CHAPTER 4 :

ATOMIC
SPECTROSCOPY
BASIC PRINCIPLES &
INSTRUMENTS

CONTENTS:

Principle of AAS.
Instrumentation.
Applications.
Experiments.

ATOMIC
SPECTROSCOPY
Absorption Spectroscopy:

Emission Spectroscopy:

AAS

FES, ICP-AES (OES)

Mass Spectrometry

PRINCIPLE

Atomic Absorption Spectroscopy utilizes the

phenomenon that atoms in ground state absorbs
radiation from the light source and goes up into
their excited state. The amount of light absorbed
is proportional to concentration
of the element.
Cu*
Cu*

Hallow
Cathode
Lamp

Cu(g)

A Process
called
Excitation

Cu(aq)

A Process
called
Atomization

DETECTOR
A=Log P0/P

Elements detectable by AA are highlighted in pink

INSTRUMENTATION

The basic design in AAS includes a light source, chopper,

atomizer (burner), monochromator and detector.
Single and double beam instruments are available,
however, double beam AAS are more sensitive and
accurate.
FIT has a double beam AAS
A=Log P0/P
Chopper

Hallow
Cathode
Lamp

Burn
er

Monochromator

Aspiratio
n

Detector
and readout

Functions
Atomizer
Chopper
Monochromator

ATOMIC ABSORPTION
SPECTROPHOTOMETER

FLAME AAS

GRAPHITE FURNACE AAS

10

SCHEMATIC DIAGRAM OF AAS:

ATOMIC SPECTROSCOPY
Nebulizer converts the
solution into a spray

Flame (or Plasma) causes the solvent to evaporate,

leaving dry aerosol particles, then volatilizes the particles,
producing atomic, molecular and ionic species

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

Gases mixture flame (1800 4500 C): air-propane, air-acetylene etc. ;

Atomic absorption spectrometry quantifies the absorption of ground state atoms in the
gaseous state ;
The atoms absorb ultraviolet or visible light and make transitions to higher electronic
energy levels . The analyte concentration is determined from the amount of absorption.

ATOMIC ABSORPTION SPECTROSCOPY (AAS)

Operation principle of AAS

Light source hollow cathode lamp. Each element has its own unique lamp.
Atomic cell flame (gas mixture) or graphite furnance (accepts solutions, slurries, or
even solids).
Detector photomultiplier.

LIGHT SOURCE:

Hollow Cathode Lamp are the most common radiation

source in AAS.

It contains a tungsten anode and a hollow cylindrical

cathode made of the element to be determined.

These are sealed in a glass tube filled with an inert gas

(neon or argon ) .

Each element has its own unique lamp which must be

used for that analysis .

Hollow Cathode Lamp:

Quartz window

Pyrex body

cathode

Anode
Cathode

NEBULIZER:

Suck up liquid samples at controlled rate.

Create a fine aerosol spray for introduction into

flame.

Mix the aerosol and fuel and oxidant thoroughly

forintroduction into flame.

ATOMIZERS:

Elements to be analyzed needs to be in atomic

state.

Atomization is separation of particles into

individual molecules and breaking molecules into
atoms. This is done by exposing the analyte to high
temperatures in a flame or graphite furnace .

ATOMIZERS:

ATOMIZER

FLAME
ATOMIZERS

GRAPHITE
TUBE
ATOMIZERS

FLAME ATOMIZER:

To create flame, we need to mix an oxidant gas and

a fuel gas.

In most of the cases air-acetylene flame or nitrous

oxide-acetylene flame is used.

Liquid or dissolved samples are typically used with

flame atomizer.

BURNERS

There are two basic types of aspirator*-burners that are used

in AAS; Total Consumption Burner and Premix Chamber
Burner.

The fuel and oxidant (support) gases are mixed and combust at
the tip of the burner. [The sample is drawn up into the flame by
the venture effect (suction effect) by the support gas, finally
it is broken into a fine spray (aerosol) at the tip of the burner
where it is mixed with the fuel and
oxidant and burned].

It is called a total consumption burner because

the entire aspirated sample enters the flame

Fuel
Oxidant

Sample

PREMIX BURNER

Premix burners have a long, narrow burner head that serves

as a sample path (b). Sample introduced via aspiration.
The nebulizer controls sample flow by producing a mist.
The mixing chamber assures that the sample mixes with the
fuel and oxidant before to entry into the flame.
Premix burners are largely used for AA analysis.
b

Capillar
y

Advantage of using a Total Combustion Burner

Can analyze viscous samples example undiluted serum and urine.

Uses entire aspirated sample.
Can be used for most types of flames both high velocity and low
velocity.

Disadvantage
Shorter path length thus larger droplets are not completely
vaporized. This partially vaporized droplets produce solids in
the light path hence causing light scattering giving inaccurate
absorbances.
Combustion is noisy.

Advantage of using a Premix Burner

Larger droplets condense and drains out only allowing

the fine droplets to enter in the flame.
Longer path length hence very sensitive/accurate
absorbances.
Quiet combustion.
Disadvantage
Out of the 100% sample that enters in and only 10% of it goes
into the flame and 90% is lost.
Limited to relatively low velocity flames.

GRAPHITE TUBE ATOMIZER:

Uses a graphite coated furnace to vaporize the

sample.

ln GFAAS sample, samples are deposited in a small

graphite coated tube which can then be heated to
vaporize and atomize the analyte.

