Absorption spectra of ions in solution

The monomer species, M, has been described by Kraus (31) as an ion pair. Although he did not elaborate on its possible structure, one may assume that he pictured this species as two ammoniated ions held together by electrostatic forces. Douthit and Dye (12) pointed out that such a picture is consistent with the absorption spectra of sodium-ammonia solutions. Becker, Lindquist, and Alder (2) proposed an expanded metal model in which an electron was assumed to circulate in an expanded orbital on the protons of the coordinated ammonia molecules of an M + ion. The latter model is difficult to reconcile with optical, volumetric, and NMR data (16). 

Many studies on the absorption spectra of lanthanides in alcoholic media have been made and the observations and anomalies have been explained in terms of entry of a chloride ion into the coordination sphere of the lanthanide ion. The composition and stability of halide complexes of lanthanides in alcohol and aqueous alcoholic solutions have been studied by spectral techniques. The halide ions have been found to cause marked changes in the spectra of lanthanides in alcoholic and aqueous media. The observed spectral changes may be attributed to changes in the immediate coordination environment of the lanthanide ion [223]. 

Jorgensen indicated that the absorption spectra of aqueous ethanolic solutions of cupric ion containing bipyridyl or phenanthroline (ratio 1 2) were compatible with the presence either of a cis-diaquobischelate cation or with a trigonal bipyramidal monoaquo species 409). The weak electrolyte behavior in nitrobenzene or nitromethane of deep blue Cu(bipy)2(C104)2 has been attributed to the following equilibrium ... 

Figure 2. Comparison of the absorption spectra of Pr in aqueous solution with the energy levels found experimentally for Pr in (A) vapor phase (free-ion levels) (7, 18), (B) LaClg crystal (17), (C) LaFg crystal (5)...

Hydroxide, aqua, and hydrates. From the similar absorption spectra of Am in aqueous solution, AmCls, and in Lads, and the linear relationship between the decay rate of the americium fluorescence and the number of inner-sphere water molecules, it has been concluded that Am " is coordinated by nine inner-sphere water molecules. Similarly, the hydration number for the Cm ion has been estimated to be nine on the basis of fluorescence lifetimes. EXAFS studies of aqueous Am and Cm, however, have suggested coordination numbers closer to 10. " EXAFS investigation of Cf " " in aqueous solution indicates a coordination number of 8.5 ( 1.5), with a Cf—O distances of 2.41 0.02 A. This coordination number was confirmed for Am in the solid state by isolation of single crystals of the triflate salt of nonaqua complex, which contains a tricapped, trigonal prismatic cation that is isostructural with the analogous Pu" compound. ... 

Aqueous solution of these cations show a strong absorption. The absorption spectra of ion pairs of these cations with various anions are shifted towards the visible region and the magnitude of that shift is almost directly proportional to the deorease in electron affinity of the anion (31). 

Fig. 48.1. Absorption spectra of ion associate of Methylene Blue with ClOf in chloroform (1) and Methylene Blue in aqueous solution (2)...

The UV-Vis aqueous phase absorption spectra of dioxouranium(VI) solution before and after the extraction are depicted in Fig. 6.2. The initial dioxouranium(Vl) solutions show characteristic absorption bands similar to those described in the literature for dioxouranium(Vl) ions in aqueous solutions (Wang et al. 2009). As it can be seen, the shifts in the absorption peaks with nitric acid concentration are negligible, i.e. the peak at 414 nm with 0.01 M nitric acid has shifted to 415 nm and to 416 nm as the nitric acid concentration is increased to 1 M and 3 M, respectively. This slight shift is probably due to the formation of dioxouranium(VI) nitrate complexes in the acid solution (Wang et al. 2009). 

The importance of this association effect is borne out by the results of Dieleman (37), who investigated the influence of temperature on the absorption spectra of sodium salt solutions of />-terphenyl negative ions and of p,p -quaterphenyl negative ions in 2-methyltetrahydrofuran. 

THE STATE OF NITRIC ACID IN INERT ORGANIC SOLVENTS The absence of ions in mixtures of acetic acid and nitric acid is shown by their poor electrical conductivity and the Raman spectra of solutions in acetic acid, nitromethane, and chloroform show only the absorptions of the solvent and molecular nitric acid the bands corresponding to the nitronium and nitrate ions cannot be detected. -... 

