UNIT-7

MASS SPECTROMETRY

Lesson Structure
7.1 Introduction
7.2 Theory
7.3 Instrumentation
7.4 Mass spectrum
7.5 The nitrogen rule
7.6 Metastable ions or peaks
7.7 Regions were metastable ions are produced
7.8 Calculation of metastable ion m/z values
7.9 Mc. Lafferty Rearrangement
7.10 High resolution mass spectrometry (HRMS)
7.11 Fragmentation assocaited with functinal groups
Solved Problems
Model Questions
References

7.1 INTRODUCTION

Mass spectrometry is the most accurate method for determining the molecular mass
of the compound and its elemental composition. In this technique, molecules are bombarded
with a beam of energetic electrons which knock off an electron from the sample leading to

a positively charged radical ions  M  . .
 Mass Spectrometry


M  e    M  .  2e

This radical ion being highly energetic, may fragment further yielding smaller fragments as
shown below

A+ + B •

[M]+.
C+ + D •
The radical ion and other fragments are separated according to their m/e ratio where
m is the mass and e is the charge of the ion. The record of m/e values of these species verses
their relative abundance is known as mass spectrum of the sample. No two compounds can
have exactly similar mass spectra.
Mass spectrometry is not a true spectroscopic technique because absorption of electro-
magnetic energy is not involved in any way. Although the mass spectrometry differs in
principle from other spectroscopic techniques, it is considered along with them because it
complements the information regarding the structure of the atoms and molecules obtained
by other spectroscopic techniques.
For most ions the charge is one and thus, m/e ratio is simply the molecular mass of
the ion. Hence for neopentane m/e ratio is 72.

CH3

-e
H3C C CH3 (C5H12)+
m/e = 72
CH3

Molecular Ion, C5H12+

C3H5+ C2H5+ C2H3+

C6H9+
m/e 57 41 29 27

Relative 100 41.5 38.5 15.7

intensity

The molecule ion (here C5H12+) is called parent ion and is designated as M+. The set of
ions /daughter ions or fragment ions) are analysed in such a way that a signal is obtained for
each value of m/e. The intensity of each signal represents the relative abundance of the ion

225
 Mass Spectrometry

producing the signal. The largest most intense peak in the structure is called the base peak
and its intensity is arbitrarily assigned a value of 100%. The intensities of other peaks are
represented relative to the base peak. The parent peak may not be confused the base peak.

7.2 THEORY
A parent ion results when one electron is removed from the parent molecule of the
substance
70 eV
M(g) + e– M+(g) + 2e–
The ionization reaction require energy (in the form of electrons, photons, electric
fields heat or electric discharge) in the order of 70 eV (~ 6688 kJ mol–1). This is greater than
the typical bond energies encountered in organic molecules when the energy of the
bombarding electron is just equal to the ionization potential, all the electron’s energy must
be used to remove an electron from the molecular orbital of the molecule M to form the
parent ion M+. With the increase in energy of the bombarding electron, the probability of
the collision inducing ionization increases. If the energy of the electron is quite high than
M+ the parent ion may retain such an excess energy sufficient enough to rupture the bond
and form a new ion N+ and a fragment O. The potential required to affect the fragmentation
is usually referred to as appearance potential of the fragment ion. The m/e value of the
parent ion [M +(g)] is equal to the molecular mass of the compound. Giving sufficient
vibrational energy, the ions may further decompose to produce new ions with loss of neutrals.
The Parent or the molecular ion represents the intact molecule which has the same molecular
weight as the starting molecule M, because the lost electron has negligible, mass. Only the
positively charged fragment ions travel towards the detector and give rise to the maxima in
the mass spectrum if their corresponding atoms have different masses. The spectrum is
recorded after scanning the beam and detected by an electrometer with appropriate focussing
devices. From the patterns of pure compounds and the samples a wealth of information can
be obtained concerning the composition of mixtures and elemental analysis of solid samples.
Neural particle, produced in the process of fragmentation (whether neutral molecular
radicals) cannot be detected in the mass spectrometer. Negative -ion spectra, although less
commonly used than positive-ion spectra, can also be obtained.
Basic functions of mass spectrometer
The mass spectra meter is designed to perform the following functions :
(i) To vapourise compounds of varying volatility.
(ii) To produce ions from the neutral compounds in the vapour phase.
(iii) To separate ions according to their mass to charge ratio.
(iv) To detect the ions and producing a corresponding signal.

226
 Mass Spectrometry

7.3 INSTRUMENTATION

Sample
Injector

Ion source Mass analyser Ion detecter

High vacuum

Recorder Signal sensor

Schematic diagram of mass spectrometer

1. Sample Injector
The sample is placed within ionization chamber either as part of the ion source or
coated on a filament. The sample ranging from 10–4 to 10–9 g is directy introduced into the
ion beam source. This method is applicable to those compounds which are sufficiently
volatile at 373–873 K.
2. Ion Source
The ion source converts molecules into gaseous ions. The most common way
of producing ions involves bombarding the sample with a beam of energetic electrons from
an ion gun. A few mgm of the substance is produced as vapour in the source at an opening
pressure of 10–6 mm.
The vapour is allowed to pass through a slit A into the ion chamber. It is then bombard
by stream of electrons produced from a tungsten filament. The bombarding electrons have
energy of about 70 eV. Due to bombardment, the molecules generally lose one electron to
form a parent ion radical.
Filament

e e
To analyser
e e
e e

Repeller
A potential B C
Ionization of sample and acceleration of ions
The bombardment of electron may result in the following types of ions

227
 Mass Spectrometry

(i) AB(g) + e   AB* + e

  AB+ + 2 e (most probably)
 AB+n + (n + 1) e (least probably)
  A + + B– + e
 A+ + B + 2e
  AB– + (electron capture-less probably)
The energy required for removing one electron from the neural parent molecule is
usually 10 eV. With this much energy, no ions are formed i.e., no fragmentation of the
parent ion takes place. But if the energy of the bombarding electron is around 70 eV, then
additional energy is consumed in fragmenting the parent ion. This results in the formation
of fragment ions or the daughter ions. The positive ion (fragment) whether even electron or
odd electron species is detected in the mass spectrometer where as the neutral molecules or
the radicals are left undetected.
3. Mass analyzer (separation of the ions in the analyser)
Theory : In a magnetic analyser ions are separated on the basis of m/z values and a
number of equation can be brought to bear on the behaviour of ions in the magnetic field. The
1 2
kinetic energy, Er of an ion of mass ‘m’ travelling with velocity ‘v’ is given by the familiar E  mv
2
The potential energy of an ion of charge z being repelled by an electrostatic field of
voltage V in zV. When the ions is repelled, the potential energy, zV, is converted into the
1 2
kinetic energy, mv , so that
2
1 2zV
zV  mv 2 2
therefore v  ....(7.1)
2 m

