1. Chapter 15 Acids and Bases

2. Copyright © Cengage Learning. All rights reserved.15 | 2 Acid–Base Concepts 1.Arrhenius Concept of Acids and Bases 2.Brønsted–Lowry Concept of Acids and Bases 3.Lewis Concept of Acids and Bases Acid and Base Strengths 4.Relative Strengths of Acids and Bases 5.Molecular Structure and Acid Strength Contents and Concepts

3. Copyright © Cengage Learning. All rights reserved.15 | 3 Self-Ionization of Water and pH 6.Self-Ionization of Water 7.Solutions of a Strong Acid or Base 8.The pH of a Solution

4. Copyright © Cengage Learning. All rights reserved.15 | 4 Learning Objectives Acid Base Concepts Arrhenius Concept of Acids and Base a.Define acid and base according to the Arrhenius concept. Brønsted–Lowry Concept of Acids and Bases a.Define acid and base according to the Brønsted–Lowry concept. b.Define the term conjugate acid–base pair. c.Identify acid and base species. d.Define amphiprotic species.

5. Copyright © Cengage Learning. All rights reserved.15 | 5 3. Lewis Concept of Acids and Bases a.Define Lewis acid and Lewis base. b.Identify Lewis acid and Lewis base species. Acid and Base Strengths 4. Relative Strengths of Acids and Bases a.Understand the relationship between the strength of an acid and that of its conjugate base. b.Decide whether reactants or products are favored in an acid–base reaction.

6. Copyright © Cengage Learning. All rights reserved.15 | 6 5. Molecular Structure and Acid Strength a.Note the two factors that determine relative acid strengths. b.Understand the periodic trends in the strengths of the binary acids HX. c.Understand the rules for determining the relative strengths of oxoacids. d.Understand the relative acid strengths of a polyprotic acid and its anions.

7. Copyright © Cengage Learning. All rights reserved.15 | 7 Self-Ionization of Water and pH 6. Self-Ionization of Water a.Define self-ionization (or autoionization). b.Define the ion-product constant for water. 7. Solutions of a Strong Acid or Base a.Calculate the concentrations of H 3 O + and OH - in solutions of a strong acid or base.

8. Copyright © Cengage Learning. All rights reserved.15 | 8 8. The pH of a Solution a.Define pH. b.Calculate the pH from the hydronium-ion concentration. c.Calculate the hydronium-ion concentration from the pH. d.Describe the determination of pH by a pH meter and by acid–base indicators.

9. Copyright © Cengage Learning. All rights reserved.15 | 9

10. Copyright © Cengage Learning. All rights reserved.15 | 10 When gaseous hydrogen chloride meets gaseous ammonia, a smoke composed of ammonium chloride is formed. HCl(g) + NH 3 (g)  NH 4 Cl(s) This is an acid–base reaction.

11. Copyright © Cengage Learning. All rights reserved.15 | 11 We will examine three ways to explain acid–base behavior: Arrhenius Concept Brønsted–Lowry Concept Lewis Concept H + and OH − H + = proton donor acceptor donor acceptor electron pair Note: H + in water is H 3 O + acidbase

12. Copyright © Cengage Learning. All rights reserved.15 | 12 Arrhenius Concept of Acids and Bases An Arrhenius acid is a substance that, when dissolved in water, increases the concentration of hydronium ion, H 3 O + (aq). An Arrhenius base is a substance that, when dissolved in water, increases the concentration of hydroxide ion, OH - (aq).

13. Copyright © Cengage Learning. All rights reserved.15 | 13 The Arrhenius concept limits bases to compounds that contain a hydroxide ion. The Brønsted–Lowry concept expands the compounds that can be considered acids and bases.

14. Copyright © Cengage Learning. All rights reserved.15 | 14 Brønsted–Lowry Concept of Acids and Bases An acid–base reaction is considered a proton (H + ) transfer reaction. H+H+ H+H+ H+H+ H+H+

15. Copyright © Cengage Learning. All rights reserved.15 | 15 A Brønsted–Lowry acid is the species donating a proton in a proton-transfer reaction; it is a proton donor. A Brønsted–Lowry base is the species accepting a proton in a proton-transfer reaction; it is a proton acceptor.

