The Nature of Acids and Bases
Transcription
The Nature of Acids and Bases
Chapter 15 Acid-Base Equilibria Section 15.1 Solutions of Acids or Bases Containing a Common Ion Alkaline water pH 8-10 Section 13.1 The Equilibrium Condition Section 14.1 The Nature of Acidsto andWatch Bases Videos http://www.bozemanscience.com/ap-chemistry/ Videos to Watch Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 Which indicator is best suited for the weak acid below? The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Section 14.1 The Nature of Acids and Bases Watch this video for an explanation: https://www.youtube.com/watch?v=tvCyrBHJfBk Section 15.1 Solutions of Acids or Bases Containing a Common Ion Common Ion Effect Shift in equilibrium position that occurs because of the addition of an ion already involved in the equilibrium reaction. An application of Le Châtelier’s principle. Copyright © Cengage Learning. All rights reserved 43 Section 15.1 Solutions of Acids or Bases Containing a Common Ion Example HCN(aq) + H2O(l) H3O+(aq) + CN-(aq) Addition of NaCN will shift the equilibrium to the left because of the addition of CN-, which is already involved in the equilibrium reaction. A solution of HCN and NaCN is less acidic than a solution of HCN alone. Section 15.2 Buffered Solutions Key Points about Buffered Solutions Buffered Solution – resists a change in pH. They are weak acids or bases containing a common ion. After addition of strong acid or base, deal with stoichiometry first, then the equilibrium. Copyright © Cengage Learning. All rights reserved 45 Section 15.2 Buffered Solutions Adding an Acid to a Buffer To play movie you must be in Slide Show Mode PC Users: Please wait for content to load, then click to play Mac Users: CLICK HERE Copyright © Cengage Learning. All rights reserved 46 Section 15.2 Buffered Solutions Buffers To play movie you must be in Slide Show Mode PC Users: Please wait for content to load, then click to play Mac Users: CLICK HERE Copyright © Cengage Learning. All rights reserved 47 Section 15.2 Buffered Solutions Solving Problems with Buffered Solutions Copyright © Cengage Learning. All rights reserved 48 Section 15.2 Buffered Solutions Buffering: How Does It Work? Copyright © Cengage Learning. All rights reserved 49 Section 15.2 Buffered Solutions Buffering: How Does It Work? Copyright © Cengage Learning. All rights reserved 50 Section 15.2 Buffered Solutions Henderson–Hasselbalch Equation A pH = pK a + log HA For a particular buffering system (conjugate acid–base pair), all solutions that have the same ratio [A–] / [HA] will have the same pH. Copyright © Cengage Learning. All rights reserved 51 Section 15.2 Buffered Solutions EXERCISE! What is the pH of a buffer solution that is 0.45 M acetic acid (HC2H3O2) and 0.85 M sodium acetate (NaC2H3O2)? The Ka for acetic acid is 1.8 × 10–5. pH = 5.02 Copyright © Cengage Learning. All rights reserved 52 Section 15.2 Buffered Solutions Copyright © Cengage Learning. All rights reserved 53 Section 15.2 Buffered Solutions Buffered Solution Characteristics Buffers contain relatively large concentrations of a weak acid and corresponding conjugate base. Added H+ reacts to completion with the weak base. Added OH- reacts to completion with the weak acid. Copyright © Cengage Learning. All rights reserved 54 Section 15.2 Buffered Solutions Buffered Solution Characteristics The pH in the buffered solution is determined by the ratio of the concentrations of the weak acid and weak base. As long as this ratio remains virtually constant, the pH will remain virtually constant. This will be the case as long as the concentrations of the buffering materials (HA and A– or B and BH+) are large compared with amounts of H+ or OH– added. Copyright © Cengage Learning. All rights reserved 55 Section 15.3 Buffering Capacity The amount of protons or hydroxide ions the buffer can absorb without a significant change in pH. Determined by the magnitudes of [HA] and [A–]. A buffer with large capacity contains large concentrations of the buffering components. Copyright © Cengage Learning. All rights reserved 56 Section 15.3 Buffering Capacity Optimal buffering occurs when [HA] is equal to [A–]. It is for this condition that the ratio [A–] / [HA] is most resistant to change when H+ or OH– is added to the buffered solution. Copyright © Cengage Learning. All rights reserved 57 Section 15.3 Buffering Capacity Choosing a Buffer pKa of the weak acid to be used in the buffer should be as close as possible to the desired pH. Copyright © Cengage Learning. All rights reserved 58 Section 15.4 Titrations and pH Curves Titration Curve Plotting the pH of the solution being analyzed as a function of the amount of titrant added. Equivalence (Stoichiometric) Point – point in the titration when enough titrant has been added to react exactly with the substance in solution being titrated. Copyright © Cengage Learning. All rights reserved 59 Section 15.4 Titrations and pH Curves Neutralization of a Strong Acid with a Strong Base To play movie you must be in Slide Show Mode PC Users: Please wait for content to load, then click to play Mac Users: CLICK HERE Copyright © Cengage Learning. All rights reserved 60 Section 15.4 Titrations and pH Curves The pH Curve for the Titration of 50.0 mL of 0.200 M HNO3 with 0.100 M NaOH Copyright © Cengage Learning. All rights reserved 61 Section 15.4 Titrations and pH Curves The pH Curve for the Titration of 100.0 mL of 0.50 M NaOH with 1.0 M HCI Copyright © Cengage Learning. All rights reserved 62 Section 15.4 Titrations and pH Curves Weak Acid–Strong Base Titration Step 1: Step 2: A stoichiometry problem (reaction is assumed to run to completion) then determine concentration of acid remaining and conjugate base formed. An equilibrium problem (determine position of weak acid equilibrium and calculate pH). Copyright © Cengage Learning. All rights reserved 63 Section 15.4 Titrations and pH Curves CONCEPT CHECK! Consider a solution made by mixing 0.10 mol of HCN (Ka = 6.2 × 10–10) with 0.040 mol NaOH in 1.0 L of aqueous solution. What are the major species immediately upon mixing (that is, before a reaction)? HCN, Na+, OH–, H2O Copyright © Cengage Learning. All rights reserved 64 Section 15.4 Titrations and pH Curves Let’s Think About It… Why isn’t NaOH a major species? Why aren’t H+ and CN– major species? List all possibilities for the dominant reaction. Copyright © Cengage Learning. All rights reserved 65 Section 15.4 Titrations and pH Curves Let’s Think About It… The possibilities for the dominant reaction are: 1. 2. 3. 4. 5. H2O(l) + H2O(l) H3O+(aq) + OH–(aq) HCN(aq) + H2O(l) H3O+(aq) + CN–(aq) HCN(aq) + OH–(aq) CN–(aq) + H2O(l) Na+(aq) + OH–(aq) NaOH Na+(aq) + H2O(l) NaOH + H+(aq) Copyright © Cengage Learning. All rights reserved 66 Section 15.4 Titrations and pH Curves Let’s Think About It… How do we decide which reaction controls the pH? H2O(l) + H2O(l) H3O+(aq) + OH–(aq) HCN(aq) + H2O(l) H3O+(aq) + CN–(aq) HCN(aq) + OH–(aq) CN–(aq) + H2O(l) Section 15.4 Titrations and pH Curves Let’s Think About It… HCN(aq) + OH–(aq) CN–(aq) + H2O(l) What are the major species after this reaction occurs? HCN, CN–, H2O, Na+ Copyright © Cengage Learning. All rights reserved 68 Section 15.4 Titrations and pH Curves Let’s Think About It… Now you can treat this situation as before. List the possibilities for the dominant reaction. Determine which controls the pH. Copyright © Cengage Learning. All rights reserved 69 Section 15.4 Titrations and pH Curves CONCEPT CHECK! Calculate the pH of a solution made by mixing 0.20 mol HC2H3O2 (Ka = 1.8 × 10–5) with 0.030 mol NaOH in 1.0 L of aqueous solution. Copyright © Cengage Learning. All rights reserved 70 Section 15.4 Titrations and pH Curves Let’s Think About It… What are the major species in solution? Na+, OH–, HC2H3O2, H2O Why isn’t NaOH a major species? Why aren’t H+ and C2H3O2– major species? Copyright © Cengage Learning. All rights reserved 71 Section 15.4 Titrations and pH Curves Let’s Think About It… What are the possibilities for the dominant reaction? 1. 2. 3. 4. 