Spectrum
Dempster’s mass spectrometer

228
 Mass Spectrometry

When ion are shot into the magnetic field of the analyser, they are drawn into a
circular motion by the field, and at equilibrium the centrifugal force of the

 mv 2 
ion  r  is equalled by centripetal force exerted on it by the magnet ( Z Bv),

 
where r is the radius of the circular motion and B is the field strength. Thus,

mv 2
 z Bv
r

ZBr
Therefore, v  ...(7.2)
m
combining equation (1) & (2)
2
2 ZV  Z Br  m B2 r 2
  or  ...(7.3)
m  m  Z 2V

From this equation, it is clear that at a given magnetic field strength and
m
accelerating voltage the ions of value will follow a circular path of radius r. The ions of
z
m
various value reach the collector, amplified and recorded. The mass spectrum can be
z
obtained either by
(1) Changing B at constant V (called magnetic scanning)
(2) Charnging V at constant B (called voltage scanning)

Limitation and Modifications

From equation (7.3) we can sec the inability of a mass spectrometer to
m
distinguish between an ion m+ and ion 2m2+, the ratio between them have the same
z

 B2 r 2 
value of  2 v  , and these three parameters B, r are V decided the path of the ions.

 

The ability of mass spetrometer to separate two ions (the spectrometer resolution) is
acceptably defined by measuring the depth of the valleys between the peaks produced by
m
the ions. If two ions of 999 and 1000, respectively can just be resolved into two peaks
z
such that the recorder trace almost reaches back down to the baseline between them, leaving
a valley which is 10 percent of the peak height, we say the resolution of the spectrometer is
‘1 part is 1000 (10 percent valley resolution).

229
 Mass Spectrometry

Simple magnetic focussing instruments have resolving power of around 1 in 7500

on this basis.
Double focussing
The problem is overcome by passing the ions through electric field prior to the
magnetic field. The electric field effects will cause focussing of the ions by
placing a slit between the electrostatic and magnetic analysers. The ions of closely defined
kinetic energies can be thus, selected prior to mass analysis. Instrument incorporating such
a system are called double focusing mass spectrometer. These instruments are capable of
attaining much higher resolving power than single focussing instruments. It is possible to
distinguish between the ions which have the same integral mass but differ in exact masses.
This may be possible for isotopes of elements which do not have integral masses.

MA
A
ES
Magn
tic analy etic
ctrosta r ser
Ele alyse
e an Co
rc lle
u t slit ctor
So sli
Passing through electrostatic &
Magnetic analyser

Different equations hold for the behaviour of ions in an electrostatic (rather than
mv 2
magnetic) fields. Here the centripetal force  zE and combining this with
r
1 2
zV = mv gives
2

mv 2
 zE
r

1 mv 2 1
 zE
2 r 2
zV 1
 zE
r 2
2V
 r ...(7.4)
E

Thus the radial path followed by ions of a given velocity is independent of m and z (
m
and values). The electrostatic analyzer focuses ions of identical kinetic energy onto the
z

230
 Mass Spectrometry

m m
monitor slit, whatever their value, and coupled with a magnetic analyser to resolve
z z
values, this double focussing spectrometer can attain resolution of 1 in 60, 000.

m
In a low resolution instrument we may identify an ions of 28 as possibly CO+ or
z
N2+ or C 2H4+; the accurate mass measurement possible at high resolution enables us to
distinguish among several possible exact formula masses. For example, CO+ ( 27.9947), N2+
(28.0062), C 2H 4+ (28.0312).
The Detector-recorder
The focussed ion beam passes through the collector slit to the detector, which must
convert the impact of a stream of positively charged ions into an electrical current. This
must be amplified and recorded either graphically or digitally.
Several different amplification systems are used by different manufactures, but the
most common is the electron multiplier which operates in a manner similar to the photo
multiplier detector.
The spectrum is recorded by using a fast scanning oscillograph. In this type of
recording, three to give records of the same peak are made with galvanometers having
different sensitivities.

7.4 MASS SPECTRUM

It is a record of the masses and the relative abundance of the molecular ion and the
m m
positively charged fragments formed it by the electron bombardment. The (or ) ratio
z e
are taken along the abscissa while the relative abundances (percentage of the total ion current)
are taken along the ordinate. Base peak is the highest peak or the most intense peak in the
spectrum.
Molecular ion or parent ion
The electron bombardment with energy 10-15 eV usually removes one
electron from the molecule of the organic compound in the vapour phase. It results in the
formation of molecular ion (Table 2). The highest occupied orbital of
aromatic system and non bonding electron orbitals on oxygen and nitrogen atoms readily
lose one electron. An electron from double bond (2- electron) or triple bond (4- electron)
is usually lost. In alkanes, the ionization of C—C sigma bonds is easier than that of C—H
bonds. Some examples are :
e
M( g )  M ( g )  2e e
M ( g)  M  ( g )  2 e

+
-e + 2e
C C
C C

231
 Mass Spectrometry


.
— H 
R—O e
 R—O
.. . . — H  2e
 
Parent ion

-e
+

Parent ion
Table 7.1: Some common loses from molecular ions

Groups associated Groves associatedwith

Ion Inferences Ions Inferences
with the mass Lost The mass loss
M 1 H 
M  41 C3 H5 Pr opyl ester
M2 H2 
Methyl, ketone ,
M  15 CH3 M  42 CH2CO
Ar  NHCOCH3
 Ar. propyl ether
Ar  NO2 ,  N  O
M  16 NH2 M  42 C3 H6
ArSO2 , NH2 ,  CONH2 Ar  n  C4 H9
Pr opyl ketone
M  17 OH , NH3  M  43 C3 H7
Ar  n  C3 H7
M  18 H2O Alcohol, Aldehyde , ketone CH3CO Methyl ketone
M  19,20 F , HF Fluorides M  44 CO2 Ester , Anhydride
M  26 C2 H2 Aromatics M  45 COOH Acids
M  27 HCN Aromatic nitriles M  45 OC2 H5 Ethyl ester
C2 H5OH Ethyl ester
M  28 CO Quinones M  46
NO2 Ar  NO2
M  28 C2 H4 Ar ether , Ethyl esters M  48 SO Aromatic sulphoxide
M  29 CHO, C2 H5 Ethyl ketones M  55 C4 H7 Butyl ester ArO  nC4 H9
CH2O Aromatic methyl ether C4 H9 Butyl ketone ,
M  30 M  57
NO Ar  NO2 C2 H5CO Ethyl ketone
M  31 OCH3 Methyl ester M  58 C4 H10 
M  32 CH3OH Methyl ester M  60 CH3COOH Acetate

The mass of the parent ion gives the molecular mass of the sample. It is important to
locate the molecular ion at the high mass region of the spectrum. The stability of the parent
ion decides is relative abundance. In some cases, parent ion peak is not formed which means
that the rate of decomposition of parent ion is too high for its detection. The rate of
decomposition of the parent ion increases with the molecular size in the homologous series
In general, the relative height of the parent peak decreases in the following
order Aromatics > conjugated olefine > Alicyclies > unbranched hydrocarbons > ketones >
Amines > Esters > Ethers > Carboxylic acid > Branched hydrocarbons > Alcohols.

