Interferences spectral

The quantum theory of spectral collapse presented in Chapter 4 aims at even lower gas densities where the Stark or Zeeman multiplets of atomic spectra as well as the rotational structure of all the branches of absorption or Raman spectra are well resolved. The evolution of basic ideas of line broadening and interference (spectral exchange) is reviewed. Adiabatic and non-adiabatic spectral broadening are described in the frame of binary non-Markovian theory and compared with the impact approximation. The conditions for spectral collapse and subsequent narrowing of the spectra are analysed for the simplest examples, which model typical situations in atomic and molecular spectroscopy. Special attention is paid to collapse of the isotropic Raman spectrum. Quantum theory, based on first principles, attempts to predict the. /-dependence of the widths of the rotational component as well as the envelope of the unresolved and then collapsed spectrum (Fig. 0.4). 

Another very appealing property of extended mixture models in PAT is the ability to explicitly account for interferences or interfering effects that cannot be present in the calibration standards. In such a case, the challenge is determining a sufficiently accurate spectral basis for the interference(s), although these can be estimated from specialized experiments or library spectra. One extension of the CLS method, prediction augmented CLS (PACLS) [50] uses results from actual predictions on process samples to determine such an interference spectral basis. 

ICP-AES analysis is susceptible to spectral and non-spectral interferences spectral interferences constitute the greatest limitation of this otherwise sensitive and practical technique. 

Physical Interferences Chemical Interferences The Literature Interpolation Problem Ionization Interferences Spectral Interferences Spectral Interferences in Flame AAS Background Correction in AAS Spectral Interferences in Flame AFS Spectral Interferences in Flame AES Conclusions about Interferences... 

There are troublesome spectral interferences, spectral line overlapping in ICP-OES, and polyatomic interferences in ICP-MS. 

Interferences for AES can be classified into two main categories, spectral and matrix interferences. Spectral interference can occur as a result of an interfering emission line from either another element or the argon source gas, impurities within or entrained into the source, e.g. molecular species such as N2. Such interferences can be eliminated or reduced either by increasing the resolution of the spectrometer or by selecting an alternative spectral emission line. 

Other sources of background include spectral line (nonanalyte atomic fluorescence) and spectral band (molecular fluorescence) interferences. Spectral line interferences are caused by the presence of another element that can absorb source radiation and emit fluorescence sufficiently close to the analyte wavelength to be collected by the detection system. Spectral band interferences involve the absorption of source light by a molecule whose fluorescence is collected by the detection system. Nonanalyte atomic fluorescence and molecular fluorescence are minimized by the use of a narrow line source and a nonresonance transition. This is in contrast to AES, where spectral interferences are sufficiently severe that a high-resolution monochromator is required. 

Interferences are physical or chemical processes that cause the signal from the analyte in the sample to be higher or lower than the signal from an equivalent standard. Interferences can therefore cause positive or negative errors in quantitative analysis. There are two major classes of interferences in AAS, spectral interferences and nonspectral interferences. Nonspectral interferences are those that affect the formation of analyte free atoms. Nonspectral interferences include chemical interference, ionization interference, and solvent effects (or matrix interference). Spectral interferences cause the amount of light absorbed to be erroneously high due to absorption by a species other than the analyte atom. While all techniques suffer from interferences to some extent, AAS is much less prone to spectral interferences and nonspectral interferences than atomic anission spectrometry and X-ray fluorescence (XRF), the other major optical atomic spectroscopic techniques. 

Because of the high excitation temperatures attained in ICP, the most serious disadvantage of this plasma is the relatively large number of spectral interferences. Spectral overlap becomes very likely in complex samples containing many elements over a wide range of concentrations. The potential spectral overlaps are often remedied with the use of high-resolution monochromators (poly chromators). 

Minimizing Spectral Interference A spectral interference occurs when an analyte s absorption line overlaps with an interferant s absorption line or band. As noted previously, the overlap of two atomic absorption lines is seldom a problem. On the other hand, a molecule s broad absorption band or the scattering of source radiation is a potentially serious spectral interference. 

An important question to consider when using a flame as an atomization source, is how to correct for the absorption of radiation by the flame. The products of combustion consist of molecular species that may exhibit broad-band absorption, as well as particulate material that may scatter radiation from the source. If this spectral interference is not corrected, then the intensity of the transmitted radiation decreases. The result is an apparent increase in the sam-... 

Accuracy When spectral and chemical interferences are minimized, accuracies of 0.5-5% are routinely possible. With nonlinear calibration curves, higher accuracy is obtained by using a pair of standards whose absorbances closely bracket the sample s absorbance and assuming that the change in absorbance is linear over the limited concentration range. Determinate errors for electrothermal atomization are frequently greater than that obtained with flame atomization due to more serious matrix interferences. 

Accuracy The accuracy of a fluorescence method is generally 1-5% when spectral and chemical interferences are insignificant. Accuracy is limited by the same types of problems affecting other spectroscopic methods. In addition, accuracy is affected by interferences influencing the fluorescent quantum yield. The accuracy of phosphorescence is somewhat greater than that for fluorescence. 

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. 

Choice of Atomization and Excitation Source Except for the alkali metals, detection limits when using an ICP are significantly better than those obtained with flame emission (Table 10.14). Plasmas also are subject to fewer spectral and chemical interferences. For these reasons a plasma emission source is usually the better choice. 

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... 

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 detection of a specific gas (10) is accompHshed by comparing the signal of the detector that is constrained to the preselected spectral band pass with a reference detector having all conditions the same except that its preselected spectral band is not affected by the presence of the gas to be detected. Possible interference by other gases must be taken into account. It may be necessary to have multiple channels or spectral discrimination over an extended Spectral region to make identification highly probable. Except for covert surveillance most detection scenarios are highly controlled and identification is not too difficult. 

Chemical Gas Detection. Spectral identification of gases in industrial processing and atmospheric contamination is becoming an important tool for process control and monitoring of air quaUty. The present optical method uses the ftir (Fourier transform infrared) interference spectrometer having high resolution (<1 cm ) capabiUty and excellent sensitivity (few ppb) with the use of cooled MCT (mercury—cadmium—teUuride) (2) detectors. 

Interference effects, which arise because of the extraordinary uniformity of thickness of the film over the spectrometer sample beam, superimposed on the absorption of incident light by parylene films, can be observed. Experimentally, a sinusoidal undulation of the baseline of the spectmm is seen, particularly in the spectral regions where there is Htde absorption by the sample. These so-called "interference fringe" excursions can amount to some... 

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