5. H2O(l) + H2O(l) H3O+(aq) + OH–(aq) HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2–(aq) HC2H3O2(aq) + OH–(aq) C2H3O2–(aq) + H2O(l) Na+(aq) + OH–(aq) NaOH(aq) Na+(aq) + H2O(l) NaOH + H+(aq) Which of these reactions really occur? Copyright © Cengage Learning. All rights reserved 72 Section 15.4 Titrations and pH Curves Let’s Think About It… Which reaction controls the pH? H2O(l) + H2O(l) H3O+(aq) + OH–(aq) HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2–(aq) HC2H3O2(aq) + OH–(aq) C2H3O2–(aq) + H2O(l) How do you know? Copyright © Cengage Learning. All rights reserved 73 Section 15.4 Titrations and pH Curves Let’s Think About It… HC2H3O2(aq) + OH– Before Change After 0.20 mol 0.030 mol –0.030 mol –0.030 mol 0.17 mol 0 C2H3O2–(aq) + H2O 0 +0.030 mol 0.030 mol K = 1.8 × 109 Copyright © Cengage Learning. All rights reserved 74 Section 15.4 Titrations and pH Curves Steps Toward Solving for pH H3O+ + C2H3O2-(aq) 0.170 M ~0 0.030 M –x +x +x 0.170 – x x 0.030 + x HC2H3O2(aq) + H2O Initial Change Equilibrium Ka = 1.8 × 10–5 pH = 3.99 Copyright © Cengage Learning. All rights reserved 75 Section 15.4 Titrations and pH Curves EXERCISE! Calculate the pH of a 100.0 mL solution of 0.100 M acetic acid (HC2H3O2), which has a Ka value of 1.8 × 10– 5. pH = 2.87 Copyright © Cengage Learning. All rights reserved 76 Section 15.4 Titrations and pH Curves CONCEPT CHECK! Calculate the pH of a solution made by mixing 100.0 mL of a 0.100 M solution of acetic acid (HC2H3O2), which has a Ka value of 1.8 × 10–5, and 50.0 mL of a 0.10 M NaOH solution. pH = 4.74 Copyright © Cengage Learning. All rights reserved 77 Section 15.4 Titrations and pH Curves CONCEPT CHECK! Calculate the pH of a solution at the equivalence point when 100.0 mL of a 0.100 M solution of acetic acid (HC2H3O2), which has a Ka value of 1.8 × 10–5, is titrated with a 0.10 M NaOH solution. pH = 8.72 Copyright © Cengage Learning. All rights reserved 78 Section 15.4 Titrations and pH Curves The pH Curve for the Titration of 50.0 mL of 0.100 M HC2H3O2 with 0.100 M NaOH Copyright © Cengage Learning. All rights reserved 79 Section 15.4 Titrations and pH Curves The pH Curves for the Titrations of 50.0-mL Samples of 0.10 M Acids with Various Ka Values with 0.10 M NaOH Copyright © Cengage Learning. All rights reserved 80 Section 15.4 Titrations and pH Curves The pH Curve for the Titration of 100.0 mL of 0.050 M NH3 with 0.10 M HCl Copyright © Cengage Learning. All rights reserved 81 Section 15.5 Acid-Base Indicators Marks the end point of a titration by changing color. The equivalence point is not necessarily the same as the end point (but they are ideally as close as possible). Copyright © Cengage Learning. All rights reserved 82 Section 15.5 Acid-Base Indicators The Acid and Base Forms of the Indicator Phenolphthalein Copyright © Cengage Learning. All rights reserved 83 Section 15.5 Acid-Base Indicators The Methyl Orange Indicator is Yellow in Basic Solution and Red in Acidic Solution Copyright © Cengage Learning. All rights reserved 84 Section 15.5 Acid-Base Indicators Useful pH Ranges for Several Common Indicators Copyright © Cengage Learning. All rights reserved 85 Section 15.5 Acid-Base Indicators Complex Ion Equilibria Section 15.5 Acid-Base Indicators Videos to Watch http://www.bozemanscience.com/ap-chemistry/ Section 15.5 Acid-Base Indicators Section 16.1 Solubility Equilibria and the Solubility Product Solubility Equilibria Solubility product (Ksp) – equilibrium constant; has only one value for a given solid at a given temperature. Solubility – an equilibrium position. Bi2S3(s) 2Bi3+(aq) + 3S2–(aq) 3+ 2 2 3 K sp = Bi S Copyright © Cengage Learning. All rights reserved 89 Section 16.1 Solubility Equilibria and the Solubility Product Section 16.1 Solubility Equilibria and the Solubility Product Section 16.1 Solubility Equilibria and the Solubility Product Section 16.1 Solubility Equilibria and the Solubility Product Section 16.1 Solubility Equilibria and the Solubility Product Section 16.1 Solubility Equilibria and the Solubility Product Section 16.1 Solubility Equilibria and the Solubility Product CONCEPT CHECK! In comparing several salts at a given temperature, does a higher Ksp value always mean a higher solubility? Explain. If yes, explain and verify. If no, provide a counter-example. No Copyright © Cengage Learning. All rights reserved 96 Section 16.1 Solubility Equilibria and the Solubility Product EXERCISE! Calculate the solubility of silver chloride in water. Ksp = 1.6 × 10–10 1.3×10-5 M Calculate the solubility of silver phosphate in water. Ksp = 1.8 × 10–18 1.6×10-5 M Copyright © Cengage Learning. All