16. Copyright © Cengage Learning. All rights reserved.15 | 16 Substances in the acid–base reaction that differ by the gain or loss of a proton, H +, are called a conjugate acid–base pair. The acid is called the conjugate acid; the base is called a conjugate base. AcidBase Conjugate acid Conjugate base

17. ? What is the conjugate acid of H 2 O? What is the conjugate base of H 2 O? The conjugate acid of H 2 O has gained a proton. It is H 3 O +. The conjugate base of H 2 O has lost a proton. It is OH -.

18. Copyright © Cengage Learning. All rights reserved.15 | 18 Label each species as an acid or base. Identify the conjugate acid-base pairs. a.HCO 3 − (aq) + HF(aq) H 2 CO 3 (aq) + F − (aq) b.HCO 3 − (aq) + OH − (aq) CO 3 2− (aq) + H 2 O(l) BaseAcid Conjugate base Conjugate acid AcidBase Conjugate acid Conjugate base

19. Copyright © Cengage Learning. All rights reserved.15 | 19 Species that can act as both an acid and a base are called amphiprotic or amphoteric species. Identify any amphiprotic species in the previous problem. HCO 3 − was a base in the first reaction and an acid in the second reaction. It is amphiprotic.

20. Copyright © Cengage Learning. All rights reserved.15 | 20 Lewis Concept of Acids and Bases A Lewis acid is a species that can form a covalent bond by accepting an electron pair from another species. A Lewis base is a species that can form a covalent bond by donating an electron pair to another species.

21. Copyright © Cengage Learning. All rights reserved.15 | 21

22. Copyright © Cengage Learning. All rights reserved.15 | 22 Relative Strengths of Acids and Bases The stronger an acid, the weaker its conjugate base. The weaker an acid, the stronger its conjugate base.

23. Copyright © Cengage Learning. All rights reserved.15 | 23

24. ? Formic acid, HCHO 2, is a stronger acid than acetic acid, HC 2 H 3 O 2. Which is the stronger base: formate ion, CHO 2 −, or acetate ion, C 2 H 3 O 2 − ? Because formic acid is stronger than acetic acid, formate ion (which is the conjugate base of formic acid) will be a weaker base than acetate ion (which is the conjugate base of acetic acid). The acetate ion is a stronger base than the formate ion.

25. Copyright © Cengage Learning. All rights reserved.15 | 25 Molecular Structure and Acid Strength The strength of an acid depends on how easily the proton, H +, is lost or removed. The more polarized the bond between H and the atom to which it is bonded, the more easily the H + is lost or donated. We will look now at factors that affect how easily the hydrogen can be lost and, therefore, acid strength.

26. Copyright © Cengage Learning. All rights reserved.15 | 26 For a binary acid, as the size of X in HX increases, going down a group, acid strength increases.

27. Copyright © Cengage Learning. All rights reserved.15 | 27 For a binary acid, going across a period, as the electronegativity increases, acid strength increases.

28. ? Which is a stronger acid: HF or HCl? Which is a stronger acid: H 2 O or H 2 S? Which is a stronger acid: HCl or H 2 S? HF and HCl These are binary acids from the same group, so we compare the size of F and Cl. Because Cl is larger, HCl is the stronger acid.

29. Copyright © Cengage Learning. All rights reserved.15 | 29 H 2 O and H 2 S These are binary acids from the same group, so we compare the size of O and S. Because S is larger, H 2 S is the stronger acid. HCl and H 2 S These are binary acids from the same period, but different groups, so we compare the electronegativity of Cl and S. Because Cl is more electronegative, HCl is the stronger acid.

30. Copyright © Cengage Learning. All rights reserved.15 | 30 For oxoacids, several factors are relevant: the number and bonding of oxygens, the central element, and the charge on the species. For a series of oxoacids, (OH) m YO n, acid strength increases as n increases. (OH)Cl n = 0 (OH)ClO n = 1 ( OH)ClO 2 n = 2 ( OH)ClO 3 n = 3 WeakestStrongest

31. Copyright © Cengage Learning. All rights reserved.15 | 31 For a series of oxoacids differing only in the central atom Y, the acid strength increases with the electronegativity of Y. StrongerWeaker

32. Copyright © Cengage Learning. All rights reserved.15 | 32 The acid strength of a polyprotic acid and its anions decreases with increasing negative charge. H 2 CO 3 is a stronger acid than HCO 3 −. H 2 SO 4 is a stronger acid than HSO 4 −. H 3 PO 4 is a stronger acid than H 2 PO 4 −. H 2 PO 4 - is a stronger acid than HPO 4 2−.

