Atomic Absorption

Spectroscopy
AAS is commonly used for metal analysis
A solution of a metal compound is
sprayed into a flame and vaporises
The metal atoms absorb light of a
specific frequency, and the amount of
light absorbed is a direct measure of the
number of atoms of the metal in the
solution
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Atomic Absorption Spectroscopy:

An Aussie Invention
Developed by Alan Walsh (below) of the
CSIRO in early 1950s.

Electromagnetic Radiation
Sinusoidally oscillating electric (E) and magnetic (M)

Electric & magnetic fields are orthogonal to each ot

Electronic spectroscopy concerns interaction of the

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electric field (E) with matter.

The Electromagnetic
Spectrum
Names of the regions are historical.
There is no abrupt or fundamental change in
going from one region to the next.
Visible light represents only a very small
fraction of the electromagnetic spectrum.
Frequency (Hz)
1020

1018

-rays

X-rays

10-11
Wavelength (m)

1016

1014

1012

UV
10-8

108
Microwave

IR
10-6

10-3

Visible
400

500

600

700

800 nm

The Visible Spectrum

< 400 nm, UV
400 nm < < 700 nm, VIS
> 700 nm, IR

The Electromagnetic
Spectrum
Remember that we are dealing with light.
It is convenient to think of light as
particles (photons).
Relationship between energy and
frequency is:

E h
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Energy & Frequency

Note that energy and frequency are
directly proportional.
Consequence: higher frequency radiation
is more energetic.
E.g. X-ray radiation ( = 1018 Hz): 4.0 x 106
kJ/mol
IR radiation ( = 1013 Hz): 39.9 kJ/mol
(h = 6.626 x 10-34 J.s)
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Energy & Wavelength

Given that frequency and wavelength
are related: =c/
Energy and wavelength are inversely
proportional
Consequence: longer wavelength
radiation is less energetic
eg. -ray radiation ( = 10-11 m):1.2 x 107
kJ/mol
Orange light ( = 600 nm):199.4 kJ/mol
(h = 6.626 x 10-34 J.s
108 m/s)

c = 2.998 x

Absorption of Light
When a molecule absorbs a photon, the
energy of the molecule increases.
Ground
state

photon

Excited
state

Microwave radiation stimulates rotations

Infrared radiation stimulates vibrations
UV/VIS radiation stimulates electronic
transitions
X-rays break chemical bonds and ionize
molecules

Absorption of Light
When light is absorbed by a sample,
the radiant power P (energy per unit
time per unit area) of the beam of
light decreases.
The energy absorbed may stimulate
rotation, vibration or electronic
transition depending on the
wavelength of the incident light.
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Atomic Absorption
Spectroscopy
Uses absorption of light to measure the
concentration of gas-phase atoms.
Since samples are usually liquids or solids,
the analyte atoms must be vapourised in a
flame (or graphite furnace).

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Absorption and Emission

Excited States

Ground State
Absorption Emission

Multiple
Transitions
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Absorption and Emission

Excited States

Ground State
Absorption

Emission

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Atomic Absorption
When atoms absorb light, the
incoming energy excites an electron
to a higher energy level.
Electronic transitions are usually
observed in the visible or ultraviolet
regions of the electromagnetic
spectrum.

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Atomic Absorption Spectrum

An absorption spectrum is the
absorption of light as a function of
wavelength.
The spectrum of an atom depends on
its energy level structure.
Absorption spectra are useful for
identifying species.
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Atomic Absorption/Emission/
Fluorescence Spectroscopy

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Atomic Absorption
Spectroscopy
The analyte concentration is
determined from the amount of
absorption.

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Atomic Absorption
Spectroscopy
The analyte concentration is determined
from the amount of absorption.

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Atomic Absorption
Spectroscopy
Emission lamp produces light frequencies
unique to the element under investigation
When focussed through the flame these
frequencies are readily absorbed by the test
element
The excited atoms are unstable- energy is
emitted in all directions hence the intensity of
the focussed beam that hits the detector plate
is diminished
The degree of absorbance indicates the amount
of element present
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Atomic Absorption
Spectroscopy
It is possible to measure the
concentration of an absorbing species in
a sample by applying the Beer-Lambert
Law:

I
Abs log
Io

= extinction coefficient

Abs cb

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Atomic Absorption
Spectroscopy
But what if is unknown?
Concentration measurements can be
made from a working curve after
calibrating the instrument with
standards of known concentration.

