Michael Ngwenya (N02221351Y)

Nothando Denhere (N02221207M)

Ndumiso Dhlomo (N02220318W)
1.Working Principle of Instrumentation (3-5)
2.What Samples are Analyzed (6)
3.Instrumentation (7-10)
4.Flame AES (11-18)
5.Inductive Coupled Plasma AES (19-23)
6.Interferences (24)
7.Strength and Limitations (25-26)
8.Typical detailed example of application (27-28)
9.Typical exam questions (29-31)
10.References (32)
2
 Working Principle of atomic emission spectroscopy
• Atomic emission spectroscopy (AES) is an analytical technique used for the quantification
of metal atoms by measuring the intensity of light emitted by the atoms in excited states,
or a method of chemical analysis of samples by the electronic transition of atoms by using
flame and argon plasma sources.
• The source of excitation influences the intensity of emission in such measurement. This
provides sufficient energy to vaporize the sample. It also causes the electronic excitation
of gaseous elementary particles. Therefore, we get band and line spectra (On next slide).
• So it is based on the excitation of electrons to higher energy levels by absorption of a
specific wavelength when heated at high temperatures.
• When an excited atom returns to the ground level, it emits radiation in a discrete
wavelength.
• When the excited species leave the high-temperature region, they return to the ground
states by emission of radiation in the form of discrete wavelength packets.
• These emissions pass through a monochromator or filter before detectors. The excited
levels have a very short lifetime (10-8seconds). 3
Emission line
spectra for almost all
the elements of the
periodic table.
4
5
What samples are analyzed?
• These can vary widely depending on the specific application.
• Common sample types include:

Industrial samples - metals, alloys and ceramics.

Biological samples - blood, urine and biological tissue.
Environmental samples - water, soil and air.

• The preparation of these samples involve careful handling to avoid

contamination, as well as various sample pretreatment techniques such as
digestion, extraction, and filtration.
• For solid samples, techniques such as grinding and homogenization may
also be required to represent the sample required.
6
What does an AE-Spectrometer look like?

7
Generalized instrumentation of AES

8
INSTRUMENTATION: Components
• Sample Cell
A cup-shaped graphite electrode acts as a sample cell in atomic emission spectroscopy. The
droplets of sample are introduced into plasma with the help of nebulizers.

• Nebulizers
Nebulizers are used for carrying samples to the plasma flame section. The most commonly used
nebulizers are concentric glass nebulizers and cross-flow nebulizers. The sample is forced into a
mixing chamber at a flow rate of 1 mL /min by a peristaltic pump and nebulized by the steam of
argon flowing at about 1L /min. Argon gas flowing at very high pressure is used for changing liquid
to an aerosol spray.

• Atomizers
Atomizers consist of flames and burners. Atomizers are used for the conversion of solid or liquid
samples to free gaseous atoms. Flame atomizers require oxidant or flame gases. The different
types of burners used for atomizing purposes are Total consumption burner, Laminar flow burner,
Meker burner and Electrothermal atomizers. Electrothermal atomizers are also used for the
atomization of samples. It is also known as a graphite furnace atomizer. Electrically heated graphite
tubes are used instead of flame for atomizing purposes in electrothermal atomizers. 9
 Components cont.
• Monochromators
Prism and diffraction grating acts as monochromators. These are used to choose the specific radiation
type, emitted by the analyte and the removal of all other unwanted radiations. For this reason, it is
sometimes called ‘the wavelength selector’.

• Detectors
Photomultiplier tubes, photoemissive cells, or array detectors act as detectors in atomic emission
spectroscopy. They are used to convert optical signals into electrical current which is then amplified
by the amplifier.

• Amplifiers
Signals from detectors are fed into the amplifiers which amplify signals several times making them
workable or comparable.

• Readout devices
Computers are used as readout devices in atomic emission spectroscopy. Computers analyze the
data in the form of spectra and plot the calibration curve using the atomic emission ranges library.
10
Flame emission spectroscopy (FAES)/ Flame
photometer
• The principle of flame photometer is based on the
measurement of the emitted light intensity when a
metal is introduced into the flame.
• The wavelength of the colour gives information
about the element and the colour of the flame gives
information about the amount of the element
present in the sample.

11
Flame emission spectroscopy (FAES)/ Flame
photometer
• The overall instrumentation of flame atomic spectroscopy is
similar to other spectrometric methods like atomic absorption
spectroscopy. A flame photometer contains:
Pressure regulator and flow meter
An atomizer
A burner
An optical system
Photosensitive detector
Recording output

12
Flame emission spectroscopy/ Flame photometer
The processes occurring during flame photometer analysis are summarized below:

Desolvation: Desolvation involves drying a sample in a solution. The metal particles in the
solvent are dehydrated by the flame and thus solvent is evaporated.

