Infrared

spectroscopy

In infrared spectroscopy a sample being analysed is irradiated (exposed to radiation) with
electromagnetic waves in the infrared region of the electromagnetic spectrum. The machine used is called
a spectrophotometer. It detects the intensity of the wavelengths of infrared radiation that passes through
the sample.

This analytical technique is particularly useful for organic chemists because all organic molecules absorb
radiation in the infrared range of wavelengths. The energy absorbed corresponds to changes in the
vibration of the bonds between atoms. The bonds can vibrate by stretching, bending and twisting. They
have a natural frequency at which they vibrate. If we irradiate the molecules with energy that corresponds
to this frequency, it stimulates larger vibrations and energy is absorbed. This is called the resonance
frequency of that vibration.

Each type of vibration will absorb characteristic wavelengths of infrared radiation. Scientists often express
these as the reciprocal of the wavelength, in a unit called wavenumbers (measured in cm−1).

Figure 18.7: The infrared spectrum of ethylamine, CH3CH2NH2. Note that the percentage absorbance and the
wavenumbers on the axes both get smaller in magnitude along each axis.

We cannot be too specific when quoting the characteristic absorption frequency of a bond: the nature of
the rest of the molecule shifts the energy absorbed in each particular molecule. However, we can say, for
example, that the amine group (─NH2) absorbs in the range 3300 to 3500 cm−1.

Therefore, we can identify the presence (or absence) of different functional groups from the absorbance
pattern on an infrared spectrum. Look at the infrared spectrum of ethylamine in Figure 18.7.

We can use the characteristic infrared spectrum of an unknown compound to identify it by ‘fingerprinting’
from a database of known spectra. Some characteristic absorption ranges of common bonds and the
functional groups containing the bonds are shown in Table 18.3.

Functional groups containing the Characteristic infrared absorption range (in wavenumbers) /
Bond bond cm−1

C─O hydroxy, ester 1040–1300

C═C aromatic compound, alkene 1500–1680

 C═O amide 1640–1690
carbonyl, carboxyl 1670–1740
ester 1710–1750

C≡N nitrile 2200–2250

C─H alkane 2850–2950

N─H amine, amide 3300–3500

O─H carboxyl 2500–3000

hydroxy 3200–3600

Table 18.3: Some characteristic infrared absorbance bands.

The values needed to answer questions will usually be given to you. You can see that absorption bands
overlap considerably. That is why we need to use a variety of techniques, such as NMR, infrared
spectroscopy and mass spectrometry, to work out the structure of a new organic compound .
As well as their wavenumber bands, particular absorbances have characteristic widths (broad or sharp
peaks)
and intensities
(strong or weak) on the infrared spectrum. For example, the presence of
hydrogen

bonding makes the absorbance
of
the O─H bonds
in alcohols
and carboxylic
acids
broad.
By contrast,
the
C═O bond in carbonyl groups has a strong,
sharp absorbance
peak.


Look at the infrared spectra of ethanol, ethanoic acid and ethyl ethanoate shown in Figures 18.8–18.10.

Using the data in Table 18.3, note the broad bands between 3200 and 3600 cm−1 in Figures 18.8 and 18.9
arising from the O─H
groups
involved in hydrogen
bonding
in
the alcohol
and in the carboxylic acid.
Contrast the width of these peaks the
with sharp peak
1710
between and 1750 cm−1 of the carbonyl
group
in the ester,
ethyl ethanoate,
in Figure 18.10.

Figure 18.8: The infrared spectrum of ethanol, CH3CH2OH.

Figure 18.9: The infrared spectrum of ethanoic acid, CH3COOH.

Figure 18.10: The infrared spectrum of ethyl ethanoate, CH3COOCH2CH3.

Question
7 Look at the two infrared spectra below:
Figure 18.2: Infrared spectra for Question 7.

a Which one of the infrared spectra is that of butanone and which one is of butan-2-ol?

b Explain your reasoning in part a.

Mass
spectrometry

A mass spectrometer (Figure 3.2) can be used to measure the mass of each isotope present in an element.
It also compares how much of each isotope is present: the relative abundance (relative isotopic

abundance). A simplified diagram of a mass spectrometer is shown in Figure 3.3. You will not be expected
to know the details of how a mass spectrometer works, but it is useful to understand how the results are

obtained.

Figure 3.2: A mass spectrometer is a large and complex instrument.

Figure 3.3: Simplified diagram of a mass spectrometer.

The atoms of the element in the vaporised sample are converted into ions. The stream of ions travels to a
detector after being deflected by a strong magnetic field. As the magnetic field is increased, the ions of
heavier and heavier isotopes move towards the detector. The detector is connected to a computer, which
displays the mass spectrum.
The mass spectrum produced shows the relative abundance (isotopic abundance) on the vertical axis and
the mass to ion charge ratio (m / e) on the horizontal axis. Figure 3.4 shows a typical mass spectrum for a
sample of lead. Table 3.1 shows how the data is interpreted.
Figure 3.4: The mass spectrum of a sample of lead.

