ALANKAR MAHILA P.G.

MAHAVIDHYALAYA,JAIPUR
SEMINAR 2020-21
MASS SPECTROSCOPY
CHEMISTRY
SUBMITTED TO:- SUBMITTED BY:-
Department of Chemistry SEEMA SHARMA
Alankar Mahila P.G. M.Sc. Chemistry (Final)
Mahavidhyalaya,Jaipur
CONTENT
 INTRODUCTION.
 PRINCIPLE.
 CORRELATION OF MASS SPECTRA WITH
MOLECULAR STRUCTURE.
 MOLECULAR IDENTIFICATION.
 METASTABLE PEAKS.

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INTRODUCTION
 Mass spectrometry is one of the most generally applicable tools
providing both qualitative and qualitative information about the
atomic and molecular materials
 Hare the compound under the investigation is bombarded with a
beam of electrons which produce an ionic molecule or ionic
fragments of the original species. the resulting charging particle is
then separated according their masses.

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PRINCIPLE
 Organic molecules are bombarded with electron and are converted to high
energetic positively charged ions (molecular ions or parent ions).
 Which will break up in to smaller ions (fragment ions or daughter ions).
 The loss of electron from a molecule leads to a radical cation
M+e M+2e
 This molecular commonly M+ decomposes to a pair of fragments which may
be either radical + anion or a small molecule + radical

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PRINCIPLE
 These molecular ions, are isolated in the electric field at an voltage v, these
charging particles which are isolated then made to enter into an magnetic field
H. Hare the field attracts the particles and move in a circle around it.
 Hare the radius of the ionised molecule depends on M, its mass. This forms the
basis of separation of particles according to their masses.
 These ions are made to impinge upon the collector in turn thus giving rise to a
spectrum.

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CORRELATION OF MASS SPECTRA WITH
MOLECULAR STRUCTURE
 The ionization efficiency of a mass spectrometer source must be high so
that a large portion of the neutral sample particles present are converted to
ions.
 High efficiency is particularly important for the analysis of nainogram
quantities of sample material and trace impurities in solids.
 When bombarded by e- in the electron-impact method of ionization, every
substance ionizes and fragments uniquely.
 A molecule may simply lose an e— of many fragments into two smaller
units,

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CORRELATION OF MASS SPECTRA WITH
MOLECULAR STRUCTURE
 A molecular ion is generally observed in considerable intensity when the
gaseous molecules are bombarded with e- of energy just su0icient to cause
ionization, but not bond leakage, about 8- 14eV for most organic molecules.
 As soon as the excess energy over the ground state energy possessed by the
molecular ion becomes equal to the dissociation energy of some particular
bond, the appropriate fragment ions are formed. Although the peak intensities
are extremely sensitive to ionizing voltage at low values of ionizing voltage,
the relative peak intensities become fairly constant once the ionization voltage
exceeds 50eV.
 • At higher ionizing energies the total production of ions is higher, but the net
effect of higher overall intensity.

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MOLECULAR IDENTIFICATION
 In the identification of a compound, the most important information is the
molecular weight. The mass spectrometer is unique among analytical methods
in being able to provide this information very accurately. often to four
decimal places when high-resolution mass spectrometer is used.
 • At ionizing voltages ranging from 9-16V in the electron-impact mode of
ionization, it is assumed that no ions, heavier than the molecular ion form.
Therefore, the mass of the heaviest ion, exclusive of isotopic contributions,
gives the nominal molecular weight with Io-resolution mass spectrometers

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MOLECULAR IDENTIFICATION
 The no. of possible molecular formulas is restricted by a study of relative
abundances of natural isotopes for different elements at masses one or more
units larger than the parent ion. observed values are compared with those
calculated for all possible combinations of the naturally occurring heavy
isotopes of the elements. For a compound CwHxOzNy a simple formula allows
one to calculate the percent of the heavy isotope contributions from a
monoisotopic peak, PM to The PM+1. peak.
 1 OO PM+1/PM = 0.015x + 1.11w + 0.37y + 0.O37z

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10
 METASTABLE PEAKS
 A one-step decomposition process may be indicated by an appropriate metastable peaks in the
mass spectrum. Metastable peaks arise from ions that decompose in the field-free region after
they are accelerated out of the ion source but before they enter the analyzer. Their life time is
about 10^-6•sec. A metastable ion transition takes the general form:
 Original ion daughter ion + neutral fragment
 The metastable peak m* appears as a weak, diffuse peak, usually at a non integral mass,
 In a spectrum that is linear with respect to mass values, the distance of m*, below the
daughter ion is of similar magnitude to the distance of the daughter ion below 1he original
ion. The foregoing relationship holds only for ions that decompose in a small portion of the
accelerating region and is more frequently observed with 60 degree and 90 degree sector
instruments where a field-free region exists after the accelerating slits and before the
magnetic analyzer. Of course, the absence of a metastable peak from the spectrum does not
preclude a particular decomposition.
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 REFRENCE
MASS SPECTROSCOPY
CHEMISTRY

SEEMA SHARMA
Thank you

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