Unit II

Atomic absorption
spectroscopy
(AAS)
Characteristics of a wave

λ
A

λ, vel, ν, ν, amp, Ψ2
 Sources of EMR
• Radiowaves-AC currents of high frequency
• IR radiations-Rare earth oxides (incandescent
objects)
• Visible radiations-tungsten filament
• UV rays-sun rays, Hg vap, Hyd gas
• γ-rays-Radioactive substances
THE ELECTROMAGNETIC SPECTRUM
 Beer-Lambert law

• The method is most often used in a quantitative way to determine

concentrations of an absorbing species in solution, using the Beer-
Lambert law:
• absorbing species in solution, using the Beer-Lambert law:
A = εcl = -log10 (I/I0)
• where A is the measured absorbance, I0 is the intensity of the
incident light at a given wavelength, I is the transmitted intensity, L
the pathlength through the sample, and c the concentration of the
absorbing species. For each species and wavelength, ε is a
constant known as the molar absorptivity or extinction coefficient
 Mathematical derivation

-dI/dx α I

-dI/dx α c

-dI/dx =kI c

-dI/I =k c dx, on integrating

lnI/I0 = -k c l

log I0/I=k c l/2.303

log I0/I=ε c l

A=εcl
A = 2-log %T
 Calibration curve method

0.6
0.5
0.4
A

0.3
0.2
0.1
0
0 10 20 30 40 50 60
Conc
 AAS-Introduction

• Introduced by Alan Walsh in the mid 1950’s

• Most powerful instrumental technique for quantitative determination
of trace metals in liquids. Is a spectroanalytical procedure
• By this technique determination of element can be made in
presence of other elements also.
• It determines total Cr content in water samples irrespective of how it
exists as nitrates, sulphates, chlorides, etc.
• Can detect as low as 1 ppm
• High sensitivity
• Disadvantage- only one element can be detected at a time
• AAS can be used to determine over 70 different elements in solution
or directly in solid samples
 Principle

• When light of a particular wavelength is is allowed to pass through a flame

having atoms of the metallic species. Part of the radiation will be absorbed.
Once the value of absorption is known, the concentration of the metallic
element can be known because the absorption is proportional to the density
of the atoms in the flame.

• Mathematically, the total amount of light absorbed is given as

= πe2 Nf/mc
total amount of light absorbed = constant x N x f

e=charge, m=mass of electron, N=total no. of atoms, c= vel of light

f=oscillator strength, ability to absorb at frequency,v

Is thus independent of λ and temperature of the atoms. Temperature

however effects the efficiency with which the atoms are produced
 Principle
• Relies on Beer-Lambert Law.
• the electrons of the atoms in the atomizer can be promoted to higher
orbitals (excited state) for a short period of time (nanoseconds) by
absorbing a defined quantity of energy (radiation of a given
wavelength).
• This amount of energy, i.e., wavelength, is specific to a particular
electron transition in a particular element. In general, each
wavelength corresponds to only one element, and the width of an
absorption line is only of the order of a few picometers (pm), which
gives the technique its elemental selectivity.
Return to Slide 10
The Atomic Absorption Spectrometer
Sample Introduction System

Nebuliser

Capillary

Solution
 Instrumentation
• Light of a certain wavelength (produced by a special kind of lamp)
which is able to emit the spectral lines corresponding to the energy
required for an electronic transition from the g.s to an e.s., is allowed
to pass through the flame.

• The sample of interest is aspirated into the flame. Once it enters the
flame it forms small droplets, evaporates to give the dry salt and
then the vapour of the salt. If that metal is present in the sample, it
will absorb some of the light, thus reducing its intensity. The
instrument measures the change in intensity. From the
monochromator the unabsorbed radiation is led into the detector
which is then registered by a photo detector the output of which is
amplified and measured on a recorder. Or a computer data system
converts the change in intensity into an absorbance.

• As concentration goes up, absorbance goes up. construct a

calibration curve by running standards of various concentrations on
the AAS and observing the absorbances.
 How it works

Applying a potential difference between the

anode and the cathode leads to the ionization of
some gas atoms .

These gaseous ions bombard the cathode and

eject metal atoms from the cathode in a process
called sputtering. Some sputtered atoms are in
excited states and emit radiation characteristic of
the metal as they fall back to the ground state .
 Components of Instrument
1. Radiation source- HCL
2. Chopper
3. Atomizer
4. Nebulizer
5. Monochromator
6. Detector
7. Amplifier
8. Read-out device
 Hollow cathode lamps
• Hollow cathode lamps (HCL) are the most common radiation source
in AAS.

• Inside the sealed lamp, filled with argon or neon gas at low
pressure, is a cylindrical metal cathode containing the element of
interest and an anode.

• A high voltage is applied across the anode and cathode, resulting in

an ionization of the fill gas.

