Solubility and hydration

Also as a result of the historical development of chemistry from analysis, the solubility of a compound, and especially the solubility in water, is still an important characteristic. 

While the solubility of organic compounds, the inert gases and such are dealt with in Chapter V, let us here discuss the solubility of the typical ionic lattices. 

The fact that many compounds are dissociated into ions in aqueous solution is incorrectly put forward as sufficient proof that these substances must also be constructed from ions in the solid state. It is just as incorrect, however, to conclude from non-solubility that there is a bonding other than ionogenic. 

That a purely energetic argument is quite inadequate appears immediately from the fact that when most salts dissolve heat is absorbed, while with only a few, but certainly not exceptionally readily soluble compounds, such as Na2S04 (anhydrous), CaS04 etc., heat is set free. 

Cases are also known in which the heat effect is greatly variable, and even changes sign, on change of the concentration (CaCl2 2aq, LiCl etc.). 

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A hydrophilic colloid is the second example—water placed on/in plasdone (PVP). PVP is both soluble and hydrates in water. On drying, PVP forms a hydrated film with 15-20% water present in the film. 

The ionic-potential concept is useful to describe why certain cations are soluble and hydrated, why other cations form insoluble oxides and hydroxides, and why still others are found only in soluble oxyanions or oxycations. Explain with examples. 

The solubility and hydration number of alkali feed, diffusion coefficient of reacted ions and interaction of ion pair affect the reactive crystallization. As a result of investigation of a number of relationships between these properties and crystallization characteristics, the key property of alkali feeds may be considered as the following. 

The heavy metal chlorates are all very soluble and hydrated salts except for monovalent mercury and thallium salts. The organo-metallic base mercarbid of K. A. Hofmann, which is explosive by itself, forms a chlorate that explodes violently when shaken, even in aqueous suspension. 

Van Oss and Good [148] have compared solubilities and interfacial tensions for a series of alcohols and their corresponding hydrocarbons to determine the free energy of hydration of the hydroxyl group they find -14 kJ/mol per —OH group. 

Although the data for the silver halides suggest that silver(I) fluoride is likely to be more soluble than the other silver halides (which is in fact the case), the hydration enthalpies for the sodium halides almost exactly balance the lattice energies. What then is the driving force which makes these salts soluble, and which indeed must be responsible for the solution process where this is endothermic We have seen on p. 66 the relationship AG = — TAS and... 

The chlorides, bromides, nitrates, bromates, and perchlorate salts ate soluble in water and, when the aqueous solutions evaporate, precipitate as hydrated crystalline salts. The acetates, iodates, and iodides ate somewhat less soluble. The sulfates ate sparingly soluble and ate unique in that they have a negative solubitity trend with increasing temperature. The oxides, sulfides, fluorides, carbonates, oxalates, and phosphates ate insoluble in water. The oxalate, which is important in the recovery of lanthanides from solutions, can be calcined directly to the oxide. This procedure is used both in analytical and industrial apptications. 

The carbonates, sulfates, nitrates, and haUdes of lead (except the yeUow iodide) are colodess. Bivalent lead forms a soluble nitrate, chlorate, and acetate a slightly soluble chloride and an insoluble sulfate, carbonate, chromate, phosphate, molybdate, and sulfide. Highly crystalline basic lead salts of both anhydrous and hydrated types are readily formed. Tetrabasic lead sulfate [52732-72-6] 4PbO PbSO, and the hydrated tribasic salt [12397-06-7] ... 

Eatty amines are insoluble in water, but soluble in organic solvents to varying degrees (26—29). Water, however, is soluble in the amines, and hydrates are formed. SolubiHty in organic solvents is dependent on solvent polarity and temperature. The solubiHties of primary amine acetates and... 

Zinc chloride melts at 275°C, bods at 720°C, and is stable in the vapor phase up to 900°C. It is very hygroscopic, extremely water-soluble, and soluble in organic Hquids such as alcohols, esters, ketones, ethers, amides, and nitrides. Hydrates with 1, 1.5, 2.5, 3, and 4 molecules of water have been identified and great care must be exercised to avoid hydration of the anhydrous form. Aqueous solutions of zinc chloride are acidic (pH = 1.0 for 6 M) and, when partially neutralized, can form slightly soluble basic chlorides, eg, ZnCl2 4Zn(OH)2 [11073-22-6] and Zn(OH)Cl [14031-59-5]. Many other basic chlorides have been reported (58). 

