Flame photometry instrumentation

Instrumental Quantitative Analysis. Methods such as x-ray spectroscopy, oaes, and naa do not necessarily require pretreatment of samples to soluble forms. Only reUable and verified standards are needed. Other instmmental methods that can be used to determine a wide range of chromium concentrations are atomic absorption spectroscopy (aas), flame photometry, icap-aes, and direct current plasma—atomic emission spectroscopy (dcp-aes). These methods caimot distinguish the oxidation states of chromium, and speciation at trace levels usually requires a previous wet-chemical separation. However, the instmmental methods are preferred over (3)-diphenylcarbazide for trace chromium concentrations, because of the difficulty of oxidizing very small quantities of Cr(III). 

Instrumentation. Flame Characteristics. Flame Processes. Emission Spectra. Quantitative Measurements and Interferences. Applications of Flame Photometry and Flame Atomic Emission Spectrometry. 

The basic instrumentation used for spectrometric measurements has already been described in the previous chapter (p. 277). Methods of excitation, monochromators and detectors used in atomic emission and absorption techniques are included in Table 8.1. Sources of radiation physically separated from the sample are required for atomic absorption, atomic fluorescence and X-ray fluorescence spectrometry (cf. molecular absorption spectrometry), whereas in flame photometry, arc/spark and plasma emission techniques, the sample is excited directly by thermal means. Diffraction gratings or prism monochromators are used for dispersion in all the techniques including X-ray fluorescence where a single crystal of appropriate lattice dimensions acts as a grating. Atomic fluorescence spectra are sufficiently simple to allow the use of an interference filter in many instances. Photomultiplier detectors are used in every technique except X-ray fluorescence where proportional counting or scintillation devices are employed. Photographic recording of a complete spectrum facilitates qualitative analysis by optical emission spectrometry, but is now rarely used. 

Five liquid membrane electrodes (Table 13.3) are now commercially available and have found wide application in the testing of electrolytes in biological and technological systems. All five electrodes perform well in the concentration range over which the Nernstian slope is maintained, i.e., from 10 -10 moldm . These electrodes to a certain extent have replaced in both chemical and clinical laboratories the more traditional instrumental methods of analysis, such as flame photometry and atomic absorption spectrometry. There are, of course, many more liquid membrane electrodes, but the availability of satisfactory solid electrodes has greatly restricted their development and practical application. 

Flame photometry provides a robust, cheap and selective method based on relatively simple instrumentation for quantitative analysis of some metals. 

A number of instrumental analytical techniques can be used to measure the total phosphorus content of organophosphorus compounds, regardless of the chemical bonding of phosphorus within the molecules, as opposed to the determination of phosphate in mineralized samples. If the substances are soluble, there is no need for their destruction and for the conversion of phosphorus into phosphate, a considerable advantage over chemical procedures. The most important methods are flame photometry and inductively coupled plasma atomic emission spectrometry the previously described atomic absorption spectrometry is sometimes useful. 

Atomic absorption and flame emission spectroscopy, also called flame photometry, are two methods of quantitative analysis that can be used to measure approximately 70 elements (metals and non-metals). Many models of these instruments allow measurements to be conducted by these two techniques, which rely on different principles. Their applications are numerous, as concentrations in the mg/l (ppm) region or lower can be accessed. 

Inasmuch as mineral matter has been defined broadly to include all inorganic elements in coals, the chemical characterization of mineral matter involves the determination of many elements. In general, chemical analyses of geological materials have progressed from the wet chemical methods to sophisticated instrumental methods. The major elements in the mineral constituents of coal, Si, Al, Ti, Ca, Mg, Fe, P, S, Na, K, are the same as those in silicate rocks and are often determined by x-ray fluorescence spectroscopy and flame photometry. 

In environmental analysis, flame photometry is most widely used for the determination of potassium, which emits at 766.5 nm. It is also often used for the determination of sodium at 589.0 nm, although spectral interference problems (see Chapter 3) then may be encountered in the presence of excess calcium because of emission from calcium-containing polyatomic species. Molecular species are more likely to be found in cooler flames than in hotter flames. Some instruments use single, interchangeable filters, while others have three or more filters, for example for the determinations of potassium, sodium and lithium,... 