• The gas ions are accelerated towards the cathode and, upon
impact on the cathode, sputter cathode material that is excited in the
glow discharge to emit the radiation of the sputtered material, i.e.,
the element of interest.i.e the element goes from g.s to e.s and then
back to g.s. with emission of radiations. It is anelectronic excitation
and the energy of transitions lies in the to UV-VIS region of the
electromagnetic spectrum.
Hollow Cathode Lamp
Quartz window
Anode-W filament
Cathode-metal to be analysed
Pyrex body
cathode

Anode

Cathode
 Chopper
• It is a rotating wheel interposed between
the HCL and the flame.
• It breaks the steady light from the lamp
into an intermittent or pulsating light.
• This gives a pulsating current (AC) in the
photocell which can be amplified and
recorded.
 Flame atomizers
• The oldest and most commonly used atomizers
in AAS are flames,
1. the air-acetylene flame with a temperature of
about 2300 °C and
2. the nitrous oxide (N2O)-acetylene flame with
a temperature of about 2700 °C.
 Three steps are involved in turning a liquid sample into
an atomic gas: sample into an atomic gas:

• Desolvation – the liquid solvent is evaporated, and the

dry sample remains

• Vaporizations – the solid sample vaporizes to a gas

• Volatilization – the compounds making up the sample

are broken into free atoms.

• The flame is arranged such that it is laterally long

(usually 10cm) and not deep. The height of the flame
must also be controlled by controlling the flow of the fuel
mixture. the flame gas flow-rates is adjusted to produce
the highest concentration of free atoms.
Processes that take place in flame
 Total consumption burner
In the total
consumption burner
the fuel, oxidant, and
sample all meet at
the base of the
flame.
The resulting flame
is turbulent and non-
homogenous-a
property that
negates its
usefulness in AA,
since the flame must
be homogeneous,.
 Premix or laminar flow burner
flame

fuel

head
oxidant

sample air

baffles
Drain

Premix burners are called Bunsen, Flame is non-turbulent

Méker, or slot burners depending Small amount of sample
on reaches the flame.
whether they have one large hole, a Efficient atomization
number of small holes Sample wasted
Sensitivity is low
 Interferences
1. Spectral interference-another element, radical,
molecule, background emission from flame, solvent,
etc.
2. Chemical interference-dissociation/association,
complex formation
3. Ionization interference- if flame temp is more then
ionization instead of atomization
4. Matrix or bulk interference due to viscosity changes on
changing solvent
5. Dissociation of metal compounds-formation of oxides
6. Role of solvent-aqueous/organic. Difficult to atomize in
aqueous solvents
 Samples
• Solids-dissolved in suitable solvent-
metals, alloys, fertilizers, ores, polymers,
cement, etc.
• Liquids-blood, urine, water pollutants,
wine, electroplating solutions
• Gas –trapping gas in solutions
 Advantages of AA
• Determination of 68 metals
• Ability to make ppb determinations on major components
of a sample
• Precision of measurements. There are few other
instrumental methods that offer this precision so easily.
• AA analysis is subject to little interference.
• Most interference that occurs have been well studied
and documented.
• Sample preparation is simple (often involving only
dissolution in an acid)
• Instrument easy to tune and operate
 Advantages of AAS

• It is highly specific as elements absorb

radiation of their own characteristic λ.

• AA Spectroscopy is independent of flame

temperature
 Disadvantages of AAS

• A separate lamp (HCL) is required for

each element
• Some elements give rise to oxides in the
flame, so cannot be successfully
estimated eg Al, Ti, Mo, etc.
• Sometimes the predominant anion affects
the signal to some extent
 Applications
1. Qualitative analysis
2. Quantitative analysis
3. Simultaneous multicomponent analysis
4. Determination of metallic elements in biological
materials
5. Determination of metallic elements in food industry
6. Determination of Ca, Mg, Na, K in blood serum
7. Determination of lead in petrol
 AAS APPLICATIONS

The are many applications for atomic absorption:

- Clinical analysis : Analyzing metals in biological
fluids such as blood and urine.
- Environmental analysis : Monitoring our
environment – e g finding out the levels of various
elements in rivers, seawater, drinking water, air,
and petrol.
- Pharmaceuticals. In some pharmaceutical
manufacturing processes, minute quantities of a
catalyst used in the process (usually a metal) are
sometimes present in the final product. By using
AAS the amount of catalyst present can be
determined
 AAS APPLICATIONS
- Industry : Many raw materials are examined and AAS
is widely used to check that the major elements are
present and that toxic impurities are lower than
specified – e g in concrete, where calcium is a major
constituent, the lead level should be low because it is
toxic.
- Mining: By using AAS the amount of metals such as
gold in rocks can be determined to see whether it is
worth mining the rocks to extract the gold .

- Trace elements in food analysis

- Trace element analysis of cosmetics
- Trace element analysis of hair