Definitions

Relative Atomic Mass (Ar)

The ratio of the average mass of one atom of an element to one twelfth of the mass of an atom of
carbon-12
Relative Isotopic Mass
The mass of an atom of an isotope compared to the mass of 1/12 of the mass of an atom in carbon-12.
Relative Molecular/Formula Mass (Mr/RFM)
Is a number equal to the sum of the atomic masses of the atoms in a molecule. The molecular mass gives the mass of
a molecule relative to that of the 12C atom
Why is it all relative
Atoms are too small to measure in grams or micrograms so we have to compare
them to other atoms.

So hydrogen is 1/12 the mass of carbon magnesium is 2x the mass of carbon

Mass
Spectrometry

1. Atoms are vapourised.

2. Ionisation of the atoms occurs by bombarding the sample with high energy
electrons, creating positive ions (fragments).
3. Acceleration of the positive ions occurs using an electric potential, so that all
fragments are moving with the same kinetic energy.
4. Deflection of the positive ions occurs due to an electromagnet. Ions are
deflected based on their mass:charge ratio.
5. Detection of the positive ions occurs using an electric detector.
Chlorine
 The molecular ion, M+
The molecular ion (M+) is usually the highest mass/ charge peak in the mass spectrum.
The molecular ion is the molecular weight of the original molecule put into the
spectrometer.

Calculate the
molecular weight
of pentan-2-one.
 The molecular ion, M+
The molecular ion (M+) is usually the highest mass/ charge peak in the mass
spectrum. The molecular ion is the molecular weight of the original molecule
put into the spectrometer. Sometimes there will be a small peak one mass
unit higher than M+ this is due to the presence of 13C in the molecule.

Calculate the
molecular weight of
2-chloropropane.
 Fragmentation Patterns
Many organic molecules do not hold their charge well and are unstable. Often they
will break up to form fragments of the original molecule. The fragments are always
smaller than the original molecule and sometimes are uncharged (so unseen in the
mass spectrum). The same molecule always fragments in the same way so patterns
can be observed.
Interpret the mass spectrum for
ethanol

2. Base peak 1. M+

3.
4. 5.
Interpret the mass spectrum for
propan-1-ol
 +
M -1 M+-29
+ +
59 31
M+ +
60
M+-17
M+-31
+ +
43 29
 Question 1: Methanol

Challenge: What fragment gives rise to the base peak at m/z = 31?