Insoluble ionic compounds

Table 8.3 Water Solubility of Some Common Ionic Compounds Insoluble Soluble in Water in Water ...

The metal-ion complexmg properties of crown ethers are clearly evident m their effects on the solubility and reactivity of ionic compounds m nonpolar media Potassium fluoride (KF) is ionic and practically insoluble m benzene alone but dissolves m it when 18 crown 6 is present This happens because of the electron distribution of 18 crown 6 as shown m Figure 16 2a The electrostatic potential surface consists of essentially two regions an electron rich interior associated with the oxygens and a hydrocarbon like exterior associated with the CH2 groups When KF is added to a solution of 18 crown 6 m benzene potassium ion (K ) interacts with the oxygens of the crown ether to form a Lewis acid Lewis base complex As can be seen m the space filling model of this... 

A precipitation reaction occurs when two or more soluble species combine to form an insoluble product that we call a precipitate. The most common precipitation reaction is a metathesis reaction, in which two soluble ionic compounds exchange parts. When a solution of lead nitrate is added to a solution of potassium chloride, for example, a precipitate of lead chloride forms. We usually write the balanced reaction as a net ionic equation, in which only the precipitate and those ions involved in the reaction are included. Thus, the precipitation of PbCl2 is written as... 

In the absence of die polyether, potassium fluoride is insoluble in benzene and unreactive toward alkyl halides. Similar enhancement of solubility and reactivity of other salts is observed in the presence of crown ethers The solubility and reactivity enhancement result because the ionic compound is dissociated to a tightly complexed cation and a naked anion. Figure 4.13 shows the tight coordination that can be achieved with a typical crown ether. The complexed cation, because it is surrounded by the nonpolar crown ether, has high solubility in the nonpolar media. To maintain electroneutrality, the anion is also transported into the solvent. The cation is shielded from interaction with the anion as a... 

Sometimes when water solutions of two different ionic compounds are mixed, an insoluble solid separates out of solution. The precipitate that forms is itself ionic the cation comes from one solution, the anion from the other. To predict the occurrence of reactions of this type, you must know which ionic substances are insoluble in water. 

Many, but not all, ionic compounds (e.g., NaCl but not CaC03) are soluble in water, a polar solvent In contrast, ionic compounds are insoluble in nonpolar solvents such as benzene (C6H6) or carbon tetrachloride (CCI4). 

Some ionic compounds are soluble, others are not. Consider what happens when we pour a solution of sodium chloride (a strong electrolyte) into a solution of silver nitrate (another strong electrolyte). A solution of sodium chloride contains Na+ cations and Cl anions. Similarly, a solution of silver nitrate, AgNO, contains Ag+ cations and NO, anions. When we mix these two aqueous solutions, a white precipitate, a cloudy, finely divided solid deposit, forms immediately. Analysis shows that the precipitate is silver chloride, AgCl, an insoluble white solid. The... 

Table 1.1 summarizes the solubility patterns of common ionic compounds in water. Notice that all nitrates and all common compounds of the Group 1 metals are soluble so they make useful starting solutions for precipitation reactions. Any spectator ions can be used, provided that they remain in solution and do not otherwise react. For example, Table 1.1 shows that mercury(I) iodide, Hg2I2, is insoluble. It is formed as a precipitate when solutions containing Hg22+ ions and I ions are mixed ... 

Use the information in Table 1.1 to classify each of the following ionic compounds as soluble or insoluble in water ... 

A1P04, used in cements and as an antacid (c) iron(II) hydroxide, Fe(OH)2 (d) Select two soluble ionic compounds that, when mixed in solution, form each of the insoluble compounds in parts (a), (b), and (c). Identify the spectator ions. 

Because the fluoride ion is so small, the lattice enthalpies of its ionic compounds tend to be high (see Table 6.6). As a result, fluorides are less soluble than other halides. This difference in solubility is one of the reasons why the oceans are salty with chlorides rather than fluorides, even though fluorine is more abundant than chlorine in the Earth s crust. Chlorides are more readily dissolved and washed out to sea. There are some exceptions to this trend in solubilities, including AgF, which is soluble the other silver halides are insoluble. The exception arises because the covalent character of the silver halides increases from AgCl to Agl as the anion becomes larger and more polarizable. Silver fluoride, which contains the small and almost unpolarizable fluoride ion, is freely soluble in water because it is predominantly ionic. 

In the first reaction, two ionic compounds in water are mixed. The AgCl formed by the swapping of anions is insoluble, causing the reaction to proceed. The solid AgCl formed from solution is an example of a precipitate. In the second reaction, a covalent compound, HzO, is formed from its ions in solution, H+ and OH, causing the reaction to proceed. In the third reaction, a solid reacts with the acid in solution to produce two covalent compounds. 

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. 

When a substance made up of ions is dissolved in water, the dissolved ions behave independently. That is, they undergo their own characteristic reactions regardless of what other ions may be present. For example, barium ions in solution, Ba2, always react with sulfate ions in solution, S04 , to form an insoluble ionic compound, BaS04(s), no matter what other ions are present in the barium solution. If a solution of barium chloride, BaCK, and a solution of sodium sulfate, Na S04, arc mixed, a white solid, barium sulfate, is produced. The solid can be separated from the solution by filtration, and the resulting solution contains sodium chloride, just as it would if solid NaCl were added to water. In other words, when the two solutions are mixed, the following reaction occurs ... 

