Course Code: 4026821-3

for Master Degree of Chemistry Students

MASS SPECTRA measure a compound’s Mol. Wt.
M+
e- +
Molecule Molecule
+ +
Mole cule +
2 e- +
Mol ecule

IONIZATION CHAMBER variable field +

magnet +
repellor plate accelerating plates
Mo lecule
Sample positively charged
inlet (M) fragments - degree
_ _ _
+ of deflection
based on mass
accelerating
electric field in
charged vacuum chamber
particles
(e- or other)
M+

This ionization type is called: electron impact MS 2

1
2 m 2 = eV where m = ion mass
 = ion velocity
mv
r= e (or z) = ion charge
eB V = potential diff. of accelerating plates
r = radius of curvature of the path
m B2r 2
e = B = magnetic field strength
2V
m/z (or m/e) proportional to 1/V when B is constant
and r is constant

z is normally +1, but sometimes eject 2 electrons,

so get M2+, so get peak at M/2

By changing V slowly, can collect fragments

in increasing order of mass
3
A MASS ‘SPECTRUM’

100 base peak = largest peak

Fragments M+
molecular
ion or
parent ion

m/e

Amount of charge (= # ions) received by collector

measured for each mass, and plotted as graph
4
of m/e (strictly m/z) vs relative abundance
Ionization Methods

Electron impact (EI) M+ from electron beam impact – lots of

fragmentation

Chemical ionization (CI) M+ and M+H+ from CH4 collisions –

relatively little fragmentation

Fast atom bombardment (FAB) M+ and M+H+ from Argon

beam collisions – low
fragmentation

Matrix-assisted laser desorption (MALDI) M+H+ from

matrix
protonation

Electrospray ionization (ESI) M+ or M- but works best if

molecule already charged –
little fragmentation 5
A MASS SPECTRUM

100 base peak = largest peak

Fragments M+
molecular
ion or
parent ion

m/e

The highest mass peak, corresponds to M+

= Molecular Weight of the compound, BUT 6
In nature there are ISOTOPES!!!

Normal isotopes are: 12C 1H 14N etc.

CH3NH2 MW = 12 +3 +14 +2 = 31

However for any molecule that happens to have

a 13C or a 2H or a 15N, its MW = 32

and if molecule happens to have a 13C and a 2H

then its MW = 33

these of course will be seen (BUT ARE SMALL)

and are called ISOTOPE PEAKS
7
8
9
Nitrobenzene = C6H5NO2 = 123

BASE PEAK

Molecular Ion, M+

ISOTOPE PEAK

How large are the isotope peaks?

10
Bromides: RBr exists as equal amounts of
R79Br and R81Br
so MW = [R+79] AND [R+81]
we call these M+ and M+2

R=CH3CH2 = 29

108 110

fragment

11
Brn
Because of the 1:1 ratio of 79Br to 81Br
higher bromides show ‘NMR’-like patterns
i.e. Br2 = 1:2:1 (M) : (M+2) : (M+4)
79Br81Br
Br3 = 1:3:3:1 M, M+2, M+4, M+6
81Br79Br
Br4 = 1:4:6:4:1 etc
{CH2Br}+ 79Br
2
81Br
2

eg. CH2Br2

M-81Br
M-79Br

12
 Cl2
M = 35Cl2
= 75% x 75%
= 56%
M+2 = 35Cl37Cl
= 75% x 25% x 2
= 38%
M+4 = 37Cl2
= 25% x 25%
= 6%
13
= 100 : 67 : 11
{CH2Cl}+

CH2Cl2

= 100 : 67 : 11

M-35Cl

14
Nitrobenzene = C6H5NO2 = 123
M+1 = 6 x 1.1% = 7%
So, the relative size
of M+1 for an organic
can be used to
establish the # of C
15
Fragmentation patterns
(we aren’t focusing on this much but it is
useful to know some common fragments)

M-1 H M-43 C3H7 (i-Pr)

M-15 CH3 (Me) M-44 CO2
M-17 OH M-45 CO2H
M-28 CO M-57 C4H9 (t-Bu)
M-29 C2H5 (Et) M-77 C6H5 (Ph)
M-31 OCH3 M-91 C6H5CH2 (Benzyl)

