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Name : Prerana
Rane
Class : M.Sc. II
Roll no. : 12
Semester IV
CONTENT
1)Terms in Mass Spectroscopy
2) Metastable Peaks
3) Fragmentation Pattern
TERMS IN MASS SPECTROSCOPY
Mass Spectrum: The mass spectrum is the
plot of mass to charge ratio of positively
charged ions against their relative
abundance.
Base Peak: The most intense peak is base
peak. It is assigned a relative intensity of
100% and the intensities of other peaks as
percentage of base peak.
Molecular Ion:
1)The ion formed from a molecule by the
removal of one electron of the lowest
ionization potential is known as molecular
ion.
2) The molecule ion is detected as mass to
charge ratio that corresponds to the
molecular weight of the molecule
Mass to Charge Ratio: It is the
dimension less ratio of the mass number ‘m’
of a given particle to the number ‘z’ of the
electrostatic unit ‘e’ carried by the particle.
Relative Intensity: The relative intensity
of the peak is the intensity relative to that
of the base peak.
Fragment Ions:
1)The ions produced from the molecular ion
by the cleavage of bonds are called
fragment ions.
2)They have lower mass and help to
construct the molecular structure.
3) Fragmentation can happen by 2 ways:
a) Homolytic Cleavage
b) Hetrolytic Cleavage
META STABLE ION PEAK
Definition:
1) Ions resulting from the decomposition
between the source region and magnetic
analyzer are called meta stable ions.
2) These appear as broard peak known as
meta stable ion peaks.
3) Meta stable ion peak can be easily detected
in mass spectrum.
Some important features of meta stable ion
peaks are:
They do not neccesary occur at integral
m/z (mass to charge)value.
The are much broader then normal peak
They generally having a low intensity in
the mass spectrum.
The meta stable ion peak is useful in some
applications because its presence
definitely links two peaks together.
The presence of meta stable ion peak in
mass spectrum is taken as a good evidence
that the parent ion undergoes
decomposition , is a 1 step to form
daughter ion.
The most likely reason for broading the
meta stable ion peak is the possibility that
some of the excitation energy leading to
bond breaking may be converted into
additional kinetic energy.
FRAGMENTATION MODES
The relative intensity of the fragment ions
depends upon:
1) Stability of the ion
2) Stability of radical loss
The stability of ion can be judged by
stabilization charge present which in turns
depends on resonance, inductive effect and
polarizability.
The radical site is reactive and can form a
new bond. The formation of new bond is a
pwerful driving force for ion decompositions
The energy released during bond formation is
available for cleavage of some bonds in the ion.
Fragmentation modes are described
below:
1)Simple Cleavage: It involves 2 types of cleavage
which are A) Homolytic Cleavage
B) Hetrolytic Cleavage
2) Retro Diels Alder Reactions
SIMPLE CLEAVAGE
A) Homolytic Cleavage:
i) In this, odd electrons have unpaired
electron which is capable of new bond
formation.
ii) Bond is formed,energy is released, help
offset the energy required for the cleavage of
some other bond in the ion.
iii) Homloytic cleavage reactions are very
common.
B) Hetrolytic Cleavage:
i)In this, it is noted that cleavage of CX
(O,N,S,Cl) bond is more difficult than that
of CC bond.
ii) In such cleavage, the positive charge is
carried by the carbon atoms snd not by
hetro atoms.
RCH₂-Cl. + Cl. + RC⁺H₂
2) RETRODIELSALDER
REACTION
This reaction is an example of multicentre
fragmentation which is characteristic of
cyclic olefins.
It involves the cleavage of two bonds of a
cyclic system, result the formation of two
stable unsaturated fragment in which two
bonds are formed.
This process is not accompanied by any
hydrogen transfer rearranngement.
The charge is carried by any one of the
fragment.
The more highly substituent or conjugated
fragment are genarally having low
ionization potential value which carries
the charge.
RULES OF FRAGMENATATION
MODES
1) The height of meta stable ion peak decreases
with increasing degree of branching.
Rule 2: The height of meta stable ion peak
decreases with increasing molecular weight.
Example: Fatty molecules, steroids.
Rule 3: The cleavage is favoured at alkyl
substituted carbons leads to formation of
carbocation.
Rule 4: Double bonds, cyclic structures and
aromatic rings stabilize meta stable ion peaks
and the probability of its appearance.
Rule 5: Double bonds favour allylic cleavage to
give the resonance stabilized carbon.
Rule 8: Carbon carbon bonds next to hetro
atoms are frequently cleaved, leaving the charge
on the hetro atom.
Rule 9: Cleavage is often associated with
elimination of small stable, neutral molecules,
such as CO, olefins, water, ammonia,HCN, or
Alcohol.
Example:Mclafferty Rearrangement
REFERENCE
Wikipedia
Ty textbook
THANK YOU