Introduction to Atomic

Spectroscopy
Lecture 10

1
 Introduction to Atomic
Spectroscopy

2
Technique – Flame Test

3
 An Introduction to Optical Atomic
Spectroscopy
The prerequisite for performing atomic spectroscopy is the:
Atomization Method
1- Compounds are first converted to gaseous molecules.
2- Gas molecules then converted to gaseous atoms.
3- Gaseous atoms absorb energy from a beam of radiation
or simply heat.
❖Measuring the absorption: (needs external light source).
❖Measuring the emission: resulted from excited atoms
(don’t need external light source).

Both Abs. and Em. Is related to concentration of analyte.

4
 Atomic Energy Level Diagrams
❖ Only valence electrons are responsible for
atomic spectra observed in a process of
absorption or emission of radiation in the UV-Vis
region.

❖ Valence electrons in their ground states are

assumed to have an energy equal to zero eV.

❖ As an electron is excited to a higher energy

level, it will absorb energy exactly equal to the
energy difference between the two states.

5
Portion of the sodium energy level diagram where sodium got
one electron in the 3s orbital: (3 S1 Val. El.)

6
 5
7s 6p 6p
6s 5d
5s 5p 5p 5682
4 4d
4p 4p
5688
Energy, electron volts

6160 3d
4s
3 8183
6154
8195
11404 3p 3p
2
1138 3302
2
2852. 3303
1
8
2853 5890 Values:  in Ao
5896
0 3s
 more intense
than others
(most prop. And
dense,
(resonance lines
(preferred for
8 measurements)
 5682.7 5688.2 Ao
5890 and 5896 Ao

4000 4400 4800 5200 5600 6000 6400

Wavelength A
- The dark lines represent most probable
transitions and in an atomic spectrum they
would appear more intense than others.
- Two transitions, of very comparable energies
(589.0 and 589.6 nm), from the 3s ground
state to 3p excited state do take place.
- This suggests splitting of the p orbital into
two levels that slightly differ in energy.
Explanation:
Splitting may be presented as a result of
electron spin where the electron spin is
either in the direction of the orbital motion or
opposed to it.
10
Both spin and orbital motion create magnetic
fields that may lead to:
Lower E line: interact in an attractive manner, if
motion is in opposite direction, lower energy.
Higher E line: interact in a repulsive manner
when both spin and orbital motion are in the
same direction.
The same occurs for both d and f orbitals but
the energy difference is so small to be
observed.
A Mg+ ion would show very similar atomic
spectrum as Na since both have one electron
in the 3s orbital.
11
For atoms of large numbers of electrons:
Atomic spectra become too complicated and
difficult to interpret.
This is mainly due to presence of a large numbers
of closely spaced energy levels.
Selection Rule:
❖ Transition from ground state to excited state is
not arbitrary and unlimited.
❖ Transitions follow certain selection rules that
make a specific transition allowed or forbidden.

12
 Atomic Emission and Absorption
Spectra
At room temperature:
All atoms are in the ground state.
Excitation of electrons:
From ground state atoms requires an input of
sufficient energy to transfer the electron to one of
the excited state through an allowed transition.
Excited electrons:
Spend a short time in the excited state (shorter
than a ms).
Relaxation an excited electron:
Emit a photon and return to the ground state.
13
Preferred transition (most probable):
• Each type of atoms would have certain preferred
or most probable transitions (sodium has the
589.0 and the 589.6 nm).

• Relaxation would result in very intense lines for

these preferred transitions where these lines are
called resonance lines.

• Absorption of energy is most probable for the

resonance lines of each element.

• Thus intense absorption lines for sodium will be

observed
14 at 589.0 and 589.6 nm.
 Atomic Fluorescence Spectra
When gaseous atoms at high temperatures are
irradiated with a monochromatic beam of radiation of
enough energy to cause electronic excitation:
• Emission takes place in all directions.
• The emitted radiation from the first excited
electronic level, collected at 90o to the incident
beam, is called resonance fluorescence.

• Photons of the same wavelength as the incident

beam are emitted in resonance fluorescence.

