TOMIC

BSORPTION

PECTROSCOPY
 ATOMS
Bohrs shell model:
SODIUM atom
Nucleus- protons
Electrons
(+ve) and neutrons
(neutral).
Electrons- (-ve)
charged particle.
Nucleus Shells- consists of
Shells
subshells.
 Shell, Subshells, Electrons
Electrons are arranged according to their
energy levels. They are arrange in subshells,
the subshells are arrange in shells and shells
are arrange around the nucleus.
Atom
(around the nucleus)
Shells
!Note:
Electrons that are near the nucleus has
a lower energy level than the electrons Subshells
that are much far away. However, they
experience stronger attraction in the
nucleus than those ones that are Electrons
further away.
 Exciting atoms
ground state: is a status where the atoms
electrons are in their lowest possible energy
level. (stable)

excited state: another status where the

atoms electrons absorb enough energy to
be promoted to a higher level. Therefore,
they are not in their lowest energy level.
(unstable)
 Since, an atoms excited
state is very unstable it
Excited atom rapidly jump back down
to its ground state. This
jump then causes the
atom to release the
Generally, atoms are energy it absorbed in the
in their ground state form of photons of light.
but when an atom
receives enough input
of energy that their
electrons requires to
be promoted to a
higher energy level.
!Note:
They will then turn to Take note that the
their excited state. electron can go back
down to its original
Ground state:
Excited state: place in more than
one jump.
sodium atom
Technique Flame Test

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The Copper Flame
The Potassium Flame
The Manganese Flame
The Cobalt Flame
 The Calcium Flame

The calcium
flame is
red. This is
intensely
red
because
the calcium
content is
high.
 Flame Atomizers (Continuous
Atomizers)
Flame Atomizers (Continuous Atomizers)
There are several types of flame atomizers available. The
simplest is a turbulent flow burner that is very similar to
conventional Bunsen burner. This type of burner suffers
from fluctuations in temperature since there is no good
mechanism for homogeneous mixing of fuel and oxidant.
The drop size of nebulized sample is also inhomogeneous
which adds to fluctuations in signal. The path length of
radiation through the flame is small which suggests a lower
sensitivity of the technique.

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Turbulent flow burners are also susceptible to
flashback. These drawbacks were overcome using
the most widely used laminar flow burner where
quite flames and long path length are obtained.
Flashback is avoided and very homogeneous mixing
between fuel, oxidant, and droplets take place.
Larger droplets are excluded and directed to a
waste container. A schematic representation of the
burner is shown below:

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Elements detectable by atomic absorption are highlighted in pink in this

periodic table
 What is AAS?
(AAS) Atomic Absorption Spectroscopy is:
Quantitative technique

Typical samples: low viscosity samples

Generally uses to determine the amount of several

metals (e.g. Cu, Fe, Zn, Mg) in the soil, blood, air,
water, and food.

Occasionally can be use as a qualitative technique

(can indentify chemicals that are present) 68
elements
 In the electromagnetic spectrum, it uses
the visible part to detect the presence of
metals (p.77 chem book)
Foundation of the technique: the
absorption of the light energy that has
the right wavelength causes the electrons
from the sample to be promoted from a
lower energy level to a higher energy
level.
 A block diagram of the AA spectrometer appears
below.
The IB does not require the inclusion of the
photomultiplier tube (PMT), but it none the less
is an important part of the instrumentation.
Overview of AA Sample
spectrometer. Compartment

Light Source Detector

Dr. Maha Daghestani
24
 1. Flame Atomization
Flames are regarded as continuous atomizers since
samples are continuously introduced and a constant
or continuous signal is obtained. Samples in
solution form are nebulized by one of the described
nebulization techniques discussed previously. The
most common nebulization technique is the
pneumatic nebulization. Nebulized solutions are
carried into a flame where atomization takes place.

