the sample is nebulized by a flow of gaseous oxidant, mixed with a gaseous fuel, and carried into a flame. A complex set of interconnected processes occur; desolvation-in which solvent is removed to produce solid molecular aerosol, Volatilization- to gaseous species Dissociation-conversion to atomic gas Also, excitation, ionization, molecular side reactions (fuel + oxidant). Atomization, thus, is the most critical step
Types of Flames- a variety of
oxidants and fuels are available. Temperature ranges from 1700 to 2400C with air as the oxidant (good for easily decomposed samples); for refractory materials O2 and N2O are used as oxidant (2500-3100C) Burning velocity: gas flow rate should match with BV (stable). If less, the flame propagates back into the burner (flashback); if more, it blows of the burner. Flame Structure: three zonesprimary combustion (very short; seldom used), interzonal (long region; widely used), and secondary combustion (the products of the inner core are converted to stable molecular oxide and dispersed to the surroundings).
Termperature Profiles for Natural
gas-air flame
Fuel
oxidant
Natural gas Natural gas Hydrogen Hydrogen Acetylene Acetylene Acetylene
be used for AAS, AFS, and AES measurements. A typical one shown in the figure is laminar flow burner. It employs a concentric tube nebulizer. The aerosol is formed by the flow of oxidant, and mixed with fuel; then it passes through a series of baffles that allows finest droplets to enter the slotted burner the length of the flame here is 5-10 cm (long path length; provides greater sensitivity)
Electrothermal Atomizers: used in
AAS and AFS measurements; sample is placed in a graphite boat or cup; heating is done via electric current in several steps; AAS and AFS measurements are done in the region above the boat. Graphite tube is open to both ends and has a hole in the middle for sample placement. It fits into a pair of graphite electrodes.Two inert gas streams are supplied; one to prevent outside air to enter the atomizer (prevent incineration) and and another to carry the atomized sample through the tube. Glow discharge, hydride formation, cold-vapor atomization (for Hg)
Bandwidths for atomic absorption are
very small (0.002 to 0.005 nm). Much less than the traditional bandwidth of a of high-quality monochromators (1 nm) And high quality filters (5 10 nm)
Radiation sources used in AAS: line sources are required, e.g., Na
vapor lamp at 5896 . Hollow Cathode Lamp-consists of tungsten (W) anode and a cylindrical metal cathode sealed in a glass tube that is filled with
Ne or Ar at 1-5 torr pressure.
High potentials leads to greater intensities, but Doppler broadening and self-absorption by the greater number of unexcited atoms thus produced are two problems. Downside - Separate lamp for each element or, a cathode of a mixture of several metals for multi-element analysis.
Electrodeless Discharge Lamp: consists
of a sealed quartz tube that contains a few torr of an inert gas, Ar, and a small quantity of the metal (or its salt) whose spectrum is being determined. The lamp contains no electrode, but discharge is created by an intense field of radio-frequency or microwave radiation. This ionizes Ar into Ar+ ions, which are accelerated by the high frequency component of the field. The high-energy Ar+ ions then excite the atoms of the metal whose spectrum is sought. Greater intensities, but less reliable than HCLs.