ATOMIC SPECTROSCOPY

INDUCTIVE COUPLED PLASMA-OPTICAL

EMISSION SPECTROSCOPY
ATOMIC SPECTROSCOPY
Presented by:
Zara Nuzhat FA-23-MPh-47

Presented to:
 Dr. Ikram Ahmad

University of sahiwal,sahiwal
 CONTENT

1. What is Inductive couple plasma optical emission

spectroscopy?
2. Basic introduction
3. Principle
4. Instrumentation
5. Applications
6. Limitations
7. MCQ
 WHAT IS ICP-OES?

ICP-OES (Inductively coupled plasma - optical emission

spectrometry) is a technique in which the composition of
elements in (mostly water-dissolved) samples can be determined
using plasma and a spectrometer.
The technique has been commercially available since 1974
and thanks to its reliability, multi-element options and high
throughput, it has become a widely applied in both routine
research as in more specific analysis purposes.
• The ICP-OES principle uses the fact that atoms and ions can
absorb energy to move electrons from the ground state to an
excited state.
• It can by explain with the excitation of atom by plasma and
emission spectrum of calcium in the visible range.
A) Excitation of an atom by plasma
A plasma is a gas, in this case argon, which contains a
significant number of argon ions. The plasma is formed by
seeding the argon gas passing through a plasma torch with
electrons.
The electrons are accelerated and collide with argon
atoms releasing more electrons and forming argon ions.
Elements, in the form of atoms, are introduced into the
plasma. A proportion of theses atoms will be become
ionized within the plasma.
 When an atom or ion is excited within the plasma, its electrons
move from a lower to higher energy level
Upon relaxation of these electrons to their initial 'ground' state,
energy is emitted in the form of photons
When an atom or ion is excited within the plasma, its electrons
move from a lower to higher energy level.
• Upon relaxation of these electrons to their initial 'ground' state,
energy is emitted in the form of photons.
• The emitted photons possess wavelengths that are characteristic
of their respective elements
B) Emission spectrum of calcium in the visible range
Emission spectra and calibration curves for the Calcium (422.7
nm line). The intensity for the calibration curves are the integrated
intensity of the emission lines.
 One element can have multiple electron
excitations and relaxations; therefore, it can
have multiple characteristic wavelengths.
. An example of an emission spectrum for
calcium is shown in figure 2
 BASIC INTRODUCTION

Inductive coupled plasma atomic emission

spectroscopy also refer to as ICP-optical emission
spectroscopy
The technique is based on the spontaneous emission
of photons from atoms and ions that have been
excited in a RF discharge.
Liquid and gas samples may be injected directly into
the instrument, while solid samples usually require
extraction or acid digestion so that the analytes are
present in a solution
 PRINCIPLE

• The solution to analyze is conducted by a peristaltic pump

though a nebulizer into a spray chamber. The produced aerosol
is lead into an argon plasma. Plasma is the forth state of
matter, next to the solid, liquid and gaseous state. In the ICP-
OES the plasma is generated at the end of a quarts torch by a
cooled induction coil through which a high frequency alternate
current flows
As a consequence, an alternate magnetic field is induced which
accelerated electrons into a circular trajectory. Due to collision
between the argon atom and the electrons ionization occurs,
giving rise to a stable plasma. The plasma is extremely hot,
6000-7000 K. In the induction zone it can even reach 10000 K.
In the torch de solvation, atomization and ionizations of the
sample takes place. Due to the thermic energy taken up by the
electrons, they reach a higher "excited" state
• (The diagram following shows the energy levels in a lead(Pb)
atom. Energy from the heat of the plasma causes electrons to
become ‘excited’ and move to higher energy levels. The
amount of energy required for the electrons to move between
levels corresponds to very specific wavelengths of light. As
the diagram shows, moving an electron from the ground state
to the first energy level (E1) requires the energy equivalent to
light at 283.3 nm. The 283.3 nm wavelength is in the
ultraviolet (UV) part of the electromagnetic spectrum.
It takes more energy to move an electron from the ground state
to the second energy level (which is further away from the
nucleus).
This transition requires more energy, equivalent to a photon of
light at 261.4 nm, which is further into the UV spectrum. As the
diagram shows, lead will emit light at 283.3, 261.4, 217.0 and
202.2 nm, depending on which energy level the electron is
returning from).
 CONTI…

