Solubility equilibria solutions

What is the effect on the solubility of AgCl if HNO3 is added to the equilibrium solution defined by reaction 6.29 ... 

A third method, or phenomenon, capable of generating a pseudo reaction order is exemplified by a first-order solution reaction of a substance in the presence of its solid phase. Then if the dissolution rate of the solid is greater than the reaction rate of the dissolved solute, the solute concentration is maintained constant by the solubility equilibrium and the first-order reaction becomes a pseudo-zero-order reaction. 

Common ion effect The tube at the left contains a saturated solution of silver acetate (AgC2H302). Originally the tube at the right also contained a saturated solution of silver acetate. With the addition of a solution of silver nitrate (AgNOs), the solubility equilibrium of the silver acetate is shifted by the common ion Ag+ and additional silver acetate precipitates. 

If a soluble thiocyanate salt is added to an equilibrium solution containing both Ft+3(aq) and... 

Expression (2) applies to a solubility equilibrium, provided we write the chemical reaction to show the important molecular species present. In Section 10-1 we considered the solubility of iodine in alcohol. Since iodine dissolves to give a solution containing molecules of iodine, the concentration of iodine itself fixed the solubility. The situation is quite different for substances that dissolve to form ions. When silver chloride dissolves in water, no molecules of silver chloride, AgCl, seem to be present. Instead, silver ions, Ag+, and chloride ions, Cl-, are found in the solution. The concentrations of these species, Ag+ and Cl-, are the ones which fix the equilibrium solubility. The counterpart of equation (7) will be... 

The complexation of Pu(IV) with carbonate ions is investigated by solubility measurements of 238Pu02 in neutral to alkaline solutions containing sodium carbonate and bicarbonate. The total concentration of carbonate ions and pH are varied at the constant ionic strength (I = 1.0), in which the initial pH values are adjusted by altering the ratio of carbonate to bicarbonate ions. The oxidation state of dissolved species in equilibrium solutions are determined by absorption spectrophotometry and differential pulse polarography. The most stable oxidation state of Pu in carbonate solutions is found to be Pu(IV), which is present as hydroxocarbonate or carbonate species. The formation constants of these complexes are calculated on the basis of solubility data which are determined to be a function of two variable parameters the carbonate concentration and pH. The hydrolysis reactions of Pu(IV) in the present experimental system assessed by using the literature data are taken into account for calculation of the carbonate complexation. 

The solubilities of 238Pu02(c) as a function of the pH of equilibrium solutions. Up to pH = 10 the solubilities after 4 and 12 months are almost identical, vi/hile at pH > 10 the values after 12 months differ from those after 4 months which are not in equilibrium. The values after 12 months and 9 months (not plotted here) are found to be identical. 

The equilibrium constant for the solubility equilibrium between an ionic solid and its dissolved ions is called the solubility product, Ksp, of the solute. For example, the solubility product for bismuth sulfide, Bi2S3, is defined as... 

When a precipitate has been formed during the qualitative analysis of the ions present in a solution, it may be necessary to dissolve the precipitate again to identify the cation or anion. One strategy is to remove one of the ions from the solubility equilibrium so that the precipitate will continue to dissolve in a fruitless chase for equilibrium. Suppose, for example, that a solid hydroxide such as iron(IIl) hydroxide is in equilibrium with its ions in solution ... 

If the concentration of a solute is lower than its solubility, additional solute can dissolve, but once the concentration of solute reaches the solubility of that substance, no further net changes occur. Individual solute molecules still enter the solution, but the solubility process is balanced by precipitation, as Figure 12-6 illustrates. A saturated solution in contact with excess solute is in a state of dynamic equilibrium. For eveiy molecule or ion that enters the solution, another returns to the solid state. We represent d Tiamic equilibria by writing the equations using double arrows, showing that both processes occur simultaneously ... 

A molecular view of the solubility equilibrium for a solution of sodium chloride in water. At equilibrium, ions dissolve from the crystal surface at the same rate they are captured, so the concentration of ions in the solution remains constant. 

When equal volumes of 0.100 M solutions of sodium bromide and silver nitrate are mixed, a white solid precipitates from the solution. Identify the precipitate, write the net ionic reaction for the solubility equilibrium, and identify any spectator ions. 

The problem asks for the g/L solubility of PbCl2 in pure H2 O and in 0.55 M NaCl. The same solubility equilibrium applies to each solution. 

