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 ?
E = hc/ = 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=Cl

Source of radiation is Hollow Cathode Lamp (HCL)

FES vs AAS instrument

Differences between AAS and FES

FES

AAS

Emission intensity is
measured

Absorption is measured

Emission intensity a No. of

atoms in excited state

Absorption intensity a No. of

atoms in ground state

Emission intensity depends

on flame temperature

Absorption intensity does not

depend on flame temperature

Does not obeys Beers law

Beers 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

Sample

Recorder

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
HCL

S1 = I + Ie

Atomizer

Thus wrong signal due to Ie,

hence, Ie must be eliminated

Thus, A = log(I0 + Ie)/(I + Ie)

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

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

S2 = Ie

Function of Chopper
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 = (e2/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
, 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-Lamberts law:
A = .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
0.000
0.100
0.200
0.300
0.400
0.500

Calculated Pb (II) concentraions (ppm)

0.357

0.000
0.116
0.216
0.310
0.425
0.520

Absorbance
0.340

The data provided in the

problem appears in the
upper left hand corner
of this MS EXCEL
worksheet.

The graph was used to

calculate the best fit line.

The equation was then

used to calculate the
concentration of Pb (II)
ions with an absorbance
of 0.340.

The result, 0.357 ppm, is

displayed above the
graph.

Lead (II) Calibration Curve

0.600

Absorbance

0.500

y = 1.0505x
R2 = 0.9988

0.400
0.300
0.200
0.100
0.000
0.000

0.100

0.200

0.300
[Pb+2] (ppm)

0.400

0.500

0.600

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

50.00 mL volumetric flasks

5 mL

Standard Addition Curve

X + 4X1

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)
Abs

0
0.27

0.1
0.37

0.2
0.53

0.3
0.65

0.4
0.75

0.5
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 g L-1.
(e.g. 0.5 mL of 10 mg/L = 5 x 10-3 mg in 100 mL = 5
g/0.1 L = 50 g L-1)
Unknown = 21.8 g L-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