When the electrons drop back to ground level energy is liberated

as light (photons). Each element has an own characteristic
emission spectrum that is measured with a spectrometer. The
light intensity on the wavelength is measured and with the
calibration calculated into a concentration.
Sufficient energy is often available to convert the
atoms to ions and subsequently promote the ions to
excited states
 Both the atomic and ionic excited state species may
then relax to the ground state via the emission of a
photon.
These photons have characteristic energies that are
determined by the quantized energy level structure for
each type of atom or ion.
Thus, the wavelength of the photons can be used to
identify the elements from which they originated.
 CONTI…

The energy level, usually the ground state, it emits light of a

very specific wavelength.
The type of atom or ion (i.e, which element it is), and the an
electron energy levels the electron is moving between,
determines the wavelength .
As returns from a higher energy level to a lower of the emitted
light.
• The diagram following shows the energy levels in a lead (Pb)
atom. Energy from the heat of the plasma causes electrons to
become ‘excited’ and move to higher energy levels. The
amount of energy required for the electrons to move between
levels corresponds to very specific wavelengths of light. As
the diagram shows, moving an electron from the ground state
to the first energy level (E1) requires the energy equivalent to
light at 283.3 nm. The 283.3 nm wavelength is in the
ultraviolet (UV) part of the electromagnetic spectrum.
• It takes more energy to move an electron from the ground state
to the second energy level (which is further away from the
nucleus). This transition requires more energy, equivalent to a
photon of light at 261.4 nm, which is further into the UV
spectrum. As the diagram shows, lead will emit light at 283.3,
261.4, 217.0 and 202.2 nm, depending on which energy level
the electron is returning from.
• When excited electrons in a lead atom return to the ground
state, they emit light at those very specific wavelengths. The
ICP-OES principle measures the amount of emitted light at
each wavelength and uses this information to calculate the
concentration of lead in the sample.
• When excited electrons in a
lead atom return to the
ground state, they emit light
at those very specific
wavelengths. The ICP-OES
principle measures the
amount of emitted light at
each wavelength and uses
this information to calculate
the concentration of lead in
the sample.
• To calibrate an ICP-OES,
solutions containing known
amounts of each element are
measured. From this data, a
calibration curve is created. The
calibration curve determines the
relationship between the
intensity of light emitted at a
specific wavelength and the
concentration of the element in
the solution
 INSTRUMENTATION

An ICP-OES instrument consists of four basic components:

1. The sample introduction system

2. Excitation source (plasma)
3. The Frequency Generator
4. The optical Spectrometer (for wavelength selection)
5. Detector
6. Computerized instrument Control
Using the ICP-OES principle, an ICP-OES instrument
works by:
• Exciting atoms or ions using an argon plasma,
• Measuring the intensity of the light emitted when the
electrons in the atoms or ions return to the ground state, or
a lower energy state,
• Calculating the concentration of specific elements in a
solution, based on a calibration graph
 1) SAMPLE INTRODUCTION SYSTEM


The liquid sample is pumped into the nebulizer, which turns the liquid
into a fine aerosol using a stream of argon gas. This aerosol passes
into the spray chamber, where larger droplets are removed from the
aerosol. The rest of the aerosol continues, into the plasma torch.


The nebulizer turns the liquid sample into a fine aerosol
 2) WHAT IS PLASMA?

• Before emission can occur, the solvent in which the sample is

dissolved must be evaporated. Also, the remainders of the
sample must be vaporized and existing molecules split into
atoms. These are all tasks of the plasma. Exactly what is a
Plasma?
• An ICP-OES plasma is a gas, which has been significantly
ionized inside an oscillating radio frequency (RF) field. The
RF field causes the gaseous ions to oscillate with the field and
this results in extreme heat. The temperature developed inside
a plasma can be as high as 10,000°C. One example of a
plasma-like state in nature is lightning. In space, stars like the
sun are largely composed of plasma.
 THE PLASMA TORCH