232
 Mass Spectrometry

Important Features of the parent ion peak

1. The molecular ion peak in aromatic compounds is relatively much intense due to the
presence of  -electron system.
2. Unsaturated compounds give more intense peak as compared to the saturated or the
cyclic molecule.
3. The relative abundance of the saturated hydrocarbon is more than the corresponding
branched chain compound with the same number of carbon atoms. For example,
the molecular ion peak for n-pentane is more intense than that of neopentane.
4. Absence of molecular ion peak in the mass spectrum means that the com pound is
highly branched or tertiary alcohol.
5. Primary and secondary alcohol give very small molecular ion peaks.
6. Conjugated olefins show more intense molecular ion peak as compound to the
corresponding non-conjugated olefins. Conjugated olefines are more stable than the
corresponding non-conjugated olefins.
7. The substituent groups like —NH2, —OH, —OR, etc. which lower than ionization
potential increase the relative abundance in case of aromatic compounds while the
groups such as —NO2, —CN etc. which increase the ionization potential, decrease
the relative abundance of aromatics.
8. In case of chloro or bromo compounds, isotope peaks are also formed alongwith the
molecular ion peak. In case of chloro and bromo compounds M+ and (M++2) peak
are formed in the intensity ratio 1 : 3 and 1 : 1 respectively.
9. A peak at mass 19 always indicates fluorine, mass 30 is always for primary amines.
The peak at masses 31, 45, 59 indicate the presence of oxygen as alcohol or ether,
mass 33 shows a thiol, mass 77 correspond to the presence of benzene ring, mass 91
indicates a monobasic carboxylic acid or the presence of a tolyl group.
10. The peak at mass 29 may be in part C2H5+ and in part C4H10+2 (The mass spectrometers
are unable to distinguish between a singly charged ion of a given mass and doubly
charged ion of the twice mass)

11. The peaks at masses 59, 44 and 30 indicates the fragments C4H102+, C 3 H7+ and C 2 H 2+
5
respectively in which either one hydrogen is replaced by a heavier isotope deuterium
or C12 is replaced by C13.
12. Nitroen containing compounds with an odd number of N atoms in the molecule must
have an odd molecular mass. An even number of N atom or absence of nitrogen atoms
in the compound shows that the molecular mass of the compound must be even.

7.5 THE NITROGEN RULE

Nitrogen rule states that a molecule of even numbered molecular mass must contain
no nitrogen or an even number of nitrogen atoms. An odd numbered molecular mass
requires an odd number of nitrogen atom. This rule holds for all compounds containing C,
H, N, O, S and halogen as well as less usual atoms like P, B, Si, As etc.
For example, the following compounds give their molecular ions at even mass number

233
 Mass Spectrometry

m  m  m  m 
CH4   16  , CH 3OH   32  , CClF3   104  , C6 H3OH   94  ,
z  z  z  z 
m 
z  z  
H2 NNH2   32  , C 5 H 5 N 2 m  94 . An odd number of nitrogen atoms causes the

m  m 
molecular ion to be at odd mass number e.g., NH3   17  , C2 H5 NH 2  z  45  .
z   
It is important to note that this relationship applies to all ions and not only to the
molecular ion. In other words, therefore, the nitrogen rule may be stated as an odd-electron
ion will be an even mass number if it contains an even number of nitrogen atoms. In the
same way, an even-electron ion with an even number of nitrogen atoms will appear at an
odd mass number (M+ . is an odd electron ion). The basis for this rule is, that for most of the
elements found in organic compounds, there is a correspondence between the most common
valence of the element and the mass of its most abundant isotope. Thus either both are even
numbers or both are odd numbers. In the case of carbon e.g., the valence is four and the
mass twelve; for hydrogen the valence is one, the mass one, for oxygen the valence is two
and the mass sixteen. The only important exception is however, the element nitrogen, here
the valence is odd i.e. three and the mass even i.e. fourteen. These numbers are the basis of
the nitrogen rule.

7.6 METASTABLE IONS OR PEAKS

Cathod

First field Free region

Anode
Ionization Electrostatic
chamber analyser

Second field free

region

Magnetic
analyser

Collector

234
 Mass Spectrometry

Sometimes fragmentation takes place during the flight rather than in the ionization
chamber. The ions thus produced are called metastable ions. They have lower kinetic energy
than the normal ions. The peaks due to these ions have the following characteristics:

m
1. They do not necessarily occur at the integral value .
z
2. These are much border than the normal peaks and

3. These are of relatively low abundance ( of ~ 10 –2 or less than the parent or

the daugher ions in 70 eV spectrum)
The molecular ions formed in the ionization chamber behave in one of the
following ways
4. They decompose rapidly and completely in the ion source and never reach
the collector (life time less than 10–5 sec)
5. They survive long enough to reach the collector and be recorded there (life
time longer than ~ –5
~ 10 sec)
We also assumed that fragment ions are produced by decomposition of a
proportion of the molecular ions in the ion source.
Depending upon the inherent stability of an ion, and on the amount of
excitation energy absorbed on bombardment ion lifetimes will vary in a
complex manner. Some molecular ion may have intermediate life times
(  10 –5 s ) and so leave the ionization chamber intact, but decompose
during the flight.

Of a larger number of M . produced, all will not possessed the same

excitation energy and so some will have longer life time than others.


The M . ions with shorter lifetimes may decompose in the ionization
•
chamber to stable daughter ions A + and radicals B , the daughter A + will be
detected at the collector normally. The M .+ ions that leave the ion source
intact will be accelerated and then posses a translational energy eV. Some
of these ions may survive upto the collector, but those which do not, will
•
decompose to A + and B after acceleration. In such a case the translational
 •
energy of M . ion will be shared between A + and B is proportions to their

masses to conserve total momentum.

The translational energy of the daugher ion (A + ) must then be lower than
that of the parent ion, an this ion A + will arive at the collector differently
from the ‘normal’ A + ion produced in the ion source. This is called metal
stable ion.

235
 Mass Spectrometry

Thus the meta stable ion has the same mass as the corresponding normal
daugher but less translational energy.

7.7 REGIONS WHERE METASTABLE IONS ARE PRODUCED

Of the metastable ions produced in the ion tube, only a fraction come to reasonable
focus at the collector (unless by the use of special techniques), we must consider the
successive regions of the ion tube to understand why this should be so.