Tropylium cation
(6p aromatic)
16
The Mass Spectrum and Structural Analysis
E.Fragmentation Patterns of Groups
Alcohols– Fragment Ions
a) Additional modes of fragmentation will cause lower M+ than for
the corresponding alkanes
1° and 2° alcohols have a low M+, 3° may be absent

b) The largest alkyl group is usually lost; the mode of cleavage

typically is similar for all alcohols:
m/z
primary OH + O H 31
H2C

OH +
O H 45
secondary

OH + O H 59
tertiary
17
c) Dehydration (M - 18) is a common mode of fragmentation –
importance increases with alkyl chain length (>4 carbons)
» 1,2-elimination – occurs from hot surface of ionization chamber

» 1,4-elimination – occurs from ionization

» both modes give M - 18, with the appearance and possible

subsequent fragmentation of the remaining alkene

d) For longer chain alcohols, a McLafferty type rearrangement can

produce water and ethylene (M - 18, M - 28)

H H
R H H R O
O
+

18
e) Loss of H is not favored for alkanols (M – 1)

f) Cyclic alcohols fragment by similar pathways

» a-cleavage

H OH H OH H OH H OH

H H +

m/z 57

» dehydration
H OH

, + H2O

M - 18
19
Phenols– Fragment Ions
a) Do not fully combine observations for aromatic + alcohol; treat
as a unique group

b) For example, loss of H· is observed (M – 1) – charge can be

delocalized by ring – most important for rings with EDGs

c) Loss of CO (extrusion) is commonly observed (M – 28); Net

loss of the formyl radical (HCO·, M – 29) is also observed
from this process
H
O O O
H
H

O
-CO -H
C

20
Example MS: phenols – phenol

-CO 66
-HCO 65

M+ 94

21
An interesting combination of functionalities: benzyl alcohols
Upon ring expansion to tropylium ions, they become phenols!

M+ 108
H H
OH
“tropyliol” - CO
+
79 M – 1, 107
“tropyliol”
HO

+ H2

77

22
Ethers– Fragment Ions
a) Slightly more intense M+ than for the corresponding alcohols
or alkanes

b) The largest alkyl group is usually lost to a-cleavage; the

mode of cleavage typically is similar to alcohols:

H2
R C O R R + H2C O R

c) Cleavage of the C-O bond to give carbocations is observed

where favorable

H
R C O R R CH + O R
R R

23
d) Rearrangement can occur of the following type, if a-carbon is
branched:

H
H
R C O C CH2 R C O +
H H R
R H
e) Aromatic ethers, similar to phenols can generate the C6H5O+
ion by loss of the alkyl group rather than H; this can expel
CO as in the phenolic degradation

R
O O
R + C O + C5H5+

24
Example MS: ethers – butyl methyl ether

45

M+ 88

25
Aldehydes - Fragment Ions
a) Weak M+ for aliphatic, strong M+ for aromatic aldehydes

b) a-cleavage is characteristic and often diagnostic for

aldehydes – can occur on either side of the carbonyl

R H
R C O + H M-1 peak

O
R + H C O m/z 29
R H

c) b-cleavage is an additional mode of fragmentation

O
O
m/z R+
R
H
R + M - 41
H can be R-subs.

26
Aldehydes - Fragment Ions
d) McLafferty rearrangement observed if g-Hs present

R H R H
O O m/z 44
+
H

e) Aromatic aldehydes – a-cleavages are more favorable, both

to lose H· (M - 1) and HCO· (M – 29)
O

H C O + H

O
m/z R+
O
H +
Remember:
H aromatic ring
can be subs.

27
Example MS: aldehydes (aliphatic) – pentanal

m/z 44
H H
O O
O +
C H
H

29

M-1
85
M+ 86

28
Ketones - Fragment Ions
a) Strong M+ for aliphatic and aromatic ketones

b) a-cleavage can occur on either side of the carbonyl – the

larger alkyl group is lost more often

O M – 15, 29, 43…

R R1
R C O + R1 m/z 43, 58, 72, etc.

