Академический Документы
Профессиональный Документы
Культура Документы
Applications
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.
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