The first field-free region in a double-focussing instrument, lies between the ion
source and the electrostatic analyser. (This region has no counter-part in single focussing
instruments). If a metastable ion is produced here, it will be focussed out by the electrostatic
analyser because of its abnormal kinetic energy. Such ions, and any metastable ions formed
in the analyser, will appear out of focus (randomly) at the collector as background current,
and will be undetected.

The second field-free region (between two analyser)

Meta stables produced in this region will be focussed by the magnetic analyser but
as a meta stable ion has the same mass with lower kinetic energy (less momentum) than the
normal daugher ion, the metastable ion is deflected more easily than the normal daugher
ion and will appear on the spectrum among ions of lower mass.

The third field-free region (between magnetic analyser and the collector)

Since no focussing takes place in this region, a parent ion is already immutably on
path, and if it decomposes to the metastable A+, then this metastable will continue on the

m
same path as the parent ion. The metastable ion is detected as the same value as the
z
parent ion.

m
7.8 CALCULATION OF VALUES OF METASTABLE IONS
z
The apparent mass of a metatable ion A+ (m*) can be calculated fairly accurately
from the masses of the parent ion (m1) and the normal daughter ion A+ (m2) using the formula
2
m 
m*  2
m1
m m
example toluene has strong peak at 91 and 65 and the broad
z z
metastable peak at 46.4.

65 2
m*   46.4
91

236
 Mass Spectrometry

CH 2 — H CH 2 — H CH 2

-e –
H•

M olecular ion
Toluene
M+
m/z 92

CH 2

C ycloheptatrienyl
B enzyl cation
cation m/z 91
tropylium ion
C 7H 7+
m/z 91

- (C 2 H 2 )

m/e 65
(m 1 + )
m
So we can interpret ion 91 is decomposing by loss of 26 mass units to the daughter
z
m
ion 65, and that some of this fragmentation takes place in the second field-free region
z
m
(i.e. between the two analyser) leading to metastable ion peak of 46.4
z

7.9 Mc LAFFERTY REARRANGEMENT

It involves cleavage of a -bond followed by a -hydrogen transfer. The rearrangement
leads to the elimination of neutral molecules from amines,aldehydes, ketones, unsaturated
compounds and substituent aromatics.
Generally a molecular ion with an even mass value cleaves to give fragment ions
with odd mass values and vice-versa. But if the even mass molecular ion yields fragments of
even mass and odd mass molecular ions yields fragments of odd mass, it indicates that a
rearrangement has taken place.

237
 Mass Spectrometry

In case the mass difference between expected and the observed fragment ion is of
one unit, rearrangement involving migration of hydrogen atom can be expected.
A rearrangement known as McLafferty rearrangement is commonly observed in the
compounds having the following structure where x and y can be C, O, S, N and P.

H
 C Y+

 C X
C


Here X = C and Y = O
Let us take the exampl e of an al dehyde or a ketone hav i ng  hydrogen. It can undergo
the McLafferty rearrangement an shown below

H HO +.
C O C
+ C
C C C
C R
C R

alkene enol

where R = H, aldehyde
R = alkyl, ketone
The mass spectrum of butanal (CH3CH2CH2CHO) is shown as

100 44
M -28
80 72 O
29
M+
intensity

60 57 C

40 H CH 2 CH 2 C H 3

20

10 20 30 40 50 60 70 80 90 100 160
m /z
mass spectrum of butanal

238
 Mass Spectrometry

m
Prominent peaks at 72, 57, 44 and 29. These peaks can be explained as follows “
z
m fragments
z
72 M+
57 
Loss of CH 3 , (M–CH3) fragment
+

29  CH CH , M-C H  + Fragment
Loss of CH 3 2 3 3 7

m
The peak at 44 (M-28) is an even mass peak from the even number
z
molecular ion and hence indicates a rearrangement. The McLaffety rearrangement explain
this peak as follows:

+
H +
H H OH
H H
C O C

H C
H H + H
C C
C
H C
 C H H 
H H
H H enol
ethene m/z 44
m/z 72 (alkene)

Double McLafferty Rearrangement

Double MR is reported in certain ketones. The second H-atom originates
exclusively from the -position. A secondary hydrogen is preferred to a primary hydrogen
atom is this process. The mechanism involves.
(a) Ketonisation of the intermediate enol ion by the hydrogen transfer
(b) Transfer of hydrogen to enolic oxygen. Consider MR in 4-heptanone.

H
+
H2C O OH

H2C C C
C CH2-CH2-CH3 H2C CH2-CH2-CH3
H
(MR ion I, enolic form)
4-Heptanone (M+ ion)

239
 Mass Spectrometry

O+
H
C

H3C CH2—CH2—CH2
Ketonisation
(Ketonic form)
- (CH2=CH2)
+OH

H3C CH2
MR ion II
m/z = 58
Thus the molecular formula of the unknown compound can be determined form
the various fragment ion and also the parent ion of the mass spectrum.

7.10 HIGH RESOLUTION MASS SPECTROMETRY (HRMS)

m
Low resolution mass spectrometer measures values to the nearest whole number
z
m
mass unit. However, high resolution mass spectrometers measure values to three or four
z
decimal places and hence provide an extremely accurate method for determining molecular
weights. HR mass spectrometer uses extra stages of electrostatic or magnetic focussing to
form a very precise beam and to detect the exact masses to an accuracy of about 1 part in
40, 000.
The determination of accurate molecular weight is possible by HRMS because the
actual masses of the atomic nuclides are not integers. For example
(i) A molecule whose molecular weight is 32 could be O 2 , N 2 H 4 or CH 3 OH.
However, these molecules have the following precise masses.
O2 = 2 × 15.9949 = 31.9898,
N2H4 = 2 × 14.0031 + 4 × 1.00783 = 32.0375
CH 3OH = 12.000 + 4 × 1.00783 + 15.9949 = 32.0262
(ii) A molecule of molecular weight 44 may correspond to C 3 H 8 , CH 3 CHO, CO 2
or CN2H4.
But their exact masses are
C3H 8 = 44.06260
C2H 4O = 44.02620
CO 2 = 43.98983

240
 Mass Spectrometry

CN2H 4 = 44.03740

In case the HRMS gives the exact mass of the ion as 44.029 mass units, the
compound must have the molecular formula of C 2 H 4 O (the two values
being closest)
(iii) Some elemental composition at nominal mass 100 are :

C3 H6 N3 O=100.0511 C 4 H8 N2 O=100.0637 C6 H10 NO=100.0762

C6 H14 N=100.1126 C7 H16 =100.1251 C 2 F4 =99.9936

HRMS provide the exact molecular formula but does not give indication of the purity
of the compound. The elemental analysis gives a cross check on the purity of a compound
and its molecular formula.

