1. Chapter 15 Acid-Base Equilibria AP*

2. AP Learning Objectives  LO 1.20 The student can design, and/or interpret data from an experiment that uses titration to determine the concentration of an analyte in a solution. (Sec 15.4-15.5)  LO 3.3 The student is able to use stoichiometric calculations to predict the results of performing a reaction in the laboratory and/or to analyze deviations from the expected results. (Sec 15.4)  LO 6.1 The student is able to, given a set of experimental observations regarding physical, chemical, biological, or environmental processes that are reversible, construct an explanation that connects the observations to the reversibility of the underlying chemical reactions or processes. (Sec 15.1-15.5)  LO 6.12 The student can reason about the distinction between strong and weak acid solutions with similar values of pH, including the percent ionization of the acids, the concentrations needed to achieve the same pH, and the amount of base needed to reach the equivalence point in a titration. (Sec 15.4)

3. AP Learning Objectives  LO 6.13 The student can interpret titration data for monoprotic or polyprotic acids involving titration of a weak or strong acid by a strong base (or a weak or strong base by a strong acid) to determine the concentration of the titrant and the pK a for a weak acid, or the pK b for a weak base. (Sec 15.4)  LO 6.15 The student can identify a given solution as containing a mixture of strong acids and/or bases and calculate or estimate the pH (and concentrations of all chemical species) in the resulting solution. (Sec 15.4)  LO 6.16 The student can identify a given solution as being the solution of a monoprotic weak acid or base (including salts in which one ion is a weak acid or base), calculate the pH and concentration of all species in the solution, and/or infer the relative strengths of the weak acids or bases from given equilibrium concentrations. (Sec 15.1-15.2)  LO 6.17 The student can, given an arbitrary mixture of weak and strong acids and bases (including polyprotic systems), determine which species will react strongly with one another (i.e. with K >1) and what species will be present in large concentration at equilibrium. (Sec 15.1-15.2)

4. AP Learning Objectives  LO 6.18 The student can design a buffer solution with a target pH and buffer capacity by selecting an appropriate conjugate acid-base pair and estimating the concentrations needed to achieve the desired capacity. (Sec 15.2)  LO 6.19 The student can relate the predominant form of a chemical species involving a labile proton (i.e. protonated/deprotonated form of a weak acid) to the pH of a solution and the pK a associated with the labile proton. (Sec 15.2)  LO 6.20 The student can identify a solution as being a buffer solution and explain the buffer mechanism in terms of the reactions that would occur on addition of acid or base. (Sec 15.2-15.3)

5. Section 15.1 Solutions of Acids or Bases Containing a Common Ion AP Learning Objectives, Margin Notes and References  Learning Objectives  LO 6.1 The student is able to, given a set of experimental observations regarding physical, chemical, biological, or environmental processes that are reversible, construct an explanation that connects the observations to the reversibility of the underlying chemical reactions or processes.  LO 6.16 The student can identify a given solution as being the solution of a monoprotic weak acid or base (including salts in which one ion is a weak acid or base), calculate the pH and concentration of all species in the solution, and/or infer the relative strengths of the weak acids or bases from given equilibrium concentrations.  LO 6.17 The student can, given an arbitrary mixture of weak and strong acids and bases (including polyprotic systems), determine which species will react strongly with one another (i.e. with K >1) and what species will be present in large concentration at equilibrium.

6. Section 15.1 Solutions of Acids or Bases Containing a Common Ion Copyright © Cengage Learning. All rights reserved 6 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.

7. Section 15.1 Solutions of Acids or Bases Containing a Common Ion Example HCN(aq) + H 2 O(l) H 3 O + (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.

