GREETINGS

Atomic absorption

Types of atomic
spectroscopy:

• emission from a thermally

populated excited state

• absorption of sharp lines

from hollow cathode lamp

• fluorescence following
absorption of laser radiation
An important difference between atomic and molecular spectroscopy is the width
of absorption or emission bands.

Absorption and emission spectra of liquids and solids typically have bandwidths of
10 to 100 nm,.

In contrast, spectra of gaseous atoms consist of sharp lines with widths of 0.001
nm
Atomic absorption spectrophotometer is used to measure concentration of trace
metals by detecting absorption of electromagnetic radiation by atoms rather than by
molecules.
Atomic emission spectroscopy first used and the underlying principles were
established in the 2nd half of the 19th century by Robert Wilhelm Bunsen and
Gustav Robert Kirchhoff, both professors at the University of Heidelberg, Germany

Modern form of AAS was developed in 1950s by a team of Australian chemists led
by Sir Alan Walsh at the Commonwealth Scientific and Industrial Research
Organisation (CSIRO), Division of Chemical Physics, in Melbourne, Australia

First commercial use in 1959

Atomic Absorption Spectroscopy provides cost-effective viable solutions for the

analysis of trace amounts of metals in the entire range of natural and manmade
materials such as Geological samples, Environmental samples, Biological
Specimens, Agricultural produce and soils, Pharmaceuticals, Foods and Drinking
62 elements
can be
detected by
AAS
Principle of Atomic Absorption Spectrophotometry
It uses the principle that free atoms generated in an atomizer can absorb radiation
at a specific frequency

Atoms absorb light in the ground state and make transition to higher energy levels.

The absorption by atoms in ground state is measured using atomic absorption

spectrometry
Basic Concepts
Metallic atom is dissociated from its chemical bond in the flame

It is in ground state (neutral atom). It can absorb radiation at a very narrow

bandwidth

Hollow cathode lamp with cathode made of material to be analysed is used to

produce wavelength of light specific for atom

Light from cathode lamp on entering the flame some of it is absorbed from the
ground state atom resulting in net decrease of intensity of beam. This process is
called as atomic absorption.
Instrumentation
Components
Hollow Cathode Lamp is made of metal of the substance to be analysed

In some cases an alloy is Hollow cathode lamp contains argon or neon at a

pressure of few mm of Hg

Argon filled lamp produces blue to purple glow

Neon filled lamp produces reddish orange glow

Quartz or specialised glass made that allows transmission of proper wavelength is

used as window

Current is applied to the cathode and metal atoms collide with neon or argon gas .
They loose their energy on collision and emit their characteristic radiation.
In an ideal interference free system only the same sample metal atoms absorb
light from cathode when it passes through the flame.

Light originating from the Cathode Lamp is pulsed while that from flame is
continuous

Detector detects all light but amplifier is tuned to pulsed signals and can subtract
the background light helping to discriminate between flame background emission
and sample atomic absorption
Nebulisation
Sample solution is drawn into the pneumatic nebulizer by the rapid flow of oxidant
(usually air) past the tip of the sample capillary. Liquid breaks into a fine mist as it
leaves the capillary. The spray is directed against a glass bead, upon which the
droplets break into smaller particles. The formation of small droplets is termed
nebulization.

Excess liquid collects at the bottom of the spray chamber and flows out to a drain.
Aerosol reaching the flame contains only about 5% of the initial sample.
 Premix burner

The sample is aspirated volatilise and burned to form atoms of metal in the gas
phase.

Gases are mixed and sample is atomised before it is burned

The advantage of this laminar flow premix burner is that large droplets go to waste
while the fine mist enters the flame.
Most flame
spectrometers
use a premix
burner, such as
that in Figure, in
which
fuel,oxidant, and
sample are mixed
before
introduction into
the flame.
Atomiser
Atomisation is separation of particles and breaking molecules into atoms.

it is important to convert an analyte in solid, liquid or solution form to a free

gaseous atom

This is done by exposing analyte to high temperature of flame or graphite furnace

 Flames
In atomic spectroscopy, analyte is atomized in a flame, an electrically heated
furnace, or a plasma. Flames were used for decades, but they have been replaced
by the (inductively coupled plasma) and the graphite furnace.

Sample solution is drawn into the pneumatic nebulizer by the rapid flow of oxidant
(usually air) past the tip of the sample capillary. Liquid breaks into a fine mist as it
leaves the capillary. The spray is directed against a glass bead, upon which the
droplets break into smaller particles. The formation of small droplets is termed
nebulization.