The inductively coupled plasma (ICP) is the energy source for

the analysis. It looks like a flame on a glass candle, with a
metal coil around the candle. The plasma torch consists of a
three concentric glass tubes. Argon gas flows between the two
outermost tubes. An electric current is passed through the
metal coil around the glass torch. The current creates a
magnetic field.
A Spark, discharge into a stream of argon gas creates the
plasma. Energy passes from the metal coil around the torch
into the argon, sustaining the plasma.
Another stream of argon gas carries the aerosol of the sample
up the middle of the plasma torch. The heat of the plasma
evaporates the solvent in the sample. The heat also breaks the
sample molecules into atoms and ions and provides the energy
to excite electrons in the atoms and ions, moving them up to
higher energy levels.
 3) THE RADIO FREQUENCY
GENERATOR
 An efficient and powerful radio frequency (RF) generator
helps develop and maintain the plasma, which is capable of
completely dissociating almost any sample matrix, thereby
reducing oxide formation and other chemical interferences to a
minimum
 Challenges during the development of an RF generator may
include size, robustness, efficiency, reliability, and ease-of-
service.
 CONTI…

 The stability of an RF generator depends largely on its ability

to adjust for changing conditions in the plasma due to different
samples or sample matrices; this is facilitated by switching
power conditions to suit the variations, a phenomenon also
called ‘matching’.
 Historically, there have been two main approaches to the
control and matching of RF generators:
1. Crystal controlled
2. Free-running
1.Free-running generators:
It match the power generated to the power required by the
plasma and allow the frequency to vary slightly.
2.Crystal-controlled generators:
It match and lock the frequency of the RF generator to the
oscillation of a reference crystal
 4) THE OPTICAL SPECTROMETER

• An optical spectrometer (spectrophotometer, spectrograph or

spectroscope) is an instrument used to measure properties of
light over a specific portion of the electromagnetic spectrum,
typically used in spectroscopic analysis to identify materials.
The variable measured is most often the irradiance of the light
but could also, for instance, be the polarization state. The
independent variable is usually the wavelength of the light or a
unit directly proportional to the photon energy, such as
reciprocal centimeters or electron volts, which has a reciprocal
relationship to wavelength.
 spectrometer is used in spectroscopy for producing spectral
lines and measuring their wavelengths and intensities.
Spectrometers may operate over a wide range of non-optical
wavelengths, from gamma rays and X-rays into the far infrared.
If the instrument is designed to measure the spectrum on an
absolute scale rather than a relative one, then it is typically
called a spectrophotometer. The majority of spectrophotometers
are used in spectral regions near the visible spectrum. A
spectrometer that is calibrated for measurement of the
incident optical power is called a Spectro radiometer.
 5) THE DETECTOR

The detectors used in an ICP-OES instrument have

changed considerably in recent years. They are now
typically charge coupled devices (CCD) that look like
computer chips.
The surface of the chip is divided up into pixels, each
of which measure the photons of light of a different
wavelength.
 CONTI….

 Historically, light intensity was measured with photomultiplier

technology.
 Currently, solid-state charge transfer devices (CTDs) are the
detectors of choice for ICP-OES and have almost completely
replaced photomultiplier tubes.
Depending on the structure of the detector and the way in
which signals are processed, two types of CTDs are used:
1. Charge injection devices (CIDs)
2. Charge coupled devices (CCDs).
1.Charge injection device
CIDs allow for individual, random access, and pixel-by-pixel
integration due to the readout electrodes being located at every pixel
site. This process can be carried out non-destructively and the CID
has excellent anti-blooming capability. Such capability allows for an
optimum signal-to-noise ratio at each integration, enabling both
intense and weak light emissions to be recorded simultaneously. CIDs
are composed of a light-sensitive surface that is subdivided into
several thousand pixels, each of which is individually addressed by
column and row electrodes and permits thorough collection and
readout of signals.
2.Charge coupled
devices
Conversely, a CCD
sequentially transfers the
charge from each pixel site to
a buffer and then to an output
register. Pixels may be
processed either by rows or
segments. During the process
of reading a CCD, the charge
in the pixel is destroyed.
 6) COMPUTERIZED INSTRUMENT CONTROL

The information collected by the instrument is fed to

the controlling computer. The computer is typically a
standard PC, running the MS Windows operating
system.
 APPLICATIONS

