Chapter 4

Atomic Absorption Spectroscopy

4.1. Theoretical Concepts

4.2. Atomic Absorption
Instrumentation
4.3. Graphite Furnace Atomic
Absorption
4.4. Control of Analytical Interferences
 4.1. Theoretical Concepts

1. The Atomic Absorption Process

2. Theoretical Concepts
3. Quantitative Analysis
4. Characteristic Concentration
5. Detection Limits
1. The Atomic Absorption Process
Fig4-2 Grotrian diagrams for K Fig 4-3Grotrian diagrams for
Na
 2. Theoretical Concepts
Integral Formula of AAS
Fig 4-4 Typical Shape of A Atomic Absorption line
 Integral Absorption Formula
By atomic theory

k dv v
e 2
mc fN 0 (4.1)

By Line Shape Function

( the Nature distribute )

0
kv dv 1
2

k vD
ln 2 0
(4.2)

The Peak Absorption Coefficient k 0 is:

k0 2
v D
ln 2 e 2
mc fN 0 (4.3)
 Peak Absorption Theory
by Lambert-Beers Law:

0 kvl
Iv I ev
(4.4)

v v
P I v dv I e 0 kvl
v dv (4.5)
0 0

v
P0 I dv 0
v (4.6)
0
The Absorbance is:
v 0 k v l
0 I v e dv
A lg PP0 lg v 0
(4.7)
0 I v dv

When v a>> v e, then k vk 0,

v 0 k v l k 0l v 0
I e dv e I dv
A lg 0 v
v 0
lg 0.4343k0l (4.8)
0
v 0
v

I dv
0 v I dv 0 v

A 0.4343 2
v D
ln 2 e 2
mc flN 0 KN 0 (4.9)
3. Quantitative Analysis

A KC (4.10)
 4. Characteristic Concentration

The characteristic concentration ( sometimes

called sensitivity) is a convention for defining the
magnitude of the absorbance signal which will be
produced by a given concentration of analyte. For flame
atomic absorption, this term is expressed as the
concentration of an element in milligrams per liter
( mg/L ) required to produce a 1% absorption
( 0.0044 absorbance ) signal.

(4.11)
 5. Detection Limit
Having obtained the data, make the calculation as follows:
1. Average the two blank readings taken immediately before
and after each standard and subtract from the standard
reading.
2. Calculate the mean and standard deviation for the set of
corrected high-standard readings. Do the same for the set
of corrected low standard readings.
3. If the ratio of the means does not correspond to the ratio of
the concentration prepared to within statistical error, reject
the data.
4. If the data pass the ratio-of-the-means test, calculate the
concentration detection limit as follows:

(4.12)
4.2. Atomic Absorption
Instrumentation
1. Photometers for AAS
A New Type Photometer for AAS
2. line source (Hollow Cathode Lamp )

Fig 4-13
 Hollow Cathode Lamp Emission Process

Fig 4-14
3. Atomizer for AAS (Pre-Mix Burner System)
Fig 4-19 Tree Type Burner Head for different Type
Flame
 4. Control of Analytical Interferences

Ionization Interference

Matrix Interference

Chemical Interference

Background Interference
Ionization Interference
Matrix Interference
Chemical Interference
 The Method Of Standard Additions

Sample Standard Concentr.of Last

No. Added Added standard Concentriation
ml ml mg/L mg/L

Vx
1 0 VL

Vx+CsVs
2 Vs VL
Vx Cs
Vx+2CsVs
3 2Vs VL

Vx+3CsVs
4 3Vs VL
Background Interference
A D2=A b, (4.13)

(4.14)
A HCL= Aa+ Ab
(4.15)
A a = AHCL- AD2
 4.3. Graphite Furnace Atomic Absorption

1. Graphite furnace atomizer components

2. The Graphite Furnace Power Supply and
Programmer
3. Quantitative analysis GFAAS
4. Effect of Matrix on Height and Area
 1. Graphite furnace atomizer components

The Graphite Furnace Atomizer

A basic graphite furnace atomizer is comprised of the following
components:
graphite tube
electrical contacts
enclosed water cooled housing
inert purge gas controls
THGA graphite tube

Fig 4-27
2. The Graphite Furnace
Power Supply and
Programmer

A Graphite Furnace
Temperature Program
1) Drying
2) Pyrolysis
3) Cool Down(optional)
4) Atomization
5) Clean Out
6) Cool Down