The graphite tubes are heated using a high current

power supply.

MONOCHROMATOR:

This is a very important part in an AA spectrometer.

It is used to separate out all of the thousands of
lines.

A monochromator is used to select the specific

wavelength of light which is absorbed by the
sample, and to exclude other wavelengths.

The selection of the specific light allows

determination of the selected element in
presence of others.

the
the

DETECTOR:

The light selected by the monochromator is directed

onto a detector that is typically a photomultiplier
tube , whose function is to convert the light signal
into an electrical signal proportional to the light
intensity.

The processing of electrical signal is fulfilled by a

signal amplifier . The signal could be displayed for
readout , or further fed into a data station for
printout by the requested format.

Photomultiplier Tube (PMT)

CALIBRATION CURVE

A calibration curve is used to determine the

unknown concentration of an element in a solution.
The instrument is calibrated using several solutions
of known concentrations. The absorbance of each
known solution is measured and then a calibration
curve of concentration vs absorbance is plotted.

The sample solution is fed into the instrument, and

the absorbance of the element in this solution is
measured .The unknown concentration of the
element is then calculated from the calibration curve

EXAMPLE 1

A 3.9877g of fish sample is charred, ashed and dissolved in nitric

acid. After filtering and diluting the filtrate to the mark of a 100
ml volumetric flask, a further diluting was performed, 10 ml diluted
to 100 ml. The following absorbance data was obtained from the
atomic absorption spectrometer.
C (ppm)
5.0
10.0
15.0
20.0
25.0
Sample

Absorbance
0.097
0.201
0.314
0.411
0.520
0.395

i. Plot the data and calculate the concentration of potassium in the

original fish sample.
ii. Calculate the amount of potassium in milligrams in the fish sample.
[K: Mr 39.09g/mol]

SOLUTION

Absorbance

Graph of concentration v/s Absorbance

0.6

y = 0.0211x - 0.0082

0.4
0.2
0
0

10

15

20

25

30

Concentration (ppm)

* Always get the concentration from the graph and not the equation
in exams, concentration of K is very close to 19ppm
* By substituting the absorbance into the equation the
concentration is
19.1ppm: 0.395=0.0211x-0.0082; x=
(0.395+0.0082)/0.0211; x= 19.1ppm
A. Concentration of K= 19.1 ppm
B. Mass= 19.1 mg/L x 0.1L = 1.9 milligram

APPLICATIONS:
Determination of even small amounts of metals
(lead, mercury, calcium, magnesium, etc) as follows:

Environmental studies: drinking water, ocean water,

soil.

Food industry.

Pharmaceutical industry.

EXPERIMENTS
DETERMINATION

OF VANDIUM IN LUBRICATING OIL

DETERMINATION

OF TRACE ELEMENTS IN CONTAMINATED SOIL

VANADIUM IN LUBRICATING OIL:

THEORY:

High temperature corrosion and fouling can be attributed to

vanadium in the
fuel. During combustion, the element oxidize and form semiliquid and low
melting salts (vanadium pentoxide), which adhere to exhaust
valves and
turbochargers. In practice, the extent of hot corrosion and
fouling are
generally

maintained

at

an

acceptable

level

through

The oil is dissolved in white spirit and the absorption of this

solution is compared with the absorption of standard.

STANDARD SOLUTION: the standard solutions are made up

from vanadium naphthenate in white spirit which contain about
3% of vanadium.

(weigh out 0.6 g of vanadium naphthenate into a 100 ml flask

and made up to mark with white spirit. dilute portions of this
stock solution to obtain a series of working standards
containing 10-40 mg ml-1 of vanadium).

PROCEDURE:

Weigh out accurately about 5 g of the oil sample, dissolve in small

volume of white spirit and transfer to 50 ml flask.

Using same solvent, make up the sol. to the mark.

Set up a vanadium hollow cathode lamp selecting a resonance line

of wavelength 318.5 nm.

Adjust gas controls to give a fuel rich acetylene-nitrous oxide

flame.

Aspirate successfully into the flame the solvent blank, standard

solutions and finally the test solution

In each case recording the absorbance reading .plot the calibration

curve and ascertain the vanadium content of the oil.

LEAD IN CONTAMINATED SOIL:

SAMPLING: samples of approx. 50g should be taken from

specified sampling points on the site.

The sampling point should include surface soil and two further
samples taken at depth, at 0.5 and 1.0m.

The exact location of these points should be noted, for it may

be necessary to take further samples.

PROCEDURE:

Weight out about 1g of seived soil and transfer to a

100ml beaker. add 20 ml of 1:1 nitric acid .

Boil gently on a hot plate until the volume of nitric

acid is reduced to 5ml.

Add 20ml of deionised water and boil gently again

until the volume is 10ml.

Cool the suspension and filter through a whatman

filter paper, washing the beaker and filter paper with
deionised water until a volume of about 25ml is
obtained.

Transfer the filtrate to a 50ml flask and make up to

the mark with deionised water.

Setup acetylene-air flame with resonance line 217.0

nm.

Standard lead solutions containing 1-10 mg ml -1 are

suitable for measurement

REFERENCES:

Vogels Textbook of Quantitative Analysis, G. Svehla,

Pearson.
Principles of Instrumental Analysis, Skoog.
Basic Concepts Of Analytical chemistry, S M Khopkar.