• This topic will not be further explained in this text as

the merits of the technique are not very clear
compared to instrumental complexity involved
15
6s27s2 S1/2

 = 535.0 nm
 = 377.6nm 6s26p2 P3/2

6s26p2 P1/2
Energy level diagram of thallium
 Atomic Line Width
• Should have infinitesimally small (or zero)
line width since transition between two
quantum states requires an exact amount of
energy.

• However, careful examination of atomic lines

reveals that they have finite width.

For example, try to look at the situation where

we expand the x-axis (wavelength axis) of the
following line:

17
 expand x-axis

18
The effective line width in terms of wavelength
units :
Is equal to D1/2
Defined as the width of the line, in
wavelength units, measured at one half
maximum signal (P).
The question which needs a definite
answer is what causes the atomic line to
become broad?

19
 Reasons for Atomic Line Broadening
There are four reasons for broadening
observed in atomic lines. These include:
1. The Uncertainty Principle
D t. D E  h
For un. of D E = zero D t must be 
• Nature places limits on the precision by
which two interrelated physical quantities
can be measured.
• Uncertainty present for calculation of the
energy required for a transition when the
lifetime of the excited state is short.
Error in E leads to error in 
20
 DE>const/Dt
DE = hc/D
Const’/D > Dt
Therefore, atomic lines should have some
broadening due to uncertainty in the lifetime of
the excited state.

The broadening resulting from the uncertainty

principle is referred to as natural line width and
is unavoidable.

21
The uncertainty principle 
Dn . Dt >1 •
Dt = 2*10-8 
D=10-5 nm •
 2. Doppler Broadening
Atoms moving fast either toward or away the detector
(transducer):
Fast moving atom toward a transducer:
More wave crests and thus higher frequency will be
measured.
Fast moving atom away from a transducer:
Lest wave crests and thus lower frequency will be
measured.
The wavelength of radiation emitted by the two
types are different.

The same occurs for sound waves

23
Assume your ear is the transducer, when a car blows
its horn toward your ear each successive wave crest is
emitted from a closer distance to your ear since the car
is moving towards you.
Thus a high frequency will be detected.

On the other hand, when the car passes you and blows
its horn, each wave crest is emitted at a distance
successively far away from you and your ear will
definitely sense a lower frequency.

24
 higher frequency detected

Lower frequency detected

25
The line width (D) due to Doppler broadening can be
calculated from the relation:
D/o = v/c
Where:
o :is the wavelength at maximum power and is equal to
(1 + 2)/2,
(resulted from an atom moving perpendicular to the transducer will
keep its original frequency and will not add to line broadening by the
Doppler effect)

v : is the velocity of the moving atom.

c : is the speed of light.
.

26
Moving atoms towards source:

❖In the case of absorption lines, you may visualize the

line broadening due to Doppler effect since fast
atoms moving towards the source will experience
more wave crests and thus will absorb higher
frequencies.

❖On the other hand, an atom moving away from the

source will experience less wave crests and will thus
absorb a lower frequency.

❖The maximum Doppler shifts are observed for atoms

of highest velocities moving in either direction toward
or away from a transducer (emission) or a source
(absorption).
28
29
 3. Pressure Broadening
(Collisional broadening)
At high pressure atoms
Line broadening caused by collisions of
emitting or absorbing atoms with other atoms,
ions, or other species in the gaseous matrix.

❖These collisions result in small changes in

ground state energy levels.

❖Thus the energy required for transition to

excited states will be different and dependent
on the ground state energy level distribution.
30
 Used as source for Fluorescence Spectroscopy
200 to 1100 nm
31
Pressure Broadening result in important line
broadening.
This phenomenon is most astonishing for xenon where
a xenon arc lamp at a high pressure produces a
continuum from 200 to 1100 nm instead of a line
spectrum for atomic xenon.

A high pressure mercury lamp also produces a

continuum output.

Both Doppler and pressure contribution to line

broadening in atomic spectroscopy are far more
important than broadening due to uncertainty principle.

