Hollow cathodes, atomic emission spectroscopy

You J., Fanning J. C. and Marcus R. K. (1994) Particle beam aqueous sample introduction for hollow cathode atomic emission spectroscopy, Anal Chem 66 3916-3924. 

In atomic emission spectroscopy, the radiation source is the sample itself. The energy for excitation of analyte atoms is supplied by a plasma, a flame, an oven, or an electric arc or spark. The signal is the measured intensity of the source at the wavelength of interest. In atomic absorption spectroscopy, the radiation source is usually a line source such as a hollow cathode lamp, and the signal is the absorbance. The latter is calculated from the radiant power of the source and the resulting power after the radiation has passed through the atomized sample. 

As indicated in Fig. 21.3, for both atomic absorption spectroscopy and atomic fluorescence spectroscopy a resonance line source is required, and the most important of these is the hollow cathode lamp which is shown diagrammatically in Fig. 21.8. For any given determination the hollow cathode lamp used has an emitting cathode of the same element as that being studied in the flame. The cathode is in the form of a cylinder, and the electrodes are enclosed in a borosilicate or quartz envelope which contains an inert gas (neon or argon) at a pressure of approximately 5 torr. The application of a high potential across the electrodes causes a discharge which creates ions of the noble gas. These ions are accelerated to the cathode and, on collision, excite the cathode element to emission. Multi-element lamps are available in which the cathodes are made from alloys, but in these lamps the resonance line intensities of individual elements are somewhat reduced. 

Essentially the same spectrometer as is used in atomic absorption spectroscopy can also be used to record atomic emission data, simply by omitting the hollow cathode lamp as the source of the radiation. The excited atoms in the flame will then radiate, rather than absorb, and the intensity of the emission is measured via the monochromator and the photomultiplier detector. At the temperature achieved in the flame, however, very few of the atoms are in the excited state ( 10% for Cs, 0.1% for Ca), so the sample atoms are not normally sufficiently excited to give adequate emission intensity, except for the alkali metals (which are often equally well determined by emission as by absorption). Nevertheless, it can be useful in cases where elements are required for which no lamp is available, although some elements exhibit virtually no emission characteristics at these temperatures. 

The most widely used spectral line source for atomic absorption spectroscopy is the hollow cathode lamp. An illustration of this lamp is shown in Figure 9.5. The internal atoms mentioned above are contained in a cathode, a negative electrode. This cathode is a hollowed cup, pictured with a C shape in the figure. The internal excitation and emission process occurs inside this cup when the lamp is on and the anode (positive electrode) and cathode are connected to a high voltage. The light is emitted as shown. 

Use of glow-discharge and the related, but geometrically distinct, hollow-cathode sources involves plasma-induced sputtering and excitation (93). Such sources are commonly employed as sources of resonance-line emission in atomic absorption spectroscopy. The analyte is vaporized in a flame at 2000—3400 K. Absorption of the plasma source light in the flame indicates the presence and amount of specific elements (86). 

Following the work of Lundegardh in the twenties, emission flame spectroscopy became established as an analytical tool in almost every branch of science. Although hollow cathode tubes were first studied by Paschen (P2) in 1916, and although atomic absorption spectroscopy had found occasional application, notably in the mercury vapor detector W20), it remained for Walsh (W2) in Australia in 1955 to recognize the essential advantages inherent in absorption over emission methods and revive general interest in this technique. Shortly thereafter but apparently independently, Alkemade and Milatz (A2, A3) in Holland devised instruments and applied atomic absorption spectroscopy in their laboratory. Walsh and his co-workers have since contributed a remarkable volume of work on instrumentation and application, and patents are held by Walsh on his method in Australia, Europe, and America. 

Several elements (Zn, Pb, Cuy Ni, Ca, Mg, Fe, and Mn) are determined routinely in water samples using atomic absorption spectroscopy. Sodium and potassium are determined by flame emission. The preparation of the samples the analytical methody the detection limits and the analytical precisions are presented. The analytical precision is calculated on the basis of a sizable amount of statistical data and exemplifies the effect on the analytical determination of such factors as the hollow cathode sourcey the ffamey and the detection system. The changes in precision and limit of detection with recent developments in sources and burners are discussed. A precision of 3 to 5% standard deviation is attainable with the Hetco total consumption and the Perkin-Elmer laminar flow burners. 

The half width of elemental lines is of the order of 0.002 nm when observed by emission spectroscopy with flame or electrothermal atomisation. A number of reasons can cause broadening of the linewidth, of which the most important and best understood are natural, pressure, resonance, and Doppler broadening. If a stable and sensitive detection is to be achieved, the linewidth of the excitation radiation must be narrower than the full width at half maximum (FWHM) of the analyte line. Under these conditions, the entire radiant energy produced by the excitation source will be available for absorption by the analyte. The typical line sources used for atomic absorption are element specific excitation sources such as the hollow cathode lamp or the electrodeless discharge lamp. But even continuum sources can be used with appropriate instrumental designs. 

As mentioned in the introduction to this chapter, visible/UV Fourier transform instruments are still found mainly as unique, one-of-a-kind instruments in a few spectroscopy laboratories. The research topics being pursued with these Fourier transform instruments include atomic spectrochemical measurements, atomic and molecular emission spectroscopy from hollow cathode discharges, and molecular absorption spectroscopy for accurate frequency standards and molecular constants. In each of these research efforts, the Fourier transform method has proven useful. In part, the success of this method is derived from the fundamental advantage originally stated by Jacquinot, and to some extend from the advantage stated by Fellgett. 

Since the foundations of atomic absorption spectroscopy were laid by Walsh a number of improvements in instrumentation and techniques have been made. Russell, Shelton, and Walsh modulated the hollow cathode signal and used an amplifier tuned to the modulating frequency so measurements could be made without interference from flame emission. Sullivan and Walsh developed very high-intensity hollow cathode lamps that led to lower detection limits. Willis proposed the use of nitrous oxide-acetylene flame as a means of overcoming certain interferences and produce a higher population of free atoms in the flame. 

Multielement atomic absorption spectroscopy is complicated by the need for a multielement emission source. Some multielement hollow cathode lamps are available and continuum sources are possibilities. Another method is to place several hollow cathode lamps along the focal plane of a spectrometer, at positions corresponding to the desired wavelengths, thus permitting all the radiation to emerge from a single slit. In this approach the... 

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