Sodium atom absorb at a wavelength of 589 nm.

What is
the energy difference between (in J) between the ground
and excited state?
At a temperature of 2500 K, what is the ratio of excited
state to ground state population (N*/N0) if the relative
degeneracy (g*/g0) is 2 ?

ΔE = hc/λ = 3.37 x 10-19 J

N*/N0 = A e-DE/kT = 1.15 x 10-4

A = g*/g0
Atomic Absorption Spectroscopy

AAS
 A=εCl

Source of radiation is Hollow Cathode Lamp (HCL)

FES vs AAS instrument
 Differences between AAS and FES

FES
Emission intensity is
measured
Emission intensity a No. of
atoms in excited state
Emission intensity depends
on flame temperature
Does not obeys Beer’s law
AAS
Absorption is measured
Absorption intensity a No. of
atoms in ground state
Absorption intensity does not
depend on flame temperature
Beer’s law is obeyed
 AAS: Instrumentation

Flame

HCL
Atomizer

Monochromator is not required between HCL and flame?

What is the role of chopper?

 Atomic Absorption Spectrophotometer

Fuel + oxidant

Flame

Light Source Detector

Recorder

Sample
Atomic Absorption Spectrophotometer
Atomic absorption spectra
Atomizer: Laminar-flow (pre-mix) Burner

Flow-spoiler: Removes large

drops from aerosol

Vaporing chamber

Convert the large droplet into small one

 Laminar-flow (pre-mix) Burner

• Sample, fuel and oxidant are thoroughly pre-mixed

before reaching the burner opening
• Gases move in non-turbulent fashion – laminar flow
• ~ 5 % of nebulized sample reaches to the flame
• Advantages:
• Small sample volume of 0.5-1.0 mL is required
• Efficient atomization
• Flame is non-turbulent, noiseless and stable
• Disadvantages
– When sample contains two solvents, more volatile solvent
evaporates leaving sample in less volatile solvent
– Therefore, smaller number of atoms would reach to the flame
Various steps in atomizer
Temperature of Premix flame
Monochromator:
• Isolate analytical lines photons passing through
the flame
• Remove scattered light of other wavelengths
from the flame
Function of Chopper
I0 I
Flame

Ie
S1 = I + Ie
HCL Atomizer

Thus wrong signal due to Ie, Thus, A = log(I0 + Ie)/(I + Ie)

hence, Ie must be eliminated in place of A = log (Io/I)
Usually, Ie > > I

I0
Flame

Ie
HCL Chopper Atomizer S2 = Ie

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

 I0 I
Flame

Ie
HCL Chopper Atomizer S1 = I + Ie

I0
Flame

Ie
HCL Chopper Atomizer S2 = Ie

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

 Function of Chopper

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.
 Hollow Cathode Lamp (HCL) : Radiation source

► The Hollow cathode is composed off the element to be analysed

► Emitted radiation by HCL has the same wave length required for
the excitation of element to be analysed
► Different lamp is required for each element
(Multi- element lamps are also available)
Hollow Cathode Lamp: Give the radiation in following steps

1. Ionization of inert gas: Ar + e-  Ar+ + e-

• In presence of 300-400 V

2. Sputtering : M(s) + Ar+  M(g) + Ar

• Gaseous ion will eject the atoms from cathode

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

4. Emission : M*(g)  M(g) + h (used to excite the atoms)

 Atomic Absorption Spectroscopy
Degree of absorption:
Total amount of light absorbed = (πe2/mc2)Nf
Where:
e = electronic charge, m = mass of electron
c = speed of light, N = total No. of atoms that can absorb light
f = Ability of each atom to absorb light
π, e, m, and c are constants, therefore

Total amount of light absorbed = constant x Nf

Since f is also constant for the same substance
A  C (N)
Therefore, absorption is independent of temperature and wavelength
 Atomic Absorption Spectroscopy

• The analyte concentration is determined from the

amount of absorption.

• Direct application of Beer-Lambert in AAS is difficult

due to matrix effect.

• Concentration is measured with the help of a

working (calibration) curve derived from standards of
known concentration.
 Atomic Spectroscopy for Metal Analysis

• Simple solutions (e.g. water): Standard curve technique

• Complex solutions (matrix): Standard addition technique

– Add small volumes higher concentration standards

(change in volume is considered negligible)
– Graph of concentration vs. absorbance
– Concentration of sample is x-intercept
– Overcomes problem of matrix effects
 AAS: Standard Curve Technique

According to Beer-Lambert’s law:

A = ε.C.l

Unknown concentration

Calibration plot
 Lead is extracted from a sample of blood and analyzed at 283 nm and gave
an absorbance of 0.340 in an AA spectrometer. Using the data provided,
graph a calibration curve and find the concentration of lead ions in the
blood sample.
[Pb+2] (ppm) Absorbance Calculated Pb (II) concentraions (ppm) Absorbance
0.000 0.000 0.357 0.340
0.100
0.200
0.116
0.216 • The data provided in the
0.300 0.310
0.400 0.425 problem appears in the
0.500 0.520
upper left hand corner
Lead (II) Calibration Curve
of this MS EXCEL
worksheet.
0.600
• The graph was used to
0.500
y = 1.0505x
calculate the best fit line.
R2 = 0.9988
0.400 • The equation was then
Absorbance

used to calculate the

0.300
concentration of Pb (II)
0.200 ions with an absorbance
of 0.340.
0.100
• The result, 0.357 ppm, is
0.000
0.000 0.100 0.200 0.300 0.400 0.500 0.600
displayed above the
[Pb+2] (ppm) graph.
AAS - Standard Addition method
• Signal intensity of unknown sample X is taken
• A series of solutions of known concentration are prepared and
signal is obtained by aspirating them in flame
• Plot is drawn between the signal intensity against conc.
• From the plot, the conc. of unknown can be determined by
extrapolating the plot on conc. axis.

1 mL pipette

Fe:
0.05
mg mL-1
1 mL 2 mL 3 mL 4 mL 5 mL
50.00 mL volumetric flasks
Standard Addition Curve

X + 4X1
o
X + 3X1 o

Absorbance X + 2X1 o
X + X1
o

XX

Conc. of unknown (x) Concentration

Question
A series of solutions is made up by adding 0.1, 0.2, 0.3, 0.4
and 0.5 mL of a 10 mg L-1 lead standard to 100 mL aliquots
of the unknown solution. The following results were
obtained:

Volume std. (mL) 0 0.1 0.2 0.3 0.4 0.5

Abs 0.27 0.37 0.53 0.65 0.75 0.88

Plot a calibration graph and determine the concentration of the unknown

Assuming constant volume of 100 mL, the
concentration increase in the 5 solutions are 10 20, 30,
40, and 50 μg L-1.
(e.g. 0.5 mL of 10 mg/L = 5 x 10-3 mg in 100 mL = 5
μg/0.1 L = 50 μg L-1)
Unknown = 21.8 g μL-1 lead
 Advantages of AAS
• AAS - specific – Atom of a particular element can absorb radiation
of their own wavelength – No spectral interference
• Much larger No. of atoms contribute in AAS signal so results are
more authentic.
• Variation in flame temperature has less effect

Disadvantages of AAS
• Different (HCL) lamp for each element is required
• Elements which for stable oxides eg. Al, Ti, W, Mo, do not
give very good results