position of the carbonyl group influences the fragmentation pattern because the
molecular ion fragments either side of the carbonyl group.

O
Example; MOLECULAR ION
CH3 C C4H9 has m/z = 100
+

O O
C4H9 C+ CH3 CH3 C+ C4H9
m/z = 85 m/z = 43

O O
C4H9 C CH3+ CH3 C C4H9+
m/z = 15 m/z = 57

A further peak occurs at m/z = 72 (100-28) due to loss of CO

 Note: Common Neutral Losses - 1
15 CH3 Alkyl branching
16 O, NH2 Nitroaromatic, oxime, sulfoxide or amines/amides
17 NH2 RCONH2
18 H2O Alcohol, (ketone, aldehyde, less common)
20 HF Alkyl fluoride
26 C2H2 Aromatic hydrocarbon
27 HCN ArCN, N-heterocylic compounds, ArNH2 rarely

C2H3 Ethyl ester (low abundance)

28 CO Quinones, some phenols

C2H4 n-Propyl ketones, ethyl esters, ArOC2H5

29 C2H5 Ethyl ketones, Ar - n-C3H7 compounds

30 CH2O Aromatic methyl esters
CH3O,CH3O
31,32 Methyl esters of carboxylic acids
H
33,34 SH, H2S RSH

For a more extensive list, see McLafferty, Table A.5, pp. 348-
 Note: Common Neutral Losses - 1
41 C3H5 Propyl ester
42 C3H6 n-butyl ketone

CH2CO RCOCH3, ArOCOCH3, ArNHCOCH3

43 C3H7 RCOC3H7, Ar-n-C4H9 compounds

44 CO2 Anhydrides, esters
45 COOH RCOOH

OC2H5 Ethyl esters of carboxylic acids

46 NO2 Aromatic nitrocompounds

48 SO Aromatic sulfoxide
55 C4H7 Butyl ester of carboxylic acid
56 C4H8 RCOC5H11, ArOC4H9, Ar-C5H11 (n- or i-)
57 C4H9 RCOC4H9

C2H5CO RCOC2H5

Acetate
60 CH3COOH

For a more extensive list, see McLafferty, Table A.5, pp. 348-
 Common Characteristic Ions
m/z 105 + 77 + 51 Benzoyl compounds
Alkyl benzenes, benzyl compounds
m/z 91 + 65 + 39

Base peak RNH2 otherwise other amines

m/z 30

Amines, amides
m/z 44, 58, 72, . . .

Primary alcohol; low intensity, other alcohols, ethers

m/z 31

Ethers
m/z 31, 45, 59, . . .

Methyl esters of carboxylic acids

m/z 74

Straight chain carboxylic acids

m/z 60

Mono- or di-substituted benzene (low intensity)

m/z 77 or 76
FRAGMENTATION PATTERNS

Computer matching of mass spectra

As you've seen, the mass spectrum of even very similar organic

compounds will be quite different because of the different
fragmentations that can occur.
Provided you have a computer data base of mass spectra, any
unkown spectrum can be computer analysed and simply matched
against the data base.
IDENTIFY THE
COMPOUNDS
 IDENTIFY THE COMPOUND

43
100
Abundance %
80

29
60
40

122 124
20

79 81

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 IDENTIFY THE COMPOUND

43
100
Abundance %
80

29
60
40

122 124
20

79 81

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C3H7Br
 IDENTIFY THE COMPOUND
100

105
Abundance %
80

77
51
60

120
43
40

28
20

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 IDENTIFY THE COMPOUND
100

105
Abundance %
80

77
51
60

120
43
40

28
20

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C6H5COCH3
 IDENTIFY THE COMPOUND
100
Abundance %

105 106
80
60

51 77
40

57
43
20

28

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 IDENTIFY THE COMPOUND
100
Abundance %

105 106
80
60

51 77
40

57
43
20

28

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C6H5CHO
 IDENTIFY THE COMPOUND
100

56 57
113
Abundance %

43
80
60

71
40

142
20

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140
 IDENTIFY THE COMPOUND
100

56 57
113
Abundance %

43
80
60

71
40

142
20

0 m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C10H22
 REVISION CHECK
What should you be able to do?

Understand how mass spectrometry can be used to calculate molecular mass

Recall the term molecular ion and understand what information it provides
Interpret simple mass spectra

CAN YOU DO ALL OF THESE? YES NO

The End