Hydration in the solid state

Many ionic compounds contain what used to be referred to as water of crystallization . For example, magnesium chloride can exist as a fully hydrated salt which was formerly written MgCla.bHjO, but is more appropriately written Mg(OH2)eCl2, since the water molecules occupy coordination sites around the magnesium ions. This is typical. In most compounds that contain water of crystallization, the water molecules are bound to the cation in an aquo complex in the manner originally proposed by Alfred Werner (1866-1919) in 1893 (Kauffman, 1981). Such an arrangement has been confirmed in numerous cases by X-ray diffraction techniques. 

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Salts are non-volatile and in the fused state or in solution eonduet an eleetrie eurrent. Many salts are hydrated in the solid state with water of erystallization. 

The question of the hydration of ions in solution (p. 98) is essentially the same as the question of the formation of complex hydrates in the solid state. 

As is pointed out in the introduction to Section II, the presence or absence of water in the solid state gives no indication as to whether or not covalent hydration occurs in aqueous solution. However, many examples are known of substances which hydrate strongly in solution and also in the solid state. Thus, 2-hydroxy- and 6-hydroxy-pteridine crystallize with one molecule of water. On heating, the former loses water rapidly only at 180°, whereas the latter retains all of the water up to 180° where it begins to darken. ... 

C03-0152. Aluminum sulfate is used in the manufacture of paper and in the water purification industry. In the solid state, aluminum sulfate is a hydrate. The formula is AI2 (804)3 18 H2 O. (a) How many grams of sulfiar are there in 0.570 moles of solid aluminum sulfate (b) How many water molecules are there in a 5.1-g sample of solid aluminum sulfate (c) How many moles of sulfate ions are there in a sample of solid aluminum sulfate that contains 12.5 moles of oxygen atoms (d) An aqueous solution of aluminum sulfate contains 1.25% by mass aluminum and has a density of 1.05 g/mL. What is the molarity of aluminum ions in the solution ... 

Several enzymes like lipases, esterases, and dehydrogenases have been active in hydrophobic environments. Thermodynamic water activity is a good predictor of the optimal hydration conditions for catalytic activity [51]. Enzyme preparation can be equilibrated at a specific water activity before the reaction [52]. When water concentration is very low, enzyme is suspended in the solid state in the water-immiscible organic solvent [46]. Enzymes are easily recovered after the reaction by the method of filtration. 

Free amine 36 was isolated as a hygroscopic hydrate which was very difficult to dry in the solid state and required azeotropic drying using THF (expensive and time consuming). 

Figure 15 75.46 MHz 13CCPMAS NMR spectra of curdlan in the solid state. (A) anhydrous, (B) hydrate, (C) annealed at 180 °C followed by slow cooling. From Ref. 120 with permission.

The initial hydration rate v and the equilibrium hydration amount were obtained as parameters reflecting the hydration behavior of LB films (see Figure 8). Temperature dependencies of the hydration behavior (v0and W ) of 10 layers of DMPE (Tc = 49 °C) LB films are shown in Figure 9. Large W and v0 values were observed only around the phase transition temperature (7C) of DMPE membranes. Thus, DMPE LB films were hydrated only near the Tc, but not in the solid state below the Tc and in the fluid state above the Tc. This indicates that the... 

Some caution is required when comparing the association constants obtained from extraction experiments with those measured under anhydrous, homogeneous conditions. Iwachido et al. (1976, 1977) have shown that the extracted cation retains part of its aqueous solvation shell on complexation. In particular, the small univalent cations (Li+, Na+) and bivalent cations give high hydration numbers for their crown-ether complexes. Water molecules completing the co-ordination sphere of the cation have frequently been encountered in the solid state of crown-ether complexes (Bush and Truter, 1970, 1971). The effect of small amounts of water on the equilibria (1) has not been studied yet for crown ethers. However, it has been found that the presence... 

Salts of O-alkyldithiocarbonatcs ( xanthates ) are hazardous as dusts, forming explosive suspensions in air. The lower-alkyl salts are claimed to be explosive in the solid state when dry [1]. Explosions reported when drying hydrated xanthate salts are probably the consequence of release of carbon disulphide to form an inflammable atmosphere of very low autoignition temperature in the oven [2], Xanthate esters are thermally unstable by a variety of eliminations and rearrangements, all distinctly exothermic and many evolving extremely flammable gases and vapours. Free xanthic acids, which may be isolated on acidification, decompose autocatalytically and perhaps explosively [3],... 

An important advantage of the inclusion complexes of the cyclodextrins over those of other host compounds, particularly in regard to their use as models of enzyme-substrate complexes, is their ability to be formed in aqueous solution. In the case of clathrates, gas hydrates, and the inclusion complexes of such hosts as urea and deoxycholic acid, the cavity in which the guest molecule is situated is formed by the crystal lattice of the host. Thus, these inclusion complexes disintegrate when the crystal is dissolved. The cavity of the cyclodextrins, however, is a property of the size and shape of the molecule and hence it persists in solution. In fact, there is evidence that suggests that the ability of the cyclodextrins to form inclusion complexes is dependent on the presence of water. Once an inclusion complex has formed in solution, it can be crystallized however, in the solid state, additional cavities appear in the lattice, as in the case of the hosts previously mentioned, which enable the inclusion of further guest molecules. ... 

A ring-chain equilibrium displaced in favor of the cyclic tautomer was observed [78JBC(253)5407 83LA1623] in neutral aqueous solutions of 5-carbamido- 66 n = 3 Xt = 5.67) and 5-guanidino-2-oxovaleric 67 n = 3 Xt = 3.17) acids. In aqueous solutions of acid 67 (w = 3), H-NMR spectroscopy detected the presence of 4% of the open-chain tautomer hydrate 67A (n = 3). In acidic medium, the amount of this hydrate is higher. The dipolar cyclic structure of 67B (n = 3) in the solid state was established on the basis of X-ray diffraction data [83AX(C)1240]. Both isomers 67A and... 

EXAFS studies on tris-maltolatoiron(III) in the solid state and in solution, and on [Fe(Ll)3] hydrate, pave the way for detailed investigation of the hydration of complexes of this type in aqueous media.Solubilities and transfer chemical potentials have been determined for tris-maltolatoiron(III) in methanol-water, and for tris-etiwlmaltolatoiron(III) in alcohol-water mixtures and in isobutanol, 1-hexanol, and 1-octanol. Solubility maxima in mixed solvents, indicating synergic solvation, is relevant to trans-membrane transport of complexes of this type. Solubilities of tris-ethylmaltolatoiron(III) and of [Fe(Ll)3] have been determined in aqueous salt solutions (alkali halides NH4 and NR4 bromides). ... 

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