In flame photometry, there is little scope for atomizer optimization, because of the simplicity of the instrument design. However, fuel flow should be carefully adjusted. 

Instrumental Requirements in FES Separated Flames Flame Photometry... 

Flame photometry (see also p. 168) is almost exclusively used for the determination of alkali metals because of their low excitation potential (e.g. sodium 5.14eV and potassium 4.34 eV). This simplifies the instrumentation required and allows a cooler flame (air-propane, air-butane or air-natural gas) to be used in conjunction with a simpler spectrometer (interference filter). The use of an interference filter allows a large excess of light to be viewed by the detector. Thus, the expensive photomultiplier tube is not required and a cheaper detector can be used, e.g. a photodiode or photoemissive detector. The sample is introduced using a pneumatic nebulizer as described for FAAS (p. 172). Flame photometry is therefore a simple, robust and inexpensive technique for the determination of potassium (766.5 nm) or sodium (589.0nm) in clinical or environmental samples. The technique suffers from the same type of interferences as in FAAS. The operation of a flame photometer is described in Box 26.2. 

The use of flame photometry as a quantitative tool can be traced to work by Kirchhoff and Bunsen in the early 1860sJ Its modern history begins, however, in the 1940s, when instruments became available that successfully addressed the problems of reproducible sample introduction and detection. Flame photometry soon developed into a reliable analytical technique for the determination of several cations of pharmaceutical interest, notably sodium, potassium, and lithium. The technique is useful in the analysis of bulk drugs, dosage forms, and clinical samples such as blood and urine. 

The analysis of clinical samples represents a typical application of flame photometry. Concentrations of sodium, potassium, and lithium in blood and urine are well within instrument working ranges. The specificity of the technique is a distinct advantage. Automated models of flame photometers, available during the past 25 years, are typically designed to serve the needs of the clinical chemist. Instrument calibration protocols are built into instruments to facilitate the timely analysis of sodium, potassium, and lithium in clinical samples. 

There are at least 25 USP or BP formulation monographs that use flame photometry to assay ions of interest (Table This technique is applicable to a variety of situations because of the relatively low cost per sample (in analyst time, instrument capital expense, and testing supplies) reasonable precision (typical relative standard deviation values are 0.6% for sodium, 1% for potassium, and 2% for lithium) low sample volume requirements (as low as 10 pi in some cases) and ease of operation. 

To be able to identify the instrumental requirements for flame photometry (FP). 

The instrumentation used for atomic emission spectroscopy (AES) consists of an atomization cell, a spectrometer/detector and a read-out device. In its simplest form, flame photometry (FP), the atomization cell consists of a flame (e.g. 

Measurements by flame photometry are carried out either using atomic absorption spectrometers with a burner (but without the light source), or flame photometers. The latter are less sophisticate instruments whose price is ten time less that atomic absorption spectrometers. These photometers are designated to make measurements of only five or six elements. They include interchangeable coloured... 

In the fourth type of identification the chemical composition of particles is studied in situ. By suitable chemical aerosol instruments the concentration and the size distribution of certain elements can be continuously monitored. The flame photometry of sodium containing particles (e.g. Hobbs, 1971) is a good example for such a method. Recently flame photometric detectors have also been developed to measure aerosol sulfur in the atmosphere (e.g. Kittelson et at., 1978). 

Three types are used. (I) Barrier-layer cells. These are satisfactory only for simple filter instruments. (2) Vacuum phototubes. These tubes require an external power supply, unlike barrier-layer cells, and their output is usually amplified before measurement. (3) Photomultiplier tubes are easily the most satisfactory detectors for use in flame photometry. The photocurrent is amplified inside the tube in such a way that much lower light levels can be detected and measured accurately than is possible with vacuum phototubes with amplifiers. A stable source of high voltage up to perhaps 2000 volts is required to operate the photomultiplier tubes, but these tubes are almost universally used in high-performance instruments and are essential if the advantages of using narrow band width are to be obtained. 

Instrumentation. Flame characteristics. Flame processes. Emission spectra. Quantitative measurements and interferences. Applicaiion.s of flame photometry and flame atomic emission spectrometry. 

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