Atomic Absorption Spectrometry (AAS)

ICP CHEMISTRY A 2011 FMIPA UNM 2013

Contents
What is AAS Theory Instrumentations Principle of AAS Applications

What is AAS ?
Atomic absorption spectroscopy is a quantitative method of analysis that is applicable to many metals and a few nonmetals. The technique was introduced in 1955 by Walsh in Australia (A.Walsh, Spectrochim. Acta, 1955, 7, 108)
The application of atomic absorption spectra to chemical analysis
Concentrations range is in the low mg/L (ppm) range.

Theory
A much larger number of the gaseous metal atoms will normally remain in the ground state. These ground state atoms are capable of absorbing radiant energy of their own specific resonance wavelength.

If light of the resonance wavelength is passed through a flame containing the atoms in question, then part of the light will be absorbed. The extend of absorption will be proportional to the number of ground state atoms present in the flame.

the gaseous metal atoms

specific resonance wavelength

extend of absorption

the extend of absorption vs the number of ground state atoms present in the flame.

AAS Instrument

The simple diagram for the AAS

4. The element in the sample will absorb some of the light, thus reducing its intensity

3. A beam of UV light will be focused on the sample

5. The monochromator isolates the line of interest

1. We set the instrument at certain wavelength suitable for a certain element

2. The element in the sample will be atomized by heat

6. The detector measures the change in intensity

7. A computer data system converts the change in intensity into an absorbance

Flame atomization
Processes occurring during atomization

Nebuliser - burner
To convert the test solution to gaseous atoms Nebuliser --- to produce a mist or aerosol of the test solution Vaporising chamber --Fine mist is mixed with the fuel gas and the carrier gas

Larger droplets of liquid fall out from the gas stream and discharged to waste

Burner head --- The flame path is about 10 12 cm

1. Nebulizer:
4. The mixture flows immediately into the burner head.

5. It burns as a smooth, laminar flame evenly distributed along a narrow slot.

1. mixes acetylene (the fuel) and oxidant (air or nitrous oxide).

3. The result is a heterogeneous mixture of gases (fuel + oxidant) and suspended aerosol (finely dispersed sample).

2. A negative pressure is formed at the end of the small diameter, plastic nebulizer tube (aspiration). 6. Liquid sample not flowing into the flame collects in the waste.

Note: When do we use NO2 ?

Elements that are highlighted in pink are detectable by AAS

Principle of Atomic Absorption Spectrophotometer

Atomized elements each absorb energy of a wavelength that is peculiar to that element. The atomic absorption method uses as its light source a hollow cathode lamp which emits light of a wavelength that is peculiar to each element. Elements within a solution are heated in a flame or electrically (2000K to 3000K) and subsequently determined using the fact that the degree of absorption will vary with its concentration.

Light absorption process of atoms

Principle of Atomic Absorption Spectrophotometer

Atomic Absorption Spectroscopy, AAS
Excited state E1 Absorption

e
Ground state E0

Atomic Emission Spectroscopy, AES

Excited state E1

Emission

e
Ground state E0

Characters of the atomic absorption spectrum Profile of the absorption line

K0 - maximal absorption
coefficient - half width

0 - central wavelength

The relationship between absorbance and the concentration of atoms

Beers law
It = I0e -Kl
A = log I0/ It= 0.4343 K l
It - intensity of the transmitted light
Io intensity of the incident light signal l the path length through the flame (cm)

Types of Pretreatment
Dilution
Dilute the sample with purified water, dilute acid, or organic solvents. Examples: food products (e.g., dairy products), pharmaceuticals, and biological samples (e.g., blood, urine).

Dry Decomposition

Heat the sample to a high temperature (400 to 500C), Decomposition is possible in a short time (a few hours) and operation is simple. Elements with low boiling points (e.g., Hg, As, Se, Te, and Sb) will vaporize

Wet Decomposition

Heat the sample together with acid to a low temperature (approx. 300C). Suitable for volatile elements. A long time is required for the decomposition of organic substances. Decompose the sample at high pressure by heating it together with acid to a temperature in the range 100 to 200C in a sealed Teflon container. The decomposition process is sealed; there is little vaporization of elements with low boiling points; the decomposition time is short; there is little contamination from the operating environment and the reagent; and only a small amount of acid is required. Examples: Sediment, soil, dust, ceramics, living organisms, food products, etc.

Microwave Decomposition

Characters of the atomic absorption spectrum Natural broadening

determined by the lifetime of the excited state
and Heisenbergs uncertainty principle10-5 nm

Doppler Broadening

10-3 nm

results from the rapid motion of atoms as they emit or absorb radiation

Collisional Broadening
collisions between atoms and molecules in the gas phase lead to deactivation of the excited state and thus broadening the spectral lines

Characters of the atomic absorption spectrum

Doppler Broadening 10-3 nm

results from the rapid motion of atoms as they emit or absorb radiation

Application of AAS

AAS

Pretreatment (dissolution) is required for solid samples.

Results of Quantitative Analysis of Cd in Rice

The following 2 methods can be used to analyze unpolished and polished rice decomposed using acid:

Flame method

Furnace method

Polished rice: 0.118 ppm

0.1 ppm 0.5 ppm

Polished rice : 0.118 ppm

Unpolished rice: 0.070 ppm

Unpolished rice : 0.073 ppm

Air-C2H2

Injected amount: 10 L

Interference inhibitor: Pd 50ppm 5 L

Ashing: 400C; Atomization: 1,800C

AAS Interferences
Spectral interferences

Chemical interferences

Physical interferences

AAS Advantages and Disadvantages'

Advantages 1. High selectivity and sensitivity 2. Fast and simple working 3. Doesnt need metals separation Disadvantages 1. Analysis doesnt simultaneous 2. Fragment have to form ready measure solution 3. Limit types of cathode lamp (expensives)

THANK YOU

Questions
How could atoms collision Sample preparation of AAS The type of sample liquid or gas Function of AAS of few nonmetals examples What happen to the sample in flame