The dichromate(VI) salts may be obtained by the addition of acid to the chromate(VI) salts. However, they are better prepared by adding one-half the acid equivalent of a metal hydrate, oxide, or carbonate to an aqueous solution of CrO, then removing the water and/or CO2. Most dichromates(VI) are water-soluble, and the salts contain water(s) of hydration. However, the normal salts of K, Cs, and Rb are anhydrous. Dichromate(VI) compounds of the colorless cations are generally orange-red. The geometry of Ci2 is described as two tetrahedral CrO linked by the shared odd oxygen (72). 

Water-soluble pAM neutral polymer interacts with ions of the solution through the complex formation between amide groups and hydrated ions. 

Rhodium halides occur mainly in the +3 state. In some cases where a soluble and insoluble form have been reported, the former may be a hydrate. 

The solubilities of the ionic halides are determined by a variety of factors, especially the lattice enthalpy and enthalpy of hydration. There is a delicate balance between the two factors, with the lattice enthalpy usually being the determining one. Lattice enthalpies decrease from chloride to iodide, so water molecules can more readily separate the ions in the latter. Less ionic halides, such as the silver halides, generally have a much lower solubility, and the trend in solubility is the reverse of the more ionic halides. For the less ionic halides, the covalent character of the bond allows the ion pairs to persist in water. The ions are not easily hydrated, making them less soluble. The polarizability of the halide ions and the covalency of their bonding increases down the group. 

Water as the solvent is essential for the acid-base setting reaction to occur. Indeed, as was shown in Chapter 2, our very understanding of the terms acid and base at least as established by the Bronsted-Lowry definition, requires that water be the medium of reaction. Water is needed so that the acids may dissociate, in principle to yield protons, thereby enabling the property of acidity to be manifested. The polarity of water enables the various metal ions to enter the liquid phase and thus react. The solubility and extent of hydration of the various species change as the reaction proceeds, and these changes contribute to the setting of the cement. 

The solubility of most metals is much higher when they exist as organometallic complexes.4445 Naturally occurring chemicals that can partially complex with metal compounds and increase the solubility of the metal include aliphatic acids, aromatic acids, alcohols, aldehydes, ketones, amines, aromatic hydrocarbons, esters, ethers, and phenols. Several complexation processes, including chelation and hydration, can occur in the deep-well environment. 

CO3 species was formed and the X-ray structure solved. It is thought that the carbonate species forms on reaction with water, which was problematic in the selected strategy, as water was produced in the formation of the dialkyl carbonates. Other problems included compound solubility and the stability of the monoalkyl carbonate complex. Van Eldik and co-workers also carried out a detailed kinetic study of the hydration of carbon dioxide and the dehydration of bicarbonate both in the presence and absence of the zinc complex of 1,5,9-triazacyclododecane (12[ane]N3). The zinc hydroxo form is shown to catalyze the hydration reaction and only the aquo complex catalyzes the dehydration of bicarbonate. Kinetic data including second order rate constants were discussed in reference to other model systems and the enzyme carbonic anhy-drase.459 The zinc complex of the tetraamine 1,4,7,10-tetraazacyclododecane (cyclen) was also studied as a catalyst for these reactions in aqueous solution and comparison of activity suggests formation of a bidentate bicarbonate intermediate inhibits the catalytic activity. Van Eldik concludes that a unidentate bicarbonate intermediate is most likely to the active species in the enzyme carbonic anhydrase.460... 

This chapter describes some of the properties of solids that affect transport across phases and membranes, with an emphasis on biological membranes. Four aspects are addressed. They include a comparison of crystalline and amorphous forms of the drug, transitions between phases, polymorphism, and hydration. With respect to transport, the major effect of each of these properties is on the apparent solubility, which then affects dissolution and consequently transport. There is often an opposite effect on the stability of the material. Generally, highly crystalline substances are more stable but have lower free energy, solubility, and dissolution characteristics than less crystalline substances. In some situations, this lower solubility and consequent dissolution rate will result in reduced bioavailability. 

The extent of hydration or solvation of a molecule also has a profound effect on the transport of the substance. The apparent solubility of the drug in both aqueous and nonaqueous media may be influenced by the absence or presence of moisture. Diffusion of drugs in polymeric systems may also be influenced by the hydration of the polymers and hydration of the membrane through which transport is occurring for example, skin hydration may enhance the diffusion of drug molecules significantly. 

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