A mass spectrometer is used to identify unknown substances, to determine the composition of mixtures and to accurately measure the relative amounts of substances present. It has many uses in the chemical, engineering and space industries, the Rovers which NASA sent to the planet Mars all had mass spectrometers on board to analysis Martian rocks, minerals and gases in the atmosphere. In the A-level chemistry specifications there are two main types of mass spectrometers that you will need to know about. If you are studying the AQA specification you will need to be able explain the working of a time of flight mass spectrometer and carry out some calculations based on this method of mass spectroscopy. So let's start here. For details on the other type of mass spectrometer, the single beam mass spectrometer and its operation click here or use the link above.

The time of flight mass spectrometer was developed during the 1950. To analyse the sample of the unknown substance under examination we need to consider what happens in each of 4 separate stages in the operation of this type of mass spectrometer. These 4 stages are:

- Ionisation
- Acceleration
- Ion-drift
- detection

Ionisation is one of the key steps that happen inside the mass spectrometer. There are 2 common methods used to ionise the sample, these are two methods are:

- electron impact ionisation
- electro-spray ionisation

If we imagine the electrons as being like fast moving solid particles
or balls/bullets; then when the molecules
or atoms in the injected sample meet these fast moving electrons, they will
have 1 of their outer
electrons removed or knocked off, this means they will have been ionised.
This will leave a positively charged ion behind (this is shown in the image opposite).

If we call the injected sample X, then we can show this as:

Where e represents the electron being knocked off the sample X. You may also see this equation written as:

Here the first e represents the electron
from the electron gun which impacts
the sample X, forming a positively charged ion,
X^{+}_{(g)} and the 2e on the product
side represent the one electron lost by the sample X
and also the electron from the electron gun.

For example the equations below represent the ionisation of of neon gas and hydrogen gas:

or simply:

Ne

And for hydrogen gas we have:

or simply:

H

The second method of ionising the sample uses a method called electro-spray ionisation. This method is often preferred for larger molecules which may be blasted to pieces by an electron gun! Here the sample is dissolved in a volatile polar solvent (volatile means it evaporates easily) such as water or methanol, next it is injected into the sample point under high pressure and through a very fine needle which has a high voltage (around 4000v) applied to it. This results in the sample being ionised and forming fine droplets or a mist containing the ionised sample. The solvent being volatile quickly evaporated leaving the positively charged sample. This is shown in the diagram below

The sample X becomes ionised not by having electrons knocked removed as is the case in electron impact
ionisation, instead the sample gains a hydrogen ion, H^{+}, from the
solvent . We can show this as:

All this takes place in the needle on the end of the injection point. This is also shown below:

The next key step in the mass spectrometer is
acceleration of the ions formed.
There is one vital assumption that we will make: we will assume that all the
ions formed in the ionisation step have
a charge of +1, that is only 1 single
electron has been removed. The positively
charged ion will be now be accelerated
up the tube by an electric field, they will be accelerated towards the negatively charged plates.

One of the main pieces of information that the mass spectrometer provides is the
A_{r} or M_{r} of the substance under analysis. If the sample contains a mixture of
substances it would be very useful if we could obtain the M_{r} for each substance present.
Now after the ionisation step we may have a range of different substances
all with a charge
of +1. The mass spectrometer will give you a read out of the mass to charge ratio,
often called m/z ratio of any substance it detects. Now if the charge (z) is simply
equal to +1, then the mass to charge ratio, m/z, is simply the mass.

In the acceleration stage in the mass spectrometer
would you expect the heavy or
light ions to be accelerated quickest up the tube? Or put another way, if you
pushed a golf ball or a bowling ball, which would move with the greatest
velocity or speed? Obviously the lightest ions will be accelerated quickest
up the tube towards the charged plates. Now you may remember from your
physics lessons that the kinetic energy of an object can be calculated
from the formula:

Where: m =mass in kilograms (kg), v= velocity in metres per second (ms^{-1}) and the KE = kinetic energy in joules (J).

A key feature of this type of mass spectrometer is that all
ions, no matter their mass
will all gain the same amount of kinetic energy during the
acceleration stage. The
kinetic energy of the ions
will depend on their mass and velocity, so lighter faster
moving ions will have the same kinetic energy as heavier slower moving ions.

In the exam your exam you could be asked to calculate any one from the list below. It is often necessary to rearrange formulae, I have given some examples below but I would try the practice questions and complete as many of the examples as possible to ensure you are completely confident with these questions.

- The kinetic energy of the particles in joules (J) using the formula:
##### Kinetic energy (KE) =

Here the mass must be in kilograms (kg) and the velocity in metres per second (ms^{1}/_{2}mv^{2}^{-1}). - The time of flight of the ions. That is the time the ions take to move through the ion-drift area. This will be in seconds (s). This is simply calculated from:
##### time (s) = distance (d) / velocity (ms

the distance (d) is simply the length of the ion-drift area (see diagram above) and the velocity is simply how fast the ions are moving. This will obviously depend on the mass of the particles, the heavier particles will be moving slowly and the lighter particles will be moving much faster.^{-1}) - To calculate the velocity of the particles it maybe necessary to rearrange the formula we have for KE, this is outlined below:
- To calculate the time for the ion to travel along the flight path (ion-drift area) in the mass spectrometer we simply use the equations above but rearrange them to make time (t) the subject of the formula this time:
- To calculate the mass of the particle we simply do a little more arithmetic and rearrange the formula we used above to give:
- To calculate the length of the flight tube(d) we simply use the formula below:

This equation tells us that time of flight (t) is proportional to the square root of the mass (√m), so lighter ions arrive at the detector before heavier ones.

The detector plate has a negative charge due to excess electrons being placed on it from an external source. When the positively charged ions arrive at the detector plate they gain an electron and are reduced. This involves the movement of electrons, or a flow of current. The more electrons that flow the more ions are present, that is their abundance is high, this will be recorded by a computer connected to the detector. Remember the ions will arrive at the detector plate at various times, since their flight time down the flight tube will obviously depend on how fast they are travelling and this as previously mentioned depends on their mass to charge ratio, or simply their mass if the charge is +1.

- The four key steps which in the operation of a TOF mass spectrometer are:
- ionisation
- acceleration
- ion-drift
- detection
- You should be able to describe what happens in each of the 4 stages and in particular the difference between electron impact ionisation and electro-spray ionisation.
- Learn the formulae above or know how to rearrange formula to arrive at the required equations to answer the exam questions.