Chapter 14. Acids and Bases
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1 Chapter 14 Acids and Bases
2 Section 14.1 The Nature of Acids and Bases Models of Acids and Bases Arrhenius: Acids produce H + ions in solution, bases produce OH - ions. Brønsted Lowry: Acids are proton (H + ) donors, bases are proton acceptors. HCl + H 2 O Cl - + H 3 O + acid base Copyright Cengage Learning. All rights reserved 2
3 Section 14.1 The Nature of Acids and Bases Brønsted Lowry Reaction 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 3
4 Section 14.1 The Nature of Acids and Bases Acid in Water HA(aq) + H 2 O(l) H 3 O + (aq) + A - (aq) Conjugate base is everything that remains of the acid molecule after a proton is lost. Conjugate acid is formed when the proton is transferred to the base. Copyright Cengage Learning. All rights reserved 4
5 Section 14.1 The Nature of Acids and Bases Acid Ionization Equilibrium 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 5
6 Section 14.2 Acid Strength Strong acid: Ionization equilibrium lies far to the right. Yields a weak conjugate base. Weak acid: Ionization equilibrium lies far to the left. Weaker the acid, stronger its conjugate base. Copyright Cengage Learning. All rights reserved 6
7 Section 14.2 Acid Strength Copyright Cengage Learning. All rights reserved 7
8 Section 14.2 Acid Strength Various Ways to Describe Acid Strength Copyright Cengage Learning. All rights reserved 8
9 Section 14.2 Acid Strength Water as an Acid and a Base Water is amphoteric: Behaves either as an acid or as a base. At 25 C: K w = [H + ][OH ] = No matter what the solution contains, the product of [H + ] and [OH ] must always equal at 25 C. Copyright Cengage Learning. All rights reserved 9
10 Section 14.2 Acid Strength Three Possible Situations [H + ] = [OH ]; neutral solution [H + ] > [OH ]; acidic solution [OH ] > [H + ]; basic solution Copyright Cengage Learning. All rights reserved 10
11 Section 14.2 Acid Strength Self-Ionization of Water 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 11
12 Section 14.2 Acid Strength CONCEPT CHECK! HA(aq) + H 2 O(l) H 3 O + (aq) + A - (aq) acid base conjugate conjugate acid base What is the equilibrium constant expression for an acid acting in water? K = H O A 3 HA Copyright Cengage Learning. All rights reserved 12
13 Section 14.2 Acid Strength CONCEPT CHECK! If the equilibrium lies to the right, the value for K a is. large (or >1) If the equilibrium lies to the left, the value for K a is. small (or <1) Copyright Cengage Learning. All rights reserved 13
14 Section 14.2 Acid Strength CONCEPT CHECK! HA(aq) + H 2 O(l) H 3 O + (aq) + A (aq) If water is a better base than A, do products or reactants dominate at equilibrium? Does this mean HA is a strong or weak acid? Is the value for K a greater or less than 1? Copyright Cengage Learning. All rights reserved 14
15 Section 14.2 Acid Strength CONCEPT CHECK! Consider a 1.0 M solution of HCl. Order the following from strongest to weakest base and explain: H 2 O(l) A (aq) (from weak acid HA) Cl (aq) Copyright Cengage Learning. All rights reserved 15
16 Section 14.2 Acid Strength Let s Think About It How good is Cl (aq) as a base? Is A (aq) a good base? The bases from strongest to weakest are: A, H 2 O, Cl Copyright Cengage Learning. All rights reserved 16
17 Section 14.2 Acid Strength CONCEPT CHECK! Consider a solution of NaA where A is the anion from weak acid HA: A (aq) + H 2 O(l) HA(aq) + OH (aq) base acid conjugate conjugate acid base a) Which way will equilibrium lie? left Copyright Cengage Learning. All rights reserved 17
18 Section 14.2 Acid Strength CONCEPT CHECK! Consider a solution of NaA where A is the anion from weak acid HA: A (aq) + H 2 O(l) HA(aq) + OH (aq) base acid conjugate conjugate acid base b) Is the value for K b greater than or less than 1? less than 1 Copyright Cengage Learning. All rights reserved 18