8. Section 15.2 Buffered Solutions AP Learning Objectives, Margin Notes and References  Learning Objectives  LO 6.1 The student is able to, given a set of experimental observations regarding physical, chemical, biological, or environmental processes that are reversible, construct an explanation that connects the observations to the reversibility of the underlying chemical reactions or processes.  LO 6.16 The student can identify a given solution as being the solution of a monoprotic weak acid or base (including salts in which one ion is a weak acid or base), calculate the pH and concentration of all species in the solution, and/or infer the relative strengths of the weak acids or bases from given equilibrium concentrations.  LO 6.17 The student can, given an arbitrary mixture of weak and strong acids and bases (including polyprotic systems), determine which species will react strongly with one another (i.e. with K >1) and what species will be present in large concentration at equilibrium.  LO 6.18 The student can design a buffer solution with a target pH and buffer capacity by selecting an appropriate conjugate acid-base pair and estimating the concentrations needed to achieve the desired capacity.  LO 6.19 The student can relate the predominant form of a chemical species involving a labile proton (i.e. protonated/deprotonated form of a weak acid) to the pH of a solution and the pK a associated with the labile proton.  LO 6.20 The student can identify a solution as being a buffer solution and explain the buffer mechanism in terms of the reactions that would occur on addition of acid or base.  Additional AP References  LO 6.18 (see APEC 15, “Buffers and Buffered Systems”)

9. 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 9

10. Section 15.2 Buffered Solutions Adding an Acid to a Buffer Copyright © Cengage Learning. All rights reserved 10 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 HERECLICK HERE

11. Section 15.2 Buffered Solutions Buffers Copyright © Cengage Learning. All rights reserved 11 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 HERECLICK HERE

12. Section 15.2 Buffered Solutions Solving Problems with Buffered Solutions Copyright © Cengage Learning. All rights reserved 12

13. Section 15.2 Buffered Solutions Buffering: How Does It Work? Copyright © Cengage Learning. All rights reserved 13

14. Section 15.2 Buffered Solutions Buffering: How Does It Work? Copyright © Cengage Learning. All rights reserved 14

15. Section 15.2 Buffered Solutions Henderson–Hasselbalch Equation  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 15

16. Section 15.2 Buffered Solutions What is the pH of a buffer solution that is 0.45 M acetic acid (HC 2 H 3 O 2 ) and 0.85 M sodium acetate (NaC 2 H 3 O 2 )? The K a for acetic acid is 1.8 × 10 –5. pH = 5.02 Copyright © Cengage Learning. All rights reserved 16 EXERCISE!

17. Section 15.2 Buffered Solutions Copyright © Cengage Learning. All rights reserved 17

18. 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 18

19. 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 19

20. Section 15.3 Buffering Capacity AP Learning Objectives, Margin Notes and References  Learning Objectives  LO 6.1 The student is able to, given a set of experimental observations regarding physical, chemical, biological, or environmental processes that are reversible, construct an explanation that connects the observations to the reversibility of the underlying chemical reactions or processes.  LO 6.20 The student can identify a solution as being a buffer solution and explain the buffer mechanism in terms of the reactions that would occur on addition of acid or base.  Additional AP References  LO 6.20 (see APEC 16, “Acids, Bases and Buffers”)

21. 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 21

22. 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 22

23. Section 15.3 Buffering Capacity Choosing a Buffer  pK a 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 23

24. Section 15.4 Titrations and pH Curves AP Learning Objectives, Margin Notes and References  Learning Objectives  LO 1.20 The student can design, and/or interpret data from an experiment that uses titration to determine the concentration of an analyte in a solution.  LO 3.3 The student is able to use stoichiometric calculations to predict the results of performing a reaction in the laboratory and/or to analyze deviations from the expected results.  LO 6.1 The student is able to, given a set of experimental observations regarding physical, chemical, biological, or environmental processes that are reversible, construct an explanation that connects the observations to the reversibility of the underlying chemical reactions or processes.  LO 6.12 The student can reason about the distinction between strong and weak acid solutions with similar values of pH, including the percent ionization of the acids, the concentrations needed to achieve the same pH, and the amount of base needed to reach the equivalence point in a titration.  LO 6.13 The student can interpret titration data for monoprotic or polyprotic acids involving titration of a weak or strong acid by a strong base (or a weak or strong base by a strong acid) to determine the concentration of the titrant and the pK a for a weak acid, or the pK b for a weak base.  LO 6.15 The student can identify a given solution as containing a mixture of strong acids and/or bases and calculate or estimate the pH (and concentrations of all chemical species) in the resulting solution.