32
 4. Magnetic Effects
Gaseous atoms in presence of a magnetic field:
Splitting of the degenerate energy levels.
The complicated magnetic fields exerted by electrons
in the matrix atoms and other species will affect the
energy levels of analyte atoms.
The simplest situation:
Is one where an energy level will be split into three
levels
1)one of the same quantum energy.
2) Second one of higher quantum energy,
3)The third assumes a lower quantum energy state.
A continuum of magnetic fields exists due to complex
matrix components, and movement of species, thus
exist.
33Electronic transitions from the thus split levels will
result in line broadening.
34
 The Effect of Temperature on Atomic
Spectra
Atomic spectroscopic methods require the conversion of
atoms to the gaseous state.
This requires the use of high temperatures (in the range
from 2000-6000 oC).
Thee high temperature can be provided through:
1) A flame.
2) Electrical heating.
3) An arc or a plasma source.
It is essential that the temperature should be :
❖ Of enough value to convert atoms of the different
elements to gaseous atoms and,
❖ In some cases, provide energy required for excitation.
❖ Remain constant throughout the analysis especially in
atomic emission spectroscopy.
35
Quantitative assessment:
The effect of temperature on the number of atoms in
the excited state can be derived from Boltzmann
equation:

Where:
Nj : is the number of atoms in excited state
No : is the number of atoms in the ground state,
Pj and Po : are constants determined by the number of
states having equal energy at each quantum level
Ej: is the energy difference between excited and
ground states.
K : is the Boltzmann constant.
T: is the absolute temperature.

36
 Boltzmann distribution

Nj /N0 at
Atom Wavelength
3000 K
Cs 852.1 nm 7.24  10-3
Na 589.0 nm 5.88  10-4
Ca 422.7 nm 3.69  10-5
Zn 213.9 nm 5.58  10-10
37
Application of Boltzmann equation:
Let us consider the situation of sodium atoms in the 3s
state (Po = 2) when excited to the 3p excited state (Pj =
6) at two different temperatures 2500 and 2510K.

Now let us apply the equation to calculate the

relative number of atoms in the ground and
excited states:
Usually we use the average of the emission
lines from the 3p to 3s where we have two lines
at 589.0 and 589.6 nm which is:

38
39
 Therefore:
At higher temperatures:
The number of atoms in the excited state increases.
Let us calculate the percent increase in the number of
atoms in the excited state as a result of this increase
in temperature of only 10 oC:
40
41
 Introduction to Atomic
Spectroscopy
Lecture 11

42
 Effect of Temperature on Atomic Absorption and
Emission
Which technique would be affected more as a result of
fluctuations in temperature?

The answer to this important question is rather simple.

Atomic emission:
It will be severely affected by fluctuations in
temperature since signal is dependent on the number
of atoms in the excited state.
This number is significantly affected by fluctuations in
temperature as seen from the example above.
Atomic absorption:
The signal depends on the number of atoms in ground
state that will absorb energy.
43
very high as related to the number of excited
atoms:
Nj/No = 1.72x10-4
or
172 excited atoms for each 106 atoms in
ground state.
This suggests a very high population of the
ground state even at high temperatures.
Therefore:
Atomic absorption will not be affected to any
significant extent by fluctuations in
temperature, if compared to atomic emission
spectroscopy.
44
Some indirect effects of temperature on atomic
absorption spectroscopy.
1. Better sensitivities are obtained at higher
temperatures since higher temperatures
can increase the number of vaporized
atoms at any time.
2. Higher temperatures will increase the
velocities of gaseous atoms, thus causing
line broadening as a result of the Doppler
and collisional effects.
3. High temperatures increase the number of
ionized analyte and thus decrease the
number of atoms available for absorption
(decrease of signal).
45
 Band and Continuum Spectra
Associated with Atomic Spectra
When the atomization temperature is
insufficient to cause atomization of all species
in the sample matrix:
• Existent molecular entities, at the
temperature of the analysis, impose very
important problems on the results of atomic
absorption and emission spectroscopy.
• The background band spectrum should be
removed for reasonable determination of
analytes.
• Otherwise, the sensitivity of the instrument
46 will be significantly decreased.
47
As the signal for the blank is considered zero
and thus the instrument is made to read zero,
when the analyte is to be determined, it got to
have an absorbance greater than the highest
point on the continuum and the instrument will
assume that the absorbance related to analyte
is just the value exceeding the background
blank value.
This will severely limit the sensitivity of the
technique.
‫يجب التخلص من المنحنى بطريقة سليمة ستدرس الحقا بتقنية‬
Back ground by correction

48
Putting this conclusion in other words we may
say that if the analyte signal is less than the
background blank, the instrument will read it
as zero.
Therefore, it is very important to correct for the
background or simply eliminate it through use
of very high temperatures that will practically
atomize all species in the matrix.

