Qualitative atomic emission spectroscopy

The focus of this section is the emission of ultraviolet and visible radiation following thermal or electrical excitation of atoms. Atomic emission spectroscopy has a long history. Qualitative applications based on the color of flames were used in the smelting of ores as early as 1550 and were more fully developed around 1830 with the observation of atomic spectra generated by flame emission and spark emission.Quantitative applications based on the atomic emission from electrical sparks were developed by Norman Lockyer (1836-1920) in the early 1870s, and quantitative applications based on flame emission were pioneered by IT. G. Lunde-gardh in 1930. Atomic emission based on emission from a plasma was introduced in 1964. 

NMR) [24], and Fourier transform-infrared (FT-IR) spectroscopy [25] are commonly applied methods. Analysis using mass spectrometric (MS) techniques has been achieved with gas chromatography-mass spectrometry (GC-MS), with chemical ionisation (Cl) often more informative than conventional electron impact (El) ionisation [26]. For the qualitative and quantitative characterisation of silicone polyether copolymers in particular, SEC, NMR, and FT-IR have also been demonstrated as useful and informative methods [22] and the application of high-temperature GC and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) is also described [5]. 

C. Schierle, M. Otto and W. Wegscheider, A neural network approach to qualitative analysis in inductively coupled plasma-atomic emission spectroscopy (ICP-AES), Fresenius J. Anal. Chem., 343(7), 1992, 561-565. 

The elemental composition of unknown materials such as engine deposits can be determined qualitatively and the information used to develop dissolution methods prior to analysis by inductively coupled plasma atomic emission spectroscopy (ICPAES). Alternatively, a semi-quantitative analysis can be provided by XRF alone, especially important when only a limited quantity of sample is available and needed for subsequent tests. The deposit does not even have to be removed from the piston since large objects can be placed directly inside an EDXRF spectrometer. 

The determination of trace metal impurities in pharmaceuticals requires a more sensitive methodology. Flame atomic absorption and emission spectroscopy have been the major tools used for this purpose. Metal contaminants such as Pb, Sb, Bi, Ag, Ba, Ni, and Sr have been identified and quantitated by these methods (59,66-68). Specific analysis is necessary for the detection of the presence of palladium in semisynthetic penicillins, where it is used as a catalyst (57), and for silicon in streptomycin (69). Furnace atomic absorption may find a significant role in the determination of known impurities, due to higher sensitivity (Table 2). Atomic absorption is used to detect quantities of known toxic substances in the blood, such as lead (70-72). If the exact impurities are not known, qualitative as well as quantitative analysis is required, and a general multielemental method such as ICP spectrometry with a rapid-scanning monochromator may be utilized. Inductively coupled plasma atomic emission spectroscopy may also be used in the analysis of biological fluids in order to detect contamination by environmental metals such as mercury (73), and to test serum and tissues for the presence of aluminum, lead, cadmium, nickel, and other trace metals (74-77). 

Flame atomic emission spectroscopy, also called flame photometry, is based on the measurement of the emission spectrum produced when a solution containing metals or some nonmetals such as halides, sulfur, or phosphorus is introduced into a flame. In early experiments, the detector used was the analyst s eye. Those elements that emitted visible light could be identified qualitatively, and these flame tests were used to confirm the presence of certain elements in the sample, particularly alkali metals and alkaline-earth metals. A list of visible colors emitted by elements in a flame is given in Table 7.1. 

In ICP-AES analysis, the liquid sample (i.e., solution) is nebulized into an inductively coupled plasma it has sufficient energy to break chemical bonds, liberate elements, and transform them into a gaseous atomic state for atomic emission spectroscopy. When this happens, a number of the elemental atoms will be excited and emit radiation. The wavelength of this radiation is characteristic of the element that emits it, and the intensity of radiation is proportional to the concentration of that element within the solution. The ICP-AES is used for both qualitative element identification and quantitative chemical composition determination. 

