TOMIC

BSORPTION
PECTROSCOPY

ATOMS
Bohrs shell
model: SODIUM
atom
Electron
s

Nucleu
s

Shell
s

Nucleus- protons
(+ve) and
neutrons
(neutral).
Electrons- (-ve)
charged particle.
Shells- consists of
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 that are
much far away. However, they
experience stronger attraction
in the nucleus than those ones
that are further away.

Subshells
Electrons

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)

Excited atom
Generally, atoms
are
in
their
ground state but
when an atom
receives enough
input of energy
that
their
electrons requires
to be promoted to
a higher energy
level. They will
then turn to their
excited state.

Since,
an
atoms
excited state is very
unstable it rapidly
jump back down to
its ground state. This
jump then causes
the atom to release
the
energy
it
absorbed
in the
form of photons of
light.

Ground state:
Excited
sodium atom

!Note:
Take note that the
electron can go
back down to its
original place in
more than one
jump.

Technique Flame Test

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.
12

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:
13

14

15

16

17

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
spectrometer.

Sample
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.
25

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
26

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.
27

28

29

Flame atomization
Processes occurring during
atomization

30

Flame atomization
Nebulizer - burner

A typical premix
burner

31

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

32

Fuel and oxidant

flame

Auxiliary
oxidant

Air- propane

Fuel

Air- hydrogen

Air acetylene

Nitrous oxide acetylene

33

Common fuels and oxidants used in

flame spectroscopy

34

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

35

Eletrothermal atomization
Graphite furnace technique

36

Plateau Graphite
Tube

37

Graphite furnace technique

process

drying

ashing

atomization

38

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

39

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)

40

Cold vapour technique

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

41

Hydride generation methods

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

As (V) 4
(sol)

[H+]

AsH3

hea
t
in
flame

As0(gas) + H2

42

43

Monochromator
--- diffraction grating

44

Detector
--- photomultiplier

45

Read-out system

--- meter
--- chart recorder
--- digital display

46

Atomic absorption
spectrophotometer

47

Interferences
Spectral interferences
Chemical interferences
Physical interferences

48

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
49

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
50

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

51

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
52

Chemical interferences
----- Formation of compound of low
volatility

Ca 2+ PO43Mg2+,
Al3+
Increase in flame temperature
Use of releasing agents (La

3+

Use of protective agents (EDTA)

Separation
53

Chemical interferences
----- Ionization

Adding an excess of an ionization

suppressant (K)

54

Physical interferences
----- viscosity
----- density
----- surface tension
----- volatility

Matrix matching

55

Experimental preliminaries
Preparation of sample solutions
Optimization of the operating
conditions
----- resonance line
----- slit width
----- current of HCL
----- atomization condition

Calibration curve procedure

56

The standard addition

technique

57

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

58

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

59

(ng/mL)
Sensitivity and detection limit

60

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
61

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.
62

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.
63

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.
65

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
1643 - 1727

Prior to this it was believed that

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
detector

monochromator
Burner

slit

meter

 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
74

A hollow cathode lamp for Aluminum (Al)

75

SpectrAA - AAS
HCL

motorized
Mirror

76

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, ICPAES

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

 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.