19 Section 14.2 Acid Strength CONCEPT CHECK! Consider a solution of NaA where A is the anion from weak acid HA: A (aq) + H 2 O(l) HA(aq) + OH (aq) base acid conjugate conjugate acid base c) Does this mean A is a strong or weak base? weak base Copyright Cengage Learning. All rights reserved 19
20 Section 14.2 Acid Strength CONCEPT CHECK! Acetic acid (HC 2 H 3 O 2 ) and HCN are both weak acids. Acetic acid is a stronger acid than HCN. Arrange these bases from weakest to strongest and explain your answer: H 2 O Cl CN C 2 H 3 O 2 Copyright Cengage Learning. All rights reserved 20
21 Section 14.2 Acid Strength Let s Think About It H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH (aq) acid base conjugate conjugate acid base At 25 C, K w = The bases from weakest to strongest are: Cl, H 2 O, C 2 H 3 O 2, CN Copyright Cengage Learning. All rights reserved 21
22 Section 14.2 Acid Strength CONCEPT CHECK! Discuss whether the value of K for the reaction: HCN(aq) + F (aq) CN (aq) + HF(aq) is >1 <1 =1 (K a for HCN is ; K a for HF is ) Explain your answer. Copyright Cengage Learning. All rights reserved 22
23 Section 14.2 Acid Strength CONCEPT CHECK! Calculate the value for K for the reaction: HCN(aq) + F (aq) CN (aq) + HF(aq) (K a for HCN is ; K a for HF is ) K = Copyright Cengage Learning. All rights reserved 23
24 Section 14.3 The ph Scale ph = log[h + ] ph changes by 1 for every power of 10 change in [H + ]. A compact way to represent solution acidity. ph decreases as [H + ] increases. Significant figures: The number of decimal places in the log is equal to the number of significant figures in the original number. Copyright Cengage Learning. All rights reserved 24
25 Section 14.3 The ph Scale ph Range ph = 7; neutral ph > 7; basic Higher the ph, more basic. ph < 7; acidic Lower the ph, more acidic. Copyright Cengage Learning. All rights reserved 25
26 Section 14.3 The ph Scale The ph Scale and ph Values of Some Common Substances Copyright Cengage Learning. All rights reserved 26
27 Section 14.3 The ph Scale EXERCISE! Calculate the ph for each of the following solutions. a) M H + ph = 4.00 b) M OH ph = Copyright Cengage Learning. All rights reserved 27
28 Section 14.3 The ph Scale EXERCISE! The ph of a solution is What is the [H + ] for this solution? [H + ] = M Copyright Cengage Learning. All rights reserved 28
29 Section 14.3 The ph Scale ph and poh Recall: K w = [H + ][OH ] log K w = log[h + ] log[oh ] pk w = ph + poh = ph + poh Copyright Cengage Learning. All rights reserved 29
30 Section 14.3 The ph Scale EXERCISE! Calculate the poh for each of the following solutions. a) M H + poh = b) M OH poh = 1.40 Copyright Cengage Learning. All rights reserved 30
31 Section 14.3 The ph Scale EXERCISE! The ph of a solution is What is the [OH ] for this solution? [OH ] = M Copyright Cengage Learning. All rights reserved 31
32 Section 14.4 Calculating the ph of Strong Acid Solutions Thinking About Acid Base Problems What are the major species in solution? What is the dominant reaction that will take place? Is it an equilibrium reaction or a reaction that will go essentially to completion? React all major species until you are left with an equilibrium reaction. Solve for the ph if needed. Copyright Cengage Learning. All rights reserved 32
33 Section 14.4 Calculating the ph of Strong Acid Solutions CONCEPT CHECK! Consider an aqueous solution of M HCl. What are the major species in solution? H +, Cl, H 2 O What is the ph? ph = 2.70 Copyright Cengage Learning. All rights reserved 33
34 Section 14.4 Calculating the ph of Strong Acid Solutions CONCEPT CHECK! Calculate the ph of a M solution of HCl. ph = 7.00 Copyright Cengage Learning. All rights reserved 34
35 Section 14.4 Calculating the ph of Strong Acid Solutions CONCEPT CHECK! Calculate the ph of a M solution of HNO 3. Copyright Cengage Learning. All rights reserved 35