7.10 FRAGMENTATION ASSOCIATED WITH FUNCTIONAL GROUPS

In simple monofunctional compounds we can with reasonable certainty predict that
the mass spectrum will bear a compound relationship to (a) the nature of the carbon skeleton
(where alkanes, alkene, aromatic etc) and (b) the nature of the functional group. For
difunctional compounds, a more complex interaction can be expected, depending on the
relative power of the two functional groups to direct the fragmentation. It is always easier to
rationalise the mass spectrum of a known structure than to deduce the structure of an
unknown compound from its mass spectrum; other spectroscopic evidence for the presence
of functional groups should ideally always be available.
Alkanes and Alkane Groups
The molecular ion will normally be seen in the mass spectra of the lower n-alkanes,
but its intensity falls off with increased size and branching of the chain. The mass spectrum
of Dodecane (C12H26) is shown in figure below :

43 57
Relative Abundance

100 C3H7+ C4H9+

90
80
70 71
60 C5H11+
50 85
40 29
30 C6H13+
C2H5
20 C7 C8 C9 C10 C11 170(m)
10
10 20 40 60 80 100 120 140 160 180
m/z values
The relative abundances of the ions are also typical, showing maximum abundance

around C3H7+ and C4H9+ with a weak M . peak. Although n-dodecane is unbranched, the

241
 Mass Spectrometry

alkane ions from C4H9+ up rearrange in the mass spectrometer to the branched chain form,
this is quite analogous to the Wagner -Meerwein shifts which occur in (for example) SNl
reactions involving cations, the more stable branched structures being preferred.
Associated with each of these CnH2n+1 ions (from C2 to C5) are lesser amounts of the
corresponding alkenyl ion (C5H2n–1) formed by loss of two hydrogen atoms : they appear at
m 27, 41, 55, 69. Loss of one hydrogen is also seen. Metastable ions of very low intensity
z
can be detected for the fragmentations in which the alkyl ions extrude a smaller molecule :
.
thus C2 H+5 and C3H7+ extrude H2 ; C4 H9+ extrude CH4; C6 H13
+ +
and C7 H15 extrude C3H6.
These are of too low abundance to be shown in figure.
Branched-chain alkanes rupture predominantly at the branching points, and the
largest group attached to the branching point is often preferentially expelled as a radical.
The normal rules of chemistry hold, in that the preference is for the formation of tertiary
over secondary over primary cations.
We might predict, therefore, in the mass spectrum of 2, 2-dimethyl pentane (a) no molecular
ion peak (b) substantial peaks for C3H7+ , C4 H9+ (because of their inherent stability). (c) a
+
much higher abundance of C5H11 than would be seen for the fragmentation of n- C7 H16

(because of the ease of C2H5 expulsion) and (d) a reasonable peak for C6 H13 due to M—CH3

ALKENES AND ALKENE GROUPS

Molecular ion peaks for simple alkene are normally distinctly seen. The commonest
fragmentation in alkene groups involves rupture of the allylic bond ( to the double bond),
which gives rise to the resonance stabilized allylic cation. Since the allylic radical is also
stabilized, the fragmentation may give rise to peaks corresponding to charge retention by
either of the fragments.

— CH = CH — CH2 — R
–e –e
or

—CH — CH —CH2 —R — CH — CH — CH2— R

— CH — CH = CH2 + R or —CH — CH = CH2 + R+

— CH = CH — CH2 — CH = CH — CH2

242
 Mass Spectrometry

A McLafferty rearrangement may occur provided that the -carbon has hydrogen
on it.

H
 H
CH3
H2C CH2
+
+
+



CYCLOALKANES
The relative abundance of the molecular ion of cycloalkane is more than that of
corresponding alkane. Fragmentation of the ring is usually characterized by the loss of two
carbon atoms as C2H4 (28 mass units) and C2 H+5 (29 mass units). The stability of the fragment
ion depends upon the size of the ring. It favours cleavage of the bond connecting the ring to
the rest of the molecule. Fragment ions are observed by the loss of alkenes or alkenyl ions.
The side chain on the ring breaks and the lone pair electron remain on the ring.
The mass spectrum of n-propyl cyclohexane which should be interpreted with these
points in mind.
83
Relative Abundance

100
90
80 55
70 41
60
50
40
30 27 126 M +
29
20
10
10 20 40 6080 100 120 140
m/z values
Mass spectrum of n-propyl cyclohexane

The molecular ion peak is quite abundance and occur at m z 128. The base peak at

m 83 is formed by the loss of the side chain. The lone electron remains on the ring. This
z

positively charged ion radical appears at m 83. A fragment ion of large abundance is formed
z

at m z 55. The ion radical shows retro Diel’s Alder reaction. The various fragmentation
modes are shown below

243
 Mass Spectrometry

+
+

-(CH2=CH2)
CH3—CH2—CH2 +

M+ (126) m/z 83
n-propyl cyclohexane CH2= CH—CH2—CH2
m/z = 55
CYCLOALKENES
Fragmentation of cycloalkenes is directed by the double bond and by the nature of
any acyclic alkane residue present, so that allylic rupture and McLafferty rearrangements
are common.
In addition, cyclohexene derivative give the important retro Diels-Alder
reaction .
+ +
• •

+ etc

ALKYNES
No simple pattern emerges for the fragmentation of alkynes, which can be applied
to complex molecule. Thus for 1-butyne and 2-butyne the molecular ion peak is the base
peak, but the molecular ion peak for higher members is weak. Loss of alkyl radical gives
prominent peaks in many cases ( at M+–15, M+–29 etc) and extrusion of alkenes may give
M+ –28 and M+–42 peaks etc.
The fragmentation modes of 2- Pentene is as follows :

+e +
CH 3 —CH 2 —CH=CH2 —CH 3   CH 3—CH 2 —CH=CH—CH3.  2 e
2  Pentene m
M ( 70)
z

CH3—CH2—CH = CH—CH3 CH3+CH2—CH =CH—CH3

m/z 55
-(CH3-CH2) - (CH3-CH=CH)

- H2
CH = CH — CH3 CH3—CH2 CH2=CH
m/z 41 m/z 29 m/z 27

244
 Mass Spectrometry

The mass spectrum of 2-pentene shows m peaks at 70, 55, 41, 39 at 27.
z
ALCOHOLS
Molecular ion peaks for primary and secondary alcohols are weak; for tertiary alcohols

the M . peak is usually absent.

A number of fragmentations are open to alcohols, and their relative importance

depends on whether the alcohol is primary, secondary tertiary, aliphatic or aromatic; the
most important fragmentation is normally rupture of the bond  to oxygen.

Aliphatic primary alcohol show a prominent signal at m z 31. This signal corresponds

  

to the formation of oxonium ion  CH 2  O H  and is formed by the cleavage of C–H bond.

 

- H•
CH3—OH CH2 = OH or R—CH2—CH2—OH
m/z 31 (1º alcohol)
H M+ - R CH2

CH2 = OH
m/z 31

Primary alcohols (alkanols) show M+–18 peaks corresponding to loss of H2O.

