Atomic emission

The basic instmment used for atomic emission is very similar to that used for AA with the difference that no primary light source is used for atomic emission. One of the more critical components for atomic emission instruments is the atomization source (Grove, 1971) because it must also provide sufficient energy to excite the atoms as well as atomize them. 

The earliest energy sources for excitation were simple flames, but these often lacked sufficient thermal energy to be traly effective. Later, electrothermal sources, such as arc/park systems were used, particularly when analyzing solid samples. These sources are useful for qualitative and quantitative work with solid samples, but they are expensive, difficult to use, and have limited applications. 

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Using Argon Plasma Atomic Emission for Analysis of Metals... 

FLAME ATOMIC EMISSION, FLAME ATOMIC ABSORPTION,... 

The detection limits in the table correspond generally to the concentration of an element required to give a net signal equal to three times the standard deviation of the noise (background) in accordance with lUPAC recommendations. Detection limits can be confusing when steady-state techniques such as flame atomic emission or absorption, and plasma atomic emission or fluorescence, which... 

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. 

Schematic diagram of a hoiiow cathode iamp showing mechanism by which atomic emission is obtained.

The release of a photon following thermal excitation is called emission, and that following the absorption of a photon is called photoluminescence. In chemiluminescence and bioluminescence, excitation results from a chemical or biochemical reaction, respectively. Spectroscopic methods based on photoluminescence are the subject of Section lOG, and atomic emission is covered in Section lOH. 

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. 

Atomization and Excitation Atomic emission requires a means for converting an analyte in solid, liquid, or solution form to a free gaseous atom. The same source of thermal energy usually serves as the excitation source. The most common methods are flames and plasmas, both of which are useful for liquid or solution samples. Solid samples may be analyzed by dissolving in solution and using a flame or plasma atomizer. 

Flame Sources Atomization and excitation in flame atomic emission is accomplished using the same nebulization and spray chamber assembly used in atomic absorption (see Figure 10.38). The burner head consists of single or multiple slots or a Meker-style burner. Older atomic emission instruments often used a total consumption burner in which the sample is drawn through a capillary tube and injected directly into the flame. 

Schematic diagram of a muitichannei atomic emission spectrometer, showing the arrangement of muitipie exit siits and detectors for the simuitaneous anaiysis of severai eiements.

Multielemental Analysis Atomic emission spectroscopy is ideally suited for multi-elemental analysis because all analytes in a sample are excited simultaneously. A scanning monochromator can be programmed to move rapidly to an analyte s desired wavelength, pausing to record its emission intensity before moving to the next analyte s wavelength. Proceeding in this fashion, it is possible to analyze three or four analytes per minute. 

Atomic emission is used for the analysis of the same types of samples that may be analyzed by atomic absorption. The development of a quantitative atomic emission method requires several considerations, including choosing a source for atomization and excitation, selecting a wavelength and slit width, preparing the sample for analysis, minimizing spectral and chemical interferences, and selecting a method of standardization. 

Atomic Emission Detection Limits for Selected Elements... 

In atomic emission, the decrease in emission intensity when light emitted by excited state atoms in the center of a flame or plasma is absorbed by atoms in the outer portion of the flame. 

Method for background correction in flame atomic emission. 

Atomic emission line at (a) low concentration of analyte, and (b) high concentration of analyte showing the effect of self-absorption. 

Description of Method. Salt substitutes, which are used in place of table salt for individuals on a low-sodium diet, contain KCI. Depending on the brand, fumaric acid, calcium hydrogen phosphate, or potassium tartrate also may be present. Typically, the concentration of sodium in a salt substitute is about 100 ppm. The concentration of sodium is easily determined by flame atomic emission. Because it is difficult to match the matrix of the standards to that of the sample, the analysis is accomplished by the method of standard additions. 

Scale of Operation The scale of operations for atomic emission is ideal for the direct analysis of trace and ultratrace analytes in macro and meso samples. With appropriate dilutions, atomic emission also can be applied to major and minor analytes. 

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. 

Sensitivity Sensitivity in flame atomic emission is strongly influenced by the temperature of the excitation source and the composition of the sample matrix. Normally, sensitivity is optimized by aspirating a standard solution and adjusting the flame s composition and the height from which emission is monitored until the emission intensity is maximized. Chemical interferences, when present, decrease the sensitivity of the analysis. With plasma emission, sensitivity is less influenced by the sample matrix. In some cases, for example, a plasma calibration curve prepared using standards in a matrix of distilled water can be used for samples with more complex matrices. 

Selectivity The selectivity of atomic emission is similar to that of atomic absorption. Atomic emission has the further advantage of rapid sequential or simultaneous analysis. 

The following sources provide additional information on atomic absorption and atomic emission. 

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