ANALYTICAL CHEMISTRY ASSIGNMENT

Submitted by:
Fasiha Ahmad (520157)
Submitted to:
Dr. Atta

BS Chemistry 7th Organic (M)

 Atomic Emission Spectroscopy (AES)
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. When an excited atom returns to the ground level, it emits
radiation in a discrete wavelength. Atomic emission spectroscopy involves both
excitation (absorption of radiation) and de-excitation (emission of radiation) of
electrons.
Atomic emission spectroscopy, also known as ICP spectroscopy stands for
inductively coupled plasma. It is named altogether as inductively coupled plasma
atomic emission spectroscopy (ICP-AES) or inductive coupled plasma optical
emission spectrometry (ICP-OES). It involves the excitation and de-excitation
processes for electrons by absorption of radiation. When an electron emits
electromagnetic radiation while coming back from an excited to de-excited state,
the EMR is measured and analyzed. It is called OES due to the optical property of
radiation during the de-excitation process.

Development of inductively coupled plasma atomic emission

spectroscopy (ICP-AES)
This technique was developed by Sir Norman Lockyer from the United Kingdom,
although it was Henrick Lundegardn who pioneered it. This was one of the best
techniques used at that time for quantitative analysis. Atomic emission
spectroscopy is a useful technique for determining the inorganic constituents in
different samples and much more.

Working Principle of atomic emission spectroscopy

AES technique is based on the excitation of electrons to higher energy levels by
absorption of a specific wavelength when heated at high temperatures. 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 (∼10-8 sec).

Instrumentation of AES
Sample Cell
A cup-shaped graphite electrode acts as a sample cell in atomic emission
spectroscopy. The sample is introduced into plasma with the help of nebulizers.

Nebulizers
Various types of 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.

Atomizer
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

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.

ICP (Inductively Coupled Plasma) source

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 (∼
27 MHz).

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’. Diffraction gratings give better results and resolution than prisms.

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.

Types of spectrophotometers
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.

Quantification process for ICP-AES/OES

Results are calculated by plotting a graph between concentration and emission.
For the quantification purpose, the instrument must be calibrated and must be free
from background interferences as background interferences affect the detection
limit. The correction factor is also applied for the removal of interferences.
Five to ten successive determinations are performed for the quantification and their
standard deviation is calculated. Many elements are ionized because of very high
plasma temperature. Therefore ionic lines are analyzed. Most of the elements even
show a detection limit of 10 ppb.
To overcome the spectral overlaps and background shifts, modern instruments are
equipped with PCs and monitors to allow the acquisition and display of spectral
regions in the vicinity of analytical lines.
After calibration and verification of samples, they are analyzed to generate a
calibration curve and results are generally printed out.

Standardizing the Method

We know that emission intensity is proportional to the population of the analyte’s
excited state, N∗ If the flame or plasma is in thermal equilibrium, then the excited
state population is proportional to the analyte’s total population, N, through the
Boltzmann distribution.
A calibration curve for flame emission usually is linear over two to three orders of
magnitude, with ionization limiting linearity when the analyte’s concentrations is
small and self-absorption limiting linearity at higher concentrations of analyte.
When using a plasma, which suffers from fewer chemical interferences, the
calibration curve often is linear over four to five orders of magnitude and is not
affected significantly by changes in the matrix of the standards.
Emission intensity is affected significantly by many parameters, including the
temperature of the excitation source and the efficiency of atomization. An increase
in temperature of 10 K, for example, produces a 4% increase in the fraction of Na
atoms in the 3p excited state, an uncertainty in the signal that may limit the use of
external standards. The method of internal standards is used when the variations in
source parameters are difficult to control. To compensate for changes in the
temperature of the excitation source, the internal standard is selected so that its
emission line is close to the analyte’s emission line. In addition, the internal
standard should be subject to the same chemical interferences to compensate for
changes in atomization efficiency. To accurately correct for these errors the analyte
and internal standard emission lines are monitored simultaneously.

Determination of Sodium in a Salt Substitute

The best way to appreciate the theoretical and the practical details discussed in this
section is to carefully examine a typical analytical method. Although each method
is unique, the following description of the determination of sodium in salt
substitutes provides an instructive example of a typical procedure. The description
here is based on Goodney, D. E. J. Chem. Educ. 1982, 59, 875–876.