Vaporization: The metal particles in the sample are also dehydrated. This also led to the
evaporation of the solvent.

Atomization: Atomization is the separation of all atoms in a chemical substance. The metal
ions in the sample are reduced to metal atoms by the flame.

Excitation: The electrostatic force of attraction between the electrons and nucleus of the atom
helps them to absorb a particular amount of energy. The atoms then jump to the higher
energy state when excited.

Emission: Since the higher energy state is unstable the atoms jump back to the ground state
or low energy state to gain stability. This jumping of atoms emits radiation with characteristic
wavelength. The radiation is measured by the photo detector 13
Instrumentation

14
Flame emission spectroscopy/ Flame photometer
• The pressure regulator and flowmeter are used for the proper adjustment of
pressure and flow gases.
• The atomizer is used to introduce a liquid sample into the flame at stable and
reproducible rates. Glycerine can be utilized as a solvent.
• The burner should produce a steady flame. A Maker burner is good for working at
low temperatures.
• A deep metal grid across the mouth of the burner to prevent the flame from striking
back is used.
• The optical system in flame atomic absorption spectroscopy functions as a collector
and monochromator of light. It focused on the photosensitive detector.
• A monochromator can isolate the characteristic of electromagnetic radiation. A good
slit with a narrow opening is necessary.
• Photosensitive detectors are not useful because the response is not amplifiable.
• A filter flame photometer in flame atomic emission spectroscopy instrumentation is
used, and amplifiers can amplify the signal to boost the output. 15
Flame emission spectroscopy/ Flame photometer

Scheibe-Lomakin equation describes intensity of light emitted with the help of following
formula:
I = k × cn

Where:
I = Intensity of emitted light
c = Concentration of the element
k = Proportionality constant
At the linear part of the calibration curve n~1,
then I = k × c. In other words, the intensity of emitted light is directly related to
the concentration of the sample

16
Flame emission spectroscopy/ Flame photometer

Advantages of flame photometer

• The method of analysis is very simple and economical.

• It is quick, convenient, selective and sensitive analysis.
• It is both and qualitative and quantitative in nature.
• Even very low concentrations (parts per million/ppm to parts per billion/ppb
range) of metals in the sample can be determined.
• This method compensates for any unexpected interfering material present in
the
sample solution.
• This method can be used to estimate elements which are rarely analysed
17
 Flame emission spectroscopy/ Flame photometer

Disadvantages of flame photometer

In spite of many advantages, this analysis technique has quite a few disadvantages:
• The accurate concentration of the metal ion in the solution cannot be measured.
• It cannot directly detect and determine the presence of inert gases.
• Though this technique measures the total metal content present in the sample, it does not
provide the information about the molecular structure of the metal present in the sample.
• Only liquid samples may be used. Also sample preparation becomes lengthy in some
cases.
• Flame photometry cannot be used for the direct determination of each and every metal
atom. A number of metal atoms cannot be analysed by this method. The elements such
as carbon, hydrogen and halides cannot be detected due to their non-radiating nature
18
ICP-AES system

This is what the plasma looks like

from the inside of the ICP-AE
19
Spectrometer
ICP-AES system

20
ICP-AES system
• An ICP-AES system can be divided up into two basic parts; the inductively
coupled plasma source and the atomic emission spectrometry detector.
• ICP source is extremely hot and produces a maximum temperature of up to
6500°K. This temperature is enough for the ionization of samples.
• ICP source comprises three concentric silica quartz tubes each of which is open
at the top. The argon stream carries the sample in the form of aerosol and passes
through the central tube. The excitation is provided by the radiofrequency range
radiations (approximately 27 MHz).
• The argon gas is ionized in the intense electromagnetic field and flows in a
particular rotationally symmetrical pattern towards the magnetic field of the RF
coil.
• A stable, high temperature plasma of about 7000°K is then generated as the
result of the inelastic collisions created between the neutral argon atoms and the
charged particles. 21
ICP-AES system cont.
• A peristaltic pump delivers an aqueous or organic sample into an
analytical nebulizer where it is changed into mist and introduced
directly inside the plasma flame.
• The sample immediately collides with the electrons and charged ions in
the plasma and is itself broken down into charged ions. The various
molecules break up into their respective atoms which then lose
electrons and recombine repeatedly in the plasma, giving off radiation
at the characteristic wavelengths of the elements involved.
• The two emission systems, FAES and ICP-AES, differ in the way atomic
species are created and excited.
• Because of the relatively low temperatures (approx. 2000-2500°C) in a
flame-based system, not all of the atoms or elements present in the
sample are excited, particularly if they exist in a polyatomic compound.22
Types of ICP-AE Spectrometers
There are two types of spectrophotometers used in ICP-AES.
Sequential spectrophotometer
Direct spectrophotometers (simultaneous multielement spectrophotometers)

