Solubility of ionic compounds

Consider now the bonds to each O2- ion in the perovskite structure. First, there are two bonds to Ti4+ ions that have a character of 4/6 each, which gives a total of 4/3. However, there are four Ca2+ ions on the corners of the face of the cube where an oxide ion resides. These four bonds must add up to a valence of 2/3 so that the total valence of 2 for oxygen is satisfied. If each Ca-O bond amounts to a bond character of 1/6, four such bonds would give the required 2/3 bond to complete the valence of oxygen. From this it follows that each Ca2+ must be surrounded by 12 oxide ions so that 12(1/6) = 2, the valence of calcium. It should be apparent that the concept of electrostatic bond character is a very important tool for understanding crystal structures. 

There are a large number of ternary compounds that are oxides for which the general formula is AB03, where A = Ca, Sr, Ba, and so on, and B = Ti, Zr, Al, Fe, Cr, Hf, Sn, Cl, or I. Many have the perovskite structure, so it is an important structural type. 

An enormous amount of chemistry is carried out in solutions that consist of ionic compounds that have been dissolved in a solvent. In order to separate the ions from the lattice in which they are held, there must be strong forces of interaction between the ions and the molecules of the solvent. The most common solvent for ionic compounds is water, and that solvent will be assumed for the purposes of this discussion. 

When an ionic compound is dissolved in a solvent, the crystal lattice is broken apart. As the ions separate, they become strongly attached to solvent molecules by ion-dipole forces. The number of water molecules surrounding an ion is known as its hydration number. However, the water molecules clustered around an ion constitute a shell that is referred to as the primary solvation sphere. The water molecules are in motion and are also attracted to the bulk solvent that surrounds the cluster. Because of this, solvent molecules move into and out of the solvation sphere, giving a hydration number that does not always have a fixed value. Therefore, it is customary to speak of the average hydration number for an ion. 

From the standpoint of energy, the processes of separating the crystal lattice and solvating the ions can be related by means of a thermochemical cycle of the Born-Haber type. For an ionic compound MX, the cycle can be shown as follows  

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As we noted in Chapter 4, the solubility of ionic compounds in water varies tremendously from one solid to another. The extent to which solution occurs depends on a balance between two forces, both electrical in nature ... 

Just as with replacement reactions, double-replacement reactions may or may not proceed. They need a driving force. The driving force in replacement reactions is reactivity here it is insolubility or covalence. In order for you to be able to predict if a double-replacement reaction will proceed, you must know some solubilities of ionic compounds. A short list of solubilities is given in Table 7-2. 

Hard water is the name given to water supplies that contain significant concentrations of Mg2+ and Ca2+ ions. Check on the solubility of ionic compounds formed with these ions and predict what problems they may cause. 

In this chapter, you will continue your study of acid-base reactions. You will find out how ions in aqueous solution can act as acids or bases. Then, by applying equilibrium concepts to ions in solution, you will be able to predict the solubility of ionic compounds in water and the formation of a precipitate. 

In this section, you learned why solutions of different salts have different pH values. You learned how to analyze the composition of a salt to predict whether the salt forms an acidic, basic, or neutral solution. Finally, you learned how to apply your understanding of the properties of salts to calculate the pH at the equivalence point of a titration. You used the pH to determine a suitable indicator for the titration. In section 9.2, you will further investigate the equilibria of solutions and learn how to predict the solubility of ionic compounds in solution. 

Explain how qualitative analysis depends on the different solubilities of ionic compounds. 

Neutral lanthanide complexes are convenient models for the cationic zirconocene systems and avoid complications due to the presence of counteranions and the limited solubility of ionic compounds. Dynamic NMR studies on yttrium complexes 44-46 has allowed the determination of the alkene binding enthalpy, the activation enthalpy of alkene dissociation, and the relative rates of dissociation and alkyl site exchange (site epimerisation) (Scheme 8.20). Compared to the Zr... 