25. Section 15.4 Titrations and pH Curves AP Learning Objectives, Margin Notes and References  Additional AP References  LO 1.20 (see APEC 4, “Analysis of Vinegar”)  LO 6.13 (see APEC 14, “Titration Curves”)  LO 6.13 (see Appendix 7.10, “Polyprotic Acid Titrations”)

26. 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 26

27. Section 15.4 Titrations and pH Curves Neutralization of a Strong Acid with a Strong Base Copyright © Cengage Learning. All rights reserved 27 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 HERECLICK HERE

28. Section 15.4 Titrations and pH Curves The pH Curve for the Titration of 50.0 mL of 0.200 M HNO 3 with 0.100 M NaOH Copyright © Cengage Learning. All rights reserved 28

29. 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 29

30. Section 15.4 Titrations and pH Curves Weak Acid–Strong Base Titration Step 1:A stoichiometry problem (reaction is assumed to run to completion) then determine concentration of acid remaining and conjugate base formed. Step 2: An equilibrium problem (determine position of weak acid equilibrium and calculate pH). Copyright © Cengage Learning. All rights reserved 30

31. Section 15.4 Titrations and pH Curves Consider a solution made by mixing 0.10 mol of HCN (K a = 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 –, H 2 O Copyright © Cengage Learning. All rights reserved 31 CONCEPT CHECK!

32. 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 32

33. Section 15.4 Titrations and pH Curves Let’s Think About It… The possibilities for the dominant reaction are: 1.H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH – (aq) 2.HCN(aq) + H 2 O(l) H 3 O + (aq) + CN – (aq) 3.HCN(aq) + OH – (aq) CN – (aq) + H 2 O(l) 4.Na + (aq) + OH – (aq) NaOH 5.Na + (aq) + H 2 O(l) NaOH + H + (aq) Copyright © Cengage Learning. All rights reserved 33

34. Section 15.4 Titrations and pH Curves Let’s Think About It…  How do we decide which reaction controls the pH? H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH – (aq) HCN(aq) + H 2 O(l) H 3 O + (aq) + CN – (aq) HCN(aq) + OH – (aq) CN – (aq) + H 2 O(l)

35. Section 15.4 Titrations and pH Curves Let’s Think About It… HCN(aq) + OH – (aq) CN – (aq) + H 2 O(l)  What are the major species after this reaction occurs? HCN, CN –, H 2 O, Na + Copyright © Cengage Learning. All rights reserved 35

36. 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 36

37. Section 15.4 Titrations and pH Curves Calculate the pH of a solution made by mixing 0.20 mol HC 2 H 3 O 2 (K a = 1.8 × 10 –5 ) with 0.030 mol NaOH in 1.0 L of aqueous solution. Copyright © Cengage Learning. All rights reserved 37 CONCEPT CHECK!

38. Section 15.4 Titrations and pH Curves Let’s Think About It…  What are the major species in solution? Na +, OH –, HC 2 H 3 O 2, H 2 O  Why isn’t NaOH a major species?  Why aren’t H + and C 2 H 3 O 2 – major species? Copyright © Cengage Learning. All rights reserved 38

39. Section 15.4 Titrations and pH Curves Let’s Think About It…  What are the possibilities for the dominant reaction? 1.H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH – (aq) 2.HC 2 H 3 O 2 (aq) + H 2 O(l) H 3 O + (aq) + C 2 H 3 O 2 – (aq) 3.HC 2 H 3 O 2 (aq) + OH – (aq) C 2 H 3 O 2 – (aq) + H 2 O(l) 4.Na + (aq) + OH – (aq) NaOH(aq) 5.Na + (aq) + H 2 O(l) NaOH + H + (aq)  Which of these reactions really occur? Copyright © Cengage Learning. All rights reserved 39

