MASS SPECTROMETRY

Presenter: Ms. S. Brown-Dewar

 Objectives of Lecture

Define Mass Spectrometry

Applications

Functional parts of the Mass

Spectrometer

Process of Mass Spectrometry

 What is Mass Spectrometry?

 Mass spectrometry (MS) is an analytical chemistry technique

that helps identify the amount and type of chemicals present
in a sample by measuring the mass-to-charge ratio and
abundance of gas-phase ions

 Applications
 Forensic science and drug testing (Identify components in
a mixture)
 Research and drug discovery (Structurally characterize
unknowns, determine molecular weights)
 Chemical industry (study gas phase reactions)
 Dating of geological samples (isotope ratio mass
spectrometry)
 Mass Spectrometer
Three components of MS
1. The Ion source receives the sample and produces ions.
2. The mass analyzer sorts these ions based on mass to charge ratio m/z .
3. The detector a continuous dynode electron multiplier produces a signal
proportional to the number of ions striking it.

All components of the system controlled by computer. Data system

software includes programmes to calibrate the MSD, acquire the data and
process the data.
Gas Chromatography Mass
Spectrometer - GCMS
 Interfacing the GC and MS
Molecules must be in gas phase and the MS must be under
vacuum. GC operates at 760- 2250 Torr of pressure. The MS
at 10-5 Torr.
MS operates at low pressure, so limit the amount of carrier
gas. Use capillary columns with flow rates consistent with
the pumping capacity of the MS. 1-2ml/min can be
inserted directly into the source.
 The vacuum system of the MS consists of :
 A mechanical pump which serves to reduce the vacuum in the
system to 10-1 Torr
 The high vacuum pump reduces the system vacuum to 10-6 Torr.
 Main reason for vacuum - sample travels from ion source
to detector without colliding with other molecules (air).
Mass Spectrometer

http://chemguide.co.uk/analysis/masspec/howitworks.html#top
 Electron Ionization
 Vaporized sample passes into the ionization chamber
 Molecules in the ion source are bombarded with high
energy electrons.
 The molecule gains sufficient energy to lose an electron
leaving a positively molecular charged M+.
 EI is a high energy process but efficiency low as one in 100
molecules is ionized.

http://chemguide.co.uk/analysis/masspec/howitworks.html#top
 Electron Ionization contd.
• The high energy electrons also destabilizes the molecule
causing rearrangement and bond breaking i.e
fragmentation. In some cases almost none of the
molecular ion remains after ionization.
• Ions are very reactive and short lived.
• The ionized fragments produced are characteristic of a
molecule.
• Masses of these fragments and abundance of these
fragments depend on the nature of the starting
molecule and this is what gives MS its diagnostic power.
• Libraries of mass spectra are commonly used in the
identification of the unknown compound with various
spectra of known compounds.
• The high energy of the EI process produces consistent
behavior by molecules exposed to the same energy.
Mass Spectrometer

http://chemguide.co.uk/analysis/masspec/howitworks.html#top
 Acceleration
 Positive ions are repelled away from the
very positive ionization chamber and pass
through three slits, the final one of which is
at 0 volts.

http://chemguide.co.uk/analysis/masspec/howitworks.html#top
Mass Spectrometer

http://chemguide.co.uk/analysis/masspec/howitworks.html#top
 Deflection
 Different ions are deflected by the magnetic field by
different amounts. The amount of deflection
depends on:

http://chemguide.co.uk/analysis/masspec/howitworks.html#top
 Mass analyser
 The most commonly used mass spectrometers in
gas chromatography are systems based on
quadrupole analyzers.
 Principle : Quadrupole mass filter has four poles or
rods arranged at the corners of a square supplied
with DC and Rf fields.
 Fragments coming from the ion source through ion
optics enters the analyzer.
 The ion separation is accomplished by applying
alternating RF frequency and DC voltage to the
quadrupole, which in turn allows as specific mass
fragment to pass through the quadrupole filter.
Schematic view of the ion source based on electron
impact ionization and the quadrupole mass filter
typically found in a GC-MS instrument.
 Data acquisition -
 Two modes of acquisition available SCAN acquisition and
Selected Ion Monitoring (SIM).
 Scan mode is the most frequently used mode since it scans all
masses (within the range specified) generated rather than
only a selected number of masses.
 It is the mode to use when analyzing unknown compounds. It
is also the mode used when performing library searches of the
data.
 In SIM mode the mass analyzer is set to acquire data at
masses of interest instead of over a wide range of masses
 In essence the instrument is focused on only the compounds of
interest. Also because only a few masses are monitored much
more time maybe spent looking at these masses, and
therefore an increase in sensitivity, accuracy and precision
Mass Spectrometer

http://chemguide.co.uk/analysis/masspec/howitworks.html#top
 Detection
 A flow of electrons in the wire is detected as an electric
current which can be amplified and recorded. The
more ions arriving, the greater the current.

http://chemguide.co.uk/analysis/masspec/howitworks.html#top
 Electron Multiplier
 High energy dynode /Electron multiplier technology.
The EM attracts positively charged ions exiting the
quadrupole. When the ions hit the EM, electrons are
emitted. The electrons are attracted to the electron
multiplier. The incoming electrons hit the inside surface of
the electron multiplier horn liberating more electrons from
the surface. These electrons cascade down the horn
ejecting more electrons with every impact. Electrical
current converted to signal.
Cocaine - Typical mass spectrum
 Mass Spectrometry Summary

 Ionization : The atom or molecule is ionized by

knocking one or more electrons off to give a
positive ion
 Acceleration: The ions are accelerated so
that they all have the same kinetic energy.
 Deflection: The ions are then deflected by a
magnetic field according to their masses and
number of positive charges on the ion.
 Detection: The beam of ions passing through
the machine is detected electrically