36 Section 14.4 Calculating the ph of Strong Acid Solutions Let s Think About It When HNO 3 is added to water, a reaction takes place immediately: HNO 3 + H 2 O H 3 O + + NO 3 Copyright Cengage Learning. All rights reserved 36
37 Section 14.4 Calculating the ph of Strong Acid Solutions Let s Think About It Why is this reaction not likely? NO 3 (aq) + H 2 O(l) HNO 3 (aq) + OH (aq) Copyright Cengage Learning. All rights reserved 37
38 Section 14.4 Calculating the ph of Strong Acid Solutions Let s Think About It What reaction controls the ph? H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH (aq) In aqueous solutions, this reaction is always taking place. But is water the major contributor of H + (H 3 O + )? ph = 1.82 Copyright Cengage Learning. All rights reserved 38
39 Section 14.5 Calculating the ph of Weak Acid Solutions Solving Weak Acid Equilibrium Problems 1. List the major species in the solution. 2. Choose the species that can produce H +, and write balanced equations for the reactions producing H Using the values of the equilibrium constants for the reactions you have written, decide which equilibrium will dominate in producing H Write the equilibrium expression for the dominant equilibrium. Copyright Cengage Learning. All rights reserved 39
40 Section 14.5 Calculating the ph of Weak Acid Solutions Solving Weak Acid Equilibrium Problems 5. List the initial concentrations of the species participating in the dominant equilibrium. 6. Define the change needed to achieve equilibrium; that is, define x. 7. Write the equilibrium concentrations in terms of x. 8. Substitute the equilibrium concentrations into the equilibrium expression. Copyright Cengage Learning. All rights reserved 40
41 Section 14.5 Calculating the ph of Weak Acid Solutions Solving Weak Acid Equilibrium Problems 9. Solve for x the easy way, that is, by assuming that [HA] 0 x about equals [HA] Use the 5% rule to verify whether the approximation is valid. 11.Calculate [H + ] and ph. Copyright Cengage Learning. All rights reserved 41
42 Section 14.5 Calculating the ph of Weak Acid Solutions CONCEPT CHECK! Consider a 0.80 M aqueous solution of the weak acid HCN (K a = ). What are the major species in solution? HCN, H 2 O Copyright Cengage Learning. All rights reserved 42
43 Section 14.5 Calculating the ph of Weak Acid Solutions Let s Think About It Why aren t H + or CN major species? Copyright Cengage Learning. All rights reserved 43
44 Section 14.5 Calculating the ph of Weak Acid Solutions Consider This HCN(aq) + H 2 O(l) K a = H 3 O + (aq) + CN (aq) H 2 O(l) + H 2 O(l) K w = H 3 O + (aq) + OH (aq) Which reaction controls the ph? Explain. Copyright Cengage Learning. All rights reserved 44
45 Section 14.5 Calculating the ph of Weak Acid Solutions EXERCISE! Calculate the ph of a 0.50 M aqueous solution of the weak acid HF. (K a = ) Copyright Cengage Learning. All rights reserved 45
46 Section 14.5 Calculating the ph of Weak Acid Solutions Let s Think About It What are the major species in solution? HF, H 2 O Why aren t H + and F major species? Copyright Cengage Learning. All rights reserved 46
47 Section 14.5 Calculating the ph of Weak Acid Solutions Let s Think About It What are the possibilities for the dominant reaction? HF(aq) + H 2 O(l) H 3 O + (aq) + F (aq) K a = H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH (aq) K w = Which reaction controls the ph? Why? Copyright Cengage Learning. All rights reserved 47
48 Section 14.5 Calculating the ph of Weak Acid Solutions Steps Toward Solving for ph HF(aq) + H 2 O H 3 O + (aq) + F (aq) Initial 0.50 M ~ 0 ~ 0 Change x +x +x Equilibrium 0.50 x x x K a = ph = 1.72 Copyright Cengage Learning. All rights reserved 48