For singly positively charged ions, the (m / e) values give the nucleon number of the isotopes detected. In
the case of lead, Table 3.1 shows that 52% of the lead is the isotope with an isotopic mass of 208. The rest
is lead-204 (2%), lead-206 (24%) and lead-207 (22%).

Isotopic mass Relative abundance / %

204 2

206 24

207 22

208 52

total 100

Table 3.1: The data from Figure 3.4.

Determination of Ar from mass spectra

IMPORTANT
You do not need to know the exact working of the mass spectrometer.

We can use the data obtained from a mass spectrometer to calculate the relative atomic mass of an
element very accurately. To calculate the relative atomic mass, we follow this method:

multiply each isotopic mass by its percentage abundance

add the figures together
divide by 100.

We can use this method to calculate the relative atomic mass of neon from its mass spectrum, shown in
Figure 3.5.
Figure 3.5: The mass spectrum of neon, Ne.

The mass spectrum of neon has three peaks: 20Ne (90.9%), 21Ne (0.3%) and 22Ne (8.8%).

Ar of neon = = 20.2

Note that this answer is given to 3 significant figures, which is consistent with the data given.

A high-resolution mass spectrometer can give very accurate relative isotopic masses. For example, 16O =
15.995 and 32S = 31.972. Because of this high level of precision, chemists can distinguish between
molecules such as SO2 and S2, which appear to have the same relative molecular mass.

Question
2 Look at the mass spectrum of germanium, Ge.

a Write isotopic formula for the heaviest isotope of germanium.

b Use the % abundance of each isotope to calculate the relative atomic mass of germanium.

Identification of an organic compound using mass spectrometry

The main use of mass spectrometry is in the identification of organic compounds. As in other forms of
spectroscopy, a substance can be identified by matching its spectrum against the spectra of known
substances stored in a database. This technique is known as ‘fingerprinting’.

The high energy electrons knock electrons from the molecules and break covalent bonds, fragmenting the
molecule. Figure 3.6 shows the mass spectrum produced by propanone, CH3COCH3.

Figure 3.6: The mass spectrum of propanone, CH3COCH3.

Figure 3.7: The mass spectrum of germanium, Ge.

IMPORTANT

A molecular ion, M+, is formed when one electron is removed from a molecule to form an ion with a
single positive charge e.g. CH4 → CH4+ + e−. Remember that no atoms are removed.

The peak at the highest mass-to-charge ratio is caused by the molecular ion (M+). This ion is formed by
the sample molecule with one electron knocked out. It gives us the relative molecular mass of the sample.
We can assume the ions detected carry a single positive charge, so the reading on the horizontal axis gives
us the mass. In the case of propanone, CH3COCH3, the molecular ion has a relative mass of 58.0. This
corresponds to CH3COCH3+, with a mass of (3 × 12.0) + (1 × 16.0) + (6 × 1.0).

We also get large peaks at 15 and 43 on the mass spectrum. These peaks are due to fragments that are
produced when propanone molecules are broken apart by the electron bombardment. Knowing the
structure of propanone, we should be able to identify the fragment responsible for each peak (Figure 3.8).

Figure 3.8: The fragmentation of propanone: +CH3 causes the peak at 15 and CH3CO+ causes the peak at 43.

IMPORTANT
Remember that fragmentation (breaking apart) of a compound in a mass spectrometer causes certain
bonds to break. You can deduce what the fragment is by adding up the atomic masses of carbon,
hydrogen and / or other atoms. So a fragment of m/e 15 is C + 3H = 12 + (3 × 1) which is +CH3 and a
fragment of m/e 43 could be +C3H7 or CH3CO+.

The electron bombardment has caused the C─C single bonds in the propanone molecules to break. This has
resulted in the fragments at m/e 15 and 43 that are observed in Figure 3.6. The breaking of single bonds,
such as C─C, C─O or C─N, is the most common cause of fragmentation.

IMPORTANT
These fragments are very common in mass spectra of organic compounds.

Mass Fragment

15 +CH
3
 28 +CO or C H +
2 4

29 CH3CH2+

43 C3H7+ or CH3CO+

Table 3.2: Common fragments in the mass spectra of organic compounds.

Question
3 Look at Figure 3.10, which shows the mass spectrum of ethanol, C2H5OH. A structural isomer of
ethanol is methoxymethane, an ether with the formula CH3OCH3.

a Predict the mass-to-charge ratio of a fragment that would appear on the mass spectrum of
methoxymethane but does not appear on ethanol’s mass spectrum.

b Give the formula of the ion responsible for the peak in your answer to part a.

c Look at the mass spectrum of ethanoic acid:

Figure 3.9: Mass spectrum of ethanoic acid.

Identify the fragments with mass-to-charge ratios of:

i 15

ii 43

iii 45

iv 60.

High-resolution mass spectra

High-resolution mass spectrometers can distinguish between ions that appear to have the same mass on a
low-resolution mass spectrum. Table 3.3 shows the accurate relative isotopic masses of the most common
atoms found in organic molecules.