Atomic absorption, along with atomic emission, was first used by Guystav Kirch-hoff and Robert Bunsen in 1859 and 1860, as a means for the qualitative identification of atoms. Although atomic emission continued to develop as an analytical technique, progress in atomic absorption languished for almost a century. Modern atomic absorption spectroscopy was introduced in 1955 as a result of the independent work of A. Walsh and C. T. J. Alkemade. Commercial instruments were in place by the early 1960s, and the importance of atomic absorption as an analytical technique was soon evident. 

A technique that utilizes a solid sample for light emission is spark emission spectroscopy. In this technique, a high voltage is used to excite a solid sample held in an electrode cup in such a way that when a spark is created with a nearby electrode, atomization, excitation, and emission occur and the emitted light is measured. Detection of what lines are emitted allows for qualitative analysis of the solid material. Detection of the intensity of the lines allows for quantitative analysis. 

Emission spectroscopy is exclusively related to atoms whereas a number of other spectroscopic techniques deal with molecules. The fundamental fact of emission spectroscopy is very simple, wherein the atoms present in a sample undergo excitation due to the absorption of either electrical or thermal energy. Subsequently, the radiation emitted by atoms in an excited sample is studied in an elaborated manner both qualitatively and quantitatively. Therefore, emission spectroscopy is considered to be an useful analytical tool for the analysis of ... 

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. 

Chemical Analysis. Plasma oxidation and other reactions often are used to prepare samples for analysis by either wet or dry methods. Plasma excitation is commonly used with atomic emission or absorption spectroscopy for qualitative and quantitative spectrochemical analysis (86—88). 

The properties of absorption and luminescence emissions of atoms are important in analytical techniques as well as in spectroscopy in general. The absorption and emission spectra of atoms are line spectra which provide the unmistakable fingerprint of each element, and this is used in the analytical technique known as atomic absorption spectroscopy for example. Although the energy levels of atoms are shown as simple lines in a qualitative picture such as that of Figure 3.3, the absorption and emission lines which correspond to transitions between these levels are not infinitely narrow (that is, absolutely monochromatic) because of several effects. 

Atomic spectroscopy is the oldest instrumental elemental analysis principle, the origins of which go back to the work of Bunsen and Kirchhoff in the mid-19th century [1], Their work showed how the optical radiation emitted from flames is characteristic of the elements present in the flame gases or introduced into the burning flame by various means. It had also already been observed that the intensities of the element-specific features in the spectra, namely the atomic spectral lines, changed with the amount of elemental species present. Thus the basis for both qualitative and quantitative analysis with atomic emission spectrometry was discovered. These discoveries were made possible by the availability of dispersing media such as prisms, which allowed the radiation to be spectrally resolved and the line spectra of the elements to be produced. 

Among the various types of atomic spectroscopy, only two, flame emission spectroscopy and atomic absorption spectroscopy, are widely used and accepted for quantitative pharmaceutical analysis. By far the majority of literature regarding pharmaceutical atomic spectroscopy is concerned with these two methods. However, the older method of arc emission spectroscopy is still a valuable tool for the qualitative detection of trace-metal impurities. The two most recently developed methods, furnace atomic absorption spectroscopy and inductively coupled plasma (ICP) emission spectroscopy, promise to become prominent in pharmaceutical analysis. The former is the most sensitive technique available to the analyst, while the latter offers simultaneous, multielemental analysis with the high sensitivity and precision of flame atomic absorption. 

Excitation of the outer ns electron of the M atom occurs easily and emission spectra are readily observed. We have aheady described the use of the sodium D-line in the emission spectrum of atomic Na for specific rotation measurements (see Section 3.8). When the salt of an alkali metal is treated with concentrated HCl (giving a volatile metal chloride) and is heated strongly in the non-luminous Bunsen flame, a characteristic flame colour is observed (Li, crimson Na, yellow K, lilac Rb, red-violet Cs, blue) and this flame test is used in qualitative analysis to identify the M ion. In quantitative analysis, use is made of the characteristic atomic spectrum in flame photometry or atomic absorption spectroscopy. 

