Atomic Absorption

Spectrophotometry (AAS)

Chemical Industries Division

Mahatma Gandhi Institute for Rural Industrialization
Maganwadi, Wardha- 442001
Types of Atomic Spectrometry
A class of spectroscopic methods in which the species examined in the
spectrometer are in the form of ATOMS ( not molecules or ions as in solution
Spectrophotometry & spectrofluorimetry)

Three important methods based on spectroscopy of atomic species are:

Flame Emission Photometry (FEP)

Atomic Absorption Spectrophotometry (AAS)
Inductively Coupled Plasma Atomic Emission Spectrometry (ICPAES )
Atomic Absorption
Spectrophotometry (AAS)
Flame photometry has limitation in determining limited no of elements like Na + ,
K + , ca ++ etc

In atomic absorption spectroscopy measurement is made of the radiation

absorbed by the non excited atoms in the vapor state.

In emission spectroscopy, measurement is made of energy emitted when atoms

in the excited state return to the ground state
 BASIC PRINCIPLE

ATOMIC ABSORPTION SPECTROSCOPY (AAS) is an

analytical technique that measures the concentrations of

elements. It makes use of the absorption of light

by these elements in order to measure their

concentration .
 - Atomic-absorption spectroscopy quantifies the
absorption of ground state atoms in the
gaseous state .
- The atoms absorb ultraviolet or visible light
and make transitions to higher electronic
energy levels . The analyte concentration is
determined from the amount of absorption.
- Concentration measurements are usually
determined from a working curve after
calibrating the instrument with standards of
known concentration.

- Atomic absorption is a very common

technique for detecting metals and
metalloids in environmental samples.
Advantages of AA
Determination of 68 metals

Ability to make ppb determinations on major components of a sample

Precision of measurements by flame are better than 1% rsd.

AA analysis is subject to little interference.

Most interference that occurs have been well studied and documented.

Sample preparation is simple (often involving only dissolution in an acid)

Instrument easy to tune and operate

Atomic absorption spectroscopy is a quantitative method of analysis that is

applicable to many metals and a few nonmetals.

The signal from the detector is transferred to the computer, and the output
registers on the monitor in a manner specified by the user.
Relationship Between Atomic Absorption and
Flame Emission Spectroscopy
Flame Emission ->
it measures the radiation emitted by the excited atoms that is related to concentration.

Atomic Absorption ->

it measures the radiation absorbed by the unexcited atoms that are determined.

Atomic absorption depends only upon the number of unexcited atoms, the absorption
intensity is not directly affected by the temperature of the flame.

The flame emission intensity in contrast, being dependent upon the number of excited
atoms, is greatly influenced by temperature variations.

An atomic absorption spectrophotometer consists of a light source, a sample

compartment and a detector.

The source of light is a lamp whose cathode is composed of the element being measured.

Each element requires a different lamp.

Atomic Absorption Spectrometry (AAS)
Light source
The light source is usually a hollow-cathode lamp of the element that is being
measured.

Lasers are also used in research instruments. Since lasers are intense enough to excite
atoms to higher energy levels, they allow AAS and atomic fluorescence measurements
in a single instrument. The disadvantage of these narrow-band light sources is that
only one element is measurable at a time.
Hollow Cathod
Lamps (HCL):
The cathode is coated
with the metal of interest.
Inert filler gas (Ne or Ar) is
ionized by an electric
current and these ions are
then attracted to the
cathode. The ions
bombard the cathode and
excite the metal ions
coated on it. This
excitation of the metal
produces the emission of
EMR with wavelengths
characteristic of the
analyte.
Hollow Cathode Lamps (HCL)
Hollow-cathode lamps are a type of discharge lamp that produce narrow
emission from atomic species.

They get their name from the cup-shaped cathode, which is made from the
element of interest.

The electric discharge ionizes rare gas atoms, which are accelerated into the
cathode and sputter metal atoms into the gas phase. Collisions with gas atoms
or electrons excite the metal atoms to higher energy levels, which decay to
lower levels by emitting light. Hollow cathode lamps are available from several
manufacturers either as single or multiple elements lamps.
 Electrodeless Discharge Lamps
(EDLs)
For most elements, the hollow cathode lamp is a source for atomic
absorption. The primary cases involve the more volatile
elements, where low intensity and short lamp life are a problem.

The atomic absorption determination of these elements can often be

dramatically improved with the use of brighter, more stable
sources such as the "electrodeless discharge lamp."

Figure 7 shows the design of electrodeless discharge lamp (EDL).

The bulb is placed inside a small, self-contained RF generator

or"driver." When power is applied to the driver, an RF field is
created. The coupled energy will vaporize and excite the atoms
inside the bulb, causing them to emit their characteristic
spectrum.

