Line sources, absorption spectroscopy

Use of glow-discharge and the related, but geometrically distinct, hoUow-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). 

A schematic diagram showing the disposition of these essential components for the different techniques is given in Fig. 21.3. The components included within the frame drawn in broken lines represent the apparatus required for flame emission spectroscopy. For atomic absorption spectroscopy and for atomic fluorescence spectroscopy there is the additional requirement of a resonance line source, In atomic absorption spectroscopy this source is placed in line with the detector, but in atomic fluorescence spectroscopy it is placed in a position at right angles to the detector as shown in the diagram. The essential components of the apparatus required for flame spectrophotometric techniques will be considered in detail in the following sections. 

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. 

Analysis of spectra such as Fraunhofer lines is called absorption spectroscopy because it deals with atoms capturing a photon that bumps an electron into a higher energy state. Emission spectroscopy uses an external source of energy—heat, radiation, or an... 

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. 

The atomic absorption characteristics of technetium have been investigated with a technetium hollow-cathode lamp as a spectral line source. The sensitivity for technetium in aqueous solution is 3.0 /ig/ml in a fuel-rich acetylene-air flame for the unresolved 2614.23-2615.87 A doublet under the optimum operating conditions. Only calcium, strontium, and barium cause severe technetium absorption suppression. Cationic interferences are eliminated by adding aluminum to the test solutions. The atomic absorption spectroscopy can be applied to the determination of technetium in uranium and its alloys and also successfully to the analysis of multicomponent samples. 

Atomic absorption spectroscopy is the term used when the radiation absorbed by atoms is measured. The application of AAS to analytical problems was considerably delayed because of the apparent need for very high resolution to make quantitative measurements. In 1953, Walsh brilliantly overcame this obstacle by the use of a line source, an idea pursued independently by Alkemade, his work being published in 1955. 

We have shown that the radiant flux spectrum, as recorded by the spectrometer, is given by the convolution of the true radiant flux spectrum (as it would be recorded by a perfect instrument) with the spectrometer response function. In absorption spectroscopy, absorption lines typically appear superimposed upon a spectral background that is determined by the emission spectrum of the source, the spectral response of the detector, and other effects. Because we are interested in the properties of the absorbing molecules, it is necessary to correct for this background, or baseline as it is sometimes called. Furthermore, we shall see that the valuable physical-realizability constraints presented in Chapter 4 are easiest to apply when the data have this form. 

Owing to aberrations, grating defects, and so on, it may not be adequate to approximate the response function by formulas based on idealized models. If a line source could be found having the spectrum that approximates a 8 function, then perhaps the measurement of such a line would adequately determine the response function. We have learned, however, that the spatial coherence of the source plays an important part in the shape of the response function. This precludes the use of a laser line source to measure the response function applicable to absorption spectroscopy. Furthermore, we... 

During the 20-plus years that mass spectrometrists lost interest in glow discharges, optical spectroscopists were pursuing these devices both as line sources for atomic absorption spectroscopy and as direct analytical emission sources [6-10]. Traditionally, inorganic elemental analysis has been dominated by atomic spectroscopy. Since an optical spectrum is composed of lines corre-... 

If a continuum source is needed for absorption spectroscopy, this can be provided by discharge lamps fdled to higher densities, such that pressures can exceed 100 bar at operational temperatures. The result is a broad continuum emission with superimposed line spectra, as shown for several lamps in Fig. 14. In commercial spectrometers the deuterium lamp is commonly used for the UV region below 350 nm while the tungsten-halogen lamp is convenient for the 350 to 900 nm range. The latter is an example of a thermal source whose radiant excitance per unit wavelength closely approximates that predicted by the Planck formula for a blackbody radiator " ... 

The sensitivity 7 is the derivative of the signal by the concentration (Eqs. 3.3-38, 45, 48). It should be as high as possible in order to reduce the detection limit and to enhance the precision. Ideally, a sample should give rise to a narrow line with a high peak intensity, and the spectrometer should only .see the. spectral band at which 7 is at its maximum. This is possible with spectrometers which use tunable lasers as radiation sources for absorption spectroscopy or by using spectrometers with high resolution, e.g., for trace analyses of atmo.spheric gases. 

It has been found, however, in practice that a perfectly straight analytical working curve (— log T plotted against concentration) is seldom obtained in atomic absorption spectroscopy. The reasons for this are usually a combination of instrumental problems broadening of the emission line of the light source due to self-reversal, Doppler and pressure broadening of the absorption lines of the atoms in the flame, failure to exclude flame emission entirely, use of a focused instead of a parallel... 

