KAA 502 - Note 5 - Chapter 8 - Intro To Optical Spectrometric Methods 212

KAA 502 Techniques (methods)
Atomic Spectroscopy
 atomic absorption spectroscopy
 atomic emission spectroscopy
Introduction to Optical  atomic fluorescence spectroscopy
Atomic Spectrometry
(Dr. Lim Gin Keat)
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Atomic Spectra
 atoms of the analyte must first be formed, usually in
the form of an atomic vapor.
 Atomization - The process by which a sample is Energy level diagrams

converted to an atomic vapor.
Atomic emission spectra
 Atomizer - convert a sample to an atomic vapor. Atomic absorption spectra

Atomic fluorescence spectra
 flame atomizer
 electrothermal atomizer
Energy Level Diagrams for Atoms with One Valence Electron
Atomic spectra
 consist of discrete lines that arise from the transition

of electrons between energy levels (orbitals).
 Every atom has a unique energy level diagram and a
unique atomic spectrum.
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Na 15-Apr-22
Mg+ 6
o
Note the similarity in pattern of lines shown in blue but not in actual wavelength (A).
1
Energy Level Diagrams for Atoms with
Two Valence Electrons
•increasing number
of valence
electrons
•number of energy singlet excited state occurs when the two valence
levels increase electron spins are opposed to one another (unparallel or
paired).
•atomic spectra
more complex, esp •triplet excited state occurs when the two valence
transition metals. electron spins are in the same direction (parallel or
unpaired).
Atomic emission spectra
 Some transitions are “forbidden”.

 eg 3s  3p  4s will occur, but 3s  4s will not  Atoms are promoted into the excited state by some
occur. source of heat (flame or electrothermal)
 The spectrum is produced by the detection of photons
emitted by the sample as it relaxes back to the ground
 allowed transitions follow selection rules that permit
state.
prediction of transitions that will occur.
Atomic absorption spectra
 Resonance lines - Result from the relaxation of an

electron from an excited state to the ground state.  result from atomized sample absorbing photons of
 Nonresonance lines - Result from the relaxation of an radiation of the appropriate energy (wavelength).
electron from an excited state to another excited  Resonance absorption lines
state. (e.g. In the Na° spectrum the relaxation of an  most prevalent observed since few of the atoms
electron from 4s to 3p) are in the excited state. (e.g. 3s  4p in Na°)
2
Atomic line widths
Uncertainty principle
 Theoretically, atomic spectra should contain lines
corresponding to wavelength of the energy transitions
in the atom that have a line width of zero.  Lifetimes of transition states is finite 
 In reality, have a finite width uncertainties in transition times and line broadening
 Heisenberg’s Uncertainty Principle
 Sources of line broadening   t  1
 Uncertainty effect  - uncertainty in the frequency ( line width)
 Doppler effect t - lifetime of the excited state
 Pressure broadening (collisional)
  varies as a function of t
 Lifetime of ground state electron is long
 Narrow lines to reduce interference due to
overlapping spectrum  Excited states lifetime – 10-7 to 10-8 s
 Natural line width – 10-4 A (10-5 nm)
Doppler effect
  of radiation emitted/absorbed by atoms moving

will  if motion is towards transducer
  of radiation emitted/absorbed by atoms moving
will  if motion is away from transducer
 In the flame, line widths are 2 orders of magnitude
higher than natural line widths.
Pressure broadening Band and Continuum Spectra
 Collisions between absorbing/emitting species and  Produced when line spectra are generated
other atoms/ions in heated medium (eg flame,  Molecular bands
lamps)
 Continuum from thermal radiation from hot
 2 or 3 orders of magnitude greater than natural line particulate matter in atomization medium
width
 Potential source of interference
3
Atomization and sample introduction
methods
 Atomization – sample is converted into atomic

vapour.
 Goal of sample introduction system
 Transfer reproducible and representative portion of
sample into atomizer
 High efficiency
 No interference effects
 Dependent on chemical and physical state of analyte
and sample matrix
Continuous sample
introduction
methods
4
Concentric tube
Pneumatic nebulizers
Cross-flow nebulizer
Fritted disk
Babington
nebulizer
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KAA 502 - Note 5 - Chapter 8 - Intro To Optical Spectrometric Methods 212

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KAA 502 - Note 5 - Chapter 8 - Intro To Optical Spectrometric Methods 212

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KAA 502 Techniques (methods)

Introduction to Optical  atomic fluorescence spectroscopy

 Atomization - The process by which a sample is Energy level diagrams

 Atomizer - convert a sample to an atomic vapor. Atomic absorption spectra

Energy Level Diagrams for Atoms with One Valence Electron

 consist of discrete lines that arise from the transition

Do Not Share Without Permission 15-Apr-22 5 Do Not Share Without Permission

Atomic emission spectra

 Some transitions are “forbidden”.

Atomic absorption spectra

 Resonance lines - Result from the relaxation of an

  of radiation emitted/absorbed by atoms moving

Pressure broadening Band and Continuum Spectra

 Atomization – sample is converted into atomic

Do Not Share Without Permission 15-Apr-22 29

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