Instrumental analysis

PHC 321

Course coordinators:
Associate Prof. Christine Maged
Dr. Heba Tarek
 Lecture (7)
Atomic spectroscopy
 References:

• J. Mendham, R.C. Denney, J. D. Barnes, M.J.K. Thomas, Vogel's

Quantitative Chemical Analysis (6th edition, 2010), Prentice Hall, ISBN
0582226287.

• Donald L. Pavia, Gary M. Lampman, George S. Kriz, James A. Vyvyan,

Introduction to Spectroscopy (4th edition, 2012), Brooks Cole, ISBN
0495114782
Interactive teaching methods and activities
https://www.jove.com/science-education/11162/metal-flame-emission
https://www.youtube.com/watch?v=BBhuXOh9vOM
https://www.youtube.com/watch?v=1F6CxVF5I9g
https://www.youtube.com/watch?v=9DYV25Ki-kc
https://www.youtube.com/watch?v=Mnbye_dwWWU

Feedback on Midterm Exam

Learning outcomes

 Understand the theory of atomic (flame) spectroscopy

 Outline the main components of flame emission

spectrophotometer.
 List the main advantages and disadvantage of laminar and
turbulent flow burners.
 Know the theory of Atomic Absorption Spectroscopy.
 Atomic (Flame Spectroscopy)
This section deals with the spectroscopy of atoms.

It is the study of absorption and emission of electromagnetic radiation by

monoatomic particles in gaseous state being present in the flame.

Advantages of atomic spectroscopy:

1. Sensitivity (ppm)
2. Speed
3. Convenience
4. High selectivity
5. Moderate instrument costs
Atomization : It is the conversion of molecules to their component atoms in
gaseous state
Basic steps involved in Flame (Atomic) spectroscopy
a) Nebulization: Sample solution, get into fine droplets by spraying through thin
nozzle M+ + A- (solution) → M+ + A- (aerosol)
b) Desolvation: solvent evaporates, just leaving analyte and other matrix
compounds. M+ + A- (aerosol) → MA (solid)
c) Vaporization: convert solid analyte /matrix into gas phase. .
MA (solid) → MA (gas)
d) Atomization (dissociation): breaking-up molecules into atoms.
. MA (gas) → M + A (gas)
e) Excitation: with light, heat, etc. for spectra measurement. M → M*
f) Emission process: the higher energy state is unstable, so the atoms jump back to
low energy level with emission of radiation of characteristic wavelength.

•Ionization : may occur with high flame temperature

Which cause the atoms to become charged. M* → M+ + e-
Basic steps involved in atomization of sample solution
 Classification of flame spectroscopic methods
1- Flame emission 2- Flame absorption or Atomic
➢ Atoms in gaseous state in the flame absorb absorption (AAS)
thermal energy from the flame itself. ➢ Atoms in the flame are subjected to
➢ Some of the atoms get excited and the outer external source of radiation which
most electrons are promoted to higher energy produces EMR of definite
levels. wavelength (monochromatic).
➢ As they return back to the ground state they ➢ This will be absorbed by the atoms.
emit radiation having energy equal to that ➢ The absorbance (A) and the sample
absorbed. concentration obey Beer´s law
➢ The emission is proportional to the number of within certain limit.
excited atoms, which is proportional to the
number of atoms in the flame i.e. The sample
concentration.

N.B. In the above methods, the energy supplied to the substance must be enough only for
atomization but not ionization (i.e. less than ionization potential of atoms)
 Flame Spectra

The spectra of gaseous, atomic particles consist of well-defined discrete lines

WHY?
The spectra of gaseous, atomic particles consist of well-defined discrete lines
WHY?
Because there are no bonds, atoms undergo electronic transition only, no
vibrational or rotational transitions. Each line represents one of the electronic
transitions of the electron.

• Thus when the atoms in the flame are subjected to thermal energy, UV or VIS
radiation, not all the energy or radiation are absorbrd or emitted WHY?

• Because atoms will absorb radiations of definite wavelength which causes

electronic transition only.

• Energy absorbed and /or emitted is exactly the difference between the
ground and excited electronic energy levels).

Eabsorbed or emitted = Eexcited state – Eground state = hc/λ

 Limitations of flame emission photometry

1- The efficiency of atomization in flame is relatively low, which means that only a
small fraction of the analyte is actually converted into atoms. This can limit the
accuracy of the technique.

2- Not all atoms can be determined by flame emission (elements such as H,C and
halides cannot be determined due to their non-radiating nature), only alkali and
alkaline earth metals can be practically determined.

3- Heavy and transition metals contains several electrons in the outermost

orbitals, each electron has several types of transitions, resulting in large number of
absorption and emission lines, so the flame spectra is very complex and are
difficult to be interpreted.

4- The number of excited atoms is affected by flame temperature, so it should be

adjusted.

5- Interferences by other elements are not easily eliminated.

Instrument of flame emission
It is formed of:
1. Flame atomizer
2. Monochromator
3. Detector
4. Readout meter

Oxidant

Fuel
 1- Flame atomizer
➢ It serves two functions:
1- Atomization of the sample
2- Source of thermal energy to excite the atoms
➢ The atomizer is composed of: nebulizer and burner

Nebulizer

➢ It is the device by which the sample solution is divided into fine droplets which
are aspirated into fine spray or aerosol.

➢ Only the fine droplets can be introduced in the flame.

 Burner:
• In the burner, the combustion of fuel occurs producing the necessary heat for
atomization and excitation.
• It may be circular or rectangular with standard dimensions and position.

