ATOMIC ABSORPTION INSTRUMENTATION, PRINCIPLE AND APPLICATION

Submitted to:

Dr. Irshid Pervez

Submitted by:

Shoaib Ahmed (FA11-R08-012)

Submitted on:

Dec 07, 2011

Sustainable water, sanitation, Health and Development, Department of Environmental Science, CIIT, Abbottabad.

Instrumentation The basic components of an atomic absorption spectrometer a shown in Figure. The function of the instrument is as follows: (i) The radiation source (a hollow cathode or an EDL) emits a sharp line spectrum characteristic of the analyte element; (ii) The emission beam from the radiation source is modulated; (iii) The modulated signal passes through the atomic vapour where the atoms of the analyte absorb radiation of the line-like radiation source; (iv) The desired spectral line (usually resonance line) is selected by the monochromator; (v) The isolated analyze line falls onto .the detector (a photomultiplier) where the light signal is converted into the electric signal; (vi) The modulated signal is amplified by a selective amplifier; (vii) The signal is finally recorded by a readout device (a meter, strip chart recorder, or through data processing to a digital display unit or printer). Single-beam and Double-beam Instruments Figure 15 shows the light path in a single alternating current (AC) spectrometer. The radiation which falls onto the detector is proportional to the transmittance. Therefore, it is necessary to run two measurements (sample and blank solutions) in order to get the corresponding absorbance reading. With a single-beam system accurate absorbance measurements are obtained provided that the radiation source is very stable. Although the emission intensity of every radiation source will change as a function of time, the modern hollow cathode lamps and EDLs meet this requirement well. The emission signal from the radiation source is divided by a rotating mirror-chopper into the sample and reference beams. The sample beam is crossing through the atomizer and the reference beam is by-passing it. The two beams are then recombined by a semi-transparent mirror behind the atomizer. The electronics of this system yields the ratio of these beams with the sample beam as the denominator and the reference beam as the numerator. Since the sample and reference beams are both generated from the same radiation source, passing through the same monochromator, and received by the same detector and amplified by the same electronics, any variations in the radiation source, sensitivity of the detector, or amplification appears in both beams and cancels out. The stability of this system is thus better than that of a single-beam system. On the other hand, as the reference beam does not cross the atomizer, variations in the atomizing conditions cannot be eliminated. A further disadvantage of double beam optics is the loss of incident energy (about 50%), which is much higher than in single-beam optics. Sample Preparation The preparation of the final sample solution from a solid sample is often the most timeconsuming step of the analytical procedure. This is also the most difficult operation to automate. Weighing, digestion, filtering, and dilution of the sample are procedures which are difficult to perform completely without human intervention. For example, the automated sample preparation procedure of geological samples could be the following: (i) Sample tubes are placed on a stand; (ii) Samples are weighed with a balance connected to a computer. Sample stands with the tubes are placed one after another on the balance. Each weighing series and sample tube is coded; (iii) An acid mixture is added into the tubes; (iv) Stands are transferred to the programmable digestion system. 34 chapter 3 This is the

slowest step, and it is often convenient to perform during the night time according to a preset temperature program; (v) Samples are measured using an auto sampler. Sample Dilution. Commercial equipment is available which enable predetermined volumes of any number of samples to be accurately diluted with another liquid (solvent, buffer, etc.). The use of this equipment saves considerable time that would be spent pipetting and making up to volume large sample series. Sample Introduction The functioning of a conventional auto sampler in flame AAS is the following: (i) When the sample tube is in analysis position, sample take-up is initiated; (ii) After a suitable delay, while the absorption signal is stabilized, the sampler gives a signal to the main instrument to carry out the peak integration and data handling steps; (iii) After the measurement, the main instrument signals to the sampler to proceed to the next sample and a similar sequence takes place. In electro thermal atomization the operation of auto samplers is somewhat different. The non-continuous nature of the sample introduction for GF-AAS requires a wash- through for the sampling capillary between samples in order to avoid contamination. The sample is then taken up and transferred by an auto pipette into the atomizer. Then the sampler gives a signal to the furnace controller to start the preset heating program. During the cooling step the controller signals to the auto sampler to change to the next sample and carry out the wash- through. Modern auto samplers are capable of making the calibration, dilutions, the method of standard additions, and matrix modification completely automatic. The appropriate series of blanks, standards, and reagents are loaded and the data handling system programmed. calibration is also possible at selected intervals during a long sample run. Using the auto sampler, precision can be improved considerably compared to that achieved by hand pipetting. Radiation Sources It is important in AA measurements that the emission line width coming from the radiation source is narrower than the absorption line width of the atoms studied. In principle, a high resolution monochromator is not needed to separate the analyte line from the other lines of the spectrum, but in practice, the spectral band pass of the source should be equal or less than the absorption line width. Otherwise, artificially low absorbance values are obtained leading to reductions in sensitivity. In the AA technique the use of continuum sources (quartz-halogen filament lamps and deuterium and xenon arc lamps) with reasonably priced monochromator is not satisfactory. In the case of (A) the emission of radiation is continuous for the whole spectral bandwidth. The energy absorbed by the atoms of the analyte is small in comparison to the whole energy falling onto the detector. In this case much light energy is passing through the monochromator slit and the measurement becomes inaccurate. In the case of (B) by using a line-like radiation source the situation is opposite and the emission and absorption profiles overlap each other. The most important radiation sources in atomic absorption spectrometry are the hollow cathode lamps and electrode less discharge lamps. Other sources which have been used