H
O +
H CH2—H2O RCH CH2
-H2O

RCH CH2
CH2 (CH2)n

Higher alcohol show a peak which correspond to M+ –CH2O + olefin)

H
O
H CH2 - CH2= CH2 +
CH2 = CHR
-H2O
RCH CH2
CH2

245
 Mass Spectrometry

The olefinic ion then decompose by successive elimination of ethylene.

Long chain members may show peaks corresponding to successive loss of H-radicals
at M-1, M-2 and M-3.

H H

+
—C—O—H —C = O — H —C = O CO+
(M+) M+-1 M+-2 M+-3
H

Secondary and tertiary aliphatic alcohols preferentially fragment by loss of alkyl

radical, the ease of elimination increasing with increased size and branching in the radical.
Thus, the alcohol shown would be expected to give rise to a prominent peak at M– C4H9,
with less abundant peak at M–C3H7 and M–C2H5.

OH OH

C4H9 — C— C3H7 C4H9 + C— C3H7

C2H5 C2H5
Aromatic alcohol show fairly intense molecular ion peaks. Some of the fragment
mode of benzyl alcohol are loss of one, two or three H atoms. The fragment ion (M+–H)
further eliminates CHO radical. The (M+–H) fragment of benzyl alcohol also rearrange to
form hydroxy trophylium ion. The —OH group in benzylic position fragments in a way
m
that favour charge retention on the aryl group. The aromatic cluster at 77, 78 and 79
z
resulting from complex disintegration is usually prominent.

OH
CH2OH
- H+

–2 H

Hydroxytropylium ion
m/z 107
- H• C H — C  O - CO C6H5 C4H3
C6H5CHO 6 5
m/z 77 m/z 51

246
 Mass Spectrometry

m
In case of 1-Phenyl ethanol the base peak at 107 corresponds to the elimination of
z
methyl radical as is represented by hydroxy tropylium ion. Loss of CO from this ion gives
m m
79 and loss of H leads on to the phenyl cation at 77, which loses C2H2 to give m/z 51.
z z
+
OH
H H
CHCH3
OH
- CO

M+ m/z 107 m/z 79

(Parent peak) (Base peak)

C4H3+ C6H5+
m/z 51 m/z 77
PHENOLS
Simple phenol give strong molecular peaks. The commonest fragmentation is loss of
CO (M–28) and CHO (M–29), which can only be represented as shown below.

OH O
H H
-H
H H

M-29
M-28
Phenols with alkyl side chains also undergo benzylic fission, leaving variants of the
hydroxytropylium ion.
OH
OH

- R•
CH2 R

X
X
m/z 107 where X = H

247
 Mass Spectrometry

ALDEHYDES
Aliphatic aldehyde give weak molecular ion peak, whereas aryl aldehyde give strong
+ peaks.
M
Loss of H. from the molecular ion is particularly favoured by aryl aldehyde because
of the stability of ArCO+, nevertheless, M-1 peaks are prominent in the mass spectra of all
m
aldehydes, whether aliphatic or aromatic  -cleavage give R+ peaks and the HCO+ ion at
z

m
29; C2 H+5 also appears at 29, and for higher aliphatic aldehydes C2 H+5 is more likely to
z

m
be the source of 29 than HCO+. The mass spectrum of pentanal and its fragmentation
z
pattern is as follows :

100 44
Relative Abundance

CH3CH2CH2CH2CHO
90 MR ion
80
70
60
50 m/z =57
40
30
20
10
20 40 60 80 100
m/z value

-cleavage
CH 3 CH 2 CH 2CH 2CHO H—C  O

M + m/z 86 m/z 29
Pentanal

CH 3 CH 2 —CH 2CH 2  CH 3CH 2CH—CH 3

m/z 57

248
 Mass Spectrometry

H OH
H3C—CH O
CH3—CH = CH2 + C
H2C C H
H2 C
C H m/z =44
H2
(MR ion peak)

KETONES AND QUINONES

Molecular ion peak for all ketones are usually strong. Most of the abundant ions in
the mass spectra of ketones can be accounted for by  -cleavages and Mc Lafferty
rearrangements, and indeed the base peak for methyl ketones and phenyl ketones is
frequently CH 3 CO + ( m/z 43) and PhCO + (m/z 105) respectively; PhCO +
fragments as usual to m/z 77 and m/z 51.
When RCOR´ undergoes  -cleavage, the larger group is preferentially
repelled as the radical, with concomitant charge retention by the smaller version of RCO+.
Common values for the Mc Lafferty rearrangement ions of aliphatic ketones are m/
z 58, m/z 72, m/z 86, etc. but he higher members of the series may undergo a second
elimination of an alkene, to generate a further series of ions. For example, m/z 86–28, and
loss of C3H6 will correspond to loss of 42 mass unis for simple aromatic ketones the Mc
Lafferty rearrangement ions might arise at m/z 120, m/z 134, etc. All of the Mc Lafferty
rearrangement ions appear at even m/z values.

O O O

O O O
p-benzoquinone -naphthoquinone 9, 10 anthraquinone

Quinones mainly undergo 2-cleavage, both  - bonds being capable of rupture. In

p-benzoquinone and naphthoquinone these fragmentations lead to peaks at m/z 54 and at
M-54, whereas -cleavage in anthraquinone gives the whole range of ions corresponding to
M—CO, M—2CO and m/z 76 (C6H4+).

249
 Mass Spectrometry

The mass spectrum of 3-pentanone and its fragmentation modes are as follows

m/z 29 (CH3CH2)

(CH3CH2C O)
100 29 57 O
Relative Abundance

90
80 CH2—CH2—CCH2—CH3
70
60 Diethyl ketone
50 3-Pentanone
40
30
20 86 M+
10
10 20 30 40 50 60 70 80 90 100 110
m/z value
Mass spectrum of 3- pentanone

Fragmentation modes in 3-pentanone

Since there is no -H atom is 3-Pentanone, so no McLafferty rearrangement peak is
formed.