R1 is larger than R

c) b-cleavage is not as important of a fragmentation mode for

ketones compared to aldehydes – but sometimes observed

O
R O
R +
R1
R1
29
Ketones - Fragment Ions
d) McLafferty rearrangement observed if g-H’s present – if both
alkyl chains are sufficiently long – both can be observed

R H R H
O O
+
R1 R1

e) Aromatic ketones – a-cleavages are favorable primarily to

lose R· (M – 15, 29…) to form the C6H5CO+ ion, which can
lose CO
O

R C O + R

m/z 105
Remember:
aromatic ring
can be subs.
+ C O

m/z 77 30
Ketones - Fragment Ions
f) cyclic ketones degrade in a similar fashion to cycloalkanes
and cycloalkanols:

O O O O

H H +

m/z 55

O O O

m/z 70

- CO

m/z 42
31
Esters - Fragment Ions
a) M+ weak in most cases, aromatic esters give a stronger peak

b) Most important a-cleavage reactions involve loss of the

alkoxy- radical to leave the acylium ion

O
R1 R C O + OR1
R O
c) The other a-cleavage (most common with methyl esters, m/z
59) involves the loss of the alkyl group

O O
R1 R + C O R1
R O

32
Esters - Fragment Ions
d) McLafferty occurs with sufficiently long esters

H H
O O
+
R1 R1
O O
e) Ethyl and longer (alkoxy chain) esters can undergo the
McLafferty rearrangement

H H
O O
+
R O R O

33
Example MS: esters (aliphatic) – ethyl butyrate

O
O
O
O
71

29
both McLafferty
O (take home
O
exercise)
m/z 88
43

M+ 116

34
Carboxylic Acids - Fragment Ions
a) As with esters, M+ weak in most cases, aromatic acids give a
stronger peak

b) Most important a-cleavage reactions involve loss of the

alkoxy- radical to leave the acylium ion

O
H R C O + OH
R O

c) The other a-cleavage (less common) involves the loss of the

alkyl radical. Although less common, the m/z 45 peak is
somewhat diagnostic for acids.

O O
H R + C O H
R O

35
Carboxylic Acids - Fragment Ions
d) McLafferty occurs with sufficiently long acids

H H
O O
+ H
H
O O

m/z 60
e) aromatic acids degrade by a process similar to esters, loss of
the HO· gives the acylium ion which can lose CO:

O O
H C
O + H

+ further loss
of CO to m/z
77 36
Example MS: carboxylic acids (aliphatic) – pentanoic
acid

H
O OH

OH OH

m/z 60

M+ 102

37
Example MS: carboxylic acids (aromatic) – p-toluic
acid

OH
O M+ 136
OH
119

91

38
Summary – Carbonyl Compounds
In tabular format:

m/z of ion observed

Aldehydes Ketones Esters Acids Amides
Fragmentation Path G=H G=R G = OR’ G = OH G = NH2
A1 -R 29 43b 59b 45 44d
a-cleavage
A2 -G 43b 43b 43b 43b 43b
a-cleavage
B -G 43a 57b 73b 59a 58a
b-cleavage
C 44a 58b,c 74b,c 60a 59a
McLafferty
b= base, add other mass attached to this chain
a= base, if a-carbon branched, add appropriate mass
c= sufficiently long structures can undergo on either side of C=O
d= if N-substituted, add appropriate mass 39
Approach to analyzing a mass spectrum:
• As with IR, get a general feel for the spectrum before
you analyze anything – is it simple, complex, groups
of peaks, etc.
• Squeeze everything you can out of the M+ peak that
you can (once you have confirmed it is the M+)
– Strong or Weak?
– Isotopes? M+1? M+2, 4, …
– Apply the Nitrogen rule
– Apply the Rule of Thirteen to generate possible formulas
(you can quickly dispose of possibilities based on the
absence of isotopic peaks or the inference of the nitrogen
rule)
– Use the HDI from the Rule of Thirteen to further reduce the
possibilities
– Is there an M-1 peak?
40
Approach to analyzing a mass spectrum:
• Squeeze everything you can out of the base peak
– What ions could give this peak? (m/z 43 doesn’t help much)
– What was lost from M+ to give this peak?
– When considering the base peak initially, only think of the most
common cleavages for each group.

• Look for the loss of small neutral molecules from M+

– H2C=CH2, HCCH, H2O, HOR, HCN, HX.

• Now consider the possible diagnostic peaks on the spectrum (e.g.:

29, 30, 31, 45, 59, 77, 91, 105 etc.).

• Lastly, once you have a hypothetical molecule that explains the

data, see if you can verify it by use of other less intense peaks on
the spectrum – not 100% necessary (or accurate) but if this step
works it can add to the confidence level.

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