The main application is environment (water, soils, sludges,

air…) as there is a strong need to monitor element presence and
content as it relates to human consumption and impact. For
QA/QC, main customers are chemical, mining, precious
metals and metallurgical companies. ICP-OES is used to
guarantee the quality of raw materials as well as final product.
Intermediate products are also analyzed so processes can be
fully monitored. Petro chemistry uses also ICP-OES, for
petroleum refining and lubricant oil production, but also for
some applications such as wear metals in oil analysis that allow
preventive maintenance to be done for engines (mining trucks,
airplanes etc.)
1) Environmental and agro-chemical analysis
Environment and agro-chemical analysis by ICP-OES. ICP-
OES can handle environmental and agro-chemical samples. The
environment field is probably the main field of activity of ICP-
OES.
This is due to the wide variety of samples concerned, and also
to the high and increasing demand for elemental analysis
worldwide.
ICP-OES became the reference technique for environmental
analysis due to the demand for sensitivity along with multiple
element analysis.
 Environmental samples not only include analysis of samples
from “natural areas” that include water (drinking water,
underground water, sea water, river water…) to soils and
sludges but it also includes analysis of workplaces with
samples such as air, fly ash, coal ash or dust analysis.
 There are multiple requirements for an ICP-OES to meet
expectations for environmental analysis. The ICP-OES
should allow analysis of major elements at mg/L to % level.
It should also be sensitive enough for the determination of
low level of heavy metals in samples such as drinking water,
underground water or river water, and exhibit reduced matrix
effects so the sensitivity remains good in more difficult
matrices such as sea water, waste water, soils or sludges.
2) Chemical analysis by ICP-OES

ICP-OES can handle chemical samples. Analysis of chemicals is

mainly done in a production quality control context with
analysis of intermediate and finished products, but also to
monitor processes. Elemental analysis in such a context is
mainly done using ICP-OES due to its multiple element analysis
capability and its short analysis time that meets the
requirement for production.
 One of the most demanding industries in terms of ICP-OES
performance is the chlorine, caustic soda, soda ash, sodium
and magnesium production industry.
 For such industries, analysis of brines, that is a saturated NaCl
solution (25 to 30% NaCl), is required. To get the best
performance for such samples, it is mandatory to use an ICP-
OES able to handle a total dissolved solids concentration, and
one able to maintain sensitivity for trace elements analysis.
Accessories such as a sheath gas and argon humidifier will be
required to meet requirements for analysis.
3) Metallurgy analysis with ICP-OES

 ICP-OES can manage metallurgical samples for ferrous,

nonferrous and precious metals. Metallurgy is one of the
oldest application fields with Geology. Multiple elements
should be analyzed from trace level (ppm in the solid) to the
high % range.
 ICP-OES is designed to handle such analysis and to give a
result in a short time for all elements, making it the ideal
instrument for this industry.
 High Resolution ICP-OES is preferred to allow for trace
analysis due to the line-rich spectra emitted by all metals at
high concentration such as W, Fe, Pt, Rh, Ni, etc. M
4) Pharmaceuticals and cosmetics analysis by ICP-OES

