Lab Technique - Mass Spectrometry

Introduction

Organic molecules have complex behavior. Their structure is

complicated and need to be clearly understood. Chemists have been
developing various techniques to see inside the organic molecules.
These techniques can be broadly classified as spectrometry,
separation and spectroscopy.

Mass Spectrometry

Mass spectrometry is a technique and an analytical tool in

the hand of chemists which is used for measuring the molecular mass
or atomic mass.

The molecular masses of biomolecules, can be measured up

to an accuracy of 0.01%. For smaller organic molecules, the molecular
mass can be measured within an accuracy of 5 ppm or less. This
accuracy is sufficient to confirm the molecular formula of a
compound

Principal of Mass Spectrometry

Ions are electrically charged particles and they can be

deflected by magnetic fields as electrically charged particles are
affected by a magnetic field.

Higher the mass less is deflection and lower the mass

more is the deflection.

Process of Mass Spectrometry

The molecules of the sample are bombarded with

electron. The atoms of molecules are ionized by losing one or more
electrons to give a positive ion. This is true even for particles which
normally produce negative ions (chlorine, for example) or never form
ions at all (argon, for example). Mass spectrometers always work
with positive ion. The largest ion is the size of original molecule less
one electron. It is a cation. For example, methane will produce a
cation of the type CH4+. This cation is called molecular ion.

The ions are accelerated through a magnetic field so that they

all have the same kinetic energy. A magnetic force is experienced by
the charged ion causing the deflection from their original path.

The ions are deflected by the magnetic field according to their

masses. Magnetic field can be varied to allow ions of different mass
to pass through the spectrometer. The lighter they are, the more they
are deflected. The amount of deflection also depends on the number
of positive charges on the ion. In other words, on how many electrons
were knocked off in the first stage. The more the ion is charged, the
more it gets deflected.

The deflection is along a curved path and radius of deflected

curved path depends upon mass to charge ratio of the ion.

The beam of ions passing through the machine is detected

electrically.

A schematic diagram of mass spectrometer is shown

Most of ions are having charge of 1+ after loosing one electron. Most
of the ions have positive one charge because it very difficult to knock
off 2nd electron after one electron is removed.

Most of the ions passing through the mass spectrometer

will have a charge of 1+, so that the mass/charge ratio will be the
same as the mass of the ion.
 The ions which have the smaller value of m/z will need less
deflection to bring them on to the detector, and less deflection is
possible by using a weaker magnetic field (a smaller sideways force).
For heavier ion, stronger magnetic field will be needed.

In other words all ions heavier or lighter can be brought to

detector by controlling the magnetic field.

The detector produces a current which is proportional to the

number of ions arriving. The mass of each ion being detected is
related to the size of the magnetic field used to bring it on to the
detector.

The output from the chart recorder is usually processed by a

computer and is represented as a mass spectrum. This spectrum
shows the relative current produced by ions of varying mass/charge
ratio.

Mass Spectrum

Mass spectrum will usually be presented as a vertical bar

graph, in which each bar represents an ion having a specific mass-to-
charge ratio (m/z) and the length of the bar indicates the relative
abundance of the ion. The most intense ion is assigned an abundance
of 100, and it is referred to as the base peak. Most of the ions formed
in a mass spectrometer have a single charge, so the m/z value is
equivalent to mass itself.

Modern mass spectrometers easily distinguish (resolve)

ions differing by only a single atomic mass unit (amu), and thus
provide completely accurate values for the molecular mass of a
compound. The highest-mass ion in a spectrum is normally
considered to be the molecular ion, and lower-mass ions are
fragments from the molecular ion, assuming the sample is a single
pure compound.

The following diagram displays the mass spectra of three

simple gaseous compounds, carbon dioxide, propane and
cyclopropane. The molecules of these compounds are similar in size.
CO2 and C3H8 both have a nominal mass of 44 amu, and C3H6 has a
mass of 42 amu. The molecular ion is the strongest in the spectra of
CO2 and C3H6, and it is moderately strong in propane. The unit mass
resolution is readily apparent in these spectra (note the separation of
ions having m/z=39, 40, 41 and 42 in the cyclopropane spectrum).
Even though these compounds are very similar in size, it is a simple
matter to identify them from their individual mass spectra.
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