Speciation Species

Quantitative speciation Species quantitations are the basis for essential mass balances, which are the only way to obtain information about losses and contaminations. The use of CRMs and intercomparisons again are helpful here. 

Normality is the number of equivalent weights (EW) per unit volume and, like formality, is independent of speciation. An equivalent weight is defined as the ratio of a chemical species formula weight (FW) to the number of its equivalents... 

Acid Deposition. Acid deposition, the deposition of acids from the atmosphere to the surface of the earth, can be dry or wet. Dry deposition involves acid gases or their precursors or acid particles coming in contact with the earth s surface and thence being retained. The principal species associated with dry acid deposition are S02(g), acid sulfate particles, ie, H2SO4 and NH HSO, and HN02(g). Measurements of dry deposition are quite sparse, however, and usually only speciated as total and total NO3. In general, dry acid deposition is estimated to be a small fraction of the total... 

As of the mid-1990s, soluble sihcates are used primarily as sources of reactive siUca (57%), in detergency (qv) (23%), in pulp (qv) and paper (qv) production (7%), for adhesives and binders (5%), and in other appHcations (8%). The stmcture and chemistry of solutions containing polymeric siHcate species have been characterized using modem analytical techniques. This improved understanding of siHcate speciation contributes to the development of new markets. Thus, the sodium silicates constitute a versatile, stable, and growing commodity and are ranked among the top 50 commodity chemicals. 

The objective ia any analytical procedure is to determine the composition of the sample (speciation) and the amounts of different species present (quantification). Spectroscopic techniques can both identify and quantify ia a single measurement. A wide range of compounds can be detected with high specificity, even ia multicomponent mixtures. Many spectroscopic methods are noninvasive, involving no sample collection, pretreatment, or contamination (see Nondestructive evaluation). Because only optical access to the sample is needed, instmments can be remotely situated for environmental and process monitoring (see Analytical METHODS Process control). Spectroscopy provides rapid real-time results, and is easily adaptable to continuous long-term monitoring. Spectra also carry information on sample conditions such as temperature and pressure. 

Speciation The process of determining the different species present in a chemical agent. 

The study of biochemical natural products has also been aided through the application of two-dimensional GC. In many studies, it has been observed that volatile organic compounds from plants (for example, in fruits) show species-specific distributions in chiral abundances. Observations have shown that related species produce similar compounds, but at differing ratios, and the study of such distributions yields information on speciation and plant genetics. In particular, the determination of hydroxyl fatty acid adducts produced from bacterial processes has been a successful application. In the reported applications, enantiomeric determination of polyhydroxyl alkanoic acids extracted from intracellular regions has been enabled (45). 

A development of the study of adsorption currents is referred to as Tensammetry, and a useful review50 refers to the application of this technique to the examination of natural waters as an aid to speciation , the procedure for deciding how a metal ion is distributed between the various species in which the metal may be present. 

The advantages of controlled-potential techniques include high sensitivity, selectivity towards electroactive species, a wide linear range, portable and low-cost instrumentation, speciation capability, and a wide range of electrodes that allow assays of unusual environments. Several properties of these techniques are summarized in Table 1-1. Extremely low (nanomolar) detection limits can be achieved with very small sample volumes (5-20 pi), thus allowing the determination of analyte amounts of 10 13 to 10 15 mol on a routine basis. Improved selectivity may be achieved via the coupling of controlled-potential schemes with chromatographic or optical procedures. 

Formation constants for complex species of mono-, di-, and trialkytin(rV) cations with some nucleotide-5 -monophosphates (AMP, LIMP, IMP, and GMP) are reported by De Stefano et al. The investigation was performed in the light of speciation of organometallic compounds in natural fluids (I = 0.16-1 moldm ). As expected, owing to the strong tendency of organotin(IV) cations to hydrolysis (as already was pointed above) in aqueous solution, the main species formed in the pH-range of interest of natural fluids are the hydrolytic ones. ... 

Repeated splitting of lineages of organisms into separate species has resulted in the great richness and diversity of life that lived in the past and is found on Earth today. Earth would be very different if speciation had been a rare event during the life s history. Biogeochemical cycles are influenced by millions of species, each adapted to live under a particular range of conditions and to use environmental resources in a particular way. 

Al(III) is an example of an aquatic ion that forms a series of hydrated and protonated species. These include AlOrf Al(OH)J, Al(OH)3, and other forms in addition to AP. (For simplicity, we omit the H2O molecules that complete the structures of these complexes.) Most of these species are amphoteric (able to act as an acid or a base). Thus the speciation of Al(III) and many other aquatic ions is sensitive to pH. In this case, an aggregate variable springs from the conservation of mass condition. In the case of dissolved aluminum, the total dissolved aluminum is given by... 

As a more complex example, we examine the stability of oxidation states of aqueous sulfur as a function of pH. This exercise will bring out the treatment of thermodynamically unstable species and the change of sulfur speciation with pH. 

The high concentration of oxygen in the atmosphere plays a central role in the photochemistry and chemical reactivity of the atmosphere. Atmospheric oxygen also defines the oxidation reduction potential of surface waters saturated with oxygen. The presence of oxygen defines the speciation of many other aquatic species in surface waters. 

Examples were given earlier of a few systems for which the theoretical speciation of metals was calculated, and a few others in which it was analyzed experimentally, at least into some subgroups if not specific species. These approaches have rarely been combined to critically evaluate data or hypotheses regarding metal transport through a real system. One study, already noted... 

The pH effect in Fenton reactions is due to the Fe speciation. In highly acidic solutions containing noncoordinating species, Fe exists as Fe(H20)f. The composition as function of the pH is represented in Figure 6.3a. At increasing pH, Fe undergoes hydrolysis forming FeOH +, Fe(OH)2+, and finally FeO via binuclear, Fe2(OH)4, and polynuclear species. The aim of optimization is to avoid Fe precipitation, either bi-, poly-, or precipitated Fe oxides that are aU inactive in... 

It must be noted that sometimes calcination is beneficial to create active species. Notable examples are the Sn-beta speciation [176] and generation of extra-framework Al-Lewis sites in beta zeolite for organic transformations... 

Today it has become clear that the effect of trace elements in living systems, in food, and in the environment depends on the chemical form in which the element enters the system and the final form in which it is present. The form, or species, clearly governs its biochemical and geochemical behaviour. lUPAC (the International Union for Pure and Applied Chemistry) has recently set guidelines for terms related to chemical speciation of trace elements (Templeton et al. 2000). Speciation, or the analytical activity of measuring the chemical species, is a relatively new scientific field. The procedures usually consist of two consecutive steps (i) the separation of the species, and (2) their measurement An evident handicap in speciation analysis is that the concentration of the individual species is far lower than the total elemental concentration so that an enrichment step is indispensable in many cases. Such a proliferation of steps in analytical procedure not only increases the danger of losses due to incomplete recovery, chemical instability of the species and adsorption to laboratory ware, but may also enhance the risk of contamination from reagents and equipment. 

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