Accuracy atomic spectroscopy

The group of rotations of a three-dimensional space stands apart in atomic spectroscopy. This is mostly due to the high accuracy of the central field approximation, on which the entire modem theory of complex atoms and ions is based. 

In the near future a small improvement in 1 can be expected from ongoing determinations of fr/me in measurements of the photon recoil in Cs atom spectroscopy and a Cs atomic mass measurement [29], The present limitation for accuracy of aj1 arises mainly from the muon mass uncertainty. Therefore any better determination of the muon mass, e.g. through a precise measurement of the reduced mass shift in Z zvls2s, will result in an improvement of 1. 

The precision of an instrument must be considered. Many typical measurements, for example, in atomic spectroscopy, are recorded to only two significant figures. Consider a dataset in which about 95 % of the readings were recorded between 0.10 and 0.30 absorbance units, yet a statistically designed experiment tries to estimate 64 effects. The /-test provides information on the significance of each effect. However, statistical tests assume that the data are recorded to indefinite accuracy, and will not take this lack of numerical precision into account. For the obvious effects, chemo-metrics will not be necessary, but for less obvious effects, the statistical conclusions will be invalidated because of the low numerical accuracy in the raw data. 

The method of standard additions is widely used in atomic spectroscopy (e.g. determination of Ca2+ ions in serum by atomic emission spectrophotometry) and, since several aliquots of sample are analysed to produce the calibration graph, should increase the accuracy and precision of the assay... 

The application of atomic spectroscopy methods to the analysis of petroleum products is important to the oil industry. All oil samples must be prepared in solution form and be at a concentration so as to be detected to quantify all metals of interest with accuracy and precision. Solutions containing petroleum products in organic solvents may be measured directly or with the use of internal standards to correct for viscosity effects. It is important that the selected solvent dissolves the oil and products and does not cause erratic flickering of the plasma, or quenches it. It is also important that the same solvent can be used to prepare calibration standards. The following methods are common sample preparation methods for metal analysis of crude and lubricating oils. 

Spectroscopic determination of atomic species can only be performed on a gaseous medium in which the individual atoms or elementary ions, such as Fe, Mg, or Al, are well separated from one another. Consequently, the first step in all atomic spectroscopic procedures is atomization, a process in which a sample is volatilized and decomposed in such a way as to produce gas-phase atoms and ions. The efficiency and reproducibility of the atomization step can have a large influence on the sensitivity, precision, and accuracy of the method. In short, atomization is a critical step in atomic spectroscopy. 

The electron-electron interaction is usually supposed to be well described by the instantaneous Coulomb interaction operator l/rn. Also, all interactions with the nuclei whose internal structure is not resolved, like electron-nucleus attraction and nucleus-nucleus repulsion, are supposed to be of this type. Of course, corrections to these approximations become important in certain cases where a high accuracy is sought, especially in computing the term values and transition probabilities of atomic spectroscopy. For example, the Breit correction to the electron-electron Coulomb interaction should not be neglected in fine-structure calculations and in the case of highly charged ions. However, in general, and particularly for standard chemical purposes, these corrections become less important. 

In atomic spectroscopy the term values depend primarily on electronic quantum numbers and the process of analysis consists of reducing a number of measurements to a term scheme. The confidence in an analysis increases as the system becomes more overdetermined, and the process becomes more definite as the accuracy of the measurements improves. Other information is also used to facilitate the assignments of the lines, e.g., relative intensities, the observation of certain lines in absorption, the splittings of lines by magnetic fields theoretical calculations of terms and multiplet splittings may sometimes be helpful. 

Catterick, T., H. Handley S. Merson, 1995. Analytical Accuracy in ICP-MS Using Isotope Dilution and its Application to Reference Materials. Atomic Spectroscopy 16 229-234. 

Analytical schemes concerned with the determination of blood ions and gases can be divided into two categories analyses done in vivo and those done in vitro. By far the most common method of determining blood ions in vitro involves atomic spectroscopy. Atomic absorption and flame emission have both been used although the latter is the most popular. In the clinical lab nearly all of the remaining determinations (both in vivo and in vitro) are performed with ion-selective (for ions, NH3 and CO2) or amperometric electrodes (O2 and H2). Two important characteristics of ion-selective electrodes, sensitivity and selectivity, should be mentioned. The applicability of a specific electrode in any particular situation can be determined by considering, on one hand, the ionic constituents of the solution to be measured and, on the other hand, the sensitivity and specificity of the electrode in question. Proper consideration of these points will allow an investigator to determine the accuracy and validity of the measurement. 

