Table Of Contents

Atopm

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Atomic Absorption Spectroscopy:
Atomic absorption spectroscopy is a technique which studies absorption of electromagnetic radiations in relationship to
molecular structure. It is a technique for measuring the concentration of various elements in the sample through their
absorption of light. It is a relatively simple and reliable technique which uses absorption of optical radiation by free atoms for
determining the contents of different elements

Atomic Absorption Spectroscopy Principle

Atomic absorption spectroscopy is based on the principle that when a beam of electromagnetic radiation is passed through a
substance, the radiation may either be absorbed or transmitted depending upon the wavelength of the radiation.

The absorption of radiation would bring about an increase in the energy of the molecule. The energy gained by the molecule is
directly proportional to the wavelength of radiation.

The increase in the energy of the molecule leads to the electronic excitations where electrons jump to higher energy levels. A
particular wavelength that a given molecule can absorb depends upon the changes in vibrational, or rotational or electronic
states

Atomic Absorption Spectroscopy Theory:

When a monochromatic radiation of frequency v is incident on a molecule, the molecule in the gaseous state E1E1 absorbs a
photon of energy hνhν, it undergoes a transition from lower energy level to higher energy level.

A detector is placed to collect the radiation after interaction with the molecule which shows that intensity has reduced. With
wide range of frequencies, the detector shows the energy has been absorbed only from the frequency.

νν = (ΔE)h(ΔE)h

Therefore we obtain an absorption spectrum which is defined as a record of the radiation absorbed by the given sample as a
function of wavelength of radiation.

The energy difference between the levels is given as,

ΔEΔE = E2−E1E2−E1 = hνhν = hcλhcλ.

Instrumentation Of Atomic Absorption Spectrometer:
The following components make up the AA spectrometer :

Hollow cathode lamp

The Hollow cathode Lamp is made with an element (metal) as the cathode encased in a bulb with a low pressure inert gas. It is
imposed with a 10mA current such that when the metal is excited electrically, characteristic spectral line/lines are emitted and
passed directionally through a glass UV/VIS window of the lamp.
This is the Source of the analytical light line for the element which is to be measured. It gives a constant and intense beam of
the specific analytical line or wavelength of the element.

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Nebulizer

The nebulizer sucks up liquid sample at a controlled rate, create a fine aerosol that mixes with fuel and oxidant for introduction
into the flame.The nebulizer uses the combustion flames to atomize and introduce the sample into the light path.

Flame

Temperature of some flames 0C

Fuel Oxidant Temp0C

Natural gas Air 1700-1900

H2 Air 2000-2100

C2H2 Air 2100-2300

C2H2 N2O 2600-2900

C2H2 O2 3050-3150

An oxidant and a fuel gas are mixed together and lit to create the flame for FAAS. The Flame is the Atomizer in which the
sample undergoes desolvation and vaporization at high temperature. It destroys any analyte ions, break up complexes and
creates the atoms of the element of interest, eg. Feo, Cuo, Zno, etc.

Burner Head
Burner heads must not be made with a composition of any of the metals determined by AA. It is normally made of solid
Titanium which is corrosian resistant to strong acids and gases.

Monochromator
The main purpose of the monochromator is to isolate a single atomic resonance line (wavelength) from the lines emitted by the
Hollow cathode lamp and transmit it to the detector. It not only selects the specific analytical line, but excludes all other

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interfering lines in that region.

Photomultiplier tube (PMT)

This is the detector. The PMT determines the intensity of photons of the analytical line exiting the monochromator. Before an
analyte is aspirated, a signal is generated by the PMT as a measurement of the light flowing from the HCL.
The PMT is the most commonly used detector for atomic absorption spectroscopy. However, solid state detectors are now
replacing conventional vacuum-type photomultipliers. data-handling and display.

Samples
The samples and standards are often prepared in duplicate with acid to match the analyte's chemical matrix as closely as
possible. Acid contents of 1% to 10% are common. High acid concentrations help keep all dissolved ions in solution. The blank is
a solution representative of the matrix of samples and standards but without the analyte.

Autosampler
With the autosampling accessory, tedious and time-consuming operations can be avoided. The autosampler is a computer-
controlled, multi-purpose system. It automates standard and sample introduction for instrument calibration and analysis, and is
a fully automated analytical workstation.

Wastes
Liquid sample not flowing into the flame collects on the bottom of the nebulizer chamber and flows by gravity through a waste
tube to a glass waste container (highly acidic).

Shutdown
Before shutdown, aspirate deionized water through the system to flush out salts and acid. Then close off fuel first, then oxidant,
and bleed gas supply cylinders. Most modern instruments control the ignition and shutdown procedures automatically.

