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Dr Vicky Barnett
University Senior College
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Electromagnetic Radiation
Electric & magnetic fields are orthogonal to each other.
Electronic spectroscopy concerns interaction of the 6 electric field (E) with matter.
1012
108 Microwave
E = h
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E.g. X-ray radiation ( = 1018 Hz): 4.0 x 106 kJ/mol IR radiation ( = 1013 Hz): 39.9 kJ/mol (h = 6.626 x 10-34 J.s)
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Absorption of Light
When a molecule absorbs a photon, the energy of the molecule increases.
Ground state photon Excited state
Microwave radiation stimulates rotations Infrared radiation stimulates vibrations UV/VIS radiation stimulates electronic transitions 12 X-rays break chemical bonds and ionize
Absorption of Light
When light is absorbed by a sample, the radiant power P (energy per unit time per unit area) of the beam of light decreases. The energy absorbed may stimulate rotation, vibration or electronic transition depending on the wavelength of the incident light.
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Atomic Absorption
When atoms absorb light, the incoming energy excites an electron to a higher energy level. Electronic transitions are usually observed in the visible or ultraviolet regions of the electromagnetic spectrum.
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Emission lamp produces light frequencies unique to the element under investigation When focussed through the flame these frequencies are readily absorbed by the test element The excited atoms are unstable- energy is emitted in all directions hence the intensity of the focussed beam that hits the detector plate is diminished The degree of absorbance indicates the amount of element present
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I A b s= lo g Io
Abs = cb
= extinction coefficient
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0.8
0.6
0.4
0.2
Concentration (ppm)
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1.0
0.8
0.6
0.4
0.2
Concentration (ppm)
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Light Sources
Hollow-Cathode Lamps (most common). Lasers (more specialised). Hollow-cathode lamps can be used to detect one or several atomic species simultaneously. Lasers, while more sensitive, have the disadvantage that they can detect only one element at a time.
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Hollow-Cathode Lamps
Hollow-cathode lamps are a type of discharge lamp that produce narrow emission from atomic species. They get their name from the cupshaped cathode, which is made from the element(s) of interest.
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Hollow-Cathode Lamps
The electric discharge ionises rare gas (Ne or Ar usually) atoms, which in turn, are accelerated into the cathode and sputter metal atoms into the gas 31 phase.
Hollow-Cathode Lamps
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Hollow-Cathode Lamps
The gas-phase metal atoms collide with other atoms (or electrons) and are excited to higher energy levels. The excited atoms decay by emitting light. The emitted wavelengths are characteristic for each atom.
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Hollow-Cathode Lamps
M* collision-induced excitation M M* spontaneous emission M
M+e M + Ar*
M* M*
M*
M + h
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Hollow-Cathode Spectrum
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Atomisation
Atomic Absorption Spectroscopy (AAS) requires that the analyte atoms be in the gas phase. Vapourisation is usually performed by: Flames Furnaces Plasmas
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Flame Atomisation
Flame AAS can only analyse solutions. A slot-type burner is used to increase the absorption path length (recall Beer-Lambert Law). Solutions are aspirated with the gas flow into a nebulising/mixing chamber to form small droplets
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Flame Atomisation
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Flame Atomisation
Degree of atomisation is temperature dependent. Vary flame temperature by fuel/oxidant mixture.
Fuel Acetylene Acetylene Acetylene Hydrogen Hydrogen Cyanogen Oxidant Air Nitrous Oxide Oxygen Air Oxygen Oxygen Tem perat ure (K) 2,400 - 2,700 2,900 - 3,100 3,300 - 3,400 2,300 - 2,400 2,800 - 3,000 4,800
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Furnaces
Improved sensitivity over flame sources. (Hence) less sample is required. Generally, the same temp range as flames. More difficult to use, but with operator skill at the atomisation step, more precise measurements can be 40 obtained.
Furnaces
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Furnaces
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Detection
Photomultiplier Tube (PMT). pp 472-473 (Ch. 20) Harris
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Photomultiplier Tubes
Useful in low intensity applications. Few photons strike the photocathode. Electrons emitted and amplified by dynode chain. Many electrons strike the anode.
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