It should be pointed out here that wavelength selection in atomic absorption spectroscopy is largely accomplished by the choice of the monochromatic sharp line source, possessing the wavelength of a resonance line of the element to be determined, a specificity of selection unobtainable by any other means. Any additional wavelength selection can be considered merely secondary and the methods to this end should be examined with this in mind. 

Zinc in atomic absorption spectroscopy is remarkably free from interferences as contrasted to the difiiculties encountered in polarography or with colorimetric methods (M4). Gidley and Jones (G4, G5) studied the influence of 27 elements and the only effect seen was a depression with silicon. The absorption enhancement encountered by these authors with haloid acids could be traced back to the attack of the brass burner by the samples and to the use of a brass hollow cathode tube as zinc line source. Methods for the determination of zinc in various metals and alloys are described by these authors. 

A Mossbauer spectrometer consists of a radioactive Co source on a transducer that continuously scans the desired velocity range, an absorber consisting of the catalyst and a detector to measure the intensity of the gamma radiation transmitted by the absorber as a function of the source velocity. This is the common mode of operation, called Mossbauer absorption spectroscopy, sometimes abbreviated as MAS. It is also possible to fix the Co containing source and move a single-line Fe absorber, in order to investigate Co-containing catalysts. This technique, called Mossbauer emission spectroscopy (MES), has successfully been applied to study Co-Mo hydrodesulphurization catalysts [42]. 

In addition to the continuum sources just discussed, line sources are also important for use in the UV/visible region. Low-pressure mercury arc lamps are very common sources that are used in liquid chromatography detectors. The dominant line emitted by these sources is the 253.7-nm Hg line. Hollow-cathode lamps are also common line sources that are specifically used for atomic absorption spectroscopy, as discussed in Chapter 28. Lasers (see Feature 25-1) have also been used in molecular and atomic spectroscopy, both for single-wavelength and for scanning applications. Tunable dye lasers can be scanned over wavelength ranges of several hundred nanometers when more than one dye is used. 

Hollow-cathode lamps for about 70 elements are available from commercial sources. For certain elements, high-intensity lamps 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. The development of the hollow-cathode lamp is widely regarded as the single most important event in the evolution of atomic absorption spectroscopy. 

Photometers At a minimum, an instrument for atomic absorption spectroscopy 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 a hollow-cathode source and filters is satisfactory for measuring concentrations of the alkali metals, which have only a few widely spaced resonance lines in the visible region. A more versatile photometer is sold with readily interchangeable interference filters and lamps. A separate fdter and lamp are used for each element. Satisfactory results for the determination of 22 metals are claimed. 

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. 

Hollow-cathode lamp A source used in atomic absorption spectroscopy that emits sharp lines for a single element or sometimes for several elements. 

Ng K. C., Ali A. H., Barber T. E. and Winefordner J. D. (1988) Multiple mode semiconductor diode laser as a spectral line source for graphite furnace atomic absorption spectroscopy, Anal Chem 62 1893-1895. 

Fig. 11. (A) Decay-associated difference spectra (DADS) of the 3-, 28-ps and the non-decaying components of Synechocystis PS-I core complex in the 380-500 nm region under reducing conditions and at room temperature. (B) The absorbance-difference spectrum AA [Ao"-Ao] (solid line) the same spectrum [see Fig. 9 (A), left panel] obtained from spinach is included for comparison. Figure source Mi, Lin and Blankenship (1999) Picosecond transient absorption spectroscopy in the blue spectral region of photosystem I. Biochemistry 38 15234. 15235.

Fig. 10. (A) Flash-induced absorbance changes at 387,430 and 455 nm in a sample of PS-I particles from Synechococcus sp. under a mild reducing condition (ascorbate+ DCIP) or containing ferricyanide (FeCy) (B) difference spectra constructed from the aA amplitudes at the beginning and end ofthe 200-ns phase, i.e., at 5 ns and 1.6 /iS, respectively. The spectrum in the inset of (B) represents AA [P700 A,-] - [P700 A,] measured at 10 K (taken from Fig. 4 above). The dotted-line difference spectrum in (B) is that for [P700 -P700]. Figure source Brettel (1988) Electron transfer fifom Ay to an iron-sulfur center with tw=2O0 ns at room temperature in photosystem I. Characterization by flash absorption spectroscopy. FEBS Lett239 95,96.

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