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 Several processes occur during atomization
including:
a. Nebulized samples are sprayed into a flame
as a spray of very fine droplets
b. Droplets will lose their solvent content due
to very high flame temperatures in a process
called desolvation and will thus be converted
into a solid aerosol.
c. The solid aerosol is volatilized to form
gaseous molecules
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d. Gaseous molecules will then be atomized
and neutral atoms are obtained which can be
excited by absorption of enough energy. If
energy is not enough for atomization,
gaseous molecules will not be atomized and
we may see molecular absorption or
emission
e. Atoms in the gaseous state can absorb
energy and are excited. If energy is too much,
we may observe ionization.

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Flame atomization

Processes occurring during atomization

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Flame atomization

Nebulizer - burner

A typical premix burner

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Nebuliser - burner

To convert the test solution to gaseous atoms

Nebuliser --- to produce a mist or aerosol of the

test solution
Vaporising chamber ---
Fine mist is mixed with the fuel gas and the
carrier gas
Larger droplets of liquid fall out from the gas
stream and discharged to waste

Burner head --- The flame path is about 10 12 cm

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Fuel and oxidant

flame Auxiliary
oxidant

Air- propane Fuel

Air- hydrogen

b Air acetylene
b Nitrous oxide acetylene

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Common fuels and oxidants used in flame
spectroscopy

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Disadvantages of flame atomization

Only 5 15 % of the nebulized sample

reaches the flame

A minimum sample volume of 0.5 1.0 mL

is needed to give a reliable reading

Samples which are viscous require dilution

with a solvent

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Eletrothermal atomization

Graphite furnace technique

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Plateau Graphite Tube

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Graphite furnace technique

process

drying ashing atomization

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Graphite furnace technique

Advantages
Small sample sizes ( as low as 0.5 uL)

Very little or no sample preparation is needed

Sensitivity is enhanced
( 10 -10 10-13 g , 100- 1000 folds)

Direct analysis of solid samples

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Graphite furnace technique

Disadvantages
Background absorption effects
Analyte may be lost at the ashing stage

The sample may not be completely atomized

The precision was poor than the flame method

(5%-10% vs 1%)
The analytical range is relatively narrow
(less than two orders of magnitude)
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Cold vapour technique

Hg2+ + Sn2+ = Hg + Sn (IV)

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Hydride generation methods

For arsenic (As), antimony (Te) and selenium (Se)

NaBH4 heat
As (V) AsH3 As0(gas) + H2
[H+] in flame
(sol)

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Monochromator

--- diffraction grating

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Detector

--- photomultiplier

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Read-out system

--- meter

--- chart recorder

--- digital display

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Atomic absorption spectrophotometer

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Interferences

Spectral interferences

Chemical interferences

Physical interferences

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Spectral interferences

----- spectral overlap

+, positive analytical error

Cu 324.754 nm, Eu 324.753 nm
Al 308.215 nm , V 308.211nm,
Al 309.27 nm

Avoid the interference by observing the

aluminum line at 309.27 nm

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Spectral interferences

----- non-absorption line Non-

absorbable suture
----- molecular absorption +

combustion products (the fuel and

oxidant mixture)
Correct by making absorption
measurements while a blank is aspirated
into the flame

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Spectral interferences

----- light scatter +

Metal oxide particles with diameters

greater than the wavelength of light
When sample contains organic species
or when organic solvents are used to
dissolve the sample, incomplete
combustion of the organic matrix
leaves carbonaceous particles that are
capable of scattering light

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Spectral interferences

----- light scatter Light Scattering+

The interference can be avoided by

variation in analytical variables, such
as flame temperature and fuel-to
oxidant ratio
Standard addition method
Zeeman background correction

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 Chemical interferences

----- Formation of compound of low volatility

Ca 2+ PO43- Mg2+, Al3+

Increase in flame temperature

b
Use of releasing agents (La 3+ )
b
Use of protective agents (EDTA)
b
b Separation

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Chemical interferences

----- Ionization

Adding an excess of an ionization

b suppressant (K)

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Physical interferences

----- viscosity
----- density
----- surface tension
----- volatility

Matrix matching
b

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Experimental preliminaries

Preparation of sample solutions

Optimization of the operating conditions

----- resonance line
----- slit width
----- current of HCL
----- atomization condition

Calibration curve procedure

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The standard addition technique