• The temperature of the flame produced depends on fuel-oxidant ratio and their
kind.

• There are two types of burners:

1- laminar flow burner (premixed burner)

2- turbulent flow burner (total consumption burner).

 The two types of burners
Turbulent flow burner
Laminar flow burner
 Laminar Flow Burner Turbulent Flow burner
Construction - Premixing chamber in which the sample - No premixing chamber.
and oxidant are mixed with fuel. The -The sample, fuel and
premixing chamber contains baffles which oxidant are mixed at the top
retain large droplets to pass to waste of the burner.
drain.
Advantage - Produce very fine droplets by the action - Consume all sample
of baffles. volume.
- Easy to be cleaned.
Disadvantage - Does not consume all the sample. - It produces large droplets
-So, needs larger sample volume. (no baffles).
- Difficult to be cleaned.
 The flame temperature must be:
1. Regular as the number of excited atoms are greatly affected by temperature,
where an increase in temp by 10°K is accompanied by 4% increase in the
excited atoms.

2. It must be sufficient to cause atomization only and not ionization.

3. It should be able to convert the constituents of the liquid sample into the vapor
state

4. It should be able to excite a fraction of the resulting atomic or molecular spectra

5. The spectrum of flame should not interfere with the observations when emission
is being measured.
 The flame temperature must be
• The temperature of flame lies between 1000oC and 3000oC.
• The flame temperature and fuel to oxidant ratio are the most important factors
which affect the nature and intensity of the spectrum for a given fuel.
• Acetylene and hydrogen are the most frequent choice in flame photometry.

List of common fuels and oxidants used to produce flames

2- Monochromator:
• Either grating or interference filters are used.
• The emitted radiation passes through a monochromator that isolates and allows the
resonance wavelength to pass.
• Radiations that reach the detector are those emitted from the sample and from the flame
itself, so we must make a blank experiment.
3- Detector:
Radiation coming from the optical system is allowed to fall on the detector which measures the
intensity of radiation falling on it. The detectors should be sensitive to all wavelengths that may
be examined.
Commonly used detectors are
•Photomultiplier tube
•Photoemissive cell
4- Readout meter:
Measure emission.
Video
 Applications of flame photometry
1) Qualitative analysis
Flame photometry is used to detect elements of group I and II of the periodic table. These
elements are sodium, potassium, lithium, magnesium, calcium, strontium and barium. Some
of these elements can be detected visually by the color in the flame. An example is sodium
which produces yellow flame. But this method is not very reliable. However, if the
radiation of characteristic wavelength is detected, this will indicate the presence of metal in
the sample.
2) Quantitative analysis
This is one of the most useful applications of flame photometry. This is used for the
rapid quantitative determination of the elements in groups I and II of the periodic
table. If high optical resolution equipment is used, other metallic elements besides
that of I and II groups can also be determined.

Calibration curve method:

1- Prepare a series of standard solution of the substance to be analyzed (KCl, NaCl,

CaCl2) containing 2,4,6,8,10 ppm (mg/L).
2- Choose the suitable filter.
3- Spray deionized water as a blank.
4- Determine the emission of each of the prepared solutions.
5- Plot a calibration curve representing the emission against the concentration in ppm.
6- Spray the unknown solution and determine the emission then the concentration can
be determined from the calibration curve.
• The colors in fireworks stem from a wide variety
of metal compounds – particularly metal salts.
• The sulfur and charcoal act as the fuel, while the
potassium-nitrate acts as an oxidizer, which is
crucial for the creation of fireworks.
• The heat given off by the combustion
reaction causes electrons in the metal atoms to
be excited to higher energy levels. These
excited states are unstable, so the electron
quickly returns to its original energy (or ground
state), emitting excess energy as light.
• Different metals will have a different energy gap
between their ground and excited states, leading
to the emission of different colors. This is the
same reason that different metals give
different flame tests.
ATOMIC ABSORPTION
SPECTROSCOPY
 Atomic Absorption Spectroscopy (AAS) Theory
❑ Atoms in gaseous state are subjected to external source of radiation which
produces one line or a beam of monochromatic light with single wavelength.

❑This wave length is the resonance wave

length for the atoms so nearly all atoms will
absorb it and the outermost electrons will be
promoted to definite higher energy levels and
there is a decrease in the intensity of radiation
due to absorption by atoms. i.e. Absorbnce
takes place.
 Comparison between atomic and molecular absorption spectra
Atomic absorption spectra Molecular absorption spectra

1- The outermost electrons occupy one of the 1- The outermost electrons occupy σ, π or n
atomic orbital s. p. d. f electronic energy levels in the ground state.

2- Upon excitation electrons are promoted to 2- Upon excitation electrons are raised to σ*,or
any permissible higher atomic energy level. π* energy level.

3- Since there are no bonds, there are no 3- Since there are bonds, there are vibrational
vibrational or rotational levels in the ground or or rotational levels in both the ground and
excited state. excited state.
4- The spectra are line form. 4- The spectra are in the form of bands due to
the presence of very close superimposed,
unresolved vibrational and rotational energy
levels in the excited state.
5- The analytical wavelength is the resonance 5- The analytical wavelength is λmax
wavelength of the analyte.
Instrument of atomic absorption
The main parts of atomic absorption spectrophotometer are:
1- Source of radiation 2- Chopper
3- Atomizer 4- Monochromator
5- Detector 6- Readout meter