33. Copyright © Cengage Learning. All rights reserved.15 | 33 A reaction will always go in the direction from stronger acid to weaker acid, and from stronger base to weaker base.

34. ? Decide which species are favored at the completion of the following reaction: HCN(aq) + HSO 3 − (aq)  CN − (aq) + H 2 SO 3 (aq) We first identify the acid on each side of the reaction: HCN and H 2 SO 3. Next, we compare their acid strength: H 2 SO 3 is stronger. This reaction will go from right to left (  ), and the reactants are favored.

35. Copyright © Cengage Learning. All rights reserved.15 | 35 Self-Ionization of Water H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH - (aq) BaseAcid Conjugate base Conjugate acid

36. Copyright © Cengage Learning. All rights reserved.15 | 36 H 2 O(l) + H 2 O(l)  H 3 O + (aq) + OH − (aq) We call the equilibrium constant the ion-product constant, K w. K w = [H 3 O + ][OH − ] At 25°C, K w = 1.0 × 10 −14 As temperature increases, the value of K w increases.

37. Copyright © Cengage Learning. All rights reserved.15 | 37 Solutions of a Strong Acid or Strong Base The concentration of hydronium or hydroxide in a solution of strong acid or base is related to the stoichiometry of the acid or base.

38. Copyright © Cengage Learning. All rights reserved.15 | 38 Calculate the hydronium and hydroxide ion concentration at 25°C in a.0.10 M HCl b.1.4 × 10 −4 M Mg(OH) 2 a.When HCl ionizes, it gives H + and Cl −. So [H + ] = [Cl − ] = [HCl] = 0.10 M. b.When Mg(OH) 2 ionizes, it gives Mg 2+ and 2 OH −. So [OH − ] = 2[Mg 2+ ] = 2[Mg(OH) 2 ] = 2.8 × 10 −4 M.

39. Copyright © Cengage Learning. All rights reserved.15 | 39 Solutions can be characterized as Acidic:[H 3 O + ] > 1.0 × 10 −7 M Neutral:[H 3 O + ] = 1.0 × 10 −7 M Basic:[H 3 O + ] < 1.0 × 10 −7 M

40. Copyright © Cengage Learning. All rights reserved.15 | 40 A has 5 H 3 O + and 5 OH -. It is neutral. B has 7 H 3 O + and 3 OH -. It is acidic. C has 3 H 3 O + and 7 OH -. It is basic. Listed from most acidic to most basic: B, A, C. Concept Check 15.3 Rank the following solutions from most acidic to most basic (water molecules have been omitted for clarity).

41. Copyright © Cengage Learning. All rights reserved.15 | 41 The pH of a Solution pH = –log[H 3 O + ] For a log, only the decimal part of the number has significant figures. The whole number part, called the characteristic, is not significant.

42. ? Calculate the pH of typical adult blood, which has a hydronium ion concentration of 4.0 × 10 −8 M. [H 3 O + ] = 4.0 × 10 −8 M pH = –log [H 3 O + ] pH = – log (4.0 × 10 −8 ) = – (– 7.40) pH = 7.40 Note:The two significant figures are the two decimal places.

43. Copyright © Cengage Learning. All rights reserved.15 | 43 pOH = –log[OH − ] pH + pOH = 14.00 (at 25°C)

44. Copyright © Cengage Learning. All rights reserved.15 | 44 [H 3 O + ] = 10 −pH [OH − ] = 10 −pOH

45. Copyright © Cengage Learning. All rights reserved.15 | 45 The pH of natural rain in 5.60. What is its hydronium ion concentration? pH = 5.60 [H 3 O + ] = 10 −pH = 10 −5.60 [H 3 O + ] = 2.5 × 10 -6 M Because the pH has two decimal places, the concentration can have only two significant figures.

46. Copyright © Cengage Learning. All rights reserved.15 | 46 The next slide summarizes the conversions involving H 3 O +, OH −, pH, and pOH. Note that you can only go around the edges of the square; it takes two steps to go from one corner to the opposite corner.

47. Copyright © Cengage Learning. All rights reserved.15 | 47 [H 3 O + ][OH − ] pHpOH