Pharmaceutical Application of Atomic Absorption Spectroscopy

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Naproxen and ibuprofen (aryl propionic acid derivatives) both are classified as non-steroidal anti-inflammatory agents. Except
HPLC, no sensitive methods were reported for both the drugs. HPLC methods suffer from two drawbacks- first; requirement of
costly chemicals and second; more time consuming. Because atomic absorption spectroscopy (AAS) methods are simple,
sensitive, rapid, reproducible and uses low cost chemicals. The objective of present research work was to develop highly
sensitive and economical analytical methods for the quantitative estimation of naproxen and ibuprofen in pharmaceutical
formulations by AAS. The methods were based on the reaction of naproxen and ibuprofen with copper and cobalt chloride to
form colored metal complexes. These complexes were extracted with organic solvents and digested with acids. Naproxen and
ibuprofen were indirectly estimated by AAS via the determination of the copper and cobalt content in the formed complexes.
The proposed methods may be used for routine analysis of pharmaceutical formulations containing aryl propionic acid
derivatives and similar pharmaceutical drugs by the analytical chemist.

Atomic Emission Spectroscopy:

When the molecule jumps from the higher energy level to lower energy level, a photon of energy is emitted. The spectrum
obtained is called emission spectrum and the spectroscopy is called atomic emission spectroscopy. Atomic emission
spectroscopy is a technique to determine the quantities of elements in the sample by using the intensity of light emitted by
plasma, spark, flame or arc.

Atomic Emission Spectroscopy Theory:

Atomic emission spectroscopy is based on the principle that when a molecule is applied energy in the form of light or heat, the
molecules get excited and move from lower energy level to higher energy level. At this state the molecules are unstable.
Therefore, the excited molecule jumps from higher energy level to lower energy level, emitting radiation. The radiations are
emitted in the form of photons. The wavelengths of photons emitted are recorded.

These radiations are recorded in the emission spectrometer. The level of emissions of a substance is the difference between the
substance in excited and lower state.

Each element has different and unique level of emission which helps the scientist to detect the elements. The frequencies are
recorded as light spectra in the emission spectrometer.

Suppose the molecule comes back from the energy level E2 to lower energy level E1 emitting radiations. Then the frequency is
given by,
v = ΔEhΔEh.

The energy difference between the levels is given as:

ΔEΔE = E2−E1E2−E1 = hv = hcγhcγ.

Instrumentation Of Atomic Emission Spectrometer:

The instrument used for recording a spectrum is known as spectrometer or spectrophotometer.

The first step is atomization or excitation. In this solid liquid or solution analyte is converted into gaseous atom. The sample is
then made excited and the excitation in emission spectrometer can be thermal or electrical, but often takes the form of
electromagnetic radiation. The most common methods of excitations are flames and plasmas. If the sample is solid, it can be
dissolved in solvent for analyzing.

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In Atomic emission spectroscopy, in the spectrometer, the sample, after undergoing excitation, is its own source. It is necessary
that only the emitted radiation is collected and analyzed and then recorded in the usual way. In case of emission spectrometer,
no analyser is necessary, the source being its own analyser. A monochromatic is employed which separates radiations into
individual wavelengths. The dispersing element is used which is generally a glass prism.

The detector over here is the device which converts spectral radiation into electrical signal that is transmitted to a recording
device called a recorder. The recorder produces a print on the chart. It is essential that the detector does not receive radiation
directly from the exciting beam and the two are placed at right angles.

A modulator placed between the source of excitation and the sample, ensures that only the emission is recorded which directly
arises from the excitation. Any other spontaneous emission in this way is ignored.

Application of Atomic Emission Spectrophotometry:

AE spectrometers have been used in many different industrial and academic settings. For example, a medical laboratory could
detect the type and amount of toxic metals that could be present in patient's urine or blood. Environmental scientists could
monitor metal pollutants in soil and water. The pharmaceutical industry uses these machines to determine if a metal catalyst
after a drug has been purified. Lastly, the mining industry would utilize these devices to detect the quantity and presence of
precious metals like gold and silver.

Academic and industrial laboratories consider several factors before selecting spectrometer. For example, some labs require a
large number of samples to be analyzed in one day while other labs might use the instrument occasionally. Specific analyzers
might require a smaller amount of sample. In addition, a toxicology lab might need an instrument to report values in micro or
nanograms. Lastly, academic (more often than industrial) facilities must consider the cost of the analyzer before purchasing.
Other options besides flame based AA/AE are graphite furnace (GFAA) and inductively coupled plasma (ICP-AE or ICP-OES). With
the GFAA method, a furnace is used to excite the metallic sample. This technique can detect lower concentrations of metal than
a flame AA/AE. Also, smaller volumes of sample are needed for a GFAA. ICP machines utilize a plasma (gas with charged ions) for
the excitation process. Some of these instruments can directly analyze solid samples. Unfortunately, ICP-AE instruments are
slower in producing data.