Isotope Relative isotopic mass

1H 1.007 824 6

12C 12.000 000 0

14N 14.003 073 8

16O 15.994 914 1

Table 3.3: Accurate masses of isotopes.

These accurate isotopic masses allow us to measure the mass of the molecular ion so accurately that it can
only correspond to one possible molecular formula. For example, a molecular ion peak at 45 could be
caused by C2H7N or CH3NO. However, a high-resolution mass spectrum would show the C2H7N+ peak at
45.057846 and the CH3NO+ peak at 45.021462. We can, therefore, be sure which molecule is being
analysed.

Using the [M + 1] peak

There will always be a very small peak just beyond the molecular ion peak at a mass of [M + 1]. This is
caused by molecules in which one of the carbon atoms is the 13C isotope. This is shown in the mass
spectrum of ethanol in Figure 3.10.

Figure 3.10: The mass spectrum of ethanol, showing the [M + 1] peak.

In any organic compound there will be 1.10% carbon-13. We can use this fact to work out the number of
carbon atoms (n) in a molecule. We apply the equation:

WORKED EXAMPLE

1 An unknown compound has a molecular ion peak, M+, with a relative abundance of 54.5% and has
an [M + 1]+ peak with a relative abundance of 3.6%. How many carbon atoms does the unknown
compound contain?

Solution
Substituting the values of relative abundance into the equation:

we get:

n = × = 6.0

There are 6 carbon atoms in each molecule.

Question
4 A hydrocarbon has a molecular ion peak at a mass-to-charge ratio of 84 (relative abundance of 62.0%)
and an [M + 1] peak with a relative abundance of 4.1%.
How many carbon atoms are in the hydrocarbon?

Using [M + 2] and [M + 4] peaks

Note: Material relating to [M + 4] peaks is extension content. It is not part of the syllabus.

IMPORTANT
 We can tell whether there is chlorine or bromine in an organic compound by comparing the relative
heights of the M and [M + 2] peaks. If the peak heights are equal, there is one atom of bromine per
molecule. If the peak heights are in the ratio 3 [M] to 1 [M + 2], there is one atom of chlorine per
molecule.

If the sample compound contains chlorine or bromine atoms, we also get peaks beyond the molecular ion
peak because of isotopes of chlorine and bromine. Chlorine has two isotopes, 35Cl and 37Cl, as does
bromine, 79Br and 81Br. Table 3.4 shows the approximate percentage of each isotope in naturally occurring
samples.

Isotope Approximate %

35Cl 75

37Cl 25

79Br 50

81Br 50

Table 3.4: Naturally occurring isotopes of chlorine and bromine.

One Cl or Br atom per molecule

Imagine a sample of chloromethane, CH3Cl. We will have molecules of CH335Cl (75%) and molecules of
CH337Cl (25%). The molecular ion will be CH335Cl+, and two units beyond that on the mass spectrum will be
the peak for CH337Cl+. The peak for CH337Cl+ will be one-third the height of the molecular ion. This is the
[M + 2] peak.
In the mass spectrum of bromomethane, CH3Br, we will have two molecular ion peaks of approximately the
same height: one for CH379Br+ and the other for CH381Br+ (the [M + 2] peak).

You should look out for the relative heights mentioned here when interpreting mass spectra.

If the [M + 2] peak is one-third the height of the M peak, this suggests the presence of one chlorine
atom per molecule.
If the [M + 2] peak is the same as the height of the M peak, this suggests the presence of one bromine
atom per molecule.

An example of the [M + 2] peak is shown on the mass spectrum of chlorobenzene (Figure 3.11).

Two Cl or Br atoms per molecule

The situation is a little more complex with two chlorine atoms in a molecule, as there are three possibilities.
Considering dichloromethane, CH2Cl2, we have:
35
ClCH235Cl+    the M peak
35
ClCH237Cl+    the [M + 2] peak
37ClCH 35Cl+    the [M + 2] peak
2

37
ClCH237Cl+    the [M + 4] peak

The relative heights of the peaks must take into account the natural abundances: it works out as 9 : 6 : 1
for molecules with two Cl atoms.
Figure 3.11: The mass spectrum of chlorobenzene, showing the [M + 2] peak. (Note that there are also tiny [M + 1] and
[M + 3] peaks corresponding to 13C in the molecule.)

The M, [M + 2] and [M + 4] peaks also occur in dibromomethane but the relative heights of peaks are
easier to work out. Because the ratio 79Br : 81Br is 1 : 1, the M : [M + 2] : [M + 4] height ratio is 1 : 2 : 1.

Question

Note: Question 5 contains extension content as [M + 4] peaks are not included in the syllabus.

5 a List the ions responsible for the M, [M + 2] and [M + 4] peaks in a mass spectrum of
dibromomethane.

b What would be the mass-to-charge ratio and relative abundances of the major peaks with the
highest charge-to-mass ratios in the mass spectrum of chloroethane?

c How many peaks would you see beyond the molecular ion peak in 1,1-dibromoethane? What
would be their mass-to-charge ratios and abundances relative to the molecular ion? (Ignore peaks
due to 13C.)