Module 2: Spectroscopy

Mass Spectroscopy

Process:
1) Vapourization by heated filament.
2) Atom/molecule bombarded by high energy electrons until
one of its electrons is removed. Cation forms ([M+] peak )
which may fragment due to the addition of energy from the
high-energy electrons.
3) Cations are accelerated through an electric field
4) Based on mass/charge ration fragments are deflected in
variable magnetic field.
5) Fragmented cations are detected and are reflected on an ion
detector screen where the current is proportional to the
abundance of each ion fragment deflected on the mass spectrum.

The abundance of each ion fragment is represented as a percentage of the most abundant(stable)
fragment- the base peak.

N.B The mass spectra of compounds are as unique as fingerprints. They are used in oil refineries for
comparison in the analysis of complex hydrocarbon mixtures.

Uses:

1) used in oil refineries for comparison in the analysis of complex hydrocarbon mixtures.

2) used in rockets to study the chemistry of outer space.

3) analysis of low concentration contaminants

4) drug testing of athlete’s

Applications:

1) Determining relative atomic mass

2) Determining relative molecular mass
3) Determining the number of carbon atoms in an organic molecule based on [m+1] peak
4) Identifying halogen compounds using [m+2] peak and [m+4] peak
5) To determine the position of reaction in a molecule by isotopic labeling.
Control:

a) Same Temperature
b) Same ionizing voltage
c) The same instrument

Figure 1 Base peak- largest peak

An [M+1] peak appears in the mass spectra of all

organic compounds because some of the molecules
contain the carbon-13 isotope.

Figure 2 [m+] (cation of organic compound) and [m+1]

peak (due to carbon-13 isotope)

Figure 3 [M+2]] peak is 1/3 the height of [M+] peak

 UV/Visible Spectroscopy

 A uv/vis spectrum measures the absorption of light in the ultraviolet and visible region of the
spectrum in the form of a plot of intensity of transmitted light against wavelength.

 The uv/vis spectra arise from the transitions between energy levels which differ in their
vibrational and rotational energies to higher electronic levels of slightly different energies when
a molecule absorbs a photon of energy (quanta).

 UV/Vis spectroscopy is carried out in a solution and solvent that absorb at different wavelength
as that of sample if possible.

 Some species will not absorb in the uv/vis region because the energy required for the electronic
transition lies outside of this region. Eg in the Xray region instead.

The possible electron jumps that light might cause are:

In each possible case, an electron is given a quanta of energy promote it from a full bonding orbital into
an empty anti-bonding orbital. Each jump takes energy from the light, and a big jump obviously needs
more energy than a small one.

Bonding molecular orbital- It is a high electron density between nuclei, which reduce the repulsion
between the nuclei and promote bonding.
Anti-bonding molecular orbital- It is a low electron density between both nuclei, which does little to
reduce the repulsion between the nuclei.

Electronic transitions possible in the N.B- the colour seen after absorption
uv/vis spectrum: in the uv-vis region is the
complementary colour of the one
 from pi bonding orbitals to pi anti-bonding orbitals; absorbed.
 from non-bonding orbitals to pi anti-bonding
orbitals; colour region wavelength (nm)
 From non-bonding orbitals to sigma anti-bonding
orbitals. violet 380 - 435

That means that in order to absorb light in the region from blue 435 - 500
200 - 800 nm (which is where the spectra are measured), the
cyan 500 - 520
molecule must contain either pi bonds or atoms with non-
bonding orbitals. Remember that a non-bonding orbital is a green 520 - 565
lone pair on, say, oxygen, nitrogen or a halogen.
yellow 565 - 590
Groups in a molecule which absorb light are known as
chromophores. orange 590 - 625

red 625 - 740

Uses of UV/Vis spectra:

1) For the identification of compounds
2) For finding the concentration of solutions eg iron in
iron tablets by plotting a calibration curve or using
Beer-Lambert’s Law.

Beer-Lambert’s Law Colours directly opposite each other on the

colour wheel are said to be complementary
colours. Blue and yellow are complementary
colours; red and cyan are complementary;
and so are green and magenta.

Mixing together two complementary colours

of light will give you white light.
Infrared Spectroscopy

 All organic compounds absorb in the infrared region of the electromagnetic spectrum.

 Absorption in the infrared region arises from transitions from different vibrational modes within
the same electronic level.

 Molecules vibrate as the bonds stretch and bend.

 The energy of vibrations are quantized.

A molecule must have a dipole moment to absorb in the IR region and the absorption of IR energy
must change the dipole moment. The symmetrical stretch does not change the dipole moment.

Compounds may be examined as solids, liquids or gases:

Solid-
Finely ground 1mg of sample with a drop of hydrocarbon to form mull; mull pressed between NaCl discs
and inserted into spectrometer.

Liquid-
Drop of liquid placed between NaCl discs , made from single crystals. Discs should not dissolve NaCl and
organic solvent must be free of water.
Solution-
Compound dissolved in tetrachloromethane or trichloromethane (neither dissolve strongly in IR region
). Solution placed in a cell made of NaCl and a similar cell, containing solvent only, is placed in the
reference beam.

Gases-
Gas placed in 10cm long cell in the path of the IR beam. End walls of cell made of NaCl which is
transparent to IR radiation.

USES OF IR SPEC:
1) Forensic science to identify the presence of certain substances
2) Monitoring air pollution
3) Following the course of a reaction eg reaction kinetics. .