rights reserved 97 Section 16.1 Solubility Equilibria and the Solubility Product CONCEPT CHECK! How does the solubility of silver chloride in water compare to that of silver chloride in an acidic solution (made by adding nitric acid to the solution)? Explain. The solubilities are the same. Copyright © Cengage Learning. All rights reserved 98 Section 16.1 Solubility Equilibria and the Solubility Product CONCEPT CHECK! How does the solubility of silver phosphate in water compare to that of silver phosphate in an acidic solution (made by adding nitric acid to the solution)? Explain. The silver phosphate is more soluble in an acidic solution. Copyright © Cengage Learning. All rights reserved 99 Section 16.1 Solubility Equilibria and the Solubility Product CONCEPT CHECK! How does the Ksp of silver phosphate in water compare to that of silver phosphate in an acidic solution (made by adding nitric acid to the solution)? Explain. The Ksp values are the same. Copyright © Cengage Learning. All rights reserved 100 Section 16.1 Solubility Equilibria and the Solubility Product EXERCISE! Calculate the solubility of AgCl in: Ksp = 1.6 × 10–10 a) 100.0 mL of 4.00 x 10-3 M calcium chloride. 2.0×10-8 M b) 100.0 mL of 4.00 x 10-3 M calcium nitrate. 1.3×10-5 M Copyright © Cengage Learning. All rights reserved 101 Section 16.2 Precipitation and Qualitative Analysis Precipitation (Mixing Two Solutions of Ions) Q > Ksp; precipitation occurs and will continue until the concentrations are reduced to the point that they satisfy Ksp. Q < Ksp; no precipitation occurs. Copyright © Cengage Learning. All rights reserved 102 Section 16.2 Precipitation and Qualitative Analysis Selective Precipitation (Mixtures of Metal Ions) Use a reagent whose anion forms a precipitate with only one or a few of the metal ions in the mixture. Example: Solution contains Ba2+ and Ag+ ions. Adding NaCl will form a precipitate with Ag+ (AgCl), while still leaving Ba2+ in solution. Copyright © Cengage Learning. All rights reserved 103 Section 16.2 Precipitation and Qualitative Analysis Separation of Cu2+ and Hg2+ from Ni2+ and Mn2+ using H2S At a low pH, [S2–] is relatively low and only the very insoluble HgS and CuS precipitate. When OH– is added to lower [H+], the value of [S2–] increases, and MnS and NiS precipitate. Copyright © Cengage Learning. All rights reserved 104 Section 16.2 Precipitation and Qualitative Analysis Separation of Cu2+ and Hg2+ from Ni2+ and Mn2+ using H2S Copyright © Cengage Learning. All rights reserved 105 Section 16.2 Precipitation and Qualitative Analysis Separating the Common Cations by Selective Precipitation Copyright © Cengage Learning. All rights reserved 106 Section 16.3 Equilibria Involving Complex Ions Complex Ion Equilibria Charged species consisting of a metal ion surrounded by ligands. Ligand: Lewis base Formation (stability) constant. Equilibrium constant for each step of the formation of a complex ion by the addition of an individual ligand to a metal ion or complex ion in aqueous solution. Copyright © Cengage Learning. All rights reserved 107 Section 16.3 Equilibria Involving Complex Ions Complex Ion Equilibria Be2+(aq) + F–(aq) BeF+(aq) K1 = 7.9 × 104 BeF+(aq) + F–(aq) BeF2(aq) K2 = 5.8 × 103 BeF2(aq) + F–(aq) BeF3– (aq) K3 = 6.1 × 102 BeF3– (aq) + F–(aq) Copyright © Cengage Learning. All rights reserved BeF42– (aq) K4 = 2.7 × 101 108 Section 16.3 Equilibria Involving Complex Ions Complex Ions and Solubility Two strategies for dissolving a water–insoluble ionic solid. If the anion of the solid is a good base, the solubility is greatly increased by acidifying the solution. In cases where the anion is not sufficiently basic, the ionic solid often can be dissolved in a solution containing a ligand that forms stable complex ions with its cation. Copyright © Cengage Learning. All rights reserved 109 Section 16.3 Equilibria Involving Complex Ions CONCEPT CHECK! Calculate the solubility of silver chloride in 10.0 M ammonia given the following information: Ksp (AgCl) = 1.6 × 10–10 Ag+ + NH3 AgNH3+ + NH3 AgNH3+ Ag(NH3)2+ K = 2.1 × 103 K = 8.2 × 103 0.48 M Calculate the concentration of NH3 in the final equilibrium mixture. 9.0 M Copyright © Cengage Learning. All rights reserved 110