Atomic Absorption Spectroscopy (AAS)
most widely used of all atomic methods because of its simplicity, effectiveness, and low cost € Atomic absorption methods were not used before this because of problems due to very narrow widths of atomic absorption lines

Line Width Effects in Atomic Absorption
€ €


The width of atomic absorption lines are very narrow (0.002 ± 0.005 nm) Even good ± quality monochromators have effective bandwidths greater than the width of atomic absorption lines This results to instrumental departures from Beer¶s law

non linear calibration curves are produced

obtain small slopes of calibration curves .€ Only a small fraction of the radiation from the monochromator slit is absorbed by the sample .poor sensitivity .

€ Solution : y Use of line sources with bandwidths narrower than the absorption band widths y Example: use sodium vapor lamp y Sodium atoms are excited by an electrical discharge to produce a line y Other sodium lines produced are filtered by a monochromator y Source temperature and pressure are kept below that of the atomizer so that the Doppler broadening of the emitted lines is less than the broadening which occurs in the flame/atomizer .


Hollow Cathode lamp .

€ € € € Application of about 300 V across the electrodes causes ionization of inert gas and generation of a current of 5 ± 10 mA Sputtering ± gaseous cations acquire enough kinetic energy to dislodge some of the metal atoms from the cathode surface and produce an atomic cloud Some of the sputtered metal atoms are in excited states and thus emit radiation as they return to their ground states Metal atoms diffuse back to the cathode suface or glass walls of tube and are redeposited .

€ Cylindrical configuration y concentrates the radiation in a limited region of the metal tube y Enhances the probability that redeposition will occur at the cathode rather than glass walls € Efficiency depends on operating voltage y high voltages and thus high currents lead to greater intensities y BUT: greater currents produce an increased number of unexcited atoms in the cloud which are capable of self absorption and leads to lowered intensities .

Electrodeless Discharge Lamp .

and Sb € . As.The inert gas ionizes in this field € The ions are accelerated by the high ± frequency component of the field until they gain sufficient energy to excite atoms of the metal whose spectrum is sought € Performance is not as reliable as hollow cathode lamps € Has better detection limits for Se. Cd.

Source Modulation € € € In atomic absorption measurement. emitted radiation corresponding in wavelength to the monochromator setting is present in the flame because of excitation and emission of analyte atoms . it is necessary to eliminate interferences caused by emission of radiation by the flame Much of this emitted radiation is removed by the monochromator However.

The source is then modulated so that its intensity fluctuates at a constant frequency € The detector receives two types of signals: € y Source: alternating y Flame: continuous These signals are converted into the corresponding types of current and an electronic system eliminates the unmodulated dc signal produced by the flame € The ac signal is passed from the source to the amplifier and to the readout device € .

Modulation can be accomplished by interposing a motor ± driven circular chopper between the source and the flame € Rotation of the disk at a constant speed provides a beam that is chopped to the desired frequency € As an alternative. the power supply for the source can be designed to pulse the hollow ± cathode lamps in an alternating manner € .

Spectrophotometers Most AAS instruments are equipped with ultraviolet ± visible monochromators. which are capable of achieving a very narrow bandwidth € Atomic absorption instruments use photomultiplier tubes as transducers € .

Beam .Single .

Double .Beam .

Atomic Absorption Analytical Techniques .


.nebulizers Nebulization ± to convert a liquid into a fine spray or mist Aerosol ± suspension of finely divided liquid or solid particles in a gas Nebulizer functions because the high velocity of the combustion gases of the fuel and oxidant rushing past a small orifice draws the liquid into the flow as small droplets.

.Types of nebulizers Pneumatic Nebulizer .liquid sample is introduced to a high velocity jet of the oxidant gas.fabricated from inert material. usually platinum-iridium alloy for capillary and tantalum or titanium or platinum for the nosepiece and annulus. and the mist produced is mixed with the fuel gas and passed via a mixing / expansion chamber to the burner .


Ultrasonic Nebulizer .

Babington and V-groove .