This chapter deals with optical atomic, emission spectrometry (AES). Generally, the atomizers listed in Table 8-1 not only convert the component of samples to atoms or elementary ions but, in the process, excite a fraction of these species to higher electronic stales.. 4, the excited species rapidly relax back to lower states, ultraviolet and visible line spectra arise that are useful for qualitative ant quantitative elemental analysis. Plasma sources have become, the most important and most widely used sources for AES. These devices, including the popular inductively coupled plasma source, are discussedfirst in this chapter. Then, emission spectroscopy based on electric arc and electric spark atomization and excitation is described. Historically, arc and spark sources were quite important in emission spectrometry, and they still have important applications for the determination of some metallic elements. Finally several miscellaneous atomic emission source.s, including jlanies, glow discharges, and lasers are presented. 

Aluminum is best detected qualitatively by optical emission spectroscopy. Solids can be vaporized directly in a d-c arc and solutions can be dried on a carbon electrode. Alternatively, aluminum can be detected by plasma emission spectroscopy using an inductively coupled aigon plasma or a d-c plasma. Atomic absorption using an aluminum hoUow cathode lamp is also an unambiguous and sensitive qualitative method for determining aluminum. 

Atomic fluorescence flame spectrometry is receiving increased attention as a potential tool for the trace analysis of inorganic ions. Studies to date have indicated that limits of detection comparable or superior to those currently obtainable with atomic absorption or flame emission methods are frequently possible for elements whose emission lines are in the ultraviolet. The use of a continuum source, such as the high-pressure xenon arc, has been successful, although the limits of detection obtainable are not usually as low as those obtained with intense line sources. However, the xenon source can be used for the analysis of several elements either individually or by scanning a portion of the spectruin. Only chemical interferences are of concern they appear to be qualitatively similar for both atomic absorption and atomic fluorescence. With the current development of better sources and investigations into devices other than flames for sample introduction, further improvements in atomic fluorescence spectroscopy are to be expected. 

Emission spectroscopy is widely used for both qualitative and quantitative analysis. The high sensitivity and the possible simultaneous excitation of as many as 72 elements, notably metals and metalloids, makes emission spectroscopy especially suited for rapid survey analysis of the elemental content in small samples at the level of 10 /ug/g or less. With control over excitation conditions to maintain constant and reliable atomization and excitation, the spectral line intensities can be used for quantitatively determining concentrations. An analytical curve must be constructed with known standards, and often the ratio of analyte intensity to the intensity of a second element contained in, or added to, the sample (the internal-standard method) is used to improve the precision of quantitative analyses. Preparation of standards for arc and spark techniques requires considerable care to match chemical and physical forms to the sample this is not commonly required for ICP discharge. 

Emission spectroscopy provides an ideal method for qualitative analysis, since each atomic species has its own unique line spectrum. Spectral lines have two characteristics useful for qualitative analysis (1) their wavelengths and (2) their intensities. It is the pattern of wavelength distribution that is primarily used for qualitative analysis, although the relative intensity distribution also can be helpful to verify spectral lines to identify an element. About 70 elements are easily identified by spectral methods. Those that are more difficult to identify include the gases and a few nonmetals, primarily because sensitive lines lie in the short ultraviolet portion of the spectrum that is difficult to observe. 

Inductively coupled plasma-atomic emission spectrometry allows the determination of anionic surfactants (LAS and AS) and inorganic compounds (phosphate, silicate, zeolite, sulfate). Other techniques, such as X-ray fluorescence spectroscopy and X-ray powder diffraction, have been used for the qualitative analysis of inorganic detergents. For surface analysis, optical light microscopy, scanning electron microscopy, and transmission electron microscopy characterize particles, deposition of surfactant, or other detergent ingredients on fabric. 

Qualitative and Semiquantitative AppUcatkms Because ICPMS is easily adapted to multielement analyses, it is well suited to the rapid characterization and semiquantitative analysis of various types of naturally occurring and manufactured complex materials. Generally, detection limits are belter than those for optical emission ICP and compete with detection limits for electrothermal atomic absorption spectroscopy. 

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