Hydration and Hydrate Anions

Benzocyclobutene-l,2-dione (74) undergoes base-catalysed ring fission between the carbonyls to give 2-formy I benzoate (75). Rate constants, activation parameters, isotope effects, and substituent effects have been measured in water.107 Rapid reversible addition of hydroxide to one carbonyl is followed by intramolecular nucleophilic attack on die otiier, giving a resonance-stabilized carbanionic intermediate (76a)-o-(76b). 

Hydration of highly duorinated ketones has been referred to under Acetals above.5 2-Acetyl-l-methylpyridinium ion is 8% hydrated in water see Enolization below. 

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For hydration of an o -aminotetrahydropyranone, and the hydrate and hydrate anion of a,a,a-trifluoroacetophenone, see under Acetals and Aldols above, respectively. 

According to this mechanism, the reaction rate is proportional to the concentration of hydronium ion and is independent of the associated anion, ie, rate = / [CH3Hg][H3 0 ]. However, the acid anion may play a marked role in hydration rate, eg, phosphomolybdate and phosphotungstate anions exhibit hydration rates two or three times that of sulfate or phosphate (78). Association of the polyacid anion with the propyl carbonium ion is suggested. Protonation of propylene occurs more readily than that of ethylene as a result of the formation of a more stable secondary carbonium ion. Thus higher conversions are achieved in propylene hydration. 

Sulfates. Sulfate ions strongly complex zirconium, removing hydroxyl groups and forming anionic complexes. With increasing acidity, all hydroxyl groups are replaced zirconium sulfate [7446-31-3] Zr(S04)2-4H20, with an orthorhombic stmcture (206), can be crystallized from a 45% sulfuric acid solution. Zirconium sulfate forms various hydrates, and 13 different crystalline Zr(S0 2 5 2 [14644-61-2] systems are described in Reference 207. 

Quinazoline [253-82-7] M 130.2, m 48.0-48.5 , b 120-121 /17-18mm, pK, -4.51 (aq H2SO4, anhydrous dication), pK 2.01 (anhydrous monocation), pK3 4.3 (equilibrium with 3,4-hydrated species), PK4 12.1 (hydrated anion). Purified by passage through an activated alumina column in benzene or pet ether (b 40-60°). Distd under reduced pressure, sublimed under vacuum and crystd from pet ether. [Armarego 7 Chem 1170 1961.]... 

The crystal structure of the cyc/<7-hcxaphos-phate anion in Nar.P OiR.fiHoO shows that all 6P atoms are coplanar and that bond lengths arc similar to those in the P Oy and p40i2 anions. See ref. 147 for the structure of the hydrated cyc/o-decaphosphate KioPit)03o.4H20. Higher cyr/r)-metaphosphates can be isolated by... 

Most of the work done in the pteridine series has been concerned with the equilibria between the neutral species and the anions. This work was more fruitful than that involving the cations because all three of the values, p /, p a , and pK/ (for definitions, see Section II, A), could be determined, and, from these, ratios of the hydrated to the anhydrous forms were calculated. Furthermore, the kinetics in the... 

In systems such as the 2- and 6-hydroxypteridine series, rapid potentiometric or spectrophotometric pA determinations on neutral solutions usually give values near to the acidic pA of the hydrated series. (Exceptions include 2-hydroxy-4,6,7-trimethyl-, 6-hydroxy-7-methyl-, and 4,6-dihydroxy-pteridine, where the neutral solution contains comparable amounts of hydrated and anhydrous species. In such cases, rapid potentiometric titrations show two well-defined and separated curves, one for the hydrated, the other for the anhydrous, species.) Similarly, from solutions of the anion, an approximate pA value for the anhydrous species is obtained. For convenience, the anhydrous molecule is referred to as HX, its anion as X , the hydrated neutral molecule as HY, and its anion as Y, and the two equilibrium constants are defined as follows ... 

The second term dominates and is characterised by p = +1.30 (using a-meta constants), E = 10.8 kcal.mole , dS = —22.8 eu and k jko > 1-8. experiments show the major source of oxygen in the acid produced is the solvent, which suggests the hydrate anion is the reactive form, viz. 

