Flame Emission Sources

Use has been made of flame emission spectra as sources for determination of lithium, copper, and some of the rare earth elements. The sensitivity is lower than for a hollow cathode source and the stability also is less. 

In spite of the apparent problems associated with the use of a continuum as an atomic absorption source, some useful absorbance data have been obtained. Sensitivities have generally been considerably poorer than with hollow cathodes by a factor of about ten. 

Several types of continuous source have been used, depending on the spectral region under consideration. Tungsten filaments can be used in the 

The continuous source is quite useful for certain purposes if it is intense and a monochromator of high resolution is available. Photographic recording of absorption spectra can be made in the same manner as arc or spark emission spectra are recorded. In this manner atomic absorption spectra are readily available for the study of a number of spectral absorption lines, in contrast to the single-line absorption usually obtained with a hollow cathode source. 

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In this section we consider three emission sources other than ihe plasma and arc and spark. sources we have just considered flame emission sources, glow-discharge sources, and Ihe laser niicroprohe. 

Since atomic absorption spectroscopy utilizes the ground state atom population for its measurements, it would appear that atomic absorption has a great advantage over flame emission in terms of detection limits and sensitivities of detection. An inspection of Appendix VIII, where detection limits are given for a number of elements for flame emission and atomic absorption, indicates this is not true. The reason for this apparent discrepancy lies in the relative stabilities of ground state and excited state atoms. An excited atom has a lifetime of the order of 10 -10 sec, and thus emits its energy very quickly after being excited. The usual flame emission source has an upward velocity of from 1 to 10 m/sec, so the excited atom will move only about 10 -10 m between the time of excitation and emission. 

Choice of Atomization and Excitation Source Except for the alkali metals, detection limits when using an ICP are significantly better than those obtained with flame emission (Table 10.14). Plasmas also are subject to fewer spectral and chemical interferences. For these reasons a plasma emission source is usually the better choice. 

Minimizing Spectral Interferences The most important spectral interference is a continuous source of background emission from the flame or plasma and emission bands from molecular species. This background emission is particularly severe for flames in which the temperature is insufficient to break down refractory compounds, such as oxides and hydroxides. Background corrections for flame emission are made by scanning over the emission line and drawing a baseline (Figure 10.51). Because the temperature of a plasma is... 

Accuracy When spectral and chemical interferences are insignificant, atomic emission is capable of producing quantitative results with accuracies of 1-5%. Accuracy in flame emission frequently is limited by chemical interferences. Because the higher temperature of a plasma source gives rise to more emission lines, accuracy when using plasma emission often is limited by stray radiation from overlapping emission lines. 

Furthermore, the ultrasonic irradiation of alkanes in the presence of N2 (or NH or amines) gives emission from CN excited states, but not from N2 excited states. Emission from N2 excited states would have been expected if the MBSL originated from microdischarge, whereas CN emission is typically observed from thermal sources. When oxygen is present, emission from excited states of CO2, CH-, and OH- is observed, again similar to flame emission. 

This chapter describes the basic principles and practice of emission spectroscopy using non-flame atomisation sources. [Details on flame emission spectroscopy (FES) are to be found in Chapter 21.] The first part of this chapter (Sections 20.2-20.6) is devoted to emission spectroscopy based on electric arc and electric spark sources and is often described as emission spectrography. The final part of the chapter (Sections 20.7-20.11) deals with emission spectroscopy based on plasma sources. 

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. 

Applications Atomic emission spectrometry has been used for polymer/additive analysis in various forms, such as flame emission spectrometry (Section 8.3.2.1), spark source spectrometry (Section 8.3.2.2), GD-AES (Section 8.3.2.3), ICP-AES (Section 8.3.2.4), MIP-AES (Section 8.3.2.6) and LIBS. Only ICP-AES applications are significant. In hyphenated form, the use of element-specific detectors in GC-AED (Section 4.2) and PyGC-AED deserves mentioning. 

Principles and Characteristics Flame emission instruments are similar to flame absorption instruments, except that the flame is the excitation source. Many modem instruments are adaptable for either emission or absorption measurements. Graphite furnaces are in use as excitation sources for AES, giving rise to a technique called electrothermal atomisation atomic emission spectrometry (ETA AES) or graphite furnace atomic emission spectrometry (GFAES). In flame emission spectrometry, the same kind of interferences are encountered as in atomic absorption methods. As flame emission spectra are simple, interferences between overlapping lines occur only occasionally. 