Sequential spectrometer
Sequential spectrometers are less expensive and more flexible than the latter. They include a single
photomultiplier tube and movable gratings to select wavelength in sequential orders. Some sequential
spectrophotometers use two to three photomultiplier tubes to reduce the analyzing time. Sequential
instruments have a longer analysis time. A greater sample volume is required for spectroscopy to
complete. They have poor accuracy and precision.

Direct spectrophotometer (simultaneous multielement spectrophotometer)

Direct spectrometers are faster, more precise, and more accurate than sequential ones. All elements (up
to Z=60 ) are determined simultaneously by increasing the analytical speed. Radiations from the plasma
enter through single slits and are dispersed by a concave reflection grating. Then these wavelengths
reach a series of exit slits which isolate specific wavelengths for specific elements.

23
Interferences encountered
Matrix effects: These occur when the sample matrix (e.g., soil, water, metal ore) affects the emission signal
of the analyte, leading to inaccurate results. This can be mitigated by using internal standards or matrix-
matched calibration standards.

Spectral interferences: These occur when other elements in the sample emit radiation at the same
wavelength as the analyte, leading to false signals. This can be addressed by using spectral resolution
techniques or background correction methods.

Chemical interferences: These occur when chemical reactions in the sample matrix affect the emission
signal of the analyte. Dilution or sample pretreatment methods can help minimize these interferences.

Physical interferences: These occur due to factors such as high viscosity or high salt content in the sample,
which can affect the atomization and excitation processes. Proper sample preparation and instrument
optimization can help reduce these interferences.

24
Strength and limitations of the AES
• Strengths of atomic emission spectrometer:

High sensitivity: Atomic emission spectrometers can detect trace elements at very low
concentrations, making them suitable for a wide range of applications, including environmental
monitoring and quality control in industrial processes.

Multi-element analysis: Atomic emission spectrometers are capable of analyzing multiple

elements simultaneously, providing comprehensive information about the composition of a
sample.

Wide elemental coverage: Atomic emission spectrometers can analyze a wide range of elements,
from alkali metals to heavy metals, making them versatile for various analytical needs.

Rapid analysis: Atomic emission spectrometers can provide quick results, making them suitable
for high-throughput analysis in research and industrial settings.

25
Strength and limitations of the AES
• Limitations of atomic emission spectrometer:

Limited quantitative accuracy: Atomic emission spectrometers may have limitations in quantifying
elements at very low or very high concentrations, and may require calibration standards to ensure
accurate measurements.

Matrix effects: The presence of complex sample matrices can lead to spectral interferences and
affect the accuracy of the analysis, requiring careful sample preparation and method development.

Limited elemental selectivity: Atomic emission spectrometers may have difficulty distinguishing
between different chemical forms of an element, leading to potential inaccuracies in the analysis.

Sample preparation challenges: Sample preparation for atomic emission spectroscopy can be
time-consuming and require specialized equipment and techniques, particularly for solid samples.

26
Typical detailed example of application of AES
• Callibirating solution is generally prepared as a sample salt dissolved in water or dilute acid.
• For calibration, there must be three to four standard solutions containing a known concentration of metals
to be analyzed and of the same concentration as sample solutions. These solutions are called primary
standards.
• Different high purity universal calibration standard solutions are available at a modest cost for the
calibration of instruments because it is very tedious to prepare a large number of calibration solutions.

Detailed analysis of sample:

• To measure the emission intensity of calcium and magnesium, standard solutions of these compounds
are prepared by diluting stock solutions of calcium nitrate and magnesium nitrate with deionized water
or dilute acid, ranging from 0 to 20 ppm.
• A blank solution of deionized water is prepared, and lanthanum chloride is added to prevent the
formation of insoluble compouds. The samples are transferred to a nebulizer and introduced into an
atomic emission spectrometer.
• The spectrometer has a photomultiplier tube detector and a monochromator that selects the emission
wavelengths of calcium (422.7 nm) and magnesium (285.2 nm). The emission intensity is recorded at
both wavelengths, and calibration curves are plotted.
• The concentration of calcium and magnesium in the unknown sample is calculated by interpolating the
emission intensity from the calibration curves and the results are reported in ppm or mg/L 27
Further application examples of AES
• Beer or wine: The traces of metals like calcium (Ca), copper (Cu), iron (Fe),
manganese (Mn), magnesium (Mg), phosphorus (P), potassium (K), and zinc (Zn)
from beer or wine can be analyzed by inductively coupled plasma atomic
emission spectroscopy.

