Presenter

Dr. Fakhar-un-Nisa Memon

Assistant Professor
(Analytical Chemistry)
Department of Chemistry UoK
Basic Principles
 Mass spectrometry is based on slightly different
principles to the other spectroscopic methods.
 Mass spectrometry is an analytical tool used for
measuring the molecular mass of a sample.
 The physics behind mass spectrometry is that a
charged particle passing through a magnetic field is
deflected along a circular path on a radius that is
proportional to the mass to charge ratio, m/e.
 In an electron impact mass spectrometer, a high
energy beam of electrons is used to displace an
electron from the organic molecule to form a radical
cation known as the molecular ion. If the molecular
ion is too unstable then it can fragment to give other
smaller ions.
 The collection of ions is then focused into a beam and
accelerated into the magnetic field and deflected
along circular paths according to the masses of the
ions. By adjusting the magnetic field, the ions can be
focused on the detector and recorded.
Terminology
 Molecular ion: The ion obtained by the loss of an
electron from the molecule.
 Base peak: The most intense peak in the MS,
assigned 100% intensity M+ Symbol.
 Radical cation: +ve charged species with an odd
number of electrons.
 Fragment ions: Lighter cations formed by the
decomposition of the molecular ion. These often
correspond to stable carbcations.
Instrumentation
Mass Spectrometer
 Single focusing is so called because a collection of ions
exiting the source with the same mass-to-charge ratio
but with small diverging directional distribution will
be acted upon by magnetic field in such a way that a
converging directional distribution is produced as the
ions leave the field.
 The ability of magnetic field to bring ions with
different directional orientations to focus is the factor
more responsible for limiting the resolution of
magnetic sector instruments (less then 200).
DEVELOPMENT OF DOUBLE FOCUSING MASS ANALYZER

 In single focusing the translational distribution of ions

leaving the source arises from the Boltzmann distribution
of energies of the molecule from which the ions are
formed and from field inhomogeneities in the source.
 The spread of kinetic energies causes the broadening of
the beam reaching the transducer and thus a loss of
resolution.
 In order to measure the atomic and molecular masses with
a precision of few parts per million, it was necessary to
design the instrument that correct for both the directional
distribution of ions and energy distribution of ions.
DOUBLE FOCUSING MASS ANALYZER

 The term double focusing is applied to mass

spectrometers in which the directional aberrations
and energy aberrations of a population of ions are
simultaneously minimized.
 Double focusing is usually achieved by the use of
carefully selected combination of electrostatic and
magnetic fields.