Ultraviolet atomic emission

Braun, W., Peterson, N. C., Bass, A. M., Kurylo, M. J. A vacuum ultraviolet atomic emission detector. Quantitative and qualitative chromatographic analysis of typical C, N, S containing compounds. J. Chromatog. 55, 237 (1971). 

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. 

Until the advent of lasers the most intense monochromatic sources available were atomic emission sources from which an intense, discrete line in the visible or near-ultraviolet region was isolated by optical filtering if necessary. The most often used source of this kind was the mercury discharge lamp operating at the vapour pressure of mercury. Three of the most intense lines are at 253.7 nm (near-ultraviolet), 404.7 nm and 435.7 nm (both in the visible region). Although the line width is typically small the narrowest has a width of about 0.2 cm, which places a limit on the resolution which can be achieved. 

Spectroscopy, aimual reviews of new analytical instmmentation from the Pittsburgh Conference on Analytical Chemistry and AppHed Spectroscopy. Analytical Chemisty, "Fundamental Reviews" (June 1994, June 1996), analytical appHcations of infrared, ultraviolet, atomic absorption, emission, Raman, fluorescence, phosphorescence, chemiluminescence, and x-ray spectroscopy. 

The metal content analysis of the samples was effected by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES Varian Liberty II Instrument) after microwaves assisted mineralisation in hydrofluoric/hydrochloric acid mixture. Ultraviolet and visible diffuse reflectance spectroscopy (UV-Vis DRS) was carried out in the 200-900 nm range with a Lambda 40 Perkin Elmer spectrophotometer with a BaS04 reflection sphere. HF was used as a reference. Data processing was carried out with Microcal Origin 7.1 software. 

Measurement techniques that can be employed for the determination of trace metals include atomic absorption spectrometry, anodic stripping voltammetry, differential pulse cathodic stripping voltammetry, inductively coupled plasma atomic emission spectrometry, liquid chromatography of the metal chelates with ultraviolet-visible absorption and, more recently, inductively coupled plasma mass spectrometry. 

The basic instrumentation used for spectrometric measurements has already been described in Chapter 7 (p. 277). The natures of sources, monochromators, detectors, and sample cells required for molecular absorption techniques are summarized in Table 9.1. The principal difference between instrumentation for atomic emission and molecular absorption spectrometry is in the need for a separate source of radiation for the latter. In the infrared, visible and ultraviolet regions, white sources are used, i.e. the energy or frequency range of the source covers most or all of the relevant portion of the spectrum. In contrast, nuclear magnetic resonance spectrometers employ a narrow waveband radio-frequency transmitter, a tuned detector and no monochromator. 

There are definite distinct lines in the atomic emission spectrum of hydrogen. These lines are seen in the visible part of the spectrum and there is also a series of lines in the infrared and another series in the ultraviolet part of the electromagnetic spectrum. So, although hydrogen is the simplest element with only one electron per atom, its atomic emission spectrum is fairly complicated. 

Atomic emission spectroscopy is one of the oldest instrumental techniques used for chemical analysis. It is used to study the transitions between electronic energy levels in atoms or ions. These energy differences are usually in the visible region (400-700 nm) of the electromagnetic spectrum, but if the energy difference is larger, then the transitions may lie in the ultraviolet region. 

Gadolinium may be measured in an acidic solution by flame or furnace atomic absorption or ICP atomic emission spectropbotometry. Also, gadolinium may be identified nondestructively and rapidly by x-ray fluorescence methods. It also may be measured by neutron activation analysis, and by various spectrophotometric techniques. The element shows sharp absorption bands in ultraviolet region at 270-280 nm. Other lanthanides also produce bands in this region however, those are low intensity minor bands. 

It is a remarkable fact that the contemporary history of absorption and emission spectroscopy began simultaneously, from the simultaneous discoveries that Bunsen and Kirchhoff made in the middle of the 19th century. They observed atomic emission and absorption lines whose wavelengths exactly coincided. Stokes and Kirchhoff applied this discovery to the explanation of the Fraunhofer spectra. Nearly at the same time approximately 150 years ago, Stokes explained the conversion of absorbed ultraviolet light into emitted blue light and introduced the term fluorescence. Apparently, the discovery of the Stokes shift marked the birth of luminescence as a science. 

GFAAS = graphite furnace (flameless) atomic absorption spectroscopy TLC = thin layer chromatography HFP-AES = high frequency plasma-atomic emission spectroscopy NAA = neutron atomic analysis ICP-AES = inductively coupled plasma-atomic emission spectroscopy AAS = atomic absorption spectrometry GSE = graphite spectroscopic electrode UV = ultraviolet spectrophotometry PD = photodensitometer and (3,5-diBr-PADAP) = 2(-3,-5-dibromo-2-pyridylazo)-5- diethyl-ami nophenol. 

Ultraviolet-visible (UV-Vis) spectrophotometric detectors are used to monitor chromatographic separations. However, this type of detection offers very little specificity. Element specific detectors are much more useful and important. Atomic absorption spectrometry (AAS), inductively coupled plasma-atomic emission spectroscopy (ICPAES) and inductively coupled plasma-mass spectrometry (ICP-MS) are often used in current studies. The highest sensitivity is achieved by graphite furnace-AAS and ICP-MS. The former is used off-line while the latter is coupled to the chromatographic column and is used on-line . 

Childress, W.L., Erickson, D. and Krull, I.S. (1992) Trace selenium speciation via high-performance liquid chromatography with ultraviolet and direct-current plasma emission detection. In Element-specific Chromatographic Detection by Atomic Emission Spectroscopy (ed. Uden, PC.). American Chemical Society, Washington, DC, pp. 257-273. 

As a result of his work, the lines in the visible spectrum are known as the Balmer series. The other series of lines in the atomic emission spectrum of hydrogen were discovered later (the next wasn t discovered until 1908). These series are named after the scientists who discovered them for example, the series in the ultraviolet region is known as the Lyman series after Theodore Lyman. 

In both total and sequential dissolutions, the result is a solution containing the components of rocks and soils. This solution is then analyzed by different methods. Mostly, spectroscopic methods are used atomic absorption and emission spectroscopic methods, ultraviolet, atom fluorescence, and x-ray fluorescence spectrometry. Multielement methods (e.g., inductively coupled plasma optical emission spectroscopy) obviously have some advantages. Moreover, elec-troanalytical methods, ion-selective electrodes, and neutron activation analysis can also be applied. Spectroscopic methods can also be combined with mass spectrometry. 

Spectroscopic detection (using ultraviolet/visible (UV/vis) absorbance, refractive index, fluorescence, atomic absorption or atomic emission). Techniques based on postcolumn reactions. 

James and Sugden have shown that the radiation emitted from flames containing traces of alkali metals consists of a continuum as well as the atomic emission lines. The continuum extends from the red to near ultraviolet its intensity depends little upon the temperature, but may be correlated with the concentration of the hydroxyl radical in the flame. It is concluded that the origin of the continuum is the radiative process... 

Sulfur-containing components exist in gasoline-range hydrocarbons and can be identified with a gas chromatographic capillary colunm coupled with either a sulfur chemiluminescence detector or an atomic emission detector (AED) (ASTM D-5623). The most widely specified method for total sulfur content uses X-ray spectrometry (ASTM D-2622), and other methods that use ultraviolet fluorescence spectroscopy (ASTM D-5453) and/or hydrogenolysis and colorimetry (ASTM D-4045) are also apphcable, particularly when the sulfur level is low. 

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