1. Atomic Absorption

5. Where g = degeneracy

10. Lines are broadened by two effects:
Doppler
Collisional
Operating conditions for lamp are chosen so that the Doppler broadening in the lamp (low P, few collisions) is less than the Doppler and collisional broadening in the flame or furnace.

11. Atomic Absorption

12. Monochromator is used to
select one of the emitted
lines
Ideally, we want the selected emission line from the lamp to be narrower than the absorption spectrum

14. Absorption lines are narrow
The selected bandwidth of light from source must be narrower than chosen absorption line
If a monochromator was able to select a narrow enough bandwidth from the output of a deuterium lamp, the power of the light would be negligible
Therefore lamps that emit spectral lines are used

15. Hollow Cathode Lamp

17. HCL Inert gas is ionized by discharge Is accelerated to cathode
Causes some element to dislodge and form atomic cloud (sputtering)
Some are excited (in collisions with ions) and emit line spectra.
Usually lamps are for one element – but can be for as many as six.

18. Electrodeless Discharge Lamp

19. Electrodeless Discharge Lamp
Microwave excited discharge tubes
Intensities x greater than from HCL
Small amount of element or halide of an element in a small sealed tube containing a few torr of inert gas
Placed in microwave cavity (2450 MHz)
Argon is ionized, the ions are accelerated and excite the metal atoms
Less stable than HCL, but more intense.
Not available for all elements

20. High-resolution continuum source AAS: the better way to perform atomic absorption spectrometry

21. Single xenon arc lamp
Today, multiple hollow cathode lamps are no longer used.
With the use of a single xenon arc lamp, all the elements can be measured from  nm.
This takes AAS into a true multi-element technique with the analysis of 10 elements per minute.

22. CCD technology - For the first time in an AAS CCD chips are now available with 200 pixels which act as independent detectors.
Simultaneous background correction - Background is now measured simultaneously compared to sequential background on conventional AAS.
Better detection limits - Due to the high intensity of the Xenon Lamp there is better signal/noise ratio thus giving better detection limits. In some cases it is up to 10 times better than conventional AAS.

24. Sample There are a variety of different sampling methods: Flame
Furnace (electrothermal atomizer)
Arc, spark
ICP
Cold vapour atomization
Hydride generation

26. Flame Stable Safe Cheap to maintain High temperature
Reducing Atmosphere - many metals form stable oxides, not easily atomized just by flame temperatures

27. Flame Typical system – spray chamber and burner
Sample is aspirated into spray chamber using nebulizer (sucked in by Venturi effect)
Produces aerosol.
Aerosol strikes obstruction – spoiler – to break it into smaller drops
Only smallest drops proceed to flame
Larger drops go down drain

29. Sequence of Events in Flame
Evaporation of Solvent (leaving fine salt particles suspended in flame)
Loss of water of hydration
Vaporization of solid particles to free atoms (due to heat and chemical reaction)
Excitation
Ionization (not always desirable)

30. Nebulization Controls fraction of sample to reach flame
Drop size is governed by viscosity, surface tension, gas flow, density, design of nebulizer
Organic solvents have lower viscosity and lower surface tension than water ( x) They also allow preconcentration
But change flame conditions – not always so beneficial
Salt increases viscosity, decreasing efficiency
The smaller the drop, the more easily it is desolvated and vaporized

31. Ultrasonic breakup of drops
High frequency vibrations
Uniform and controllable drop size
BUT
Drops are larger and equipment more expensive

32. Desolvation Critical to number of free atoms
Usually occurs at base of flame
Solvent then water of crystallization
Depends on droplet size and solvent

33. Vaporization Atomization to free atoms
Ideally – want high temperature and long residence time (slow burn rate of the gases) - lots of time for atomization
Depends on nature of molecules and atoms
Al2O3 atomizes more slowly than NaCl particle of the same size
Important if analyzing mixtures – different conditions are needed for different atoms

34. Ionization Ions undergo different transitions than atoms
Want one or the other
Ions not desirable in flame method
In ICP, ions are the desired species
For alkali and alkaline earths, ions form above 2000K

35. Ionization Increases at low sample concentration
With increasing flame temperature
With decreasing ionization potential
Prevent by:
Low flame temperature
Excess of easily ionizable metal eg Li
Called a SUPPRESSOR
Eg: add lots of Li to solution to be analyzed for K

36. Premix (Laminar flow) Burner
Most common
Gases premixed before entering burner
Stable flame
Use long narrow flames – long path length for light absorption
Use at right angles for emission
Small (narrow) flame keeps atom concentration high

37. Width of slot depends on gases
Narrow slots prevent flame backing into mixing chamber and causing explosion
But must allow enough gas through to support rate of burning
Too narrow:
Cooling by adjacent air
Salt deposition clogs burner
Use different burners for different gases

38. Gases Gas mixtures with high-burning velocities are less safe
Also want long residence times
C2H2-N2O (220cm/s) is better than C2H2-O2 (1130 cm/s). They have similar flame temperatures.

40. Air-C2H2
Yellow
Colorless
Blue
C2H2-N2O
Red (CN., NH.)
Whitish-blue

42. Flame Atomizer Advantages
Convenient
Rapid
Suitable for all AA-determinable elements
Limitations
Limited Sensitivity
Large Sample Volume
Cannot handle some sample types

43. Sensitivity Limitation

44. Interferences
Spectral
Vaporization
Chemical

45. Spectral
Mg nm
Na nm
Not usually much of a problem – can change to another wavelength
Problem worse in emission because more lines – High T – lots of excitation
Choice of line dictates concentration range
able to be analyzed

47. Vaporization Interferences
When one component of a sample influences the rate of vaporization of the species of interest
Physical – changes matrix it vaporizes from
Chemical – changes the species to be vaporized

48. Chemical Vaporization Interferences
Metal oxides form
Metal ions form thermally stable complexes with anions
The effects usually occur during formation of the solid particle
CaPO4 formation – a well known example.
CaPO4 is harder to vaporize than Ca2+

49. CaPO4 - Interference Prevention
Put light path higher in flame to allow a longer residence time
Add releasing agent – La2+ or Sr2+ (added in excess) will preferentially combine with PO43- and leave Ca2+ free to be analyzed
Protective agent – add EDTA. Ca-EDTA complex is easily destroyed in flame
Glucose – burns easily and helps droplets shatter apart
Hotter flame – then need ionization suppressor