 ICP-OES can manage pharmaceutical and cosmetics samples. ICP-

OES is well adapted for the analysis of heavy metals in cosmetic or
pharmaceutical products, as most of them can be digested with
acids or dissolved in volatile solvents such as methanol or ethanol.
 As volatile solvents can be introduced in the ICP-OES, it
simplifies the sample preparation, and as more and more elements
have to be analyzed on cosmetics, ICP-OES is more and more
attractive.
5) Geology / Mining / Rare Earth Elements analysis
by ICP-OES
 ICP-OES can handle geological, mining and rare earth
elements. ICP-OES is widely used in mining processes,
mining purity control, rocks analysis, etc.
 Many mines use ICP-OES to check for the purity of the
extracted ores of manganese, nickel or precious metals.
 As mining resources decrease, there is also a huge activity to
mine scrap metals and mainly precious metals from electronic
wastes.
 Analysis of geological and mining samples, and especially of
Rare Earth Elements, is very demanding for ICP-OES. Due to
the need of sensitivity as purity of the final product has to be
checked, the ICP-OES should be able to handle high
concentration of total dissolved solids.
 Moreover, due to the line-rich spectrum emitted, especially
for Rare Earth Elements, only high resolution ICP-OES
spectrometers can handle such analysis as they are the only
ones able to separate the wavelengths from major element and
trace elements.
6) Materials sciences analysis by ICP-OES
 ICP-OES can manage samples from materials sciences. ICP-
OES is well designed for the analysis of samples from
materials sciences and it is widely used for cements, ceramics
or glass analysis due to its capability to analyze both major
and trace elements simultaneously, with a good sensitivity
 As the use of magnetic materials becomes more and more
important, ICP-OES is increasingly used for such
applications, as it is designed to determine major and trace
elements.
 For applications involving Rare Earth Elements, high
resolution is often required to ensure quality of results
7) Nuclear energy analysis by ICP-OES
 ICP-OES can manage all kinds of samples for nuclear energy
applications. Elemental analysis for nuclear energy applications
is done in many fields: environment, metallurgy, geology and
mining, nuclear plant monitoring, nuclear waste management,
nuclear fuel analysis...
 For all active samples, special adaptation of the ICP-OES
should be done with a glove-box to protect people and isolate
the sample. As soon as analysis is done for metallurgical samples
or on nuclear fuel related samples, high resolution ICP-OES
spectrometers are required due to the line-rich spectra emitted by
the elements of the matrices.
8) Petro chemistry analysis by ICP-OES
 ICP-OES can manage petrochemical samples. ICP-OES is able to
analyze directly organic solvents, simplifying analysis of petrochemical
samples as most of them can be dissolved directly in solvents such as
kerosene, xylene, or volatile solvents such as methanol, ethanol.
Applications for ICP-OES can be found in refineries for crude oil
analysis and also analysis of finished products such as bitumen or Fuel.
 Analysis of additive elements in lubricating oils can also be managed
easily by ICP-OES, as well as the analysis of wear metals in oil which is
very similar. Analysis of wear metals in oils is usually performed for
plane or helicopter engines to plan for preventive maintenance.
 LIMITATION

Common problems with ICP-OES include

1. Poor precision
2. 49 sample drift
3. 50 non-ideal detection limits
4. Inaccurate identification
Each of these problems will be discussed in turn. Poor precision
is defined as a lack of reproducibility in results obtained for the
same sample.
 MCQ

1) ICP’s principle is similar to which of the following?

a) Flame emission spectroscopy
b) Fourier transforms spectroscopy
c) Atomic emission spectroscopy
d) Absorption spectroscopy
2) ICP is used to analyse samples in which of the following
states?
a) Solids
b) Liquids
c) Gases
d) Solids and liquids
3) Solid samples are introduced into the ICP spectrometer using
which of the following
a) Nebulizer
b) Curvette having glass windows
c) Probe
d) Laser ablation system
4) Atomization or ionization occurs at which of the following
conditions?
a) Vacuum pressure
b) Atmospheric pressure
c) Low pressure
d) High pressure
5) Ions flow is pumped into the vacuum system using
which of the following?
a) Orifice
b) Nozzle
c) Venturi meter
d) Dall tube
5) Which of the following is not the characteristic of ICP
spectrometer?
a) Easy sample introduction
b) It can trace multiple elements
c) High detection limits
d) Accurate
6) CP spectrometer is a sequential multi-element analyser that has
scan times less than __ for one sweep
a) 10ms
b) 20ms
c) 50ms
d) 100ms
7) Double focusing section analysers offer better resolution than
ICP spectrometry system.
a) True
b) False
8) The most common type of ion detector found in ICP system is
which of the following?
a) Faraday cup collector
b) Channeltron
c) Micro-channel plate
d) Flame ionization detector
9) Which of the following is the disadvantage of ICP mass
spectroscopy?
a) Incapable of multi-element analysis
b) Less sensitivity
c) Impossible to obtain isotopic information
d) Not useful for detection of non-metals
10) The isobaric interference is not caused in which of the
following elements?
a) Argon
b) Oxygen
c) Helium
d) Nitrogen
 REFERENCES

https://www.agilent.com/en/support/atomic-spectroscopy/indu
ctively-coupled-plasma-optical-emission-spectroscopy-icp-oe
s/icp-oes-faq#:~:text=The%20ICP%2DOES%20principle%20
relies,of%20a%20very%20specific%20wavelength
.
Inductively Coupled Plasma Optical Emission Spectrometry
Xiandeng Hou College of Chemistry, Sichuan University,
Chengdu, China
ICP-OES principle, ICP-OES Analysis, ICP-OES FAQ's |
Agilent