.Sample Preparation € Flame Spectroscopic methods y Disadvantages The sample must be introduced in the form of a solution . the decomposition and solution steps are time-consuming and error-prone. The reagents used can also introduce chemical and spectral interferences. Moreover. Decomposition of materials may lead to loss of analyte.

Sample Preparation Treatment with hot mineral acids € Oxidation with liquid reagents € Combustion in an oxygen bomb € Ashing at a high temperature € High-temperature fusion € .

advantageous for samples with high level of salts or suspended solids. .Sample Introduction by Flow Injection € Flow injection analysis (FIA) y An excellent method of sample introduction especially when sample conservation is important y The carrier system of the FIA system (deionized water or dilute electrolyte) provides continuous flushing of the flame atomizer.

Organic Solvents € Enhanced absorbances due to increased nebulizer efficiency . € The added organic material may be offset by leaner fuel-oxidant ratios. y Lower surface tension results in smaller drop sizes which eventually leads to an increase in the amount that reaches the flame. Rapid solvent evaporation contributes to the enhanced absorbance. € .

.Organic Solvents € Methyl butyl ketone y To extract chelates of metallic ions y The sensitivity of the method is enhanced and interferences are reduced.

€ In addition. the number of uncontrolled variables in atomization and absorbance measurements is large to allow measurement of one standard solution each time an analysis is performed. € .Calibration Curve A calibration curve that covers the range of concentrations found in the sample should be prepared periodically.

Curve is linear over region of interest and background correction is made € Advantage: Matrix matching is achieved automatically € .Standard Addition Method Applied only when calib.

With special precautions.Accuracy y the relative error is of the order of I% to 2%. y Errors encountered with electrothermal atomization usuallv exceed those for flame atomization by a factor of 5 to 10 . this can be lowered to a few tenths of a percent.

Detection Limits .

Sample Atomization Techniques € Atomization ± process in which a sample is converted into gas ± phase atoms or elementary ions y Flame Atomization y Electrothermal Atomization y Special Atomization Techniques .

Flame Atomization € Analyte € Dissociation Ionization Excitation € Nebulization Desolvation Volatilization € € € € .

€ .Types of Flames € Temperature of 1700 °C to 2400 °C when air is the oxidant. Temperature of 2500 °C to 3100 °C when oxygen or nitrous oxide is used as oxidant.


Flame Atomizers .

Flame Atomizers € Aerosol € Most of the sample solution Mixing chamber Waste container € Mixes with fuel € € Runs through a series of baffles € € Collects the finest solution droplets .

Performance Characteristics of Flame Atomizers Flame atomization ± most reproducible € Low sampling efficiency € y A large portion of the sample flows down the drain. y Residence time of individual atoms in the optical path of the flame is brief. .

€ Long residence of atoms in the optical path € Used in atomic absorption or atomic fluorescence but not for atomic emission.Electrothermal Atomization Enhanced sensitivity because the entire sample is atomized in a short period of time. € .

Evaporation € Ashing in an electrically heated graphite tube € . Temperature is consequently increased.Electrothermal Atomization € A small volume of sample (in L) € € Current is rapidly increased.

Electrothermal Atomizers .

Electrothermal Atomizers € Graphite Tube y Where atomization occurs y Open at both ends and has a central hole for sample introduction y Fits into a pair of cylindrical graphite contacts which are held in a water-cooled metal housing .

Electrothermal Atomizers € Two inert gas streams y External stream prevents outside air from entering and incinerating the tube. . y Internal stream excludes air and carries away the vapors generated from the sample matrix during the initial heating stages.

.Electrothermal Atomizers € L¶vov Platform y Made of graphite and located below the sample entrance. y Where the sample is evaporated and ashed y Improves reproducibility of analytical signals The sample is not in contact with the furnace wall so atomization occurs in an environment where the temperature is not rapidly changing.

