Emission lines

The relative intensities of X-ray emission lines from targets varies for different elements. However, one can assume a ratio of KaJKa2 = 2 for the commonly used targets. The ratio of Ko2lKjii from these targets varies from 6 to 3.5. The intensities of Kj32 radiations amount to about 1 percent... 

Table 7.8 contains values of p,/p for the common target elements employed in X-ray work. A more extensive set of mass absorption coefficients for K, L, and M emission lines within the wavelength range from 0.7 to 12 A is contained in Heinrich s paper in T. D. McKinley, K. F. J. Heinrich, and D. B. Wittry (eds.). The Electron Microprobe, Wiley, New York, 1966, pp. 351-377. This article should be consulted to ascertain the probable accuracy of the values and for a compilation of coefficients and exponents employed in the computations. 

In spectroscopy, the separation between two spectral features, such as absorption or emission lines. 

The emission spectrum from a hollow cathode lamp includes, besides emission lines for the analyte, additional emission lines for impurities present in the metallic cathode and the filler gas. These additional lines serve as a potential source of stray radiation that may lead to an instrumental deviation from Beer s law. Normally the monochromator s slit width is set as wide as possible, improving the throughput of radiation, while being narrow enough to eliminate this source of stray radiation. 

The intensity, I, of an emission line is proportional to the number of atoms, N, populating the excited state... 

X 10 J/K), and T is the temperature in kelvin. From equation 10.35 we can see that excited states with lower energies have larger populations and, therefore, the most intense emission lines. Furthermore, emission intensity increases with temperature. 

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... 

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

Standardizing the Method Equation 10.34 shows that emission intensity is proportional to the population of the excited state, N, from which the emission line originates. If the emission source is in thermal equilibrium, then the excited state population is proportional to the total population of analyte atoms, N, through the Boltzmann distribution (equation 10.35). 

When possible, quantitative analyses are best conducted using external standards. Emission intensity, however, is affected significantly by many parameters, including the temperature of the excitation source and the efficiency of atomization. An increase in temperature of 10 K, for example, results in a 4% change in the fraction of Na atoms present in the 3p excited state. The method of internal standards can be used when variations in source parameters are difficult to control. In this case an internal standard is selected that has an emission line close to that of the analyte to compensate for changes in the temperature of the excitation source. In addition, the internal standard should be subject to the same chemical interferences to compensate for changes in atomization efficiency. To accurately compensate for these errors, the analyte and internal standard emission lines must be monitored simultaneously. The method of standard additions also can be used. 

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. 

The reaction path shows how Xe and Clj react with electrons initially to form Xe cations. These react with Clj or Cl- to give electronically excited-state molecules XeCl, which emit light to return to ground-state XeCI. The latter are not stable and immediately dissociate to give xenon and chlorine. In such gas lasers, translational motion of the excited-state XeCl gives rise to some Doppler shifting in the laser light, so the emission line is not as sharp as it is in solid-state lasers. 

The first polyatomic molecule was detected in 1968 with use of a telescope having a dish 6.3 m in diameter at Hat Creek, California, USA, designed to operate in the millimetre wave region. Emission lines were found in the 1.25 cm wavelength region due to NH3. The transitions are not rotational but are between the very closely spaced 2 = 0 and 2 = 1 levels of the inversion vibration V2 (see Section 6.2.5.4). 

Figure 7.29 The d 77 — electronic transition of AlH in emission. Lines marked with a cross are not due to AlH...

Single-Bubble Sonoluminescence. The spectra of MBSL and SBSL are dramatically different. MBSL is generally dominated by atomic and molecular emission lines, but SBSL is an essentially featureless emission that iacreases with decreasiag wavelength. For example, an aqueous solution of NaCl shows evidence of excited states of both OH- and Na ia the MBSL spectmm however, the SBSL spectmm of an identical solution shows no evidence of either of these peaks (30). Similady, the MBSL spectmm falls off at low wavelengths, while the SBSL spectmm continues to rise, at least for bubbles containing most noble gases (38). 

The arc and spark spectra of the individual lanthanides are exceedingly complex. Thousands of emission lines are observed. For the trivalent rare-earth ions in soUds, the absorption spectra are much better understood. However, the crystal fields of the neighboring atoms remove the degeneracy of some states and several levels exist where only one did before. Many of these crystal field levels exist very close to a base level. As the soUd is heated, a number of the lower levels become occupied. Some physical properties of rare-earth metals are thus very sensitive to temperature (7). 

Analysis. Lithium can be detected by the strong orange-red emission of light in a flame. Emission spectroscopy allows very accurate determination of lithium and is the most commonly used analytical procedure. The red emission line at 670.8 nm is usually used for analytical determinations although the orange emission line at 610.3 nm is also strong. Numerous other methods for lithium determinations have been reviewed (49,50). 

Ultraviolet light sources are based on the mercury vapor arc. The mercury is enclosed ia a quart2 tube and a potential is appHed to electrodes at either end of the tube. The electrodes can be of iron, tungsten, or other metals and the pressure ia a mercury vapor lamp may range from less than 0.1 to >1 MPa (<1 to >10 atm). As the mercury pressure and lamp operating temperatures are iacreased, the radiation becomes more iatense and the width of the emission lines iacreases (17). 

Sihcon has strong optical emission lines at 251.6113 and 288.1579 nm that can easily be detected by emission spectrography and that give sensitivities in the 1—100-ppm range. For nondestmctive analysis, either x-ray diffraction or x-ray fluorescence may be used (see Spectroscopy X-ray technology). 

Qualitative. The classic method for the quaUtative determination of silver ia solution is precipitation as silver chloride with dilute nitric acid and chloride ion. The silver chloride can be differentiated from lead or mercurous chlorides, which also may precipitate, by the fact that lead chloride is soluble ia hot water but not ia ammonium hydroxide, whereas mercurous chloride turns black ia ammonium hydroxide. Silver chloride dissolves ia ammonium hydroxide because of the formation of soluble silver—ammonia complexes. A number of selective spot tests (24) iaclude reactions with /)-dimethy1amino-henz1idenerhodanine, ceric ammonium nitrate, or bromopyrogaHol red [16574-43-9]. Silver is detected by x-ray fluorescence and arc-emission spectrometry. Two sensitive arc-emission lines for silver occur at 328.1 and 338.3 nm. 

Both the wavelength dispersive and energy dispersive spectrometers are well suited for quaUtative analysis of materials. Each element gives on the average only six emission lines. Because the characteristic x-ray spectra are so simple, the process of allocating atomic numbers to the emission lines is relatively simple and the chance of making a gross error is small. 

Plasma atomic emission spectrometry is also employed as a detection method for gc (see Plasma technology). By monitoring selected emission lines a kind of selective detection based on elemental composition can be achieved (see Spectroscopy). 

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