7.

Mass Spectrometry

To do:
1. An unknown compound has the following mass composition:
C, 40.0%; H, 6.7%; O, 53.3%
The largest mass recoded on the mass spectrometer of the compound corresponds to a
relative molecular mass of 60. Calculate the empirical formula and determine the
molecular formula of the compound.
The IR spectrum shows an absorption band at 1700 cm-1 and a very broad band between
2500-3000 cm-1. Deduce its molecular structure.
The fragmentation pattern of a compound can provide useful evidence from which its
structure can be deduced. A compound can therefore be characterized by its
fragmentation pattern.

Figure 7.3.1: The mass spectrum of ethanol

In fig 7.3.1 above the molecular ion corresponds to the peak at . . the ion that
appears at a relative mass of 45, one less than the parent ion, corresponds to the loss of
a Fig. 7.3.2 below shows a fragmentation path which
explains the pattern.

Figure 7.3.2: Possible fragmentation pattern produced when ethanol is bombarded with high
energy electrons
Note, for each fragmentation one product keeps the positive charge. Thus, if the CC bond
breaks in an ethanol molecule the two possible fragments areas shown in fig. 7.3.3. Remember,
only the species which are charged can be detected because electric and magnetic fields have
no effect on neutral fragments.

Figure7.3.3: Two possible fragments produced by the cleavage of the CC bond in

ethanol

In general, the fragment formed is the one with gives the most stable ion. Hence, the
CO bond breaks to give the C2H5+ ion instead of the OH+, resulting in a peak at 29 but
not at 17.
Mass charge

Possible group

Sample calculation
A molecule with an empirical formula CH2O has the simplified mass spectrum seen
below. Deduce the molecular formula and possible structure of the compound.

Answer
Empirical formula = CH2O; then, molecular formula = CnH2nOn
The molecular ion has a relative mass of 60.
Mr = n (12.01) + 2n (1.01 + n (16.00) = 30.3n
n = 60 30.03 = 2
molecular formula =
C2H4O2
From the spectrum the following peaks can be identified:
Peaks
15
(i.e. 60-45)
43
(i.e. 60-17)
45
(i.e. 60-15)

Reason(explanation)
presence of CH3+
loss of COOH from molecule
presence of C2H3O+
loss of OH from molecule
presence of COOH+
Loss of CH3 from molecule

Hence, the structure consistent with this fragmentation pattern is:

3

2. The mass spectra of two compounds are given below. One is propanone
(CH3COCH3) and the other is propanal (CH3CH2CHO). Identify the compound in each
case and explain the similarities and differences between the two spectra.

3.
The simplified mass spectrum of a compound with empirical formula C2H5 is shown
below.
(i)
Explain which ions give rise to the peaks shown.
(ii)
Deduce the molecular structure of the compound.