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Note: If the sample is not already a gas, then substance must be vapourised, i.e.
the material must be in the gaseous state to be analysed in a mass
spectrometer.
The resulting (+) ions are accelerated down a tube (from + to - plates, P in left
diagram) and then through a powerful magnetic field.
The charged or ionised particles are deflected by this powerful magnetic field (R in
left diagram).
How much they are deflected depends on the particle mass and the speed of
the particle and the strength of a magnetic field i.e. lighter particles of lower mass
(and momentum) are deflected more than heavier particles of bigger mass (see
right diagram below) for a given set of conditions.
By varying the strength of the magnetic field, it is possible to bring into focus
onto an ion detector (N in left diagram) at the end of the tube (effectively an
electrical event is detected), every possible mass in turn and a measure the
strength of the ion current, which is a measure of how much of that ion has
been formed from the sample under analysis.
IONISATION
Q = high voltage (high +/- p.d.) electron gun which fires a beam of high
speed/energy electrons from a heated 'metal element' into the vaporised sample
under analysis and causes ionization of the atoms (or molecules) forming
positive ions (mainly monopositive in charge).
The collision of high KE electrons with atoms or molecules causes another electron
to be knocked off the particle leaving a negative deficit i.e. a positively charged
particle is formed e.g.
The ions formed should be written as [M]+, a notation that is handy if you are
dealing with ionised molecule fragments with an overall single positive charge e.g.
[CH3]+ is seen in the mass spectrum of methane gas, CH4.
The low pressure (~vacuum) is needed to prevent the ions from colliding with air
particles which would stop them reaching the ion detector system.
ACCELERATION
P = are negative plates which accelerate the positive ions down the tube (there
are positive plates at the start of the tube). A moving beam of charged particles
creates a magnetic field around itself, and this 'ion beam' magnetic field interacts
with the magnetic field at R.
DEFLECTION-SEPARATION
R = the magnetic field that causes deflection of ions, this is can be varied to
change the extent of deflection for a given mass and to focus a beam of ions of
particular mass down onto the detector. Hence, by programming the mass
spectrometer to 'sweep' through all likely particle masses, in terms of the right hand
diagram, you can increase the strength of the magnetic field to bring into focus
onto the ion detector monopositive ions of increasing mass.
DETECTION
MASS SPECTRUM
The resulting record of the ion peaks is called the mass spectrum or mass
spectra. The highest peak is called the base peak and is often given the relative
and arbitrary value of 100, particularly in the mass spectra of organic
compounds.
MASS SPECTRA
For elements you get a series of signals or ion peaks for each isotope present and
the ratio of peak heights gives you the relative proportion of each isotope in the
element so that you can calculate the relative atomic mass of an element. This
'simple' spectra of mononuclear ions like Sr+ is only true for non-molecular
elements like metals (see mass spectrum of strontium diagram below) or
noble gases, but for molecular elements like nitrogen or the halogens things are not
so simple (see chlorine example below).
For larger e.g. organic molecules, things can be very complex indeed, as molecules
fragment and many different ions can be formed BUT you can get the relative
molecular mass of a molecule by identifying what is called the molecular ion
peak, that is, when one electron is knocked of the molecule but the molecule
retains its full molecular structure.
e.g. benzoic acid (Mr = 122) gives a molecular ion peak of m/e = 122, due
to [C6H5COOH]+
but you also get fragments such as [C6H5]+ with an m/e of 77 as the molecule
breaks up on further electron impact.
CHLORINE EXAMPLE
BUT, chlorine consists of Cl2 diatomic molecules, which, on ionisation, can split into
chlorine atoms.
The result is a series of 5 different mass peaks from the various isotopic atomic or
molecular ion possibilities.
2. [37Cl35Cl]+ m/z = 72 (note that you must show the two isotopes separately)
4. [37Cl]+ m/z=37
5. [35Cl]+ m/z=35
m/z means the relative mass of the ion over its charge, which for our purposes the
charge is taken +1 (little z) and the mass (little m) is the relative atomic/formula
mass of the particle. m/z sometimes quoted as m/e. You should write the structure
of the ion in square brackets and put the charge on the outside of them in the top
right - this is an important and universally accepted notation in mass spectrometry.
The mass spectra of organic compounds can be very complex as the molecules
fragment under electron bombardment, but the resulting mass spectra can used
to identify compounds from their 'finger-print' pattern of ion peaks of different
mass and particular proportions for a given set of experimental conditions.
The largest m/z value gives the molecular mass of a molecule, i.e. the ion of
largest mass, prior to fragmentation, is formed when the original whole and neutral
molecule, loses one electron e.g. for ethane it would be due to the formation of
[C2H6]+, m/z = 30 and is called the molecular ion peak.
STRONTIUM EXAMPLE
The relative atomic mass of an element, Ar, is the weighted average mass
of the isotopes present, compared to 1/12th of the relative mass of the carbon-
12 isotope. [ 12C is given the relative mass value of 12.0000 ]
Quite often the highest m/e peak is arbitrarily given the relative value of 100, as in
this case and referred to as the base peak, but the peak lines might well indicate
% abundance of isotopes. The diagram of abundances is sometimes called a stick
diagram.
Relative peak height = relative abundance as measured from the ion current
detector signal.
The mass spectrum shows strontium consists of four isotopes, 84Sr (peak height =
0.68), 86Sr (peak height = 12.0),87Sr (peak height = 8.47) and 88Sr (peak height =
100.0)
The book value is 87.62, BUT this calculation does NOT take into account the very
accurate relative atomic masses based on the carbon-12 scale, it merely uses the
mass numbers, which are always integer.
Very accurate isotopic masses are usually a tiny fraction different from a whole
number but provide invaluable information.
The very accurate molecular ion masses are [N2]+ = 28.0061, [CO]+ = 27.9949 and
[C2H4]+ = 28.0313
A very accurate mass spectrometer (for high resolution mass spectroscopy) can
even differentiate between organic molecules of the same integer molecular mass.
e.g. for the molecular mass 103, some possible, however unlikely, molecular
formulae could theoretically be
The Time of Flight Mass Spectrometer (for advanced level students only!)
• The smaller the mass of the ionised particle (ionized atom, fragment
or whole molecule) the shorter the time of flight in the drift region
where no electric field operates.
• The general principles of the separation are required knowledge but the
mathematics is NOT needed by A level students, but if you are
interested, a simplified summary is given below
o t = Kinst√(m/q)
o The acceleration, for a fixed electric field, results in an ion having the
same kinetic energy (KE) as any other ion of the same charge q but
the velocity v of the ion depends on the m/e (m/z) value.
o The diagram makes the method look simple, but far from it, the
instrument works in a pulsed manner i.e. pulsed electric field, and
some pretty sophisticated electronics are used to analyse the signals
from the detector and the software calculates the mass of the ion
based on the drift flight time.