SCH3U7/4U7 Mass Spectrometry

A mass spectrometer is an instrument which separates particles according to their masses

and records the relative proportions of these. The following is a simple diagram of a mass
spectrometer.
C
B

F
A

Region A contains the vapourized substance. Therefore, if the substance is a solid or a

liquid, it has to be heated to produce the vapour. The transfer of the substance into the body
of the instrument occurs very slowly to ensure there are no collisions with other particles.

In Region B, the neutral atoms or molecules of the substance are bombarded by fast moving
electrons which have been accelerated in an electric field. These electrons collide with
electrons in the neutral substance, knocking them out, and leaving a positive ion.

Region C is where the positive ions are accelerated by a high electrical potential difference.

These fast moving ions enter a magnetic field at Region D produced by an electromagnet.
This causes the fast moving ions to deflect. The amount of deflection experienced by an ion
is dependent on its size. The larger the mass of the ion, the less the deflection (and vice
versa for smaller ions).

Ultimately, the deflection depends on the charge-to-mass ratio (m/z). By varying the strength
of the magnetic field, ions of different masses can be brought into focus on the detector at
Region E. Detection is usually based on the current flow required to neutralize the positive
charge that the positive ions carry. The greater the number of particles of a certain mass that
are present, the greater the current required for neutralization.

The entire body of the instrument must be maintained at a high vacuum by a pump at Region
F (again, to minimize particle collisions).

To summarize, the main operations are:

A Vapourized sample introduced. D Ions deflected by a magnetic field.
B Ionization by electron bombardment. E Detector records ions of a particular mass.
C Positive ions accelerated by electric field. F Vacuum prevents collisions with gas molecules.
The mass spectrometer has many applications, but one of the simplest is to determine the
isotopic abundances of a particular element, therefore allowing the calculation of its atomic
mass. For example, a sample of boron vapourized in the mass spectrometer would produce
a spectrum that looks something like this:

The Mass Spectrum of Boron

The relative abundance is recorded so that
either the most abundant isotope is given a
value of 100 and the others recorded as a
proportion of this, or the abundances are
given as percentages of the whole.

The Mass Spectrum of Chlorine The Mass Spectrum of Molybdenum

The Mass Spectrum of Molecular Chlorine

Relative Isotope Abundance of Common Elements

Relative Relative Relative

Element Isotope Isotope Isotope
Abundance Abundance Abundance
12 13
Carbon C 100 C 1.11
1 2
Hydrogen H 100 H .016
14 15
Nitrogen N 100 N .38
16 17 18
Oxygen O 100 O .04 O .20
32 33 34
Sulfur S 100 S .78 S 4.40
35 37
Chlorine Cl 100 Cl 32.5
79 81
Bromine Br 100 Br 98.0

Further Applications of the Mass Spectrometer

In the case of molecules, the bonds frequently break as a result of the ionization process,
resulting in fragments of a lower mass than the original molecule.

The ion detected with the highest mass will usually correspond to a molecule that has only
lost a single electron. This is called the molecular ion. The mass of the molecular ion gives
the relative molecular mass of the molecule, which can be combined with data from elemental
analysis to calculate the molecular formula of the substance.

The impact of the electron forming the molecular ion will often cause it to break down or
fragment inside the mass spectrometer. The resulting fragmentation pattern of lower
molecular mass ions will frequently give clues as to the structure of the molecule. For
example, sometimes only a hydrogen will break off, giving a peak at one mass number less
than the main peak. If two fragments differ by 15, then this probably corresponds to the loss
of a CH3- group. Similarly, a loss of 29 corresponds to the loss of C2H5- or H-CO-; 31 to the
loss of CH3-O-; and 45 to the loss of COOH.

This information can provide a useful way of distinguishing between structural isomers.

The Simplified Mass Spectra of 2 Structural Isomers (pentane or 2-methylbutane?)

The Simplified Mass Spectra of 2 Structural Isomers (2-pentanone or 3-pentanone?)

Example:

Two isomers, A and B, of empirical formula C5H12 give mass spectra showing peaks
corresponding to molecular ions and other major fragments with mass-to-charge values as
follows:
A 72 57 42 27 12
B 72 57 43 29 15

(a) Give the molecular formula of A and B.

(b) Give the structural formulas of three isomers of this hydrocarbon.

(c) With respect to the mass spectrum of A, identify (with an explanation) one fragment
which would cause the observed mass losses.

(d) With respect to the mass spectrum of B, identify (with an explanation) one different
fragment which would cause the observed mass losses.

(e) Give the structures of A and B and name each of them.