are lasers, flames, analytical plasmas, and normal continuum sources like deuterium and xenon arc lamps. Hollow Cathode Lamps Hollow cathode lamps are the most widely used radiation sources in the AA technique. A hollow cathode lamp consists of a glass cylinder, and an anode and a cathode (Figure 18). The cylindrical cathode is either made of the analyte element or filled with it. The diameter of the cathode is 3 to 5 mm. The anode is in the form of a thick wire and usually made of tungsten, nickel, tantalum, or zirconium. The glass tube is first evacuated and then filled with an inert gas (argon or neon). The pressure of the inert gas is about 0.5 to 1.3 kPa. The choice of the inert gas depends upon two factors. Firstly, emission lines of the filler gas must not coincide with the resonance lines of the analyte element. The main emission regions from neon and argon. The filler gas used in the hollow cathode lamp is easy to detect by the colour of the emission beam of the lamp. Argon gives a blue and neon an orange discharge. Secondly, the relative ionization potentials of the inert gas and cathode metal must be taken into account. The ionization potential of neon is much higher than that of argon. Neon is therefore used in lamps of metals with high ionization potentials. The kinetic energy of ions hitting the surface of the cathode must be higher than the energy of metal bonds. Normally, the emission intensity of the lamp can be increased by raising the applied current. This increases the number of metal atoms excited by filler gas ions in the gas phase. In the case of easily volatilized metals, the increased current and resulting higher temperature lead to increased vaporization of the cathode material, which increases the number of collisions with neutral and charged particles. This is seen as a broadening (Dopplerbroadening) of the emission line. The cloud of neutral metal atoms in the ground state at the cathode opening can now absorb radiation at the emission maximum which is seen in the resulting distorted emission line profile. This phenomenon is called selfabsorption. At the position of the greatest probability of absorption there is a minimum on the emission line.

The lifetime of a hollow cathode lamp depends, especially, on the consumption of the filler gas and the purity of the cathode material. Filler gas will be absorbed and adsorbed on metal deposited on the tube walls. The decrease of the filler gas depends on the applied current and voltage. The cathode must be made from the purest metal available in order to get the pure emission spectrum. Pure metals are manufactured by electrolytic deposition and during the process hydrogen may be absorbed into the metal. Hydrogen is especially difficult to distinguish from the group 8, 9, and 10 transition metals. Hydrogen in the cathode material will diminish the emission intensity. It also has intensive, continuum emission

in the UV region. To get rid of these difficulties lamps are kept in vacuum and at high temperature during their manufacture. Electrode less Discharge Lamps (EDLs). Among the line-like radiation sources, electrode less discharge lamps exhibit the highest radiation intensity and the narrowest emission linewidths. They are used both in atomic absorption and fluorescence spectrometry. The biggest advantage of the EDL is the high intensity of the radiation which can be several orders of magnitude higher than hollow cathode lamps, especially, for easily vaporizable elements. The signal to noise ratio is generally improved which gives higher precision and improved detection limits. EDLs are of great advantage, especially, working in the UV region. The EDLs consist of sealed quartz tubes, 3-8 cm in length and about 0.5-1 cm in diameter. The tube is filled with a few milligrams of the pure analyte metal or its volatile salt (halide) and an inert gas (agon) at a pressure of a few hundred pascals. The lamp is mounted within the coil of a high frequency generator. The excitation energy is produced by a microwave- (> 100 MHz) or radio-frequency (100 kHz- 100 MHz) electromagnetic field. In general, the intensity of the microwave lamps is better than that of radiowave lamps, but the radiowave lamps are more stable and they do not need a thermostat. Monochromator The principal function of the monochromator is to isolate the measured line (resonance radiation) from the other emission lines of the cathode material and lines of the filler gas. Atomic absorption is a very selective method when an element specific radiation source is used. It is practically free of spectral interferences caused by overlapping atomic lines of other elements. The unmodulated molecular emission and other background continua originated in the flame or graphite furnace are eliminated by means of selective amplification. The monochromator consists of two slits (an entrance slit and an exit slit) and a dispersing component (a prism or a grating). The quality of an instrument in other spectrometric techniques, such as in UV-visible spectrometry or plasma-AES, depends mainly on the resolution of the monochromator or on its spectral band pass. The resolution or resolving power (R) of a monochromator is its ability to distinguish adjacent absorption bands or two very close spectral lines as separate entities. Resolution is dependent on the size and dispersing characteristics of the prism or grating, the optical system of the spectrometer, and the slit width of the mono- chromator. The resolution of any dispersing device is: where w is the effective aperture width and d/d angular dispersion. The spectral band pass is the range of radiation that passes through the exit slit. Detector Photo multiple tubes (PMTs) are used nowadays almost exclusively in AAS. A photomultiplier contains a photo-emissive cathode and several anodes (dynodes) in a vacuum. The cathode is coated with an easily ionized material such as alloys of alkali metals with antimony, bismuth, and/or silver. The spectral sensitivity of a PMT depends primarily on the coating material of the photo-emissive cathode (Figure 25). Practically, the lowest measurable

