Aqueous electrons, compared

Aqueous electron transfer reactions vanadium(V) as reductant compared to iron(II). D. R. Ros-seinsky, Chem. Rev., 1972, 72, 215-229 (116). 

In spite of considerable similarities between the chemical properties of lanthanides and actinides, the trivalent oxidation state is not stable for the early members of the actinide series. Due to larger ionic radii and the presence of shielding electrons, the 5f electrons of actinides are subjected to a weaker attraction from the nuclear charge than the corresponding 4f electrons of lanthanides. The greater stability of tetrapositive ions of actinides such as Th and Pu is attributed to the smaller values of fourth ionization potential for 5f electrons compared to 4f electrons of lanthanides, an effect that has been observed in aqueous solution of Th and Ce (2). Thus, thorium... 

Aminofurans substituted with electron-withdrawing groups e.g. NO2) are known and 3-amino-2-methylfuran is a relatively stable amine which can be acylated and diazotized. 2-Amino-3-acetylfurans are converted into 3-cyano-2-methylpyrroles on treatment with aqueous ammonia. This transformation is a further illustration of the relative instability of the amino derivatives of five-membered ring heterocycles compared with anilines (Scheme 67) (781003821). 

It is not possible to tell by inspection whether the a- or P-pyranose fonn of a pai-ticulai- caibohydrate predominates at equilibrium. As just described, the p-pyianose fonn is the major species present in an aqueous solution of D-glucose, whereas the a-pyianose foi-m predominates in a solution of D-mannose (Pioblem 25.8). The relative abundance of a- and p-pyianose fonns in solution depends on two factors. The first is solvation of the anomeric hydroxyl group. An equatorial OH is less crowded and better solvated by water than an axial one. This effect stabilizes the P-pyranose foi-m in aqueous solution. The other factor, called the anomeric effect, involves an electronic interaction between the ling oxygen and the anomeric substituent and preferentially stabilizes the axial OH of the a-pyianose foi-m. Because the two effects operate in different directions but are comparable in magnitude in aqueous solution, the a-pyianose foi-m is more abundant for some carbohydrates and the P-pyranose foi-m for others. 

The Dissociation Constant of Nitric Acid. The largest value of K in Table 9 is that for the (HS04) ion. In Fig. 36 there is a gap of more than 0.2 electron-volt below the level of the (H30)1 ion. As is well known, several acids exist which in aqueous solution fall iu the intermediate region between the very weak acids and the recognized strong acids the proton levels of these acids will fall in this gap. The values of K for these acids obtained by different methods seldom show close agreement. Results obtained by various methods were compared in 1946 by Redlich,1 who discussed the difficulties encountered. 

The crystallographic radius assigned to the ion Fc+++ is comparable with that assigned to the scandium ion Sc+++. The ions K, Ca+t, and Sc+++ have the same number of electrons, and the same closed electronic shells as the argon atom. In aqueous solution there will be electrostatic forces of attraction between Ca++ and Cl, and between 8c+ t+ and Cl- but the quantum-mechanical forces between these ions will be forces of repulsion only. Between Fe+++ and Cl-, on the other hand, there may be quantum-mechanical forces of attraction. In view of the rather intense electrostatic attraction between Fe+++ and a negative ion, a 1 E. Rabinowitch and W. H. Stockmayer, J. Am. Chern. Soc., 64, 341 (1942). 

The Sulfate Ion. In Fig. 36 we see that the vacant level of the (SO ) ion in aqueous solution lies only 0.13 electron-volt above the occupied level of HCOOH. If the interval has a comparable value when sulfate ions are present in formic acid as solvent, the thermal agitation should transfer a large number of protons from solvent HCOOH molecules to the (SO4)" ions. This was found to be the case when Na2SC>4 was dissolved in pure formic acid. Such a transfer of protons from molecules of a solvent to the anions of a salt is analogous to the hydrolysis of the salt in aqueous solution and is known as solvolysis, as mentioned in Sec. 76. In a 0.101-molal solution of Na2SC>4 in formic acid the degree of the solvolysis was found to be 35 per cent.1... 

Although benzene-sulfonic acid, CnITsSChH, is a strong acid in aqueous solution, it is not completely dissociated in formic acid solution. In a 0.1-molal solution the degree of dissociation was estimated at 60 per cent.2 This is comparable with the dissociation of HIOs in aqueous solution and is compatible with J = 0.14 electron-volt for the formation of (HCOOH2)+. Using this value the level has been included in Fig. 65. 

Here L, S, and J are the quantum numbers corresponding to the total orbital angular momentum of the electrons, the total spin angular momentum, and the resultant of these two. Hund predicted values of L, S, and J for the normal states of the rare-earth ions from spectroscopic rules, and calculated -values for them which are in generally excellent agreement with the experimental data for both aqueous solutions and solid salts.39 In case that the interaction between L and S is small, so that the multiplet separation corresponding to various values of J is small compared with kT, Van Vleck s formula38... 

Bimetallic nanoparticles, either as alloys or as core-shell structures, exhibit unique electronic, optical and catalytic properties compared to pure metallic nanopartides [24]. Cu-Ag alloy nanoparticles were obtained through the simultaneous reduction of copper and silver ions again in aqueous starch matrix. The optical properties of these alloy nanopartides vary with their composition, which is seen from the digital photographs in Fig. 8. The formation of alloy was confirmed by single SP maxima which varied depending on the composition of the alloy. 

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