O O

-e -CH3CH3
CH3CH2CCH2CH3 CH3—CH2—C—CH2—CH3
3-Pentanone m/z 86
– CO
CH3CH3 CH3—CH2—C O+
m/z 29 m/z 57

CARBOXYLIC ACIDS
Molecular ion peaks are usually obervable, but weak common peaks arising from
 -cleavage and Mc Lafferty rearrangements have already been discussed. The mass spectrum
of Pentanoic acid and its fragmentation pattern are as follows

250
 Mass Spectrometry

100 60 (MR ion peak)

Relative Abundance
90
80
70
60
50 73
40
30
20
10 102 M+

10 20 30 40 50 60 70 80 90 100 110
m/z value
Mass spectrum of pentanoic acid

Fragmentation pattern of pentanoic acid is as follows

O O
-e
CH3CH2CH2CH2C—OH CH3—CH2—CH2—CH2—C—OH
Pentanoic acid
M+ (m/z 102) – (CH3—CH2)
–CH3CH2
OH
CH2=CH—C COOH
OH
m/z 73 m/z 45
Resonance
stabilised

OH
H
H 3C C O C
OH
C CH H 2C
C
H2 m/z 60
(M + )

ESTERS
Methyl esters are usually more convenient to study than the free acids, because they
are more volatile. The molecular ion peak is weak but discernible in most cases, and the
fragmentation is a mixture of  - cleavage and (where appropriate) McLafferty
rearrangements. Common ion values for  -cleavage are, therefore, RCO+ , R  ,

251
 Mass Spectrometry

   
CH 3 O+ m 31 and CH3 OCO+ m 59 ; the McLafferty ion at m 74 (CH2=C(OH)OCH3)+.
z z z
is the base peak in the saturated straight chain methyl esters from C6 to C26.
Higher esters are complicated by the possibility of two fragmentation modes -
fragmentation of the acyl group (RCO—) and of the alkyloxy group (ROCO—). The acyl
group fragmentation is a simple extension of that discussed under methyl esters, but where
the alkyloxy group is C2H5O ( ethyl esters) or higher, the McLafferty ion (m/z 88 for ethyl
esters) undergoes loss of both an alkene and an alkenyl radical, to give ions at m/z 60 and
m/z 61 (CH 3CO2H+ and CH 3CO2H2+). The mass spectrum of 1-Propyl ethanoate and its
fragmentation modes are as follows :
O
100
Relative Abundance

90 CH3CO—CH2CH2CH3
80
70
60
50
40 m/e 102
61
30
20
10
30 50 70 90 110
m/z value
Mass spectrum of n-propyl ethanoate

O
OH

H3C—C—OCH2CH2CH3 C3H5 + CH3—C

M+ m/z 61 OH
m/z 102 +
CH3CH2CH2O
CH3CHCH3 m/z 59
m/z 43

AMINES

If the parent peak is formed at the odd mass number, then the molecular carries and
odd number of nitrogen atoms for primary aliphatic amines, the base peak is

CH 2 = N H2 (at m 30) formed by expulsion of a radical from M . . Higher homologues may
z

252
 Mass Spectrometry

also appear at m 44, m 58 etc, but these are less abundant ions. Loss of an alkene 1 for
z z
example, loss of C2H4) may give peaks at M-28, etc.
Secondary and tertiary amines behave analogously, and loss of the substituent alkyl
radicals is also observed. Primary aryl amines principally fragment by loss of H (M–1) and

HCN (M—27); thus aniline give rise to an ion at m z 66 (93—27) whose structure can be
represented as the cyclopentadienyl radical cation. For N-alkylanilines,  -cleavage of the
alkyl group is common. The mass spectrum and fragmentation mode of ethyl amine are as
follows :

100
Relative Abundance

90
80 30
70
60
50
40
30 29 44 45 (M+)
20
10
20 40 60 80 100
m/z value
Mass spectrum of ethyl amine
Fragmentation modes are

- CH3
CH3—CH3—NH2 CH2 = NH2
m/z 45 m/z 30
M+ (molecular ion)

-[H ]
CH3—CH2—N — H CH3 — CH2 = NH
m/z 44

The molecular ion peak in ethyl amine appears at m z 45 . The  - cleavage results in

the formation of a base peak at m z 30. The parent ion loses a hydrogen radical.

253
 Mass Spectrometry

NITRO COMPOUNDS
Molecular ion peaks for aliphatic members are usually absent, while for many aromatic
nitro compounds the M . peak is strong . The mass spectra of aliphatic nitro compounds


mainly correspond to fragmentation of the alkyl chain, although peak for NO+ m z 30 and 
 
NO2 m 46 appear also.
z


For aryl nitro compounds, peak corresponding to NO+ m z 30  ,

 
NO2 m 46 , M-NO (M—30) and M—NO2 (M–46) all appear commonly, and successivee
z
loss of NO and CO (M—58) is also observed. Loss of NO from the molecular ion leaves an
ion of structure ArO+, which can only arise if ArNO2. rearranges in the spectrometer..

Ortho effects are frequently encountered in aryl nitro compounds where a group
ortho to NO2 contains hydrogen; peaks corresponding to M—OH (M—17) appear, indicating
loss of oxygen from NO2 together with H from the ortho substituent.

ETHERS, ACETALS AND KETALS

Aliphatic ethers show molecular ion peak almost of negligible abundance. The

presence of oxygen atom in ethers can be known from strong peaks at m z 31, 45, 59 etc.


These peaks represent RO+ and ROCH fragments. The characteristic fragmentation mode
2
is the loss of one of the ally cation. The ion so formed is the result of  -cleavage. The ion
may further fragment to lose an alkene and this step becomes important when -C atom is
substituted out of the two alkyl groups around the oxygen atom is ether (R—O—R´), the
longest or the bulkier group is preferentially lost. Consider fragmentation modes in diethyl
ether.

CH3—CH2—O—CH2—CH3

CH3—CH2 = O —CH2—CH3
CH3CH=OH CH2 = OH m/z 59
m/z 45 m/z 31

Acetals are a special class of ethers. Parent peak is very weak. Like aliphatic ethers,
the first formed oxygen containing fragments can decompose with hydrogen rearrangement
and olefine elimination. ketals behave similarly. The mass spectrum of isopropyl. n-pentyl
ether is shown below.

254
 Mass Spectrometry

Relative Abundance 100 43

90
80
70 Isopropyl-n-pentyl ether
60
50 71
40 115
30 29
130
20
10
20 40 60 80 100 120 140
m/z value
Mass spectrum of isopropyl n-pentyl ether
The various fragmentation modes are
H3C
CH—O—CH2—CH2—CH2—CH2—CH3
H3C
M+ ion m/z 130

CH3—CH = O(CH2)4—CH3+CH3

CH3 CH2—CH—CH2—CH—CH3 m/z 115

CH m/z 71
CH3—CH = OH
CH3
m/z 45
m/s 43 (100%) CH3
CH—O = CH2
CH3
m/z 73
ARYL ETHERS
The molecular ion peak is prominent. Primary cleavage occurs at the bond beta to
the ring. Loss of methyl gives an ion M—15 which further splits to lose CO. Methyl phenyl
ethers show two main fragmentations.