Electrodeless discharge lamps are typically much more intense and, in

some cases, more sensitive than comparable hollow cathode lamps.
They therefore offer the analytical advantages of better precision and
lower detection limits where an analysis is intensity-limited.
Atomizer
AAS requires that the analyte atoms be in the gas phase. Ions or atoms in a sample
must undergo desolvation and vaporization in a high-temperature source such as a
flame or graphite furnace.

Flame AAS can only analyze solutions, while graphite furnace AA can accept
solutions, slurries, or solid samples.

Flame AAS uses a slot type burner to increase the path length, and therefore to
increase the total absorbance. Sample solutions are usually aspirated with the gas
flow into a nebulizing/mixing chamber to form small droplets before entering the
flame.
Basic
Principle
The technique of flame atomic
absorption spectroscopy (FAAS)
requires a liquid sample to be
aspirated, aerosolized, and
mixed with combustible gases,
such as acetylene and air or
acetylene and nitrous oxide.
The mixture is ignited in a flame
whose temperature ranges from
2100 to 2800 O C. During
combustion, atoms of the
element of interest in the
sample are reduced to free,
unexcited ground state atoms,
which absorb light at
characteristic wavelengths
AAS Nebulization
Chamber A solution of the sample was sprayed as an
aerosol through a nebulizer into a flame.

The nebulizer functions because the high velocity of

the combustion gases of the fuel and oxidant rushing
past a small orifice draws the liquid into the flow as
small droplets.

A simple burner head and nebulizer chamber are

shown at the right. The design of the nebulizer is to
limit the size of the atomized sample or droplets
introduced to the flame to a very small size (~5-10
mm). Droplets larger than this are stopped by baffles
or spoilers and end up flowing to waste.
The variables that control the size of
droplets

• Difference in the velocity gas and the liquid

• The density of the liquid,
• The viscosity of the liquid, and
• The volume flow rates of both the gas and the
liquid.
Types of flame
Different flames can be achieved using different mixtures of gases, depending on
the desired temperature and burning velocity.

Some elements can only be converted to atoms at high temperatures. Even at high
temperatures, if excess oxygen is present, some metals form oxides that do not
redissociate into atoms.

To inhibit their formation, conditions of the flame may be modified to achieve a

reducing, nonoxidizing flame.
Characteristics of different flames
Source
Max. flame speed (cm/s) Max. temp. ( o C)
Atomic Absorption Methods Other
Than Flame
Electrothermal atomisation : This type of atomisation requires a graphite furnace,
where after thermal pre-treatment the sample is rapidly atomized. To maintain a dense
fraction of free ground state elements in the optical path, an inert gas atmosphere is
used. Since the dilution and expansion effects of flame cells are avoided, and the atoms
have a longer residence time in the optical path, a higher peak concentration of atoms
is obtained.

Carbon rod analyser: This device can be used to convert a powdered sample into atomic
vapour. A current is applied to a very thin, heated carbon rod that contains the solid
sample in order to vaporise it.

Tantalum boat analyser: This is another technique that produces an atomic vapour from
a solid sample. A Tantalum boat is electrically heated in a manner similar to the carbon
rod system, within an inert atmosphere
Graphite furnace
The graphite furnace has several advantages over a flame.

It is a much more efficient atomizer than a flame

It can directly accept very small absolute quantities of sample.

It also provides a reducing environment for easily oxidized elements.

Samples are placed directly in the graphite furnace and the furnace is electrically
heated in several steps to dry the sample, ash organic matter, and vaporize the analyte
atoms.
Three types of high-temperature
plasmas
The direct current plasma (DCP).

The microwave induced plasma (MIP).

Inductively coupled plasma (ICP).( it is the most important of these plasmas)

The Direct Current Plasma
Technique
The direct current plasma is created by the electronic release of the two electrodes. The
samples are placed on an electrode. In the technique solid samples are placed near the
discharge to encourage the emission of the sample by the converted gas atoms.
Light separation and detection
AAS use monochromators and detectors for uv and visible light.

The main purpose of the monochromator is to isolate the absorption line from
background light due to interferences. Simple dedicated AAS instruments often replace
the monochromator with a bandpass interference filter.

Photomultiplier tubes are the most common detectors for AAS

Applications of AAS
Determination of 68 metal, only limitation on type of sample is hat it must be
capable of giving solution.

Metallurgical and inorganic analysis for determination of alloys as Co, Cr, Mg, Mn,
Pb, and Zn.

Analysis of Ores eg. Ag, Co, Cu, Fe, etc

Biochemical Analysis of various element or determination of Fe level in blood.

Pollution analysis

Agriculture industry, Analysis of Wines, Oils, Petrochemicals, Pharmaceuticals etc.

Pharmaceutical application of AAS
For analysis of Ca in calcium gluconate injection.

Analysis of ORS for Na, K, ca

Analysis of Zn in Zinc Insulin prep.

Analysis of Fe in Haematonics

Analysis of co in radiopharmaceuticals

Analysis of Zn in dusting powders