Overview of spectroscopy

• These are measurements based on light and other forms of

electromagnetic radiation.
• Spectroscopic analytical methods are based on measuring
the amount of radiation produced or absorbed by
molecular or atomic species of interest
• They are classified according to the region of the
electromagnetic spectrum involved in the measurement.
The regions include gamma–ray, X-ray, ultraviolet (UV),
visible (VIS), infrared (IR), microwave, and radio
frequency (RF).
Electromagnetic radiation
• Consists of waves with electrical and magnetic components
vibrating in particular directions
• does not require a medium and hence can travel in a vacuum.
• Is quantized. It is transmitted in discrete packets/particles of
energy called photons or quanta.
• Can be described as a wave with properties of wavelength,
frequency, velocity, and amplitude.
• Electromagnetic radiation has a dual nature (can be thought of
as a wave and a particle).
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 Properties of electromagnetic
radiation

Wavelength, Frequency, Amplitude, Velocity, Magnetic Field, Electric Field,

Wave number,
Speed of light equation
• Light photons travel at a velocity, c, of 2.99792 x 108 m
s-1 in a vacuum.
c = νλ = 3.00 x 108m s-1 = 3.00 x 1010 cm s-1
• The velocity of light in a vacuum is constant, hence only
the wavelength and frequency change.
• Photons can only travel at the speed stated above.
 Energy of light
• German physicist Max Planck deduced that the energy of a photon E and
the frequency of the electromagnetic radiation associated with it are related
via the following equation:

where h is a universal constant of nature called Planck’s constant with the

value 6.6262 × 10–34 J s.
Calculating energy
• An electron falling from an excited state, emits radiation
of wavelength 500 nm (1 m = 10-9 nm). Calculate the
energy emitted in kJ:
1. By one single electron (c = 3.0 x 108 m/s)
2. By one mole of these electrons (Avogadro’s constant =
6.02 x 1023)

• Calculate the
energy, per mole, of an electron transition
which emits radiation of frequency 2.12 x 1011 Hz.
 Problem Questions
Determine the frequency, wavelength, speed and energy in a
vacuum of each of the types of electromagnetic radiation
listed below:

a) Blue-green light; λ = 500 nm.

b) Heat rays emitted from hot asphalt pavement; v = 1.5 ×
1014 s–1
c) A gamma ray emitted with λ = 3.402 pm (10-12 m)
d) An FM radio transmission; v = 91.5 MHz.
Energy answers
a)

b)

c)

d)

‘a’ stands for atto = 1.0x10-18

 Quantization of energy levels in
atoms and molecules
Planck suggested that radiation (light, energy) can only
come in quantized packets that are of size hν.
There are two types of
energy that can exist in
atoms and molecules that
provide a source for EM
radiation:
•Energy in movement of the
electrons
•Energy in movement of
nuclei or the entire molecule
Non-quantization examples
Quantization of energy levels in
atoms
Types of molecular motion
 Vibrations of the water molecule

The energies of each of these vibrational motions

are also quantized.
 Spectroscopic measurements
• Depending on the energy levels within an analyte, it will
absorb energy from different regions of the electromagnetic
spectrum.
• IR spectroscopy – uses the infrared region of the spectrum to
excite vibrational movements in covalent bonds
• UV/VIS spectroscopy – uses the UV and Visible regions of
the spectrum to excite valence electrons to higher energy
levels.
 Dangers of exposure to high
energy wavelengths
• Energyrequired to break a single C—C (dividing the enthalpy by
avogadro’s constant)

= 5.78 × 10–19 J
The results show that:
• visible light has comparable energy to a C-C bond
• infrared and radio waves have far less energy per photon than a C-C bond
• and gamma rays have a lot more energy per photon than a C-C bond.
 Dangers of exposure to high
energy radiation
• Gamma-ray photons have enough energy to break open
about 100 000 chemical bonds and as a result cause
chemical changes.
• High densities of microwave radiation are known to
cause health problems such as burns, cataracts, nervous-
system damage, and sterility
• UV-B is of intermediate wavelength and is the type of
sun emission that causes sunburn and, over long periods
of exposure, skin cancer
Wavelength of various regions in
the electromagnetic spectrum
 Wavelength ranges and relative energies
of various regions in the EM spectrum
Region Wavelength/m Energy per photon/J

Gamma rays 10-12 10-13

X-ray 10-10 10-15
UV/VIS 10-6 – 10-8 10-17 – 10-19
Infrared 10-4 – 10-6 10-19 – 10-20
Radiofrequency 1 - 103 10-25 – 10-27
 Examples of use of electromagnetic
radiation
• Radio frequency - Car alarms, radios
• X-ray regions – X-ray machines, luggage scanning @ airports
• Far
Infrared - heat given off from objects, humans, night vision
googles utilize this region
• Near Infrared – remote controls
• UV Region – detect blood, semen, urine @ crime scenes, view
DNA, sterilization & disinfectant, tanning beds, stimulates
production of vitamin D.
• VisibleRegion – the blue region is used to cure/harden fillings,
light bulbs, projectors, the human eye
• Gamma rays – kill cancer cells, released when unstable atoms
decay
 Spectroscopic measurements
• The analyte is predominately in its lowest-energy or
ground state
• It is stimulated by applying energy
• The stimulus then causes some analyte species to undergo a
transition to a higher-energy or excited state.
• information about the analyte can be obtained by measuring
the electromagnetic radiation emitted as it returns to the
ground state OR
• by measuring the amount of electromagnetic radiation
absorbed as a result of excitation.
END OF TOPIC