40. Section 15.4 Titrations and pH Curves Let’s Think About It…  Which reaction controls the pH? H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH – (aq) HC 2 H 3 O 2 (aq) + H 2 O(l) H 3 O + (aq) + C 2 H 3 O 2 – (aq) HC 2 H 3 O 2 (aq) + OH – (aq) C 2 H 3 O 2 – (aq) + H 2 O(l)  How do you know? Copyright © Cengage Learning. All rights reserved 40

41. Section 15.4 Titrations and pH Curves Let’s Think About It… K = 1.8 × 10 9 Copyright © Cengage Learning. All rights reserved 41 HC 2 H 3 O 2 (aq) +OH – C 2 H 3 O 2 – (aq)+ H 2 O Before0.20 mol 0.030 mol0 Change–0.030 mol +0.030 mol After0.17 mol 0 0.030 mol

42. Section 15.4 Titrations and pH Curves Steps Toward Solving for pH K a = 1.8 × 10 –5 pH = 3.99 Copyright © Cengage Learning. All rights reserved 42 HC 2 H 3 O 2 (aq) +H2OH2OH3O+H3O+ + C 2 H 3 O 2 - (aq) Initial 0.170 M~00.030 M Change –x+x Equilibrium 0.170 – xx0.030 + x

43. Section 15.4 Titrations and pH Curves Calculate the pH of a 100.0 mL solution of 0.100 M acetic acid (HC 2 H 3 O 2 ), which has a K a value of 1.8 × 10 –5. pH = 2.87 Copyright © Cengage Learning. All rights reserved 43 EXERCISE!

44. Section 15.4 Titrations and pH Curves Calculate the pH of a solution made by mixing 100.0 mL of a 0.100 M solution of acetic acid (HC 2 H 3 O 2 ), which has a K a 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 44 CONCEPT CHECK!

45. Section 15.4 Titrations and pH Curves Calculate the pH of a solution at the equivalence point when 100.0 mL of a 0.100 M solution of acetic acid (HC 2 H 3 O 2 ), which has a K a value of 1.8 × 10 –5, is titrated with a 0.10 M NaOH solution. pH = 8.72 Copyright © Cengage Learning. All rights reserved 45 CONCEPT CHECK!

46. Section 15.4 Titrations and pH Curves The pH Curve for the Titration of 50.0 mL of 0.100 M HC 2 H 3 O 2 with 0.100 M NaOH Copyright © Cengage Learning. All rights reserved 46

47. 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 K a Values with 0.10 M NaOH Copyright © Cengage Learning. All rights reserved 47

48. Section 15.4 Titrations and pH Curves The pH Curve for the Titration of 100.0 mL of 0.050 M NH 3 with 0.10 M HCl Copyright © Cengage Learning. All rights reserved 48

49. Section 15.5 Acid-Base Indicators AP Learning Objectives, Margin Notes and References  Learning Objectives  LO 1.20 The student can design, and/or interpret data from an experiment that uses titration to determine the concentration of an analyte in a solution.  LO 6.1 The student is able to, given a set of experimental observations regarding physical, chemical, biological, or environmental processes that are reversible, construct an explanation that connects the observations to the reversibility of the underlying chemical reactions or processes.  Additional AP References  LO 1.20 (see APEC 4, “Analysis of Vinegar”)

50. 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 50

51. Section 15.5 Acid-Base Indicators The Acid and Base Forms of the Indicator Phenolphthalein Copyright © Cengage Learning. All rights reserved 51

52. 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 52

53. Section 15.5 Acid-Base Indicators Useful pH Ranges for Several Common Indicators Copyright © Cengage Learning. All rights reserved 53