OCH3

O
– CH3 – CO
+
(i)

m/z 93 m/z 65
M+ m/z 108

255
 Mass Spectrometry

In general

O
CH2

H
– CH2O –H
(ii)

M+ m/z 108 m/z 78 m/z 77

O
O
CH2 CH2
H
CHR
(iii)
H H
m/z 94

HALIDES
The appearance of the mass spectrum of a halogen containing compound is profoundly
affected by the number of halogen atoms present because of isotopic abundances. Fluorine
and iodine, being monoisotopic, present no problems in this respect. The fragmentation of
mixed halogen compounds is very complicated.
Aliphatic fluorine compounds, apart from fragmentations appropriate to the alkyl
chain, show principally a peak of M—HF (M – 20). Aliphatic chlorine compounds fragment

mainly by loss of HCl (giving M—36 and M—38). HCl+ peaks may also be seen at m z 36

and 38. Loss of chlorine as Cl+ or Cl• gives rise to low-abundance peak at m
35 and 37, and
z
at M—35 and M—35 and 37. Aliphatic bromine compounds fragment similarly to chloro
compounds, but loss of Br is preferred fragmentation. Aliphatic iodine compounds show

peaks corresponding to I+ ( m z 127), M—I (M—127) and M—H2I (M—129).

Aryl halides, with halogen directly attached to the ring, show abundant at molecular
ion peaks, but the fragmentation is dominated by the relative stability of the aryl cation.
SULPHUR COMPOUNDS
Fragmentations of thiols (mercaptans and thiophenols) and sulphides bear close

256
 Mass Spectrometry

comparison with their oxygen-analogs, with the additional complication due to M +2 and
m+2 peaks because of 32s and 34s isotope abundances. Normally, molecular ion peaks are
clearly seen.
Aliphatic thiols may also give rise to the following ions : S+, HS+, H2S+ & M–H2S. The
commonest sulphur hetrocycles are thiophene derivatives : thiophene itself gives a strong

M peak, together with HCS+ ( the thioformyl ion) and M—HCS. As for Ph+, loss of CH 
CH produces a peak at M—26. For sulphides (RSR´)  - cleavage gives RS+, often followed
by loss of CS, to give RS —CS peaks. Ions also arise due to M—HS processes.

Some Solved Problems

1. Predit the structure of the compound which shows m at 88, 70, 55, 42, 31
z
(much intense) and 29. [Hint : 1-Pentanol]
2. Determine the structure of the compound whose peaks in the mass

spectrum have m z values 57 (100 % abundance), 41, 29 and 27.

CH3 CH3
- (CH3)
Hint : H3C — C — OH CH2—C—OH
m/z 59
CH3
Tertiary butyl alcohol

3. Determine the structure of the compound whose peaks at m values 124,

z
122, 81, 79, 43 (base peak), 41, 29 and 27 in the mass spectrum.
[Hint : CH3—CH2—CH2Br]

4. Predict the structure fo the compound showing signals at m z 99, 71, 57, 43, 41
and 29.

CH3

Hint : CH3—CH2—C—CH2—CH2—CH3

CH3

257
 Mass Spectrometry

5. An organic compound forms peaks in the mass spectrum at m values 162, 134
z
(MR ion), 120, 91 and 65. Write its structure.

CH2—C—CH2—CH2—CH3
Hint :

6. Predict the structure of the base peak in the mass spectrum of (a) n-octane and
(b) 2-methyl pentane.
[Hint : (a) As an unbranched alkane, we would predict the base peak to be the same

as for other long chain n-alkanes such as n-decane. and be m 57, C4H9+] (b) the
z
molecular ion will fragment preferentially at the branch in the chain, and since

rupture at the bond between C—2 and C—3 gives two fragments each with m 43
z
(C3H7+)

2-methylpentane
43 43
–CH3
43
100
Relative Abundance

C3H7 CH3—CH—CH2—CH2—CH3
90
80 15 71 57 29
70
60 Mr, 86
50 71
40 C5H11+
30
15 29 57
20 86 (M+)
10 CH3 C2H5+ C4H9+

10 20 30 40 50 60 70 80
m/z value
Simplified mass spectrum of 2 methylpentane showing how the chain
can break in several places; but breaks occur preferentially at the branching
point, the most abundant ion being m/z 43 (C3H7+)

258
 Mass Spectrometry

7. Write various fragmentation modes of 1-Hexanol.

Hint :
–2e–
(CH3)—(CH2)4—CH2—O—H CH3(CH2)4—CH2—O—H
—[CH3—(CH2)3—CH2]
1-Hexanol
m/z 102 CH2 = OH
M+
m/z 31

—H2O
–2 H
CH2—CH2 (i) - H2O (ii) -(C2H4))

CH3—(CH2)4—CH =O
(CH2)4
CH3—(CH2)4—CH=CH2
m/z 100
m/z 84
m/z 56
Base peak –H

CH3—(CH2)4—C O+

m/z 99
8. What is the probable composition of a molecule of mass 142 whose M+1
peak 1.1% of the parent peak?
[Hint : CH 3 I. It consists of only one C atom and has a heavy monoisotopic
element.]

9. An organic compound forms a molecular ion peak at m z 114 and other

other prominent peaks at m z 85, 72 (MR ion), 57, 41 and 29. Name the
compound

CH2—O—C—CH3

Hint : O

10. Predict the structure of the compound having molecular formula, C 5 H 12 O

and exhibiting metastale peak (m*) at 43.2
[Hint C5H11OH (1-pentanol)]

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 Mass Spectrometry

C4H9—CH2OH2 C4H9 + CH2 = OH H— C  O

m/z 31 m/z 29
M + (Parent ion)

m/z 88 –H2O
–CH3
CH3—(CH2)2—CH = CH2 C4H7+

m/z 70 m* 43.2 m/z 55

Model questions
1. Describe some basic principles of mass spectrometry.
2. Write a brief note anon the molecular ion or the parent ion.
3. Write a notes on McLafferty rearrangement.
4. What do you understand by metastable ions or peaks ? How these are recognized in
the mass spectrum and what is their importance ?
5. Describe same important features of the mass specta of amines. Give example.
6. Describe some important features of the mass spectra of (i) Aldehyde
(ii) ketones and (iii) Acids.
7. Write notes on (a) double McLafferty rearrangement (b) HRMS
8. Name the five basic sections of a magnetic deflection mass spectrometer ? What is
the function of each ?
9. Explain the principles of the double focussing is spectrometers ?
10. Explain the nitrogen rule ?
References
1. D.H. Williams and I. Howe, Principles of Mass spectrometry, Mc Grow Hill, London
(1972).
2. Millard, B.J. (ed.), Quantitative Mass spectrometry, Lond, Heydon and Son, 1978.
3. McLafferty, F.W. Interpretation of Mass spectra, University Science Books, Mill
Hill, California (1980).
4. Howe. I., Williams. D.H and Bowen. R.D, Principles of organic mass spectrometry,
McGraw Hill, London (2nd edn. 1982)
5. Davis. R and Frearson. M, Mass spectrometry, Wiley, chichester (1987).
6. Chapman. J.R. Practical organic Mass spectrometry, Wiley New York, (1985).

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