Absorption of complexes

The use of visible and UV spectrometry for quantitative analysis by comparing the absorbance of standards and samples at a selected wavelength is one of the most widespread of all analytical techniques. It is also one of the most sensitive. The analysis of mixtures of two or more components is facilitated by the additivity of absorbances. This has been discussed earlier (p. 356). Other applications include measurement of the absorption of complexes as a function of solution conditions or time to establish their composition, and to determine thermodynamic and kinetic stability for analytical purposes or for more fundamental studies. 

IR spectroscopy has been used to study complex formation in solution and the absorption of complex cyano anions on 200-400 mesh Dowex-A-1 anion exchange resin.8 To complement these studies the Raman spectra have been obtained for solid KAg(CN)2 and for the complex... 

Arden, T. V. and Wood, G. A. Absorption of complex anions from uranyl sulphate solution by anion-exchange resins. J. Chem. Soc. p. 1596 (June 19S6). 

F1 pure 11. Ideal frontalograms for interacting compounds M+L = ML. The curves A and B refer to total (constituent) concentrations of the components, respectively. The shaded areas describe the fractions v4iere complex ML is found. The binding ratio is calculable from the concentration of free L and from its (known) total concentration and thus molar absorptivity of complexed L is not needed when eluent is monitored by light absorption. 

The data for binding constants of the systan are directly available without knowing molar absorptivity of complexed L or possible absorption by M, since the total ligand concentration in the original sample is independently known. By repeating frontal analysis in different concentrations of L, the binding ratio and stoichiometry is obtained (see equation 2). 

Postcolumn derivatization with absorbance spectroscopy Postcolumn derivatization reactions involve the chemical reaction of the analyte with a chromophore, after the analyte has passed through the column, followed by the detection of the analyte by UV-Vis absorbance spectroscopy. This type of detection system is typically used for transition and lanthanide metal cations due to the incompatibilities between the transition metal complexing eluent and the conductivity supressor. The properties of the postcolumn derivatization species should include high molar absorptivity of complexes, reactivity with most metals, formation of stable metal com-... 

Predicting the Reiative Waveiengths of Absorption of Complex Ions... 

Predicting the relative wavelengths of absorption of complex ions Given two complexes that differ only in the lig-... 

Unfortunately, addition of copper(II)nitrate to a solution of 4.42 in water did not result in the formation of a significant amount of complex, judging from the unchanged UV-vis absorption spectrum. Also after addition of Yb(OTf)3 or Eu(N03)3 no indications for coordination were observed. Apparently, formation of a six-membered chelate ring containing an amine and a ketone functionality is not feasible for these metal ions. Note that 4.13 features a similar arrangement and in aqueous solutions, likewise, does not coordinate significantly to all the Lewis acids that have been... 

The determination of an analyte s concentration based on its absorption of ultraviolet or visible radiation is one of the most frequently encountered quantitative analytical methods. One reason for its popularity is that many organic and inorganic compounds have strong absorption bands in the UV/Vis region of the electromagnetic spectrum. In addition, analytes that do not absorb UV/Vis radiation, or that absorb such radiation only weakly, frequently can be chemically coupled to a species that does. For example, nonabsorbing solutions of Pb + can be reacted with dithizone to form the red Pb-dithizonate complex. An additional advantage to UV/Vis absorption is that in most cases it is relatively easy to adjust experimental and instrumental conditions so that Beer s law is obeyed. 

EDTA forms colored complexes with a variety of metal ions that may serve as the basis for a quantitative spectrophotometric method of analysis. The molar absorptivities of the EDTA complexes of Cu +, Co +, and Ni + at three wavelengths are summarized in the following table (all values of e are in cm )... 

The absorption of sulfonylureas from the upper gastrointestinal tract is faidy rapid and complete. The agents are transported in the blood as protein-bound complexes. As they are released from protein-binding sites, the free (unbound) form becomes available for diffusion into tissues and to sites of action. Specific receptors are present on pancreatic islet P-ceU surfaces which bind sulfonylureas with high affinity. Binding of sulfonylureas to these receptors appears to be coupled to an ATP-sensitive channel to stimulate insulin secretion. These agents may also potentiate insulin-stimulated glucose transport in adipose tissue and skeletal muscle. 