As mentioned earlier, optical atomic spectroscopy is only able to analyze solution sample. As a result, ceramic powders to be tested should be made into solution. The solution is then broken into line droplets and vaporized into individual atoms by heating, which is the step critical to the precision and accuracy of the analysis. Flame is generally used to vaporize the solution, which is therefore also known as flame atomic absorption spectrometry or flame AA. 

For the analysis of ceramic powders by optical atomic specfroscopy, a portion of the powder has to be converted into individual atoms. In practice, this is achieved by dissolving the powder in a liquid to form a solution, which is then broken into fine droplets and vaporized into individual atoms by heating. The precision and accuracy of optical atomic spectroscopy are critically dependent on this step. Vaporization is most commonly achieved by introducing droplets into a flame (referred to as flame atomic absorption spectrometry or flame AA). Key problems with flame AA include incomplete dissociation of the more refractory elements (e.g., B, V, Ta, and W) in the flame and difficulties in determining elements that have resonance lines in the far ultraviolet region (e.g., P, S, and the halogens). While flame AA is rapid, the instruments are rarely automated to permit simultaneous analysis of several elements. 

The major strengths of atomic spectroscopy techniques over other methods is that they are relatively inexpensive, and they provide outstanding flexibility in terms of automation and multielement analysis capabilities (almost the whole Periodic Table). These advantages, coupled with high precision and accuracy, make atomic spectoscopy a preferred method of analysis. 

Most of these techniques have either limited applicability or suffer from inconsistent precision and accuracy and therefore have not been adopted as routine approaches. Laser ablation is probably one of the most promising methods in the above list, with high potential to provide an alternative sample introduction route for the different atomic spectroscopy techniques. 

Sample introduction has been called the Achilles heel of atomic spectroscopy because in many cases this step limits the accuracy, the precision, and the detection limits of atomic spectrometric measurements. The primary purpose of the sample-introduction system in atomic spectrometry is to transfer a reproducible and... 

Another inaccuracy is found in the correction term d(n), which had to be estimated for many of the lanthanides (fig. 4). The estimations are somewhat more accurate for the heavier (n > 7) lanthanides than for the lighter elements. (However, the deviations between AEmiv and XPS measurements shown in fig. 6 seem to behave smoothly.) If these two types of uncertainties could be avoided it might be that the so-refined values for AEuuv will show a nearly constant shift relative to the XPS experiments. However, it must be stressed that this discussion is presently rather academic, since neither of these inaccuracies are greater than the XPS experimental uncertainty ( + 0.2eV). If the accuracy of experiments improves in the future, hopefully experimental values of d(n) for all the lanthanides will have become available from atomic spectroscopy, so that more accurate AEjn jy values are at our... 

The major role of TOF-SARS and SARIS is as surface structure analysis teclmiques which are capable of probing the positions of all elements with an accuracy of <0.1 A. They are sensitive to short-range order, i.e. individual interatomic spacings that are <10 A. They provide a direct measure of the interatomic distances in the first and subsurface layers and a measure of surface periodicity in real space. One of its most important applications is the direct determination of hydrogen adsorption sites by recoiling spectrometry [12, 4T ]. Most other surface structure teclmiques do not detect hydrogen, with the possible exception of He atom scattering and vibrational spectroscopy. 

The possibility of preconcentration of selenium (IV) by coprecipitation with iron (III) hydroxide and lanthanum (III) hydroxide with subsequent determination by flame atomic absorption spectroscopy has been investigated also. The effect of nature and concentration of collector and interfering ions on precision accuracy and reproducibility of analytical signal A has been studied. Application of FefOH) as copreconcentrant leads to small relative error (less than 5%). S, is 0.1-0.2 for 5-100 p.g Se in the sample. Concentration factor is 6. The effect of concentration of hydrochloric acid on precision and accuracy of AAS determination of Se has been studied. The best results were obtained with HCl (1 1). 

Phosphorus has only one stable isotope, J P, and accordingly (p. 17) its atomic weight is known with extreme accuracy, 30.973 762(4). Sixteen radioactive isotopes are known, of which P is by far the most important il is made on the multikilogram scale by the neutron irradiation of S(n,p) or P(n,y) in a nuclear reactor, and is a pure -emitter of half life 14.26 days, 1.7()9MeV, rntan 0.69MeV. It finds extensive use in tracer and mechanistic studies. The stable isotope has a nuclear spin quantum number of and this is much used in nmr spectroscopy. Chemical shifts and coupling constants can both be used diagnostically to determine structural information. 

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