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Sensitivity and detection limit

Sensitivity
----- the concentration of an aqueous
solution of the elements which absorbs
1% of the incident resonance radiation

----- the concentration which gives an

absorbance of 0.0044

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Sensitivity and detection limit

Detection limit
----- the lowest concentration of an analyte
that can be distinguished with reasonable
confidence from a field blank

D = c 3 / A

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Sensitivity and detection limit (ng/mL)

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Advantages and disadvantages

High sensitivity
[10-10g (flame), 10-14g (non-flame)]
Good accuracy
(Relative error 0.1 ~ 0.5 % )
High selectivity

Widely used

A resonance line source is required for

each element to be determined

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The different processes occurring in flames are
complicated and are not closely controlled
and predicted. Therefore, it can be fairly
stated that the atomization process in flames
may be one of the important parameters
limiting the precision of the method. It is
therefore justified that we have a closer look
at flames and their characteristics and the
different variables contributing to their
performance.

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 Types of Flames
Flames can be classified into several types depending
on fuel/oxidant used. For example, the following
table summarizes the features of most familiar
flames.
Therefore, it can be clearly seen that significant
variations in flame temperatures can be obtained
by changing the composition of fuel and oxidant.

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64
On the other hand, flames are only stable at certain
flow rates and thus the flow rate of the gas is very
important where at low flow rates (less than the
maximum burning velocity) the flame propagates
into the burner body causing flashback and, in some
cases, an explosion. As the flow rate is increased,
the flame starts to rise above the burner body. Best
flames are obtained when the flow rate of the gas is
equal to the maximum burning velocity. At this
equity ratio the flame is most stable. At higher
ratios, flames will reach a point where they will no
longer form and blow off the burner.

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 Discovery of AAS
1952, the Australian scientist Alan Walsh was working
on the measurement of small concentrations of metals
at the CSIRO using atomic emission spectroscopy.

The idea of AAS came into his mind as he was gardening

at his Melbourne home. On the normal Sunday morning
he had the idea about looking at the light absorbed by
the atoms except than looking at the light they emits.

Alan Walsh did not just discover a process that has the
ability to save lives but also proven that atoms will only
absorb light that has the EXACT value requires to
promote their electron to a higher level.
A Quantitative Study of Light
Sir Isaac Newton was one of the
first people to study light
scientifically.
In 1672, Newton directed a beam
of white light through a triangular
bar of glass, called a prism. He
discovered that the light coming
out of the prism was separated into
bands of colors.
The arrangement of colors
produced by a prism is called a
spectrum.
Sir Isaac Newton Prior to this it was believed that
1643 - 1727 white light was equal to purity.
Original Studies Of Light Used Only One Prism

When a narrow band of light from a white light source is

sent through a prism, a continuous spectrum containing all
wavelengths of visible light is formed.
 Newtons Contribution to Spectroscopy
Newton contributed more to spectroscopy than scientifically
proving that sunlight traveling through a prism was always
broken down into the components of the rainbow.

In fact, his main contribution was to show that after the sunlight
had been broken down into its components by one prism, if a
narrow ray of the light from the first prism was passed through
another prism there would be no further breakdown.
Classification of Electromagnetic Radiation

The color components of light are separated along the visible

range of light. The visible range of light (400-700 nm) is
merely a small portion of the entire electromagnetic spectrum.
 How does AAS works?

Lamp
monochromator detector
meter
Burner slit
 The source of light is a lamp whose cathode is
composed of the element being measured.
Each analyzed element requires a different lamp.
For example, a hollow cathode lamp for
Aluminum (Al) is shown below
 The cathode lamps are
stored in a compartment
inside the AA spectrometer.
The specific lamp needed
for a given metal analysis is
rotated into position for a
specific experiment.
 Hollow cathode lamp (HCL)

Cathode--- in the form of a cylinder, made

of the element being studied in the flame
Anode---tungsten
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A hollow cathode lamp for Aluminum (Al)

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SpectrAA - AAS

HCL

motorized
Mirror

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How can we obtain the data?
The intensity of the light
coming through the cathode
lamp is measured
The higher the concentration
of the metal that is being
observe in the sample the
greater the absorbance.
The intensity of the light is
then again measured and
compared to the first result.
= absorbance
The light can then be absorbed
by the atoms from the sample
that has been vaporized in the
flame.
This wavelength can then
promote the electrons to a higher
energy level = excited state
 How do we analyze the data?
By comparing the light intensity that has passed through the
sample (refer to previous diagram) with that of the same light
after it has passed through a blank, the absorbance is measured.

