Department of Chemical and

Environmental Engineering

J12ANM Analytical Measurement

Lecture 1

Atomic Absorption
Spectroscopy

Outline

Atomic structure and spectroscopy

Principles of operation in Atomic Absorption

Spectroscopy

What happens when

Energy is provided to an atom?

3 possible transitions:
1.

Absorption

2.

Emission

3.

Where optical radiation is absorbed by the electrons to excite them.

Where thermal or electrical radiation is absorbed by the electrons to
excite them, and they proceed to emit the radiation to return to the
ground state.

Fluorescence

Where optical radiation is absorbed by the electrons to excite them, and

then they go on to emit some of this radiation.
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Optical Spectroscopy Components

Atomic Absorption

Fluorescence and
scattering
spectroscopy

Emission
Spectroscopy
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Atomic Spectrometry

Applicable to most gas/liquid phase elements over a

wide range of concentrations

sensitivity in ppt region possible.

Involves detecting, measuring, and analysing radiation

that is either absorbed or emitted from the atoms or ions
of the element.

The sample is decomposed by intense heat into hot

gases consisting of free atoms and ions of the element.
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Ground State of an Atom (Sodium)

Excitation

Excited State of an Atom (Sodium)

Emission

Excitation and Emission

Excitation

Emission
~ 3

Excited
States

~ 2

Excited
States

~ 1
Ground State

Ground State
Light Energy

E = h

or

E = hc/
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Spectrophotometric Techniques

Techniques exploiting properties of the

electromagnetic spectrum

Rabbits Mate In Very Unusual Expensive Gardens

Long Wavelength

Low Energy

Short Wavelength
High Energy
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AAS Applications

Environmental
Food
Pharmaceutical
Petrochemical
Biomonitoring
Chemical / industrial

Geochemical/mining
Agriculture
Semi-conductor
Nuclear energy
Renewable energy
Nanomaterials

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Atomic Absorption Instrument

AAnalyst 400 AA Spectrometer (Perkin Elmer)

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Simplified drawing of a Flame AA system.

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Flame Atomic Absorption Spectroscopy

Atomic Absorption (AA) occurs when a ground state atom absorbs energy in the
form of light of a specific wavelength and is elevated to an excited state.

The amount of light energy absorbed at this wavelength will increase as the
number of atoms of the selected element in the light path increases.

The relationship between the amount of light absorbed and the concentration
of analytes present in known standards can be used to determine unknown
sample concentrations by measuring the amount of light they absorb.

Performing atomic absorption spectroscopy requires:

1.
2.
3.
4.

a primary light source,

an atom source,
a monochromator to isolate the specific wavelength of light to be measured,
a detector to measure the light accurately, electronics to process the data signal and a data
display or reporting system to show the results (See Figure on previous slide).
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Principles

The light source normally used is a hollow cathode lamp (HCL).

In general, a different lamp is used for each element to be determined,
although in some cases, a few elements may be combined in a multi-element
lamp.
photomultiplier tubes have been used as the detector in the past.
However, in most modern instruments, solid-state detectors are now used.

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Principles (2)

Whatever the system, the atom source used must produce free analyte atoms from the
sample.

The source of energy for free atom production is heat, most commonly in the form of an
air/acetylene or nitrous-oxide/acetylene flame.

The sample is introduced as an aerosol into the flame by the sample-introduction system
consisting of a nebulizer and spray chamber.

The burner head is aligned so that the light beam passes through the flame, where the
light is absorbed.
The major limitation of Flame AA is that the burner-nebulizer system is a relatively
inefficient sampling device.

Only a small fraction of the sample reaches the flame, and the atomized sample passes quickly through the
light path.
An improved sampling device would atomize the entire sample and retain the atomized sample in the light
path for an extended period of time, enhancing the sensitivity of the technique.
Option electrothermal vaporization using a graphite furnace.
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The basic components:

Every absorption spectrophotometer must have

components
which
fulfil
three
basic
requirements:
1.
2.
3.

light source
sample cell
a means of specific light measurement.

(1)

(2)

(3)
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Instrument configuration

(1)
1.

(3)

A light source that emits sharp atomic lines of the element to be determined is required.

(2)

One of the most widely used sources: hollow cathode lamp.

These lamps are designed to emit the atomic spectrum of a particular element, and the specific
lamps are selected for use, depending on the element to be determined.

It is also required that the source of radiation be modulated (switched on and off rapidly)
to provide a means of selectively amplifying light emitted from the source lamp and
ignoring emission from the sample cell.

Source modulation can be accomplished with a rotating chopper located between the source
and the sample cell, or by pulsing the power on the source.

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2.

Special considerations are also required for a sample cell for atomic absorption.

3.

An atomic vapour must be generated in the light beam from the source.
This is generally accomplished by introducing the sample into a burner system or electrically
heated furnace aligned in the optical path of the spectrometer.

Several components are required for specific light measurement.

A monochromator is used to disperse the various wavelengths of light which are emitted from
the source and to isolate the particular line of interest.
The selection of a specific source and a particular wavelength in that source is what allows the
determination of a selected element in the presence of others.
The wavelength of light which is isolated by the monochromator is directed onto the detector,
which serves as the 'eye' of the instrument.
This is a photomultiplier tube, which produces an electrical current dependent on the light
intensity.
The electrical current from the photomultiplier is then amplified and processed by the
instrument electronics to produce a signal which is a measure of the light attenuation occurring
in the sample cell.
This signal can be further processed to produce an instrument readout directly in concentration
units.
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Homework

What are the respective advantages and

disadvantages of AAS?

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