• Solid metals: Spark or arc atomic emission spectroscopy is used for the analysis
of metallic elements in solid samples. For non-conductive materials, the sample
is ground with graphite powder to make it conductive. In traditional arc
spectroscopy methods, a sample of the solid is commonly ground and destroyed
during analysis.

• Water samples: Flame atomic emission spectroscopy is used for the analysis of
alkali metals, such as sodium (Na), potassium (K), lithium (Li), and cesium (Cs), in
water samples. The sample is introduced into the flame as a sprayed solution
and the emission intensity is measured at the characteristic wavelength of each
element. 28
Typical exam question one
• What processes occur to produce light emission from the flame when a solution
containing sodium ions is introduced into the instrument?
1. Atomization: Introduce sample solution into the This relaxation process involves the electrons transitioning back to
flame, where it undergoes atomization. The molecules lower energy levels. As they do so, they emit photons of light with
are broken down the into individual atoms. The specific wavelengths corresponding to the energy difference
sodium atoms are generated by the dissociation of between the excited and ground states.
sodium chloride (NaCl) in the flame.
4. Light Emission: The emitted photons of light from the sodium
2. Excitation: Once atomized, the sodium atoms are atoms have characteristic wavelengths in the visible region of the
then excited to higher energy levels. This excitation electromagnetic spectrum. These wavelengths are specific to
occurs when the atoms absorb energy from the high- sodium and can be separated and measured using a spectrometer.
temperature flame. The energy absorbed causes the The intensity of the emitted light is proportional to the
electrons in the sodium atoms to move to higher concentration of sodium ions in the sample.
energy levels.
By analyzing the emitted light from the flame, AES can determine
3. Relaxation: After being excited, the sodium atoms the concentration of sodium ions in the sample solution.
return to their ground state by releasing the excess
energy they absorbed.
29
Typical exam question two
• Explain the basic differences between atomic emission and atomic absorption
spectroscopy.
• Atomic emission spectroscopy (AES) and atomic absorption spectroscopy (AAS) are both analytical
techniques used to determine the concentration of elements in a sample. The main difference
between the two techniques lies in the measurement principle and the type of radiation detected.

• In atomic emission spectroscopy, a sample is excited by a high-energy source, such as a flame or

plasma, causing the atoms to transition from their ground state to higher energy levels. As the
excited atoms return to their ground state, they emit characteristic wavelengths of light. These
emitted wavelengths are then separated and detected using a spectrometer. The intensity of the
emitted light is proportional to the concentration of the element in the sample.

• On the other hand, atomic absorption spectroscopy involves measuring the absorption of light by
atoms in the ground state. A specific wavelength of light, typically from a hollow cathode lamp, is
passed through the sample. If the atoms in the sample absorb this wavelength, their concentration
can be determined. The absorption is directly proportional to the concentration of the element in
the sample. 30
Typical exam question two cont.
• Therefore, the key difference between AES and AAS is the measurement principle:
AES measures emitted light from excited atoms, while AAS measures absorbed
light by atoms in the ground state.

• Another difference lies in the sensitivity and selectivity of the two techniques. AES
is generally more sensitive than AAS because it measures emitted light, which can
be easily detected and amplified. Additionally, AES can provide information about
multiple elements simultaneously, making it useful for multi-element analysis. AAS,
on the other hand, is highly selective because it measures absorption at specific
wavelengths, allowing for accurate determination of individual elements.

• In terms of instrumentation, both techniques require a light source, a sample

introduction system, a spectrometer, and a detector. However, the specific
components and configurations may vary depending on the instrument and
application. 31
(1) 10.7: Atomic Emission Spectroscopy - Chemistry LibreTexts.
https://chem.libretexts.org/Courses/Northeastern_University
/10%3A_Spectroscopic_Methods/10.7%3A_Atomic_Emission_
Spectroscopy.
(2) Atomic emission spectroscopy - Wikipedia.
https://en.wikipedia.org/wiki/Atomic_emission_spectroscopy.
(3) Atomic spectroscopy - Wikipedia.
https://en.wikipedia.org/wiki/Atomic_spectroscopy.
(4) 9 Facts On Atomic emission spectroscopy :Beginner's Guide
- Lambda Geeks. https://lambdageeks.com/atomic-emission-
spectroscopy-applications/.

32
33