Spectroscopic

Methods of Analysis

CH117
Spectroscopy

• the study of the interaction of

matter and electromagnetic
radiation

• Radiation is transmitted, absorbed,

reflected, refracted or scattered
when it interacts with matter.
Electromagnetic Radiation

• energy that is transmitted at the

speed of light through oscillating
electric and magnetic fields

• consists of particles
called photons
travelling in a
wave-like pattern
Diagram of a Wave
Properties of a Wave
• Peak/Crest – highest point

• Trough – lowest point

• Wavelength – distance between two

successive crests or troughs

• Amplitude maximum amount of

displacement from rest to crest.
Properties of a Wave

• Frequency – the number of

complete waveforms passing a
given point in a second

- measured in Hertz, Hz

- or cycles per second, s-1

Relationship Between
Frequency and Wavelength
• Frequency and wavelength are inversely
proportional and related by the equation:
c = λν

where c = speed of light in a vacuum; 3.0 x 108 m/s

λ (lambda) = wavelength in meters

ν (nu) = frequency in Hertz or s-1

Useful Conversions

• 1 cm = 10-2 meter

• 1 nm = 10-9 meter

• 1 Ångström (Å) = 10-10 meter

 Planck’s Equation
• shows that the energy of the photon is directly
proportional to the frequency of the radiation
E = hv
• Where E = energy of a photon (in Joules, J)

• h = Planck’s constant (6.626 x 10-34Joule seconds,

Js)

ν (nu) = frequency in Hertz or s-1

The Electromagnetic
Spectrum
The Electromagnetic
Spectrum
Exposure

• Electromagnetic radiation is used

on a daily basis as radio-waves in
televisions and cell phones,
microwaves in satellites and
microwave ovens, infrared in
toaster ovens and night-vision, and
X-rays in medical imaging.
• Exposure to high energy
wavelengths are dangerous to
humans.

• X-rays have great penetrating

power and can damage living
tissue resulting in birth defects and
cancer.
• Large doses of UV radiation can cause
skin cancer and damage the retina of
the eye.

• Exposure to very high levels of low

energy radiation can also be harmful
due to the ability of radio frequency
energy to heat biological tissues rapidly
(microwaves)
• The health effects of low levels
of exposure to low energy
radiation such as radio
frequency energy used in cell
phones over prolonged periods
of time is as yet unknown.
Atomic Spectroscopy

Atomic spectroscopy is used mainly

to determine the concentration of
metals in samples of air, water and
solids regardless of how the atoms
are combined.
Energy Changes Associated
with Electronic Transitions
• Electrons normally exist in the
ground state.

• When it absorbs a photon with the

right amount of energy (specific
wavelength) to transition to a
higher energy state, it does so.
Energy Changes Associated
with Electronic Transitions
• It is, however, unstable in this excited
state and quickly returns to ground
state (relaxation) releasing a
photon/light as it does so.

• The energy of the photon determines

the wavelength of the light emitted.
• The wavelengths of the light
emitted and absorbed during the
transitions from one energy level
to another usually fall within the
UV-visible region.
 Atomic Absorption
Spectroscopy
• The absorption of an element
corresponds to specific wavelengths
and appear as dark lines on the
absorption spectrum.

• The degree of absorption depends on

the concentration of the metal being
analyzed.
Atomic Absorption
Spectrophotometer
• An atomic absorption spectrophotometer is an
instrument used to analyze the concentration
of metals in solution.

• The sample is introduced into the spectrum as

aqueous ions.

• The solution is suctioned into a nebulizer where

it is mixed with an oxidant (air or nitrous oxide)
and a gaseous fuel to convert it into a fine mist.
• The mist is suctioned into the atomizer
which is a low temperature flame that
sits in the path of a light source.

• The atomizer converts atoms and

molecules into gaseous ions in the
ground state before it interacts with
the light source.
• As the sample is ignited by the
flame, the solvent evaporates and
the gaseous elements are excited by
the light passing through the flame.

• The amount of light absorbed is

proportional to the amount of atoms
in the ground state in the flame.
• The light is usually a hollow
cathode lamp of the element being
measured.

• Eg. A sodium lamp is used to

measure sodium concentration.
• The light then passes through a
monochromator that filters out the
unwanted light and minimizes
interferences.

• The detector then converts the

light into an absorbance and gives
a readout.
Atomic Absorption
Spectrophotometer
Double-Beam
Spectrophotometer
• In a double beam
spectrophotometer, a beam
splitter divides the light into two
equal beams.

• One passes through the sample

and the other passes through the
reference cell.
• The detector compared the
intensities of the sample and the
reference beam.
Double Beam Atomic Absorption
Spectrophotometer
Beam Splitter
Atomic Emission
Spectroscopy
• Analyzing a sample by emission
spectroscopy is similar to that of
absorption spectroscopy analysis.

• A higher temperature energy source is

used to provide enough energy to
promote the atoms to the higher energy
levels.
• So the hollow cathode lamp and the
beam splitter are not necessary.

• Since all the atoms in a sample are

excited at the same time, they can
be detected simultaneously, which
is an advantage over absorption
spectroscopy.
AES experiment set-up
Atomic emission spectrometer
Comparing Atomic Absorption
and Emission Spectroscopy
Absorption Emission
 Calibration Curves
• As sensitivity varies from instrument
to instrument, each instrument must
first be calibrated using a set of
standards and a blank to produce a
calibration curve

• Common units of concentration =

ppm or mg/dm3
Primary Stock

• the first and most concentrated

solution made

• diluted to produce the other

standards
 References
• www.anachem.umu.se/jumpstation.htm
• www.anachem.umu.se/cgi/jumpstation.exe?
AtomicSpectroscopy
• www.anachem.umu.se/cgi/jumpstation.exe?
OpticalMolecularSpectroscopy
• www.minyos.its.rmit.edu.au/~rcmfa/mstheory.html
• http://science.widener.edu/sub/ftir/intro_it.html
• http://www.s-a-s.org/
• http://www.chemsw.com
• http://www.scimedia.com/chem-ed/spec/atomic/aa.htm
• http://nercdg.org
• http://www.analyticon.com
• www.lcgmag.com/
• www.lcms.com/
• www.dq.fct.unl.pt/QOF/Chroma.html
• www-ssg.chem.utas.edu.au/
 References (Cont’d.)
• www.yahoo.com/science/chemistry/chromatography/
• www.onlinegc.com
• http://www.aurora-instr.com
• http://www.chem.ufl.edu/~itl/3417_s98/spectroscopy/
aes.htm
• http://www.rohan.sdsu.edu/staff/drjackm/chemistry/
chemlink/analytic/analyt1.html
• http://www.cofc.edu/~deavorj/521/jpd521.htm
• http://www.scimedia.com/chem-ed/spec/atomic/aes.htm
• http://elchem.kaist.ac.kr/vt/chem-ed/spec/atomic/aes.htm
• http://www.chemistry.adelaide.edu.au/external/soc-rel/
content/icp.htm
• http://employees.oneonta.edu/schaumjc/chm361/iron.doc