Acarbose is a nonabsorbable a-glucosidase inhibitor which blocks the digestion of starch, sucrose, and maltose. The digestion of complex carbohydrates is delayed and occurs throughout the small intestine rather than in the upper part of the jejunum. Absorption of glucose and other monosaccharides is not affected. Acarbose is adrninistered orally three times a day and chewed with the first mouthful of food. 

The pale blue tris(2,2 -bipyridine)iron(3+) ion [18661-69-3] [Fe(bipy)2], can be obtained by oxidation of [Fe(bipy)2]. It cannot be prepared directiy from iron(III) salts. Addition of 2,2 -bipyridine to aqueous iron(III) chloride solutions precipitates the doubly hydroxy-bridged species [(bipy)2Fe(. t-OH)2Fe(bipy)2]Cl4 [74930-87-3]. [Fe(bipy)2] has an absorption maximum at 610 nm, an absorptivity of 330 (Mem), and a formation constant of 10. In mildly acidic to alkaline aqueous solutions the ion is reduced to the iron(II) complex. [Fe(bipy)2] is frequentiy used in studies of electron-transfer mechanisms. The triperchlorate salt [15388-50-8] is isolated most commonly. 

In analogy to the situation for bipyridine, the blue tris(l,10-phenanthroline)iron(3+) ion [1347949-7], [Fe(phen)2], must be obtained by oxidation of the corresponding iron(II) ion. [Fe(phen)2] has an absorption maximum at 590 nm, an absorptivity of 600 (Mem), and a formation constant of 10 . In solutions of pH > 4, this species is reduced to the iron(II) complex. The reduction is instantaneous in alkaline solution. At pH < 2, protons compete with iron(III) for the phenanthroline nitrogens and coordination is incomplete. [Fe(phen)2] is used most often in solution as an oxidant, but the trichloride [40273-22-1] and the triperchlorate monohydrate [20774-81-6] salts have been prepared. 

The induction of systemic toxicity may involve a variety of complex interrelationships between the absorbed parent material, any conversion products, and their concentration and distribution in body tissues and fluids. The general pathway that a material may foUow after its absorption is shown schematically in Eigure 2. 

Choline reineckate is used in the spectrophotometric determination of choline. Ammonium reineckate [13573-16-5] forms a water-insoluble complex with choline. The complex is soluble in acetone and a widely used method for determination of choline is by light absorption of acetone solutions... 

Annelation increases the complexity of the spectra just as it does in the carbocyclic series, and the spectra are not unlike those of the aromatic carbocycle obtained by formally replacing the heteroatom by two aromatic carbon atoms (—CH=CH—). Although quantitatively less marked, the same trend for the longest wavelength band to undergo a bathochromic shift in the heteroatom sequence O < NH < S < Se < Te is discernible in the spectra of the benzo[Z>] heterocycles (Table 17). As might perhaps have been anticipated, the effect of the fusion of a second benzenoid ring on to these heterocycles is to reduce further the differences in their spectroscopic properties (cf. Table 18). The absorption of the benzo[c]... 

With a reactive solvent, the mass-transfer coefficient may be enhanced by a factor E so that, for instance. Kg is replaced by EKg. Like specific rates of ordinary chemical reactions, such enhancements must be found experimentally. There are no generalized correlations. Some calculations have been made for idealized situations, such as complete reaction in the liquid film. Tables 23-6 and 23-7 show a few spot data. On that basis, a tower for absorption of SO9 with NaOH is smaller than that with pure water by a factor of roughly 0.317/7.0 = 0.045. Table 23-8 lists the main factors that are needed for mathematical representation of KgO in a typical case of the absorption of CO9 by aqueous mouethauolamiue. Figure 23-27 shows some of the complex behaviors of equilibria and mass-transfer coefficients for the absorption of CO9 in solutions of potassium carbonate. Other than Henry s law, p = HC, which holds for some fairly dilute solutions, there is no general form of equilibrium relation. A typically complex equation is that for CO9 in contact with sodium carbonate solutions (Harte, Baker, and Purcell, Ind. Eng. Chem., 25, 528 [1933]), which is... 

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