The absorbance of different standard solutions of a compound of

the element are also measured and a calibration curve is
constructed.

Absorbance is plotted against concentration. We then use the

calibration curve to determine the unknown concentration.
 Example of a Calibration curve
An AAS was used to determine the concentration of lead ions (in ppm)
in fish. The AAS was set up with a lamp that emitted light with a
wavelength that is absorbed by lead atoms. The AAS was calibrated
using different solutions containing known concentrations of lead ions.
The graph on the next slide shows the variation of absorbance with the
concentration of lead.

A 2.0g sample of the fish was ground up and heated on a hot plate with
10 ml of nitric acid. This mixture was filtered and then sprayed into the
flame of the AAS. The absorbance reading was 6.0. Determine the
concentration of lead ions in the fish.
Graph:
Solution:
 AAS, Flame test, UV-Vis, ICP-AES
Flame test: uses the basic
principle of AAS. The flame test
is basically done by exposing a
sample that is in observation into
a non-luminous Bunsen burner
flame.

UV-Vis spectroscopy: is also similar to

AAS in number of ways:
Have the similar basic principle which is
promoting electrons from lower energy
level to a higher energy level.
Both techniques uses similar steps to
interpret results.
Dissimilarity:
AAS uses visible part of the emission
spectrum
UV-Vis ultraviolet part of the emission
spectrum
 ICP-AES
Inductively coupled plasma (ICP) can produce very
high temperatures (7 000 10 000 K) to create the
plasma instead of a flame.

All the atoms in the sample are excited and able to

emit electromagnetic radiation as they return to
their unexcited ground state.
Some of its advantages over AAS:
- can be used to identify most elements
- Can identify many elements at once-50 elements simultaneously
(AAS can only determine one at a time)
- Is very fast (analysing 70 elements takes 2 minutes).
Common application of AAS
Mostly used in: mines, food industries,
environmental control, petroleum products
as they:

detect deficiencies / excessive amounts of

certain metals in our body fluids such as:
our blood and urine

Tracks harmful metals in our food/drinks

 analyze metal ions that are polluting the soil,
air and water.

Investigating different locations to test for

different elements present and how much of
these elements are present.

Analyze metals present in engine oils.

 ADVANTAGES & DISADVANTAGES:
Precise and very sensitive
accurate results can be obtained.

Moderately expensive
Can only process one element at a time.
Slower than ICP-AES
Can only identify limited types of elements
 A life-saving technique
Canada: AAS was used to determine unsafe levels of
lead in children who was lives nearby a lead smelter.
Japan: From 1932 to 1968, AAS was used to identify
the reason why over 3,000 residents who lives near
the Minimata Bay started showing neurogical
problems and pregnant women starts giving birth to
impaired children. Scientist starts taking samples and
performing AAS process; AAS results shows a very
high concentration of mercury in their blood. This
result on stopping the company, Chisso
corporation who dumped approximately 27
tones of mercury in the bay.
 Safety Precautions
Exhaust System: AAS flames produce large amounts of heat & the
resultant fumes & vapours may be toxic.
Gas Cylinders: should be located outside of the laboratory in a
cool well-ventilated area.
Flammable Solvents: The combination of flame & solvent is a
hazardous situation. Always use a solvent with the highest
flashpoint consistent with the analysis being conducted. Use
covered containers & the smallest practical volume.
Burners: Keep burners clear & do not allow them to block.
UV Radiation: Hazardous UV radiation is emitted by flames, hollow
cathode lamps, analytical furnaces. Never look directly at any of
these. Operate the AAS with the door or flame shield closed and
wear appropriate safety glasses.