Mass Spectrometry

The basic principle of mass spectrometry (MS) is to generate ions from either inorganic or
organic compounds by any suitable method, to separate these ions by their mass-to-charge
ratio (m/z) and to detect them qualitatively and quantitatively by their respective m/z and
abundance.

Components
The instrument consists of three major components:

1. Ion Source: For producing gaseous ions from the substance being studied.

2. Analyzer: For resolving the ions into their characteristics mass components
according to their mass-to-charge ratio.

3. Detector System: For detecting the ions and recording the relative abundance
of each of the resolved ionic species.
In addition, a sample introduction system is necessary to admit the samples to be
studied to the ion source while maintaining the high vacuum requirements (~10 -6 to
10-8 mm of mercury) of the technique; and a computer is required to control the
instrument, acquire and manipulate data, and compare spectra to reference libraries.

With all the above components, a mass spectrometer should always perform
the following processes:

1. Produce ions from the sample in the ionization source.

2. Separate these ions according to their mass -to-charge ratio in the mass
analyzer.
 3. Eventually, fragment the selected ions and analyze the fragments in a
second analyzer.

4. Detect the ions emerging from the last analyze r and measure their
abundance with the detector that converts the ions into electrical signals.

5. Process the signals from the detector that are transmitted to the computer
and control the instrument using feedback.

How does a mass spectrometer work?

There are four stages in a mass spectrometer which we need to consider, these are –
ionisation, acceleration, deflection, and detection. Let’s go through these in order.

Ionisation

The sample needs to be vapourised first, before being passed into the ionisation
chamber. Here, an electrically heated metal coil gives off a stream of electrons. The
atoms or molecules in the sample are bombarded by this stream of electrons, and in
some cases, the collision will knock an electron from the particle, resulting in a
positively charged ion. Most of the ions formed have a +1 charge, as it is difficult to
remove a second electron from an already positive ion.

Acceleration

The positively charged ions are repelled from the ionisation chamber (which is
positively charged), and pass through negatively charged slits which focus and
accelerate this into a beam.

Deflection

The stream of positively charged ions are then deflected by a magnetic field. The
amount ions are deflected by depends on

-the mass of the ion (lighter ions will be deflected more than heavier ones)

-the charge of the ion (ions with a greater charge than +1 are deflected more)
We can consider these properties as a mass/charge ratio (m/z), where the mass of the
ion is divided by its positive charge.

Detection

By varying the strength of the magnetic field, the different ion streams (after
deflection) can be focused on the ion detector, in order of increasing mass/charge
ratio (as the lightest ions would need to be deflected the less). When an ion hits the
detector, the charge is neutralised, and this generates an electrical current. This current
is proportional to the abundance of the ion, these are sent to a computer for analysis.

A mass spectrum is generated, which shows the different m/z values of ions present,
and their relative abundance.

The importance of peaks in Mass Spectrometry

The base peak is the tallest peak because it represents the commonest fragment ion
to be formed - either because there are several ways in which it could be produced
during fragmentation of the parent ion, or because it is a particularly stable ion.

The peak representing the molecular ion is called the molecular ion peak (symbol:
M peak). Excluding any peaks due to the presence of heavier isotopes, the molecular
ion peak is the peak with the highest mass-to-charge ratio.

the M+1 peak in a mass spectrum can be used to estimate the number of
carbon atoms in an organic compound.
What is an M+1 peak?

If you had a complete (rather than a simplified) mass spectrum, you will find a
small line 1 m/z unit to the right of the main molecular ion peak. This small
peak is called the M+1 peak.