Ksp | \ \ S © To deal quantitatively with an equilibrium, you must know the equilibrium constant. equilibrium constants. * Once you find these values for various ionic compounds, you can use them to answer questions about solubility or precipitation. Solubility Equilibria + Many netural processes depend on the precipietion or cssolving oF Ail solu In the next section, we look at the equilibria of slightly soluble, or nearly insoluble, ionic compounds. Their equilibrium constants can be used to ansiver questions regarding solubility and ~procipitation.* When an ionie compound is insoluble or slightly goluble, an equilibrium is established ato wn oe ene ——whin ieee + ‘The equilibrium constant for this typ= of reaction is called the solubility-produet constant, Ky. * For the above reaction, oe Ky = (MXD ‘The Solubility Product Constant + In general, the solubility product constant is the equilibrium constant for Lae solubility equilibrium of a slightly soluble (or neatly insoluble) ionic compound, It equals the product of the equilibrium concentrations of the ions in the compound. For example, lead iodide, Pbl,, is another slightly soluble salt. Its equilibrium is: PbI,(6) ZL PHF (aq) 2K ag) : Kse ~ [evs ese y© When an excess of a slightly soluble ionic compound is mixed with water, an equilibrium is established between the solid and the ions in the saturated solution, For the salt calelum oxalate, CaC,0,, you have the following equilibrium €aC,0,(8) #2 Ca® (aq)+€,0," (aa) he equiliorium constant for this process is called the solubility product constant.* Write the solubility-product expression for the following salts; + a Hg,Cl, +b. Hel, o aHgCh _. + HgCh(s)— He2*(aq) + 2Ci(ag) + Ky = Ug 1ICIP + b.HeCl, + HgCh(s) <2 Hg?"(aq) + 2Cr(ag) © K= (Hg {CrP > Exactly 0.133 mg of AgBr will dissolve in 1.00 L of water, What is the velue of K,, for AgBr? Solubility equilibrium AgBr(s) == Agt(aq) + Br(aq) Solubility-praduct constant expression: Ko = fAg'IB]\ aA Lo" loo V7 OY ae : as _ 7 83x04 M 7 - © 6K) x * ae R Agb(y Not - oct aS Cou et oT Keg ecagpters va = Cov 0" SETS ° Vg? 9:02 ¥10CaCO, contains 0.0061-g of t 25°C. Calculate the K,, “or this salt at 2 We must first convert the solubilly of ¢ oxalate from 0.0061 gilter to moles Lmol CaC; M CaCO, = (0.0061 g CaC,0,/1)* acs0,=( ee e986 CaCO =4,8%10* mol CaC,0,/L =U4e2 Hse M 4% SM C1 Oy” “Cay io p4&e-5 M 48e¢°5MColeviating K,, from the Solubility nt, it is founc that 1.2 x 10 mol of le, Pbl,, dissolves in 1.0 L of water at s the Ky, at this temperature? Note that in his exam, you find that 4.2 « of the solid dissolves to give 1.2 x 10 rd 2 x (1.2 x 10°) mol of | 40, pyr : Pbi,(s) 22s Pb" (aq) +20 (aq) {Sree [Ano Change Equilron +12x 107 2.x 109 1.2107 [2x (12x 109 “Check answer on slida 7 Ksg= eisgece bn ish ye+ An experimenter finds that the solubility of barium fluoride is 4.1 g in [,00 Lof water at 25°C. What is the value of K,, for barium fluoride, BaP,, at th.s temperature? Solubility equilibrium: ars) Ba’(aq) + 2F (aq) Solubilty_product constan: expression: | a tL Sty <(b- 2 43 [A oo ao" ~1%et Ks¢ ( r 4Calculating the Solubility from K,, » ‘The mineral fluotite is calcium fluoride, Cal, Calculate the solubility (in grams per liter) of calcium fluoride in water from the Ky (3.4 x 10) Let xe the molar solubility of CaF | CaF,(s) Hol og (aq) + 2F (aq) | [_ Starting (oJ 0 ge lesa a lesan x es) apokeSolubility and the Common-lon !ffect * In this section we will look at calculating solubilities in the presence of other ions. The importance of the K,, becornes apparent wien you consider the solubility of one salt in the solution of another having the same cation. For example, suppose you wish to know the solubility of calcium oxalate in a solution of calcium chloride, Each salt contributes the same cation (Ca) The elfect is to make calcium oxalate less soluble than it would be in cure water. %6 ence of a common * What effect does the pr ion have on solubility? © Given: MX(9) = MH(ag) + Xaq) * Qualitatively, we can use Le Chatelier’s principle to predict that the reaction will shift in the reverse direction when M* or X° is added, reducing the solubility. + In the next problem, we will explore this, situation quantitatively.A Problem To Consider + What is the molar solubility of calcium oxalate in 0,15 M calcium chloride? The K, oxalate is 2.3 x 10%. Note that before the calcium oxalate dissolves, for calcium there is already 0.15 Mf Ca**in the solution. Cal; 0465) 222Ca" faq) + €,0 Siarting 15 a Change + + Equilibaum ots [x 4 You substitule into the 2quilibrium-constant equation [Ca*11C,0)7"1=K,, (0.15 + x)(x) = 2.3% 10° Now rearrange this equation to give = 23X10? _ 2.310" OSD "O15 We expect x to be negligible compared to 0.15. \ i 1 QO0OGOHO15tx OAS 15x10" Therefore, the molar solubility of calcium oxalate in 0.15 M CaCl, is 1.5 x 10° M, In pure water, the mclarity was 4.8 x 10M, which is over 3000 times greater. Precipitation Calculations + Precipitation is merely another way of looking at solubility equilibrium. Rather than considering how much of a substance will dissolve, we as! ‘Will precipitation occur for a given starting ion concentration? a “