Description of Method
Salt substitutes, which are used in place of table salt for individuals on low-sodium
diets, replaces NaCl with KCl. Depending on the brand, fumaric acid, calcium
hydrogen phosphate, or potassium tartrate also are present. Although intended to
be sodium-free, salt substitutes contain small amounts of NaCl as an impurity.
Typically, the concentration of sodium in a salt substitute is about 100 μg/g The
exact concentration of sodium is determined by flame atomic emission. Because it
is difficult to match the matrix of the standards to that of the sample, the analysis is
accomplished by the method of standard additions.
Procedure
A sample is prepared by placing an approximately 10-g portion of the salt
substitute in 10 mL of 3 M HCl and 100 mL of distilled water. After the sample
has dissolved, it is transferred to a 250-mL volumetric flask and diluted to volume
with distilled water. A series of standard additions is prepared by placing 25-mL
portions of the diluted sample into separate 50-mL volumetric flasks, spiking each
with a known amount of an approximately 10 mg/L standard solution of Na+, and
diluting to volume. After zeroing the instrument with an appropriate blank, the
instrument is optimized at a wavelength of 589.0 nm while aspirating a standard
solution of Na+. The emission intensity is measured for each of the standard
addition samples and the concentration of sodium in the salt substitute is reported
in μg/g.

Evaluation of Atomic Emission Spectroscopy

Scale of Operation
The scale of operations for atomic emission is ideal for the direct analysis of trace
and ultratrace analytes in macro and meso samples. With appropriate dilutions,
atomic emission can be applied to major and minor analytes.

Accuracy
When spectral and chemical interferences are insignificant, atomic emission can
achieve quantitative results with accuracies of 1–5%. For flame emission, accuracy
frequently is limited by chemical interferences. Because the higher temperature of
a plasma source gives rise to more emission lines, accuracy when using plasma
emission often is limited by stray radiation from overlapping emission lines.

Precision
For samples and standards in which the analyte’s concentration exceeds the
detection limit by at least a factor of 50, the relative standard deviation for both
flame and plasma emission is about 1–5%. Perhaps the most important factor that
affect precision is the stability of the flame’s or the plasma’s temperature. For
example, in a 2500 K flame a temperature fluctuation of ±2.5±2.5 K gives a
relative standard deviation of 1% in emission intensity. Significant improvements
in precision are realized when using internal standards.

Sensitivity
Sensitivity is influenced by the temperature of the excitation source and the
composition of the sample matrix. Sensitivity is optimized by aspirating a standard
solution of analyte and maximizing the emission by adjusting the flame’s
composition and the height from which we monitor the emission. Chemical
interferences, when present, decrease the sensitivity of the analysis. Because the
sensitivity of plasma emission is less affected by the sample matrix, a calibration
curve prepared using standards in a matrix of distilled water is possible even for
samples that have more complex matrices.

Selectivity
The selectivity of atomic emission is similar to that of atomic absorption. Atomic
emission has the further advantage of rapid sequential or simultaneous analysis of
multiple analytes.

Time, Cost, and Equipment

Sample throughput with atomic emission is rapid when using an automated system
that can analyze multiple analytes. For example, sampling rates of 3000
determinations per hour are possible using a multichannel ICP, and sampling rates
of 300 determinations per hour when using a sequential ICP. Flame emission often
is accomplished using an atomic absorption spectrometer, which typically costs
between $10,000–$50,000. Sequential ICP’s range in price from $55,000–
$150,000, while an ICP capable of simultaneous multielemental analysis costs
between $80,000–$200,000. Combination ICP’s that are capable of both sequential
and simultaneous analysis range in price from $150,000–$300,000. The cost of Ar,
which is consumed in significant quantities, can not be overlooked when
considering the expense of operating an ICP.

Applications of Atomic Emission spectroscopy

AES is used for the following purposes:
1. Metallic deficiency in living organisms can be diagnosed.
2. Clinical diagnosis of different metals i.e Na, K, Ca, Mg, Fe, Zn, etc in body
fluids like blood, urine, etc.
3. Trace metal and rare earth elemental detections.
4. The analysis of agricultural substances like fertilizers, composts, etc.
5. Different metals like Fe, Ni, Mn, etc can be analyzed in motor lubricants.
6. Pharmaceutical tablets can be analyzed for hazardous substances.
7. Determination of alkali and alkaline earth metals.
8. Igneous and metamorphic rocks can be analyzed for mineral compositions
which can then be used for the dating process.
9. Detection of metallic ions and minerals in water i.e. sea and freshwater have
such differences.
10. The analysis of trace and other elements, including multi-elemental analysis
in stainless steel, frozen lava, emerging islands, etc.