By convention, [HA(s)] = [B(s)] = 1. Eqs. (6.1) represent the precipitation equilibria of the uncharged species, and are characterized by the intrinsic solubility equilibrium constant, Sq. The zero subscript denotes the zero charge of the precipitating species. In a saturated solution, the effective (total) solubility S, at a particular pH is defined as the sum of the concentrations of all the compound species dissolved in the aqueous solution ... 

Figure 10.19 Equilibrium solubility of solutes versus temperature.

An ion pair is a close association of a cation and an anion in solution, whereas the ion product is the value obtained when the initial concentrations for the dissolved ions involved in the solubility equilibrium are inserted into the equilibrium constant expression. 

If a slightly soluble salt solution is at equilibrium and we add a solution containing one of the ions involved in the equilibrium, the solubility of the slightly soluble salt decreases. For example, consider the PbS04 equilibrium ... 

The structural constraints used in the first case study namely, Eqn s 27,28 and 29 are used again. The melting point, boiling point and flash point, are used as constraints for both solvent and anti-solvent. Since the solvent needs to have high solubility for solute and the anti-solvent needs to have low solubility for the solute limits of 17 <8 < 19 and 5 > 30 (Eqn s. 33 and 37) are placed on the solubility parameters of solvent and anti-solvents respectively. Eqn.38 gives the necessary condition for phase stability (Bernard et al., 1967), which needs to be satisfied for the solvent-anti solvent pairs to be miscible with each other. Eqn. 39 gives the solid-liquid equilibrium constraint. 

The solubility equilibrium, subject to natural processes in the subsurface matrix, was examined in Chapter 2. The process of contaminant dissolution is affected by the molecular properties of the compound, the composition of the aqueous solution, and the ambient temperature. Here, we focus our discussion on pollutant behavior. 

Using specific metal combinations, electrodeposited alloys can be made to exhibit hardening as a result of heat treatment subsequent to deposition. This, it should be noted, causes solid precipitation. When alloys such as Cu-Ag, Cu-Pb, and Cu-Ni are coelectrodeposited within the limits of diffusion currents, equilibrium solutions or supersaturated solid solutions are in evidence, as observed by x-rays. The actual type of deposit can, for instance, be determined by the work value of nucleus formation under the overpotential conditions of the more electronegative metal. When the metals are codeposited at low polarization values, formation of solid solutions or of supersaturated solid solutions results. This is so even when the metals are not mutually soluble in the solid state according to the phase diagram. Codeposition at high polarization values, on the other hand, results, as a rule, in two-phase alloys even with systems capable of forming a continuous series of solid solutions. 

STRATEGY As usual, we begin by writing the chemical equation for the solubility equilibrium and the expression for Ksp. The molar solubility is the molarity of formula units in the saturated solution. Because each formula unit produces a known number of cations and anions in solution, we can express the molarities of the cations and anions in terms of s. Then we express Ksp in terms of s and solve for s. Assume complete dissociation. 

The formation of a complex can also remove an ion and disturb the solubility equilibrium until more solid dissolves. We first met complexes in Section 2.13, where we saw that they were species formed by the reaction of a Lewis acid and a Lewis base. In this section, we consider complexes in which the Lewis acid is a metal cation, such as Ag+. An example is the formation of Ag(NH3)2+ when an aqueous solution of the Lewis base ammonia is added to a solution of silver bromide ... 

Ksp, limits the concentrations in solution so that the actual redox potential is not the value calculated, which represents the values when [Ag+] = 1 M and tn = 1 M. If we use the concentrations established by the solubility equilibrium and the Nernst equation, we can calculate the actual redox potential ... 

Let s consider the solubility equilibrium in a saturated solution of calcium fluoride in contact with an excess of solid calcium fluoride. Like most sparingly soluble ionic solutes, calcium fluoride is a strong electrolyte in water and exists in the aqueous phase as dissociated hydrated ions, Ca2+(aq) and F (aq). At equilibrium, the ion concentrations remain constant because the rate at which solid CaF2 dissolves to give Ca2+(aq) and F aq) exactly equals the rate at which the ions crystallize to form solid CaF2 ... 

FIGURE 16.12 The solubility of CaC03 at 25°C increases as the solution becomes more acidic because the CO32- ions combine with protons, thus driving the solubility equilibrium to the right. Note that the solubility is plotted on a logarithmic scale. 

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 ... 

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