These problems involve mixing two solutions. Each solution is a water solution of an ionic compound. From the mixture of the two solutions, at least one insoluble precipitate will form. The other ions present are probably soluble and are called spectator ions they are not included in the net ionic equation. You must know your solubility rules to do these problems. 

According to the electrostatic model the solvation is due to electrostatic interaction between the charged ions and the dipolar solvent molecules. Thus the solvating and ionizing properties of a solvent are considered as being due primarily to the dipole moment of the solvent molecules. Thus, ionic compounds such as sodium chloride are insoluble in non-polar solvents such as carbon tetrachloride. Actually, rather than the dipole moment the field action of the dipoles should be considered. This approach might explain why acetonitrile (p = 3.2) is poor in its ionizing properties compared to water (p = 1.84). However, no numerical values are available for this quantity. 

One way to identify cations in solution is hy selectively precipitating them out of solution. As you know, cations may form soluble or insoluble ionic compounds, depending on the anions that are present. For example, copper(II) chloride, CuCl2 is soluble in water. Copper(II) sulfide, CuS, is insoluble in an acidic solution. Knowing about the relative solubility of cations when combined with various anions helps chemists identify them. 

While many ionic compounds are soluble in water, many are not. The term solubility is somewhat subjective. There are actually degrees of solubility. A substance is considered soluble if 0.1 moles of it can dissolve in 1 liter of water. If less than 0.001 mole of the substance dissolves in water, a substance is considered insoluble. Partially soluble substances fall between these two extremes. Table 11.3 summarizes the solubility of some major groups of ionic compounds in water. 

The insolubility of ionic compounds in nonpolar solvents is a similar phenomenon. The solvation energies are limited to those from ion-induced dipole forces, which are considerably weaker than ion-dipole forces and not large enough to overcome the very strong ion-ion forces of the lattice. 

In many cases the enthalpy of solution for ionic compounds in water is positive. In these cases we find the solution cooling as the solute dissolves. The mixing tendency of entropy is forcing the solution to do work to pull the ions apart, and since in an adiabatic process such work can be done only at the expense of internal energy, the solution cools. If the enthulpy of solution is sufficiently positive, favorable entrapy may not be able to overcome it and the compound will be insoluble. Thus some ionic compounds, such as KCI04, are essentially insoluble in water at room temperature. 

The properties of lithium metal are well known, but the properties of its alkyls have until recently received much less attention. The lowest member of the series, methyllithium, is a non-volatile microcrystalline powder insoluble in hydrocarbons. Ethyllithium is a colourless crystalline compound melting at 95°. n-Propyl and n-butyllithium are almost colourless fairly viscous non-volatile oils soluble in hydrocarbons and ethers. These properties are to be compared with those of the corresponding sodium alkyls which are all colourless, non-volatile crystalline solids, insoluble in hydrocarbons. The difference in properties is usually attributed to differences in the type of bond between lithium and sodium alkyls, the former being considered covalent and the latter ionic compounds. Thus Coates (17) distinguishes between two types of compounds ... 

Commonly referred to as salting out, adding a salt (e.g., NaCl) to the sample changes the ionic environment and occupies water. Water-soluble compounds concentrate in the available water and equilibrate into the headspace at higher concentrations. Other compounds (insoluble in water) may be unaffected or may decrease in volatility. Changing the pH has a similar effect. Additionally, adjusting the ionic state of compounds will increase or decrease volatility, since ionized compounds do not volatilize. 

Use the information in Table 1.1 to classify the following ionic compounds as soluble or insoluble in water (a) lead(II) nitrate, Pb(N03)2 (b) lead(II) chloride, PbCl2 (c) silver nitrate, AgNOa (d) sodium sulfate, Na2S04. 

J.12 Identify the following as a strong acid, a weak add, a base, a soluble ionic compound, or an insoluble ionic compound in water (a) HN03 (b) KOH ... 

Precipitation reactions are processes in which soluble reactants yield an insoluble solid product that drops out of the solution. Formation of this stable product removes material from the aqueous solution and provides the driving force for the reaction. Most precipitations take place when the anions and cations of two ionic compounds change partners. For example, an aqueous solution of lead(II) nitrate reacts with an aqueous solution of potassium iodide to yield an aqueous solution of potassium nitrate plus an insoluble yellow precipitate of lead iodide ... 

Use the Ionic Compounds activity (eChapter 4.4) to determine the formula of each of the insoluble iron(III) salts. Then, using your knowledge of the solubility rules, write a molecular, ionic, and net ionic equation for an aqueous reaction that would produce each salt. 

No ionic compound is 100% V / insoluble. In order for an equilibrium to exist, all ionic compounds must dissolve to some extent. 

The solubility of an ionic compound increases dramatically if the solution contains a Lewis base that can form a coordinate covalent bond (Section 7.5) to the metal cation. Silver chloride, for example, is insoluble in water and in acid, but it dissolves in an excess of aqueous ammonia, forming the complex ion Ag(NH3)2 + (Figure 16.13). A complex ion is an ion that contains a metal cation bonded to one or more small molecules or ions, such as NH3, CN-, or OH-. In accord with Le Chatelier s principle, ammonia shifts the solubility equilibrium to the right by tying up the Ag+ ion in the form of the complex ion ... 

When solutions of soluble ionic compounds are mixed, an insoluble compound will precipitate if the ion product (IP) for the insoluble compound exceeds its fCsp. The IP is defined in the same way as /equilibrium concentrations. Certain metal cations can be separated by selective precipitation of metal sulfides. Selective precipitation is important in qualitative analysis, a procedure for identifying the ions present in an unknown solution. 

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