Less uncertainty surrounds the structure of hydrated anions the hydrogen atoms are almost collinear with the oxygen atoms and the centres of the ions (Briant Burton, 1976). Monte-Carlo calculations have shown that F is surrounded by four hydrogen atoms each 0-17 nm away (Watts, dementi Fromm, 1974). 

In the present analyses [49], 34 ions are classified into five groups (1) hydrated cations, (2) nonhydrated cations, (3) hydrated anions, (4) nonhydrated anions, and (5) polyanions. Here, the term hydrated or nonhydrated means that the ion is associated with some water molecules in the O phase or not, respectively. 

Calculated using Eqs. (45), (49), (46), (50), and (51) for hydrated cations, nonhydrated cations, hydrated anions, nonhydrated anions, and polyanions, respectively. 

The ionic mobility and diffusion coefficient are also affected by the ion hydration. The particle dimensions calculated from these values by using Stokes law (Eq. 2.6.2) do not correspond to the ionic dimensions found, for example, from the crystal structure, and hydration numbers can be calculated from them. In the absence of further assumptions, diffusion measurements again yield only the sum of the hydration numbers of the cation and the anion. 

Remarkable data on primary hydration shells are obtained in non-aqueous solvents containing a definite amount of water. Thus, nitrobenzene saturated with water contains about 0.2 m H20. Because of much higher dipole moment of water than of nitrobenzene, the ions will be preferentially solvated by water. Under these conditions the following values of hydration numbers were obtained Li+ 6.5, H+ 5.5, Ag+ 4.4, Na+ 3.9, K+ 1.5, Tl+ 1.0, Rb+ 0.8, Cs+0.5, tetraethylammonium ion 0.0, CIO4 0.4, NO3 1.4 and tetraphenylborate anion 0.0 (assumption). 

Very interesting behavior of incorporating anions can be observed when a multicomponent electrolyte is used for oxide formation. Here, anion antagonism or synergism can be observed, depending on the types of anions used. The antagonism of hydroxyl ions and acid anions has been observed in a number of cases. Konno et a/.181 have observed, in experiments on anodic alumina deterioration and hydration, that small amounts of phosphates and chromates inhibit oxide hydration by forming monolayer or two-layer films of adsorbed anions at the oxide surface. Abd-Rabbo et al.162 have observed preferential incorporation of phosphate anions from a mixture of phosphates and chromates. 

Zinc is a bluish-white metal which dissolves readily in strong acids. In nature it occurs as a sulfide, oxide, or carbonate. In solution, it is divalent and can form hydrated Zn2+ cations in acids, and zincated anions — probably Zn(OH)42 — in strong bases (USEPA 1980, 1987). Zinc dust and powder are sold commercially under a variety of trade names Asarco, Blue powder, Cl 77949, Cl pigment metal 6, Emanay zinc dust, granular zinc, JASAD Merrillite, LI 5, and PASCO (USPHS 1989). Selected physical and chemical properties of zinc, zinc chloride, and zinc sulfate are listed in Table 9.2. 

Let us now extend the long-period hydronium ice-like model for the IHP on Pt(lll) to explain the observations in electrolytes other than sulphate. In acid chloride, both the observations and the model carry-over directly from the case of sulphate. In fluoride, perchlorate, bicarbonate and hydroxide, in Which the anomalous features shift considerably in both potential and appearance (especially in the basic media) from sulphate, another model is needed. Both (bi)sulphate and chloride are large weakly hydrated anions, and in the double-layer model of Figures 4-5, they interact strongly with both the hydronium ions and the Pt surface. The contact adsorption... 

Theoretical considerations show that the free energy of dissociation of an acid in water, and hence the dissociation constant, is governed by the algebraic sum of the free energies for the solution of the undissociated acid in water, for vaporisation of the acid, for the formation of a free proton and an anion from the molecule of acid in the gas phase, and for hydration of the proton and anion. Thus the true acidity, given by the third of these... 

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