Principles and Applications of AAS
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arunmahatoPrinciples and Applications of AAS
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arunmahatoATOMIC ABSORPTION SPECTROSCOPY
Unit I
Principle, interferences, instrumentation and
applications
BY
Dr. ARUN KUMAR MAHATO
INTRODUCTION
• Atomic absorption spectrometry (AAS) is an analytical technique that measures
the concentrations of elements.
• Atomic absorption is so sensitive that it can measure down to parts per billion
of a gram (µg dm–3 ) in a sample.
• The technique makes use of the wavelengths of light specifically absorbed by
an element.
• They correspond to the energies needed to promote electrons from one energy
level to another, higher, energy level.
Principle
• Atoms of a metal are volatilised in a flame and their absorption of a narrow
band of radiation produced by a hollow cathode lamp, coated with the
particular metal being determined is measured.
• For example with Zinc , a lamp containing Zinc emits light from excited Zinc
atoms that produce the right mix of wavelengths to be absorbed by any Zinc
atoms from the sample. In AAS, the sample is atomised – ie converted into
ground state free atoms in the vapour state – and a beam of electromagnetic
radiation emitted from excited Zinc atoms is passed through the vaporised
sample. Some of the radiation is absorbed by the Zinc atoms in the sample.
• The greater the number of atoms there is in the vapour, the more radiation is
absorbed. The amount of light absorbed is proportional to the number of Zinc
atoms. A calibration curve is constructed by running several samples of known
Zinc concentration under the same conditions as the unknown. The amount
the standard absorbs is compared with the calibration curve and this enables
the calculation of the Zinc concentration in the unknown sample.
Principle
Strengths
• AAS is more sensitive than AES as atomic absorbance lines are
remarkably narrow 0.002 to 0.005nm.
Instrumentation
Atomic absorption spectrometer needs the following three components:
• a light source;
• a sample cell to produce gaseous atoms: (Flame)
• and a means of measuring the specific light absorbed.
Fig: Single beam Atomic absorption spectrometer
Instrumentation
Fig: Double beam Atomic absorption spectrometer
Instrumentation
1. Light Source: Hollow cathode lamp coated with the element being analysed.
This contains a tungsten anode and a cylindrical hollow cathode made of the
element to be determined.
• When current flows between anode and cathode, metal atoms are sputtered
with filler gas (Argon/Neon) at 1 Nm–2 and 5 Nm–2.
• These gaseous ions bombard the cathode and eject metal atoms from the
cathode in a process called sputtering. Some sputtered atoms are in excited
states and emit radiation characteristic of the metal as they fall back to the
ground state.
eg Zn* → Zn + hv
• The shape of the cathode concentrates the radiation into a beam which
passes through a quartz window, and the shape of the lamp is such that most
of the sputtered atoms are redeposited on the cathode.
Instrumentation
Instrumentation
2. Flame: The flame is usually air/acetylene providing a temperature about 2500 oC.
Nitrous oxide/acetylene may be used to produce temperature upto 3000 oC which
are required to volatilise salts of elements such as aluminium and calcium.
Atomisation of the sample: Two systems are commonly used to produce atoms
from the sample. Aspiration involves sucking a solution of the sample into a flame;
and electrothermal atomisation is where a drop of sample is placed into a graphite
tube that is then heated electrically.
Instrumentation
2. Flame: The flame is usually air/acetylene providing a temperature about 2500 oC.
Nitrous oxide/acetylene may be used to produce temperature upto 3000 oC which
are required to volatilise salts of elements such as aluminium and calcium.
Atomisation of the sample: Two systems are commonly used to produce atoms
from the sample. Aspiration involves sucking a solution of the sample into a flame;
and electrothermal atomisation is where a drop of sample is placed into a graphite
tube that is then heated electrically.
Instrumentation
Flame aspiration: It has a a typical burner and spray chamber.
Ethyne/air (giving a flame with a temperature of 2200–2400 °C) or
ethyne/dinitrogen oxide (2600– 2800 °C) are often used. A flexible capillary tube
connects the solution to the nebuliser. At the tip of the capillary, the solution is
‘nebulised’ – ie broken into small drops. The larger drops fall out and drain off while
smaller ones vaporise in the flame. Only ca 1% of the sample is nebulised.
Fig: Flame aspiration
Instrumentation
Electrothermal atomisation: It has a hollow graphite tube with a platform.
25 µl of sample (ca 1/100th of a raindrop) is placed through the sample hole and
onto the platform from an automated micropipette and sample changer. The
tube is heated electrically by passing a current through it in a pre-programmed
series of steps. The details will vary with the sample but typically they might be 30–
40 seconds at 150 °C to evaporate the solvent, 30 seconds at 600 °C to drive off any
volatile organic material and char the sample to ash, and with a very fast heating
rate (ca 1500 °C s-1) to 2000– 2500 °C for 5–10 seconds to vaporise and atomise
elements (including the element being analysed). Finally heating the tube to a still
higher temperature 2700 °C – cleans it ready for the next sample. During this
heating cycle the graphite tube is flushed with argon gas to prevent the tube
burning away. In electrothermal atomisation almost 100% of the sample is atomised.
This makes the technique much more sensitive than flame AAS
Instrumentation
3. Detector: Photosensitive cell
Applications:
1. AAS is used in limit test of metals in drugs prior to their incorporation in
formulations.
2. Assay of calcium and magnesium in hemodialysis fluid.
3. Assay of total zinc in insulin suspension.
4. Assay of palladium in carbenicillin sodium.
5. Assay of lead in sugars.
6. Detection of trace metals in silicone foam cavity wound dressing.
Interferences:
1. Other chemicals that are present in the sample may affect the atomisation
process. For example, in flame atomic absorption, phosphate ions may react
with calcium ions to form calcium pyrophosphate. This does not dissociate in the
flame and therefore results in a low reading for calcium. This problem is avoided
by adding different reagents to the sample that may react with the phosphate to
give a more volatile compound that is dissociated easily. Lanthanum
nitrate solution is added to samples containing calcium to tie up the phosphate
and to allow the calcium to be atomised, making the calcium absorbance
independent of the amount of phosphate. With electrothermal atomisation,
chemical modifiers can be added which react with an interfering substance in
the sample to make it more volatile than the analyte compound. This volatile
component vaporises at a relatively low temperature and is removed during the
low and medium temperature stages of electrothermal atomisation.
2. Spectral Interferences