Electrothermal Atomizers € Two ways of heating y Longitudinal mode continuously varying uniform temperature temperature profile y Transverse mode profile optimum condition for the formation of free atoms .

y Detection limits lie in the range of 10-10 to 10-13 g of the analyte.Performance Characteristics of Electrothermal Atomizers € Advantages y High sensitivity for € Disadvatages y The method is slow. is narrow. . less than two orders of magnitude. y The analytical range small volumes of sample.

Specialized Atomization Techniques € Glow-Discharge Atomization Hydride Atomization Cold Vapor Atomization € € .


Chemical Interferences
y from chemical processses during atomization,

altering absorption characteristics of analyte
€ €

Physical Interferences
y Any influence of present materials in the sample

Spectral Interferences
y occur when absorption/emission of interfering

species overlaps or lies close to analyte absorption

Dissociation Equilibria

Dissociation and association reactions lead to conversion of metallic constituents to the elemental state.


Dissociation reactions play an important part in determining the nature of the emission or absorption spectra for an element

Dissociation Equilibria
Dissociation equilibria that involve anions other than oxygen may also influence flame emission and absorption. € For example, the line intensity for sodium is markedly decreased by the presence of HCl.

€ There is a significant concentration of free electrons produced by the equilibrium € .Ionization Equilibria Ionization is important in higher temperature flames where oxygen or nitrous oxide serves as the oxidant.

is a decrease in concentration of atoms A decrease in emission or absorption may be observed in hotter flames. Counteracting this effect. according to the Boltzmann relationship .Ionization Equilibria € € € Increased temperatures cause an increase in the population of excited atoms. . Thus lower excitation temperatures are usually specified for the determination of alkali metals.

Ionization Equilibria The effects of shifts in ionization equilibria can be eliminated by addition of an ionization suppressor € Higher temperature with nitrous oxide enhances the degree of decomposition and volatilization of the compounds € .

€ € Interferences due to overlapping lines are rare .Spectral Interferences From combustion products which exhibit broadband absorption of particulate products that scatter radiation € Often occur with aspirated concentrated solutions with : Ti. Zr and W € Caused by scattering ± due to carbonaceous particles from incomplete combustion of organic matrix.

an excess of the interfering substance can be added to both sample and standards. € y The added substance is sometimes called a radiation buffer. .Spectral Interferences Avoided by varying analytical variables such as flame temp. And fuel-to-oxidant ratio € If source of interference is known.

Methods of Correction Two-line Correction Method € Continuum-Source Correction Method € Background Correction Based on the Zeeman Effect € .

y This line should lie as close as possible to the analyte line but must not be absorbed € € Any decrease in power of the reference line observed during calibration arises from absorption or scattering by the matrix products of the sample This decrease in power is then used to correct the absorbance of the analyte line .Two-Line Correction Method € Uses a line from the source as a reference.

Continuum-Source Correction Method A background corrector compensates for the background absorption .

Background Correction Based on the Zeeman Effect € Zeeman Background correction y An applied magnetic field to the source or atomizer is used to split the resonance line into its Zeeman components ( and ). y The background is monitored by the polarizers y The analyte and signal background are monitored with the central component .

absorb only radiation polarized at 90° to the field . y The line absorbs only that radiation that is plane polarized in a direction parallel to the external magnetic field y the lines.Background Correction Based on the Zeeman Effect € Application y based on the differing response of the two types of absorption lines to polarized radiation.

Background Correction Based on the Zeeman Effect .

Background Correction Based on the Zeeman Effect A more accurate correction for background € Particularly useful for electrothermal atomizers and permit the direct determination of elements in samples such as urine and blood € The decomposition of organic material in these samples leads to large background corrections (background A > I) € .

htm . [4]http://weather. CRC Handbook of Atomic Absorption Analysis Vol. [3] Skoog. 2004.Sources [1] Skoog. Thomson Brooks/Cole. /soil698/Student_Reports/Spectroscopy/re port. 2007.nmsu. Thomson Brooks/Cole. Fundamentals of Analytical Chemistry 8th edition.1987. 1. et al. USA. USA. [2] Verma. Principles of Instrumental Analysis 6th edition. CRC Press Inc. A. et al.

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