Excess liquid collects at the bottom of the spray chamber and flows out to a drain.
Aerosol reaching the flame contains only about 5% of the initial sample.
 Furnaces
Furnaces: An electrically heated graphite furnace is more sensitive than a flame and
requires less sample. From 1 to 100 mL of sample are injected into the furnace tube
through the hole at the center.

n non flame AA (carbon rod or graphite furnace) sample is placed in a depression on

a carbone rod in an enclosed chamber

Stripes of tantalum or platinum metal are used as sample cups

Temperature of rod is raised in steps to dry, char (remove organic material) and
finally atomizes the sample into gas phase.

This technique is more sensitive and permits determination of trace metals in small
samples

Zeeman correction is used with flameless AA

Monochromators
It is used to separate out all of the thousands of lines

It is used to select wavelength absorbed by the sample and to exclude other

wavelengths

This can be done by

Prism

Diffraction Grating
Detectors
It is a photomultiplier tube whose function is to convert light signal into an electrical
signal proportional to the intensity

Amplifiers are used for processing of signal

Background Correction Method
Background correction is required to distinguish analuyte signal from absorption,
emission and optical scattering of the sample matrix, the flame, plasma or a
graphite furnace.

It can be done by:

Electrical modulation or On/Off of light source aka beam chopper method

Deuterium lamp background correction

Zeeman effect
Chopper open: Flame + Cathode lamp
light reaches detector

Chopper closed: Only flame signal

reaches detector

Background scattering not solved by

this method
Deuterium lamp background correction
Deuterium lamp background correction, broad emission from a D2 lamp is passed
through the flame in alternation with that from the hollow cathode.

Analyte atomic transitions absorb a negligible fraction of D2 radiation

Light from the hollow-cathode lamp is absorbed by analyte and absorbed and
scattered by background.

Light from the D2 lamp is absorbed and scattered only by background.

The difference between absorbance measured with the hollow-cathode lamp and
absorbance measured with the D2 lamp is the absorbance of analyte.
Zeeman effect
When a magnetic field is applied parallel to the light path through a furnace, the
absorption (or emission) line of analyte atoms is split into three components. Two
are shifted to slightly lower and higher wavelengths and one component is
unshifted.

Unshifted component does not have the correct electromagnetic polarization to

absorb light traveling parallel to the magnetic field and is therefore “invisible.”

Strong magnetic field is pulsed on and off. Sample and background are observed
when the field is off. Background alone is observed when the field is on. The
difference is the corrected signal.
Advantage of Zeeman
background correction is that it
operates at the analytical
wavelength. In contrast, D2
background correction is made
over a broad band
Interference in Atomic absorption Spectometry

Interference is any effect that changes the signal while analyte concentration
remains unchanged. It is of two types: Spectral and non spectral

Spectral Interference:

It is absorption by other closely absorbing atomic species, absorption by

molecular species and background emission (which can be filtered)

Absorption by molecular species are particularly problematic in lower atomising

temperature
Non spectral interference
It can be nonspecific or specific

Nonspecific: It affects nebulisation by altering viscosity, surface tension or density

of analyte solution

Solute volatilisation : Contaminant forms non volatile species with the analyte

Phosphate interferes with the determination of Ca which is resolved by addition of

Lanthanum /Strontium
Enhancement effects are also observed, in which the addition of contaminants
increases the volatilization efficiency. Eg aluminum, which normally forms
nonvolatile oxides, but in the presence of hydrofluoric acid forms more volatile
aluminum fluoride.

.Dissociation interferences affect the degree of dissociation of the analyte.

Analytes that form oxides or hydroxides are susceptible to dissociation
interferences.

Ionization interference occurs when the presence of an easily ionized element,

such as potassium, affects the degree of ionization of the analyte, which leads to
changes in the analyte signal. It is controlled by adding a relatively high
concentration of an element that is easily ionized to maintain a more consistent
concentration of ions in the flame and to suppress ionization of the analyte.
Excitation interference, the analyte atoms are excited in the atomizer, with
subsequent emission at the absorption wavelength. This type of interference is
more pronounced at higher temperature
ICP MS vs AAS
Inductively coupled plasma mass spectrophotometry can also be used for Metal
analysis and has begun to replace Atomic absorption spectrophotometry

ICP MS can measure multiple metals simultaneously and with greater sensitivity

AAS advantage is in overall cost and ease of use

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