We will come to background correction

methods in the next chapter.

49
 Atomization Methods
It is essential, as we have seen from previous
discussion, that all sample components
(including analytes, additives, etc.) should be
atomized.

The atoms in the gaseous state absorb or emit

radiation and can thus be determined.

Many atomization methods are available which

will be detailed in the next two chapters.
50
 Generally, flame atomization methods can be summarized
by:

51
 Sample Introduction Methods

The method of choice for a specific

sample will mainly depend on:
whether the sample is in solution or solid
form.
The method for sample introduction in
atomic spectroscopy affects the
precision, accuracy and detection limit of
the analytical procedure.

52
 Introduction of Solution Samples

1. Pneumatic ‫ هوائي‬Nebulizers :
Samples in solution are usually easily
introduced into the atomizer by a simple
nebulization, aspiration, process.
Nebulization:
Converts the solution into an aerosol of very
fine droplets using a jet of compressed gas.
The flow of gas carries the aerosol droplets to
the atomization chamber or region.
Several versions of nebulizers are available and few
are shown in the figure below:
53
Predominates in
most instruments Concentric Tube Nebulizer

54
 Concentric Tube Pneumatic
Nebulizer
High-velocity
gas breaks the
High velocity liquid up into
Capillary tube gas flow fine droplets.

Suction

Sampl
e

High pressure Gas inlet

gas flow
Also, predominates
in most instruments Cross Flow Nebulizer

56
Cross-Flow Pneumatic Nebulizer

High pressure
gas flow
Sample
 Babington Nebulizer

58
Babington Pneumatic Nebulizer

Solution film
Sample

High pressure
gas flow
 Fritted Disc Nebulizer

Porous base

60
Fritted Disk Pneumatic Nebulizer

Sample

High pressure
gas flow
 2. Ultrasonic Nebulizers
• In this case samples are pumped onto the
surface of a piezoelectric crystal (that
vibrates in the kHz to MHz range.
• Such vibrations convert samples into
homogeneous aerosols that can be driven
into atomizers.
• Ultrasonic nebulization is preferred over
pneumatic nebulization:
Because: finer droplets and more
homogeneous aerosols are usually achieved.
However, most instruments use pneumatic
nebulization.
62
 Vibrated plate gives
aerosol droplets

63
 3. Electrothermal Vaporization
‫تسخين كهربي‬
An accurately measured quantity of sample (few
mL) is introduced into an electrically heated
cylindrical chamber through which an inert gas
flows.
Constituent:
Usually, the cylinder is made of pyrolytic carbon but
tungsten cylinders are now available.
‫مواد تتحمل الحارة العالية‬
The signal produced by instruments which use
electrothermal vaporization (ETV) is a discrete
signal for each sample injection (not
continuous).
Electrothemal vaporizers are called discrete
atomizers to differentiate them from nebulizers
which are called continuous atomizers
64
65
 4. Hydride Generation Techniques

Samples that contain arsenic, antimony,

tin, selenium, bismuth, and lead (‫ (سهلة‬can
be vaporized by converting them to
volatile hydrides by addition of sodium
borohydride.

Volatile hydrides are then swept into the

atomizer by a stream of an inert gas.

66
 Sodium borohydride + acid
on sample
67
 For production of gas
68
 Introduction to Atomic
Spectroscopy
Atomic Absorption Spectroscopy

Lecture 12

69
 Introduction of Solid Samples
A variety of techniques were used to introduce solid
samples into atomizers. These include:

1. Direct Sample Insertion:

Samples are first powdered and placed in a boat-like

holder (from graphite or tantalum) which is placed in a
flame or an electrothermal atomizer.