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AAS - Calibration Curve

The instrument is calibrated before use by
testing the absorbance with solutions of known
concentration.
Consider that you wanted to test the sodium
content of bottled water.
The following data was collected using solutions
of sodium chloride of known concentration
Concentration
(ppm)

Absorbance

0.1

0.3

0.5

0.722

Calibration Curve for

Sodium
A
b
s
o
r
b
a
n
c
e

1.0

0.8

0.6

0.4

0.2

Concentration (ppm)

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Use of Calibration curve to determine

sodium concentration {sample
absorbance = 0.65}
A
b
s
o
r
b
a
n
c
e

1.0

0.8

0.6

0.4

Concentration
Na+ = 7.3ppm

0.2

Concentration (ppm)

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Atomic Absorption
Spectroscopy
Instrumentation
Light Sources
Atomisation
Detection Methods

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Light Sources
Hollow-Cathode Lamps (most common).
Lasers (more specialised).
Hollow-cathode lamps can be used to
detect one or several atomic species
simultaneously. Lasers, while more
sensitive, have the disadvantage that they
can detect only one element at a time.

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Hollow-Cathode Lamps
Hollow-cathode lamps are a type of
discharge lamp that produce narrow
emission from atomic species.
They get their name from the cupshaped cathode, which is made from
the element(s) of interest.

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Hollow-Cathode Lamps

The electric discharge ionises rare gas

(Ne or Ar usually) atoms, which in turn,
are accelerated into the cathode and
sputter metal atoms into the gas phase.
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Hollow-Cathode Lamps

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Hollow-Cathode Lamps
The gas-phase metal atoms collide
with other atoms (or electrons) and are
excited to higher energy levels. The
excited atoms decay by emitting light.
The emitted wavelengths are
characteristic for each atom.

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Hollow-Cathode Lamps
M*
collision-induced
excitation

M
M

+
+

e
Ar*

M*
M*

M
M*
spontaneous
emission
M

M*

M + h
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Hollow-Cathode Spectrum

Harris Fig.
21-3:
Steel hollowcathode

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Atomisation
Atomic Absorption Spectroscopy (AAS)
requires that the analyte atoms be in the
gas phase.
Vapourisation is usually performed by:
Flames
Furnaces
Plasmas
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Flame Atomisation
Flame AAS can only analyse solutions.
A slot-type burner is used to increase
the absorption path length (recall
Beer-Lambert Law).
Solutions are aspirated with the gas
flow into a nebulising/mixing chamber
to form small droplets prior to
entering the flame.
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Flame Atomisation

Harris
Fig 214(a)

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Flame Atomisation
Degree of atomisation is temperature
dependent.
Vary flame temperature by fuel/oxidant
mixture.
Fuel
Acetylene
Acetylene
Acetylene
Hydrogen
Hydrogen
Cyanogen

Oxidant
Temperature (K)
Air
2,400 - 2,700
Nitrous Oxide
2,900 - 3,100
Oxygen
3,300 - 3,400
Air
2,300 - 2,400
Oxygen
2,800 - 3,000
Oxygen
4,800

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Furnaces
Improved sensitivity over flame sources.
(Hence) less sample is required.
Generally, the same temp range as
flames.
More difficult to use, but with operator
skill at the atomisation step, more
precise measurements can be obtained.
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Furnaces

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Furnaces

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Inductively Coupled Plasmas

Enables much higher temperatures to be
achieved. Uses Argon gas to generate the
plasma.
Temps ~ 6,000-10,000 K.
Used for emission expts rather than
absorption expts due to the higher
sensitivity and elevated temperatures.
Atoms are generated in excited states and
spontaneously emit light.
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Inductively Coupled Plasmas

Steps Involved:
RF induction coil wrapped around a gas
jacket.
Spark ionises the Ar gas.
RF field traps & accelerates the free
electrons, which collide with other
atoms and initiate a chain reaction of
ionisation.
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Detection
Photomultiplier Tube (PMT).
pp 472-473 (Ch. 20) Harris

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Photomultiplier Tubes
Useful in low intensity applications.
Few photons strike the photocathode.
Electrons emitted and amplified by
dynode chain.
Many electrons strike the anode.
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