UNIT V

Mass Spectroscopy

Principle

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.

The molecules are ionized and broken up into many fragments.

Each kind of ion has a particular ratio of mass to charge, i.e., m/e ratio.

For most ions, the charge is one and thus, m/e ratio is simple the molecular mass of the ion.

Example:

Consider neopentane

The molecular ion (C5H12)+ is called parent ion and is usually designated as M+.

The set of ions (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.

The largest peak in the structure is called the base peak and its intensity is taken as 100.

Theory

A parent ion results when one electron is removed from the parent molecule.
The m/e value of the parent ion is equal to the molecular mass of the compound.

The mass spectrometer is designed to perform three basic functions. These are:

(i) To vaporize compounds

(ii) To produce ions from the neutral compounds in the vapour phase

(iii) To separate ions according to their m/e ratio and to record them.

The plot of m/e values taken along abscissa and their relative intensities along the ordinate ic called the
mass spectrum.

The mass spectrum of neopentane is shown as follows:

Fig 7.1 Y.R. Sharma Page 292

Mass spectrometer consists of the following parts:

Ion source

Mass analyser

Ion detector

Ion source

The first and an important step in obtaining the mass spectrum is to ionize the sample.

The common technique used for the production of ion in mass spectrometer is by the bombardment of
electrons.

The bombarding electrons are produced from an electrically heated tungsten filament.

A few milligram of the substance is produced as a vapour in the source at a pressure of 10-6 mm.

The vapour is allowed to pass through a slit ‘A’ into the ion chamber. Here, it is bombarded by a stream
of electrons produced from a tungsten filament.

Due to the bombardment, the molecules generally loss one electron to form a parent ion.

If the energy of the bombarding electron is around 70 ev, then additional energy is consumed in
fragmenting the parent ion to form fragment ions (positive ions).
The positive ion (fragment) is detected in the mass spectrometer whereas the neutral molecules or the
radicals are left undetected.

Fig 7.2 Y.R. Sharma Page 293

Mass Analyzer

The positively charged ion (parent or fragment ions) produced in the ion chamber are accelerated by
applying an acceleration potential.

These ions then enter into mass analyzer. Here the fragment ions are differentiated on the basis of their
m/e ratio.

The positive ions are directed through a slit B. Repeller potential is applied between A and B.

The ions are accelerated by applying an acceleration potential, of the order of 8 kV through the slit C.

The positive ions travel through whole of the analyzer with high velocity are separated according to their
m/e ratio.

Dampster’s mass spectrometer is used for the purpose. The positive ions travel in a circular path
through 180o under a magnetic field H.

Suppose an ion having a charge e is accelerated through a voltage V. Then the K.E of the ion is expressed
as:
1
2
𝑚𝑣 2 = 𝑒𝑉 ----------- 1

where,

v = velocity of the ions after acceleration

V = potential applied.

Fig 7.3 Y.R. Sharma Page 294

In a magnetic field H, any ion will experience force Hev. It produces an acceleration of v2/r in a circular
path of radius r.

Hence, from Newton’s second law,

𝑚𝑣 2
𝐻𝑒𝑣 = 𝑟
----------- 2

Squaring both sides,

𝑚2 𝑣 2
𝐻2 𝑒 2 = 𝑟2
----------- 3

1
But 2
𝑚𝑣 2 = 𝑒𝑉 from Eqn.1

𝑚𝑣 2 = 2𝑒𝑉

Putting the value of 𝑚𝑣 2 in Eqn.3,

𝑚. 2𝑒𝑉
𝐻2 𝑒 2 =
𝑟2
2𝑚𝑉
𝐻2𝑒 =
𝑟2

𝑚 𝐻2 𝑟2
=
𝑒 2𝑉

The ions of various m/e values reach the collector, amplified and recorded.

Ion Detector

The ions which are separated by the analyzer are detected and measured electrically or
photographically.

Molecular ion peak

When a sample is bombarded with electrons of energy 10-15 eV, the molecular ion is produced with the
loss of one electron. The peak due to this molecular ion is called molecular ion peak or parent peak.

Uses

It gives the molecular weight of the sample, from which the molecular formula can be determined.

Base peak

The largest peak in the mass spectrum, corresponding to the most abundant ion is called base peak.

The base peak may be aren’t ion peak or some other fragmented ion peak depending upon the nature of
the compound.

