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Chemistry FIFTH EDITION by Steven S. Zumdahl University of Illinois Chapter 15 Applications of Aqueous Equilibria Schedule Chapter 15 on Website Copyright©2000 by Houghton Mifflin Company. All rights reserved. 1 Section 15.6 Solubility Equilibria & the Solubility Product The typical ionic solid dissolves in water and Dissociates completely into separated hydrated Anions and cations. CaF2 (s) Ca2+ (aq) + 2 F- (aq) BUT once the ions are in solution, they can collide and reform CaF2 (s). THEREFORE, Equilibrium is reached!!! Copyright©2000 by Houghton Mifflin Company. All rights reserved. 2 CaF2 (s) Ca2+ (aq) + 2 F- (aq) Equilibrium Expression: K = [Ca2+] [F-]2 K = Ksp (Solubility Product) [ ] = moles/L CaF2 (s) not included in K. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 3 Solubility Product •For solids dissolving to form aqueous solutions. •Bi2S3(s) 2Bi3+(aq) + 3S2(aq) •Ksp = solubility product constant •and – Ksp = [Bi3+]2[S2]3 Copyright©2000 by Houghton Mifflin Company. All rights reserved. 4 Ksp Values at 25C for Common Ionic Solids • See Table 15.4 on page 759. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 5 Solubility Product • “Solubility” = s = concentration of Bi2S3 that dissolves, which equals 1/2[Bi3+] and 1/3[S2]. or [Bi3+] = 2s & [S2-] = 3s • Note: Ksp is constant (at a given temperature) • s is variable (especially with a common ion present) – Copyright©2000 by Houghton Mifflin Company. All rights reserved. 6 Important: 1. Experimentally determined solubility of an ionic solid can be used to calculate its Ksp value. 2. Solubility of an ionic solid can be calculated if its Ksp value is known. 3. Relative solubilities can be predicted by comparing Ksp values only for salts that produce the same total # of ions. 4. Solubility of a solid is lowered if the solution already contains ions common to the solid. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 7 The pH of a solution can greatly affect a salt’s solubility. General Rule: If the anion, X-, is an effective base (i.e., HX is a weak acid) Then, the salt, MX, will show increased solubility in an acidic solution. These salts are much more soluble in an acidic solution than in pure water. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 8 Added H+ will react with the base X- forming the conjugate acid. As the base is removed, more of the salt will dissolve to replenish the basic anion, X-. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 9 Let’s Do 81a & b, 85a, 87, 89 a & b, 91, 93, 95 Copyright©2000 by Houghton Mifflin Company. All rights reserved. 10 Section 15.7 Precipitation & Qualitative Analysis So far solids dissolving in solutions Now--Look at formation of solid from solution That is, the REVERSE Process. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 11 Section 15.7 Precipitation & Qualitative Analysis Calculate Q, ion product Like Ksp , but use initial conc. rather than equilibrium conc. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 12 CaF2 (s) Ca2+ (aq) + 2 F- (aq) Q = [Ca2+]o [F-]o2 Q = Ion Product [ ] = moles/L CaF2 (s) not included in Q. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 13 If Q > Ksp , then precipitation occurs. If Q < Ksp , then no precipitation occurs. If precipitation occurs, you can also do calculations to determine equilibrium conc. in solution after precipitation. Let’s do: # 97 & 99 Copyright©2000 by Houghton Mifflin Company. All rights reserved. 14 Selective Precipitation Method to separate a mixture of ions in which reagents are added to precipitate single ions or small groups of ions Example: Solution of Ba2+ and Ag+ ions Add NaCl only AgCl precipitates, Ba2+ still in solution Copyright©2000 by Houghton Mifflin Company. All rights reserved. 15 Qualititative Analysis Scheme See Fig 15.11 & 15.12 on page 771 Read pages 770-772 Sulfide ion is often used to separate metal ions. See page 770. Let’s do: # 101 Copyright©2000 by Houghton Mifflin Company. All rights reserved. 16 Section 15.8 Equilibria Involving Complex Ions • Complex Ion: A charged species consisting of a metal ion surrounded by ligands. • Ligand - a Lewis base - a molecule or ion having a lone electron pair that can be donated to an empty orbital on the metal ion to form a covalent bond. • Common Ligands: H2O, NH3, Cl-, CNCopyright©2000 by Houghton Mifflin Company. All rights reserved. 17 Coordination Number: Number of ligands attached to a metal ion. (Most common are 6 , 4 and 2.) Examples: Co(H2O)62+, CoCl42-, Ag(NH3)2+ Copyright©2000 by Houghton Mifflin Company. All rights reserved. 18 Metal ions can add ligands one at a time in steps. + NH3 Ag(NH3)+ K1 = 2.1 x 103 Ag(NH3)+ + NH3 Ag(NH3)2+ K2 = 8.2 x 103 Ag+ ________________________________________________________________ Ag+ + 2NH3 Ag(NH3)2+ K = K1 x K2 Formation (Stability) Constants: The equilibrium constants characterizing the stepwise addition of ligands to metal ions. Copyright©2000 by Houghton Mifflin Company. All rights reserved. 19 Let’s do Exercises # 103, 107, 109, 111, 115 Copyright©2000 by Houghton Mifflin Company. All rights reserved. 20