Typically, buffers in the region of pH 7-9 have been used in MEEKC. At these pH values the buffers generate a high electroosmotic flow (EOF). Extreme values of pH have been used in MEECK specifically to suppress solute ionization. For example, a pH of 1.2 of the buffer has been used to prevent the ionization of acids (30,31). To eliminate the ionization of basic compounds, a buffer at pH 12 has been used. These pH values were used in MEEKC to measure the solubility of ionic compounds (30). High-pH carbonate buffers (31) were applied in place of the standard borate or phosphate buffers. 

Many different types of reversible reactions exist in chemistry, and for each of these an equilibrium constant can be defined. The basic principles of this chapter apply to all equilibrium constants. The different types of equilibrium are generally denoted using an appropriate subscript. The equilibrium constant for general solution reactions is signified as or K, where the c indicates equilibrium concentrations are used in the law of mass action. When reactions involve gases, partial pressures are often used instead of concentrations, and the equilibrium constant is reported as (p indicates that the constant is based on partial pressures). and are used for equilibria associated with acids and bases, respectively. The equilibrium of water with the hydrogen and hydroxide ions is expressed as K. The equilibrium constant used with the solubility of ionic compounds is K p. Several of these different K expres-... 

The roles of hydration enthalpies and entropies in determining the solubilities of ionic compounds... 

Properties that Favour Solubility of Ionic Compounds... 

Solubilities of ionic compounds in water were discussed, and trends explained. The effects of ionic charges and sizes were explained. 

Equilibria govern diverse phenomena from the folding of proteins to the action of acid rain on minerals to the aqueous reactions used in analytical chemistry. This chapter introduces equilibria for the solubility of ionic compounds, complex formation, and acid-base reactions. Chemical equilibrium provides a foundation not only for chemical analysis, but also for other subjects such as biochemistry, geology, and oceanography. 

For a vary thorough discusson of enthalpy, entropy, and the solubility of ionic compounds, see Johnson. D. A. Some Thermodynamic Aspects of Inorganic Chemistry Cambridge University London. 1968. Chafrter 5. 

Many interrelated factors affect the solubility of substances in water. This makes it challenging to predict which ionic substances will dissolve in water. By performing experiments, chemists have developed guidelines to help them make predictions about solubility. In Investigation 9-A, you will perform your own experiments to develop quidelines about the solubility of ionic compounds in water. 

How can you develop guidelines to help you predict the solubility of ionic compounds in water ... 

The solubility of ionic substances in water varies greatly. For example, sodium chloride is quite soluble in water, whereas silver chloride (contains Ag+ and Cl- ions) is only very slightly soluble. The differences in the solubilities of ionic compounds in water typically depend on the relative affinities of the ions for each other (these forces hold the solid together) and the affinities of the ions for water molecules [which cause the solid to disperse (dissolve) in water]. Solubility is a complex issue that we will explore in much more detail in Chapter 17. However, the most important thing to remember at this point is that when an ionic solid does dissolve in water, the ions are dispersed and are assumed to move around independently. 

Other important physical chemical properties are polarity and dielectric constant. Water has a high dielectric constant (78.5 at STP), which would effectively mask ionic charges and lead to high solubility of ionic compounds. The dielectric constant of CO2 at 200 bar and 40°C is approximately 1.5, and CO2 is considered a very non polar solvent. As would be expected, polarity influences solubility for supercritical fluids. Carbon dioxide has a dipole moment of 0.0 Debye, while the value for NH3 is approximately 1.5. Therefore, C02 by itself is poorly suited for dissolving polar compounds. 

The aqueous solubility of ionic compounds is important in synthetic and analytical chemistry (see... 

Table 4.1 Water Solubility of Ionic Compounds Objective 9...

It is more difficult to predict the solubility of polar molecular substances than to predict the solubility of ionic compounds and nonpolar molecular substances. Many polar molecular substances are soluble in both water and hexane. For example, ethanol is miscible with both water and hexane. The following generalization is helpfiil ... 

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