wavelength is 193.7 nm (As) and the highest one 852.1 nm (Cs). A photon falling on the surface of the cathode causes the emission of an electron, provided the photon is sufficiently energetic to ionize the material. The signal is amplified by the process of secondary emission. Modulation of the Signal The optical signal falling upon the detector consists of the resonance line radiation and emission from the atomizer. The emission originated from the flame or graphite furnace consists of molecular band emission and scatter from small particles. Only the resonance signal of the radiation source is wanted, since other radiation falling on the detector diminishes the absorbance value that can be recorded. The output of the radiation source is therefore coded by modulation, and an amplifier placed after the detector is tuned to the same modulated frequency. The radiation source can be modulated either electrically or mechanically. Electric modulation can be performed by using an AC supply current to the lamp (frequency of 280 or 300 Hz, for instance). In mechanical modulation, the radiation beam is interrupted using a rotating sector (chopper) before the atomizer. This method is used, especially, in the double-beam instruments. The chopper splits the light beam into sample and reference beams at a fixed frequency. A beam of regularly varying intensity is produced which will generate an alternating signal at the detector. An AC amplifier is tuned to amplify the Atomic Absorption Spectrometry 45 signals only at the same frequency as the beam modulation. Principle The technique makes use of absorption spectrometry to assess the concentration of an analyte in a sample. It requires standards with known analyte content to establish the relation between the measured absorbance and the analyte concentration and relies therefore on Beer-Lambert Law. In short, the electrons of the atoms in the atomizer can be promoted to higher orbitals (excited state) for a short period of time (nanoseconds) by absorbing a defined quantity of energy (radiation of a given wavelength). This amount of energy, i.e., wavelength, is specific to a particular electron transition in a particular element. In general, each wavelength corresponds to only one element, and the width of an absorption line is only of the order of a few picometers (pm), which gives the technique its elemental selectivity. The radiation flux without a sample and with a sample in the atomizer is measured using a detector, and the ratio between the two values (the absorbance) is converted to analyte concentration or mass using Beer-Lambert Law. Beer's law Physical law stating that the quantity of light absorbed by a substance dissolved in a nonabsorbing solvent is directly proportional to the concentration of the substance and the path length of the light through the solution; the law is sometimes also referred to as the BeerLambert law or the Bouguer-Beer law. Beer's law is commonly written in the form A=cl, where A is the absorbance, c is the concentration in moles per liter, l is the path length in centimeters, and is a constant of proportionality known as the molar extinction coefficient. The law is accurate only for dilute solutions; deviations from the law occur in concentrated solutions because of interactions between molecules of the solute, the substance dissolved in the solvent.

Applications Application in environmental field Environmental safety is more important than ever before. The monitoring of our environment, especially our drinking water resources, surface and waste waters but also earth and waste is an important task for national and private environmental laboratories and this technique is at large scale for all above determination. 3.1) Application in chemical chemistry Plenty of determinations are carried out easily and comfortably using spectrophotometer. This include blood tests e:g the determination of iron. For all the different kinds of beer ingredient analysis AAS can be used for maintain quality in beer industries. AA instruments are used in food industry for much analysis for quality control and product monitoring. 3.2) Application in Pharmacy It is the basic instrument that is use in this field for diverse analysis. AA is especially studied for versatile application in the field of cosmetics. e:g in dental cosmetics it is use for analysis of dental materials. 3.3) Application in material analysis The optical analysis of different materials is an attribute of their quality. The AA spectrophotometer can be equipped with specific accessories and is the best suitable for determination of optical properties like transmittance, reflectance, color and many other and these tasks used at paper industry, Plastic industry, Color industry etc