70
2) If the sample is conductive and is of a shape that
can be directly used as an electrode:

❖ (like a piece of metal or coin), that would be the

choice for sample introduction in arc and spark
techniques.
❖ Otherwise, powdered solid samples are mixed with
fine graphite and made into a paste.
▪ Upon drying, this solid composite can be used as an
electrode.
▪ The discharge caused by arcs and sparks interacts
with the surface of the solid sample creating a
plume )‫ (سحب‬of very fine particulates and atoms that
are swept into the atomizer by a flow of an inert gas.
▪ This process of sample introduction is called
ablation
72
3. Laser Ablation ‫بعثرة‬
❖ Sufficient energy from a focused intense
laser will interact with the surface of samples
(in a similar manner like arcs and sparks)
resulting in ablation.
❖ The formed plume of vapor and fine
particulates are swept into the atomizer by
the flow of an inert gas.
❖ Laser ablation is becoming increasingly
used since it is applicable to conductive and
nonconductive samples

73
74
75
 Introduction of Solid Samples
• Direct sample insertion
• Electrothermal
vaporization
• Arc and spark ablation
• Laser ablation
 4. The Glow Discharge Technique
A low pressure envelope (1 to 10 torr argon) with two
electrodes with the conductive solid sample is the
cathode, as in the figure below.
❖ The technique is used for sample introduction and
atomization as well.

❖The electrodes are kept at a 250 to 1000 V DC.

❖This high potential is sufficient to cause ionization of argon

which will be accelerated to the cathode where the sample is
introduced.

❖Collision of the fast moving energetic argon ions with the

sample (cathode) causes atomization by a process called
77
sputtering.
 Sputtering

78
79
80
81
 Atomic Absorption Spectroscopy

We will cover two main techniques of

atomic absorption spectroscopy (AAS),
depending of the type of atomizer.
Two atomization techniques are usually
used in AAS:

82
 1. Flame Atomization
Flames are regarded as continuous atomizers:
Because 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.
83
Several processes occur during atomization including:

a. Nebulization: Sample aspirated and nebulized

samples are sprayed into a flame as a spray of very
fine droplets.

b. Desolvation: Droplets will lose their solvent content

due to very high flame temperatures and will thus be
converted into a solid aerosol.

c. Volatilization: The solid aerosol is volatilized to form

gaseous molecules

84
d. Dissociation: Gaseous molecules will then be
atomized and neutral atoms are obtained which can
be excited by absorption of enough energy.
Note: If energy is not enough for atomization, gaseous
molecules will not be atomized and we may see
molecular absorption or emission.

e. Excitation: Atoms in the gaseous state can absorb

energy and are excited.
Note: If energy is too much, we may observe
ionization.

85
86
87
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.

88
 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.

89
 Max. Burning velocity

90
On the other hand, flames are only stable at certain
flow rates and thus the flow rate of the gas is very
important. (the flow rate is defined the volume of gas in
second).

At low flow rates:

( i.e. 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
91 higher ratios: flames will reach a point where they
will no longer form and blow off the burner.
 Flame Structure
Three well characterized regions can be identified in a
conventional flame.
1) The lower region:
Which close to the burner tip, with blue luminescence.
This region is called the primary combustion zone.
❖ Characterized by:
The existence of some non atomized species and
presence of fuel species (C2 and CH, etc.) that emit in the
blue region of the electromagnetic spectrum.
2)The second is interzonal region:
It is well defined region which is the just above the
primary combustion zone.
❖Characterized by: 1)is rich in free atoms and is the
region of choice for performing atomic spectroscopy.
2) It also contains the regions of highest temperatures.
92
 3) The third region is the outer region :
which is called the secondary combustion region.
Characterized by:
Reformation of molecules as the temperature at the
edges is much lower than the core.

93
 Schematically representation of flame:

94
 Flame Absorption Profiles
We have seen that there are different temperature profiles
in a flame and temperature changes as the distance from
the burner tip is change

95