Uses

Base peak gives an idea about which ion is abundant when the molecule under study is bombarded with
electrons. This helps to identify the molecular structure of the compound.

Isotopic peak (Satellite peak)

These peaks are due to the presence of isotopes of elements present in the molecule. These peaks are
called isotopic peaks or satellite peaks.

C, N and H have isotopes with one mass unit greater than the common isotope. Therefore, the presence
of these elements in a compound will give rise to a small isotopic peak at M++1.

Thu, the ion CH3+ shows a peak at m/e = 15 corresponding to the molecular ion peak and another peak
at m/e = 16 which s due to 13CH3+.

Uses

Isotopic peaks are useful for determining the molecular formula of a compound.

Metastable peak

Metastable peaks can be easily determined in a mass spectrum. Some important characteristics of these
peaks are:

They do not necessarily occur

These are much broader than the normal peaks

These are of relatively low abundance.

Formation of metastable ions

Consider M1+ is the parent ion and m1+ is the daughter ion.

If the reaction M1+→m1+ takes place in the source, then the daughter ion, m1+ may travel the whole
analyzer and is recorded as m1+.

On the other hand, if the reaction M1+→m1+ occurs after the source exist and before arrival at the
collector, then m1+ is called a metastable ion and the corresponding peak is called metastable peak.

Uses

The metastable peaks in the mass spectrum greatly contribute in structure elucidation.

Nitrogen Rule

It states that, if a compound contains even number of nitrogen atoms (or no nitrogen atoms), its
molecular ion will appear at an even mass number. If, however, a compound contains an odd number of
nitrogen atoms, then its molecular ion will appear at an odd mass number.

Uses

This rule is very useful for determining the nitrogen content of an unknown compound.
Ring Rule

The total number of rings and double bonds present in a molecule can be determined by the formula,

1
𝑅= (2𝑤 − 𝑥 + 𝑦 + 2)
2

This is called ring rule.

Uses

After deciding the exact molecular formula of an unknown compound we can use the above rule to fix
up the number of rings and double bonds present in the molecule.

If the molecular formula is CwHxOzNy

Then,
1
𝑅= (2𝑤 − 𝑥 + 𝑦 + 2)
2

The molecular formula of benzene is C6H6

Here, w = 6 and x = 6

1
𝑅= (2 × 6 − 6 + 0 + 2)
2

1
= (8) = 4
2

R is sometimes referred as double bond equivalent (DBE).

If DBE = R = 1, then it means that either one double bond or one ring is present in the molecule.

DBE = R = 4 suggests that the presence of an aromatic ring with three double bonds.

Fragmentation

When the molecules are bombarded with an electron beam of sufficient energy molecular ions are
formed. When the energy of the electron beam is increased, further bond cleavage takes place and
smaller ions are produced. These are called fragment ions or fragments and the process is called
fragmentation.

Some important fragmentation modes are described below:

1. Simple cleavage

This process involves the cleavage of a single covalent bond.

Homolytic cleavage

Heterolytic cleavage

(i) Homolytic cleavage: Ions with odd electrons have unpaired electrons and form a new bond. During
bond formation energy is released. This energy is used to cleave some other bonds in the same
molecule.

Homolytic cleavage can be classified in the following types:

(a) Mode I: When a hetero atom is bonded to carbon atom with a single bond, parent ion is formed by
the removal of one electron from the hetero atom.

A new bond is formed with the adjacent atom through the donation of the unpaired electron and the
transfer of an electron from the adjacent bond.

Mode II: When a hetero atom is attached to a carbon atom by a double bond, α-cleavage is the
preferred fragmentation mode.

Mode III: This can be regarded as benzylic cleavage. It involves the cleavage of a C-C bond which is β to
the aromatic ring.

(ii) Heterolytic cleavage: The cleavage of C-O, C-N, C-S and C-X (X=Cl, Br, I) bonds is more difficult than
that of C-C bond.
In such a cleavage, the positive charge is carried by the carbon atom and not by the hetero atom.

McLafferty Rearrangement

It involves the migration of γ-hydrogen atom followed by the cleavage of a β-bond.

This rearrangement leads to the elimination of neutral molecules from aldehydes, ketones, amines etc.,

The rearrangement proceeds through a sterically hindered six membered transition state.