A certain fraction of the atoms produced will become thermally excited and hence will not absorb radiation from an external source. These thermally excited atoms serve as the basis of flame photometry, or flame emission spectroscopy they can de-excite radiationally to emit radiant energy of a definite wavelength. 

Table 8.7). Thus, intensity and concentration are directly proportional. However, the intensity of a spectral line is very sensitive to changes in flame temperature because such changes can have a pronounced effect on the small proportion of atoms occupying excited levels compared to those in the ground state (p. 274). Quantitative measurements are made by reference to a previously prepared calibration curve or by the method of standard addition. In either case, the conditions for measurement must be carefully optimized with reference to the choice of emission line, flame temperature, concentration range of samples and linearity of response. Relative precision is of the order of 1-4%. Flame emission measurements are susceptible to interferences from numerous sources which may enhance or depress line intensities. 

The optical path for flame AA is arranged in this order light source, flame (sample container), monochromator, and detector. Compared to UV-VIS molecular spectrometry, the sample container and monochromator are switched. The reason for this is that the flame is, of necessity, positioned in an open area of the instrument surrounded by room light. Hence, the light from the room can leak to the detector and therefore must be eliminated. In addition, flame emissions must be eliminated. Placing the monochromator between the flame and the detector accomplishes both. However, flame emissions that are the... 

Recalling Figure 9.4, we know that thermal energy sources, such as a flame, atomize metal ions. But we also know that that these atoms experience resonance between the excited state and ground state such that the emissions that occur when the atoms drop from the excited state back to the ground state can be measured. While there are several techniques that measure such emissions, including flame emissions... 

Carlsson, H., Nilsson, U., and Ostman, C. Video display units an emission source of the contact allergenic flame retardant triphenyl phosphate in the indoor environment, Environ. Sci. Technol, 34(18) 3885-3889, 2000. 

One often unsuspected source of error can arise from interference by the substances originating in the sample which are present in addition to the analyte, and which are collectively termed the matrix. The matrix components could enhance, diminish or have no effect on the measured reading, when present within the normal range of concentrations. Atomic absorption spectrophotometry is particularly susceptible to this type of interference, especially with electrothermal atomization. Flame AAS may also be affected by the flame emission or absorption spectrum, even using ac modulated hollow cathode lamp emission and detection (Faithfull, 1971b, 1975). 

In flame emission spectroscopy, light emission is caused by a thermal effect and not by a photon, as it is in atomic fluorescence. Flame emission, which is used solely for quantification, is distinguished from atomic emission, used for qualitative and quantitative analyses. This latter, more general term is reserved for a spectral method of analysis that uses high temperature thermal sources and a higher performance optical arrangement. 

Figure 14.16—Elements determined by AAS or FES. Most elements can be determined by atomic-absorption or flame emission using one of the available atomisation modes (burner, graphite furnace or hydride formation). Sensitivity varies enormously from one element to another. The representation above shows the elements in their periodic classification in order to show the wide use of these methods. Some of the lighter elements, C, N, O, F, etc. in the figure can be determined using a high temperature thermal source a plasma torch, in association with a spcctropholometric device (ICP-AbS) or a mass spectrometer (1CP-MS).

The nature of the radiation processes is not fully understood. Ball (10,11), with the aid of a stroboscopic shutter, visually observed cool flames as actual flame fronts moving across the combustion chamber of a motored engine. This was later confirmed by Getz (53). The source of cool flame emission in tube experiments has been attributed to excited formaldehyde by Emeleus (51) and Gaydon (52). Cool flame spectra in engines obtained by Levedahl and Broida (70) and Downs, Street, and Wheeler (35) were reported to be due to excited formaldehyde. The nature of the blue flame spectra has not been fully explored, although some evidence points to carbon monoxide emission (35). 

The determinations of sodium and potassium constitute ihe majority of published applications. However, the flame is a suitable emission source lor at least 45 elements, which may be grouped a.s follows ... 

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