Atomic Absorption Spectrometry

Flame atomic absorption spectroscopy (AAS) is currently the most widely used of all atomic methods because of its simplicity, effectiveness and relatively low cost. Line Width Effects in Atomic Absorption No ordinary monochromator is capable of yielding a band of radiation as narrow as the width of an atomic absorption line (0.002 to 0.005 nm). As a result, the use of radiation that has been isolated from a continuum source by a monochromator inevitably causes instrumental departures from Beer's Law. Since the fraction of radiation absorbed from such a beam is small, the detector receives a signal that is less attenuated and the sensitivity of the measurement is reduced. The problem created by narrow absorption lines was surmounted by the use of radiation from a source that emits not only a line of the same wavelength as the one selected for absorption measurements but also one that is narrower. For example, a mercury vapor lamp is selected as the external radiation source for the determination of mercury. Gaseous mercury atoms electrically excited in such a lamp return to the ground state by emitting radiation with wavelengths that are identical to the analyte mercury atoms in the flame. Since the lamp is operated at temperatures and pressures lower than those of the flame, the Doppler and pressure broadening of the mercury emission lines from the lamp is less than the corresponding broadening of the analyte absorption lines in the hot flame that holds the sample. Line Sources Most useful radiation source is the Hollow Cathode Lamp. It consists of a tungsten anode and a cylindrical cathode sealed in a glass tube containing an inert gas, such as argon at 1-5 Torr. The cathode is fabricated from the analyte metal or serves as a support for coating of that metal. The application of about 300V across the electrodes causes ionization of the argon and generation of a current of 5 to 10 mA as the argon cations and electrons migrate to the two electrodes. If the potential is sufficiently large, the argon cations strike the cathode with sufficient energy to dislodge some of the metal atoms and thereby produce an atomic cloud; this process is called sputtering. Sputtering is a process in which atoms or ions are ejected from a surface by a beam of charged particles. Some of the sputtered metal atoms are in the excited state and emit their characteristic wavelengths as they return to the ground state. It is important to recall that the atoms producing emission lines in the lamp are at a significantly lower temperature and pressure than the analyte atoms in the flame. Thus, the emission lines from the lamp are broadened less than the absorption peaks in the flame. The sputtered metal atoms eventually diffuse back to the cathode surface or to the walls of the lamp and are deposited. Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3

Hollow cathode lamps for about 70 elements are available. These provide an intensity that is about an order of magnitude higher than that of normal lamps. Some hollow cathode lamps are fitted with a cathode containing more than one element; such lamps provide spectral lines for the determination of several species. In addition to HCL, electrodeless-discharge lamps are useful sources of atomic line spectra. These lamps are often one or two orders of magnitude more intense than their hollow-cathode counterparts. The lamps contains no electrode but instead is energized by an intense field of radio-frequency or microwave radiation. The argon ionizes in this field, and the ions are accelerated by the highfrequency component of the field until they gain sufficient energy to excite (by collision) the atoms of the metal whose spectrum is sought. They are particularly useful for elements such as As, Se, and Te. Source Modulation In a AAS measurement, it is necessary to discriminate between radiation from the HCL or EDL and radiation from the atomizer. Much of the later is eliminated by the monochromator, which is always located between the atomizer and the detector. The thermal excitation of a fraction of the atoms in a flame, however produces radiation of the wavelength at which the monochromator is set. Because such radiation is not removed, it acts as a potential source of interference. The effect of analyte emission is overcome by modulating the output from the HCL so that intensity fluctuates at a constant frequency. Modulation is defined as the changing of some property of a carrier wave by the desired signal in such a way that the carrier wave can be used to convey information about the signal. Properties that are typically altered are frequency, amplitude, and wavelength. In AAS, the source radiation is amplitude modulated, but the background and analyte emission are not and are observed as dc signals. The detector thus receives an alternating signal from the hollow-cathode lamp and a continuous signal from the flame and converts these signals into the corresponding types of electric current. Photometers An instrument for AAS must be capable of providing a sufficiently narrow bandwidth to isolate the line chosen for a measurement from other lines that may interfere with or diminish the sensitivity of the method. A photometer equipped with HCL and filters is satisfactory for measuring concentrations of the alkali metals, which have only a few widely spaced resonance lines in the visible region. Spectrophotometers

Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3

Most measurements in AAS are made with instruments equipped with an UV/visible grating monochromator. Radiation from the HCL is chopped and mechanically split into two beams, one of which passes through the flame; the other passes around the flame. A half-silvered mirror returns both beams to a single path by which they pass alternately through the monochromator to the detector. The signal processor then separates the ac signal generated by the chopped light source from the dc signal produced by the flame.

Skoog, West et al, Fundamentals of analytical chemistry, 8th ed, ISBN-13: 978-0-03-035523-3