Atomic Absorption Spectroscopy (AAS)

E2
Absorption
hv AAS

E1

Ground state Excited state

Atomic Absorption Spectroscopy: Fundamentals

 Atoms are involved  Atomization occurs; Flame atomizer

 Flame induces thermal excitation (Boltzmann distribution)
 Only 0.1% atoms are excited; leads to emission
 99.9% atoms are in the ground state: absorbs incident light
 Independent of the flame temperature
 Wavelength and Intensity of the transmitted light are measured
 Follows Lambert-Beer law (Beer’s law)  A = ε c l = log (1/T)
 M Bhattacharya
Basic difference between AAS and FES: Set-up perspective

http://faculty.sdmiramar.edu/fgarces/LabMatters/Instruments/AA/AA.htm
 M Bhattacharya
Basic difference between AAS and FES: Set-up perspective

Atomic Absorption Spectroscopy

http://faculty.sdmiramar.edu/fgarces/LabMatters/Instruments/AA/AA.htm
 M Bhattacharya
 Atomic Absorption Spectrophotometer
Fuel
+
Oxidant Recorder

Chopper Flame
Mono
Light chromator
Source
Detector

Sample
 M Bhattacharya
 Flame Atomizer: Composition of Flame

Fuel Oxidant Flame temperature (K)

Propane Air 1900

Propane Oxygen 2800

Hydrogen Air 2100

Hydrogen Oxygen 2800

Air
Acetylene 2300

Acetylene Oxygen
3100

 M Bhattacharya
 Laminar Flow or Premix Burner
• Sample, fuel and oxidant are thoroughly mixed
before reaching the burner opening and then
enters in the flame
• Gases move in non-turbulent fashion – laminar
flow
• Only 5% of the sample in the form of small
droplets reaches to the flame and gets
decomposed
• Efficient atomization
• Larger droplets move out as condensate
• Flame is non-turbulent, noiseless and stable
• Disadvantages
– When sample contains two solvents, more
volatile solvent evaporates leaving sample
Sequence: in less volatile solvent
Nebulization  Desolvation  – Therefore, smaller number of atoms would
Liquefaction  Vaporization  reach to the flame and emission intensity
Atomization  Excitation  Emission reduces
 M Bhattacharya
 AAS: Schematic Design of the Instrument

Laminar Flow (Premix) Burner  Isolates analytical lines (λ)

(non-turbulent, noiseless, steady flame)  Removes scattered light
Width of Flame  Path-length of sample !

Additional components w.r.t. FES/FP instrumental set-up:

 Light Source: Hollow cathode lamp: What is it? How does it work?
 Chopper: Why is it needed?
 M Bhattacharya
 Incident Light Source: Hollow Cathode Lamp

 The cathode in Hollow Cathode Lamp is composed of

the element which is to be analyzed
 Radiation emitted by the lamp has the same
wavelength as the one which is required for the
excitation of the element present in the analyte
 Different lamps are required for the analysis of a
sample containing multiple elements
 M Bhattacharya
 Incident Light Source: Hollow Cathode Lamp

Hollow Cathode Lamp: Emits the radiation in following steps

1. Ionization of inert gas (Ar or Ne): Ar + e- → Ar + e-+

• In presence of high voltage; inert gas becomes ionized

2. Sputtering: M(s) + Ar+ → M(g) + Ar

• The +ve-ly charged inert gas ions accelerate towards -ve-ly charged cathode
• Bombard onto cathode  dislodge metal atoms from cathode surface
• Conversion of metal atoms from solid to gas phase  forms atomic cloud

3. Excitation: M(g) + Ar+ → M*(g) + Ar

• Atomic cloud containing gas phase metal atoms collide with inert gas ions
• Excited to higher energy levels

4. Emission: M*(g) → M(g)+ MhνBhattacharya

(used to excite the atoms in flame)
Chopper: Creates Intermittent Pulsed Radiation

I0 I
Flame
Atomizer
Ie
Hollow
Cathode Lamp

S1 = I + Ie
Chopper
I0
Flame
Atomizer
Ie
Hollow
Cathode Lamp S2 = Ie

Corrected Signal (S) = S1 – S2 = I + Ie – Ie = I

 M Bhattacharya
 Chopper: Creates Intermittent Pulsed Radiation

I I
Pulsating signal

I + Ie Ie I + Ie Ie

• Breaks steady radiation from the HCL into the intermittent

• Pulsating signal is generated by photodetector.
• Absorption is measured without any interference

This correction method for background emission in flames is called

source modulation.
 M Bhattacharya
 AAS and FES: Overall Differences

FES
Emission intensity is
measured
Emission intensity depends on
the no. of atoms in the excited
state
Emission intensity depends
on flame temperature
Does not obey Beer’s law
AAS
Transmitted intensity is
measured
Absorbance/Transmitted
intensity depends on the no. of
atoms in the ground state
Transmitted intensity does not
depend on flame temperature
Beer’s law is obeyed

 M Bhattacharya
 Quantification of Analyte using AAS
• The analyte concentration is determined from the extent of absorption
• If there are chemical interferences which affect the chemistry of analyte in
the flame (atomization efficiency), then direct application of Lambert-Beer
law in AAS becomes difficult due to matrix effect

Quantification Techniques

Standard Calibration Curve Standard Addition Method

 No chemical interferences  Chemical interferences

 M Bhattacharya
Quantification of Analyte using AAS: Standard Curve Technique

Concentration is measured with the help of a working (calibration) curve

derived from standards of known concentration.

Numerical: Lead is extracted from a Conc (ppm) Absorbance

sample of blood and analyzed at 283 nm 0.1 0.116
and gave an absorbance of 0.340 in an AA
0.2 0.216
spectrometer. Using the data provided,
plot a calibration curve and find the 0.3 0.310
concentration of lead ions in the blood 0.4 0.425
sample.
x 0.340

Calibration Curve Solution:

Absorbance

X  Plot the given data points on a graph paper

X  Using a ruler (scale), draw a straight line
through those data-points  gives a
X calibration curve
X  Mark the given absorbance of the unknown
conc. on the Y-axis of the calibration curve
Concentration (ppm)  Mark the corresponding conc. on the X-axis
 unknown conc. is determined = 0.357 ppm
 M Bhattacharya
Quantification of Analyte using AAS: Standard Addition Technique

 A series of solutions are prepared

 Same volume of unknown
 Different volumes of standard
 Total volumes of solutions equal
 Conc. of analyte = unknown + std.
 Total conc. varies linearly

 Graph is plotted as signal intensity

vs. all the sample solutions
 From the plot, the conc. of
unknown can be determined by
extrapolating the plot on X- axis.

 M Bhattacharya
Atomic Absorption Spectroscopy: Advantages & Disadvantages

Advantages:
 Atoms of a particular element can absorb radiation of their own
wavelength  No spectral interference
 Large no. of atoms contribute towards transmitted intensity or
absorption and hence, quantification is more accurate
 Can determine trace metals even if they are present with other
elements in a given sample solution
 Variation in flame temperature has negligible effect on AA intensity

Disadvantages:
 Different hollow cathode lamps for detection and quantification of each
element are required
 Elements which form stable oxides e.g. Al, Ti, W, Mo, etc. do not give
very good results
 M Bhattacharya