49 Section 14.5 Calculating the ph of Weak Acid Solutions Percent Dissociation (Ionization) amount dissociated (mol/l) Percent dissociation = 100% initial concentration (mol/l) For a given weak acid, the percent dissociation increases as the acid becomes more dilute. Copyright Cengage Learning. All rights reserved 49
50 Section 14.5 Calculating the ph of Weak Acid Solutions EXERCISE! A solution of 8.00 M formic acid (HCHO 2 ) is 0.47% ionized in water. Calculate the K a value for formic acid. K a = Copyright Cengage Learning. All rights reserved 50
51 Section 14.5 Calculating the ph of Weak Acid Solutions EXERCISE! Calculate the ph of an 8.00 M solution of formic acid. Use the data from the previous slide to help you solve this problem. ph = 1.42 Copyright Cengage Learning. All rights reserved 51
52 Section 14.5 Calculating the ph of Weak Acid Solutions EXERCISE! The value of K a for a 4.00 M formic acid solution should be: higher than lower than the same as the value of K a of an 8.00 M formic acid solution. Explain. Copyright Cengage Learning. All rights reserved 52
53 Section 14.5 Calculating the ph of Weak Acid Solutions CONCEPT CHECK! The percent ionization of a 4.00 M formic acid solution should be: higher than lower than the same as the percent ionization of an 8.00 M formic acid solution. Explain. Copyright Cengage Learning. All rights reserved 53
54 Section 14.5 Calculating the ph of Weak Acid Solutions CONCEPT CHECK! The ph of a 4.00 M formic acid solution should be: higher than lower than the same as the ph of an 8.00 M formic acid solution. Explain. Copyright Cengage Learning. All rights reserved 54
55 Section 14.5 Calculating the ph of Weak Acid Solutions EXERCISE! Calculate the percent ionization of a 4.00 M formic acid solution in water. % Ionization = 0.67% Copyright Cengage Learning. All rights reserved 55
56 Section 14.5 Calculating the ph of Weak Acid Solutions EXERCISE! Calculate the ph of a 4.00 M solution of formic acid. ph = 1.57 Copyright Cengage Learning. All rights reserved 56
57 Section 14.6 Bases Arrhenius: bases produce OH ions. Brønsted Lowry: bases are proton acceptors. In a basic solution at 25 C, ph > 7. Ionic compounds containing OH - are generally considered strong bases. LiOH, NaOH, KOH, Ca(OH) 2 poh = log[oh ] ph = poh Copyright Cengage Learning. All rights reserved 57
58 Section 14.6 Bases CONCEPT CHECK! Calculate the ph of a M solution of sodium hydroxide. ph = Copyright Cengage Learning. All rights reserved 58
59 Section 14.6 Bases CONCEPT CHECK! Calculate the ph of a M solution of calcium hydroxide. ph = Copyright Cengage Learning. All rights reserved 59
60 Section 14.6 Bases Equilibrium expression for weak bases uses K b. CN (aq) + H 2 O(l) HCN(aq) + OH (aq) K b = HCN OH CN Copyright Cengage Learning. All rights reserved 60
61 Section 14.6 Bases ph calculations for solutions of weak bases are very similar to those for weak acids. K w = [H + ][OH ] = poh = log[oh ] ph = poh Copyright Cengage Learning. All rights reserved 61
62 Section 14.6 Bases CONCEPT CHECK! Calculate the ph of a 2.0 M solution of ammonia (NH 3 ). (K b = ) ph = Copyright Cengage Learning. All rights reserved 62
63 Section 14.7 Polyprotic Acids Acids that can furnish more than one proton. Always dissociates in a stepwise manner, one proton at a time. The conjugate base of the first dissociation equilibrium becomes the acid in the second step. For a typical weak polyprotic acid: K a1 > K a2 > K a3 For a typical polyprotic acid in water, only the first dissociation step is important to ph. Copyright Cengage Learning. All rights reserved 63
64 Section 14.7 Polyprotic Acids EXERCISE! Calculate the ph of a 1.00 M solution of H 3 PO 4. K a1 = K a2 = K a3 = ph = 1.08 Copyright Cengage Learning. All rights reserved 64
65 Section 14.7 Polyprotic Acids CONCEPT CHECK! Calculate the equilibrium concentration of PO 4 3- in a 1.00 M solution of H 3 PO 4. K a1 = K a2 = K a3 = [PO 4 3- ] = M Copyright Cengage Learning. All rights reserved 65