Absorption and Fluorescence Spectra. The absorption spectra of actinide and lanthanide ions in aqueous solution and in crystalline form contain narrow bands in the visible, near-ultraviolet, and near-infrared regions of the spectmm (13,14,17,24). Much evidence indicates that these bands arise from electronic transitions within the and bf shells in which the Af and hf configurations are preserved in the upper and lower states for a particular ion. 

Absorption Spectra, of Aqueous Ions. The absorption spectra of Pu(III) [22541-70 ] Pu(IV) [22541 4-2] Pu(V) [22541-69-1] and Pu(VI) [22541-41-9] in mineral acids, ie, HCIO and HNO, have been measured (78—81). The Pu(VII) [39611-88-61] spectmm, which can be measured only in strong alkaU hydroxide solution, also has been reported (82). As for rare-earth ion spectra, the spectra of plutonium ions exhibit sharp lines, but have larger extinction coefficients than those of most lanthanide ions (see Lanthanides). The visible spectra in dilute acid solution are shown in Figure 4 and the spectmm of Pu(VII) in base is shown in Figure 5. The spectra of ions of plutonium have been interpreted in relation to all of the ions of the bf elements (83). 

The optical absorption spectra of Pu ions in aqueous solution show sharp bands in the wavelength region 400—1100 nm (Fig. 4). The maxima of some of these bands can be used to determine the concentration of Pu ions in each oxidation state (III—VI), thus quantitative deterrninations of oxidation—reduction equiUbria and kinetics are possible. A comprehensive summary of kinetic data of oxidation—reduction reactions is available (101) as are the reduction kinetics of Pu + (aq) (84). 

The ultraviolet absorption spectra of the anhydro-bases in acid solution or in protic solvents are those of the 3,4-dihydro-)3-carbolinium ion (Ajnax 355 mp, for 438b and 438c). In alkaline solution and in nonionizing solvents absorption at a shorter wavelength (A ax 315 m/x) is observed. In general, solutions of the anhydro-bases in acid and in protic solvents are more deeply colored than their solutions in basic or in non-ionizing media. 

The UV absorption spectra of sodium nitrite in aqueous solutions of sulfuric and perchloric acids were recorded by Seel and Winkler (1960) and by Bayliss et al. (1963). The absorption band at 250 nm is due either to the nitrosoacidium ion or to the nitrosyl ion. From the absorbancy of this band the equilibrium concentrations of HNO2 and NO or H20 —NO were calculated over the acid concentration ranges 0-100% H2S04 (by weight) and 0-72% HC104 (by weight). For both solvent systems the concentrations determined for the two (or three) equilibrium species correlate with the acidity function HR. This acidity function is defined for protonation-dehydration processes, and it is usually measured using triarylcarbinol indicators in the equilibrium shown in Scheme 3-15 (see Deno et al., 1955 Cox and Yates, 1983). 

There is an interesting similarity in the character of the solution absorption spectra of the isoelectronic ions Np3+ and Pu1 even though the absorption bands in Pu1 + are all shifted toward higher energies due to increases in both the electrostatic (Fk) and spin-orbit ( ) parameters, Table VI. We have also examined the spectra of complex alkali-metal Pu(IV)... 

A determination of dimethyl sulphoxide by Dizdar and Idjakovic" is based on the fact that it can cause changes in the visible absorption spectra of some metal compounds, especially transition metals, in aqueous solution. In these solutions water and sulphoxide evidently compete for places in the coordination sphere of the metal ions. The authors found the effect to be largest with ammonium ferric sulphate, (NH4)2S04 Fe2(S04)3T2H20, in dilute acid and related the observed increase in absorption at 410 nm with the concentration of dimethyl sulphoxide. Neither sulphide nor sulphone interfered. Toma and coworkers described a method, which may bear a relation to this group displacement in a sphere of coordination. They reacted sulphoxides (also cyanides and carbon monoxide) with excess sodium aquapentacyanoferrate" (the corresponding amminopentacyanoferrate complex was used) with which a 1 1 complex is formed. In the sulphoxide determination they then titrated spectrophotometrically with methylpyrazinium iodide, the cation of which reacts with the unused ferrate" complex to give a deep blue ion combination product (absorption maximum at 658 nm). 

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