Chapter 9-AAS and AFS

Flame Atomization- a solution of

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

air
oxygen
air
oxygen
air
oxygen
N2O

temp.
1700-1900
2700-2800
2000-2100
2500-2700
2100-2400
3050-3150
2600-2800

Flame Absorption Profile for 3

elements

 Flame atomizers: can

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.

Single Beam Atomic

Absporption

Double Beam Atomic

Absporption

Continuum source Background Correction