Flame emission spectrometry, lithium

Fixation, COj, reaction modeling, 43 426-431 Flame emission spectrometry, lithium, 36 54 Flash photolysis, 46 106, 137, 139-140 organometallics, 19 81-83... 

Clinical measurements of lithium may be performed using atomic absorption spectrometry (AAS) or flame emission spectrometry (FES) 64). AAS is regarded as the more reliable of the two techniques for blood lithium. FES is rather more sensitive, but suffers from interference from the high sodium and potassium concentrations in blood. Recent developments include inductively coupled plasma (ICP) emission spectrometry, electrothermal atomization atomic absorption spectrometry (ETAAS), and spectrofluorimetric methods. Spectrofluorime-try and ETAAS offer greater sensitivity than the traditional methods and are useful research tools 65, 66). 

Potassium can be determined by flame emission spectrometry (flame photometry) using a lithium internal standard. The following data were obtained for standard solutions of KCl and an unknown containing a constant known amount of LiCl as the internal standard. All the intensities were cor-... 

In the early years of flame photometry, only relatively cool flames were used. We shall see below that only a small fraction of atoms of most elements is excited by flames and that the fraction excited increases as the temperature is increased. Consequently, relatively few elements have been determined routinely by flame emission spectrometry, especMly j ew of those that emit line spectra (several can exist in flames as molecular species, particularly as oxides, which emit molecular band spectra). Only the easily excited alkali metals sodium, potassium, and lithium are routinely deterniined by flame emission spectrometry in the clinical laboratory. However, with flames such as oxyacetylene and nitrous oxide-acetylene, over 60 elements can now be determined by flame emission spectrometry. This is in spite of the fact that a small fraction of excited atoms is available for emission. Good sensitivity is achieved because, as with fluorescence (Chapter 16), we are, in principle, measuring the difference between zero and a small but finite signal, and so the sensitivity is limited by the response and stability of the detector and the stability (noise level) of the flame aspiration system. 

Fig. 3. Energy level diagram for the lithium atom showing the wavelength in nm for a number of transitions. Note the transition at 671 nm is used in flame emission spectrometry.

The concentration of lithium in serum, plasma, urine, or other body fluids has been determined by flame emission photometry, atomic absorption spectrometry, or electro-chemically using an ion-selective electrode. Serum analysis, the most useful specimen for lithium monitoring, is most commonly quantified by automated spectrophotometric assay. 

The addition of a spectroscopic buffer such as lithium carbonate has a stabilizing effect on the flame temperature and decreases the ionization of elements with low ionization potentials as well. At a constant flame temperature, the intensity of a given emission line is directly proportional to the concentration of analyte according to the equations given for emission spectrometry in the theoretical section. In practice, a standard curve is usually prepared in order to assess linearity between intensity and concentration. Alternatively, the method of standard addition (24) can be utilized. 

The human eye is a useful detector for qualitative analysis but not for quantitative analysis. Replacing the human eye with a spectrometer and photon detector such as a PMT or CCD permits more accurate identification of the elements present because the exact wavelengths emitted by the sample can be determined. In addition, the use of a photon detector permits quantitative analysis of the sample. The wavelength of the radiation indicates what element is present, and the radiation intensity indicates how much of the element is present. Flame atomic emission spectrometry is particularly useful for the determination of the elements in the first two groups of the periodic table, including sodium, potassium, lithium, calcium, magnesium, strontium, and barium. The determination of these elements is often called for in medicine, agriculture, and animal science. Remember that the term spectrometry is used for quantitative analysis by the measurement of radiation intensity. 

Flame atomic emission spectrometry Basic information on FAES is presented elsewhere in this encyclopedia. Sodium measurements are performed at 590 nm with the use of a propane flame (1925°C). Physiological samples for sodium determination are highly diluted before measurement. The diluent and the calibrator solution contain the same concentration of lithium ions so as to balance flame instability by a concomitant measurement of lithium in the reference beam (the so-called lithium guideHne). At the same time, lithium ions inhibit the ionization of sodium atoms. This procedure cannot be used in the case of therapy with lithium salts. That is why some authors prefer the concomitant measurement of caesium to that of lithium. Dilution adjusts the viscosity of the sample to that of the calibrator solution to produce identical aspiration rate and drop size on nebulization. As other electrolytes interfere with sodium measurement, their concentration in the caH-brator solution must be similar to their concentration in the sample. For the measurement of sodium in urine, calibrator solutions different from those for serum measurement are needed as the electrolyte concentrations in urine samples are quite different from those in serum and their relations are very variable. As the concentration of the electrolytes in serum is rather constant, calibrator solutions for serum measurements can fulfill their function better than those for urine in other words, urine determinations are usually less accurate. FAES proved to be sufficiently reliable to be used as the basic principle of the sodium reference measurement procedure. In routine use, however, FAES is less accurate. Its application is given up by most clinical laboratories in favor of potentiometric measurements... 

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