66 Section 14.8 Acid-Base Properties of Salts Salts Ionic compounds. When dissolved in water, break up into its ions (which can behave as acids or bases). Copyright Cengage Learning. All rights reserved 66
67 Section 14.8 Acid-Base Properties of Salts Salts The salt of a strong acid and a strong base gives a neutral solution. KCl, NaNO 3 Copyright Cengage Learning. All rights reserved 67
68 Section 14.8 Acid-Base Properties of Salts Salts A basic solution is formed if the anion of the salt is the conjugate base of a weak acid. NaF, KC 2 H 3 O 2 K w = K a K b Use K b when starting with base. Copyright Cengage Learning. All rights reserved 68
69 Section 14.8 Acid-Base Properties of Salts Salts An acidic solution is formed if the cation of the salt is the conjugate acid of a weak base. NH 4 Cl K w = K a K b Use K a when starting with acid. Copyright Cengage Learning. All rights reserved 69
70 Section 14.8 Acid-Base Properties of Salts Acidic Cation Anion or Basic Example neutral neutral neutral NaCl neutral conjugate acid of weak base conjugate acid of weak base conjugate base of weak acid basic NaF neutral acidic NH 4 Cl conjugate base of weak acid depends on K a & K b values Al 2 (SO 4 ) 3 Copyright Cengage Learning. All rights reserved 70
71 Section 14.8 Acid-Base Properties of Salts Qualitative Prediction of ph of Salt Solutions (from Weak Parents) Copyright Cengage Learning. All rights reserved 71
72 Section 14.8 Acid-Base Properties of Salts EXERCISE! HC 2 H 3 O 2 K a = HCN K a = Calculate the K b values for: C 2 H 3 O 2 and CN K b (C 2 H 3 O 2- ) = K b (CN - ) = Copyright Cengage Learning. All rights reserved
73 Section 14.8 Acid-Base Properties of Salts CONCEPT CHECK! Arrange the following 1.0 M solutions from lowest to highest ph. HBr NaOH NH 4 Cl NaCN NH 3 HCN NaCl HF Justify your answer. HBr, HF, HCN, NH 4 Cl, NaCl, NaCN, NH 3, NaOH Copyright Cengage Learning. All rights reserved 73
74 Section 14.8 Acid-Base Properties of Salts CONCEPT CHECK! Consider a 0.30 M solution of NaF. The K a for HF is What are the major species? Na +, F -, H 2 O Copyright Cengage Learning. All rights reserved 74
75 Section 14.8 Acid-Base Properties of Salts Let s Think About It Why isn t NaF considered a major species? What are the possibilities for the dominant reactions? Copyright Cengage Learning. All rights reserved 75
76 Section 14.8 Acid-Base Properties of Salts Let s Think About It The possibilities for the dominant reactions are: 1. F (aq) + H 2 O(l) HF(aq) + OH (aq) 2. H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH (aq) 3. Na + (aq) + H 2 O(l) NaOH + H + (aq) 4. Na + (aq) + F (aq) NaF Copyright Cengage Learning. All rights reserved 76
77 Section 14.8 Acid-Base Properties of Salts Let s Think About It How do we decide which reaction controls the ph? F (aq) + H 2 O(l) H 2 O(l) + H 2 O(l) HF(aq) + OH (aq) H 3 O + (aq) + OH (aq) Determine the equilibrium constant for each reaction. Copyright Cengage Learning. All rights reserved 77
78 Section 14.8 Acid-Base Properties of Salts EXERCISE! Calculate the ph of a 0.75 M aqueous solution of NaCN. K a for HCN is Copyright Cengage Learning. All rights reserved 78
79 Section 14.8 Acid-Base Properties of Salts Let s Think About It What are the major species in solution? Na +, CN, H 2 O Why isn t NaCN considered a major species? Copyright Cengage Learning. All rights reserved 79
80 Section 14.8 Acid-Base Properties of Salts Let s Think About It What are all possibilities for the dominant reaction? The possibilities for the dominant reaction are: 1. CN (aq) + H 2 O(l) HCN(aq) + OH (aq) 2. H 2 O(l) + H 2 O(l) H 3 O + (aq) + OH (aq) 3. Na + (aq) + H 2 O(l) NaOH + H + (aq) 4. Na + (aq) + CN (aq) NaCN Which of these reactions really occur? Copyright Cengage Learning. All rights reserved 80
81 Section 14.8 Acid-Base Properties of Salts Let s Think About It How do we decide which reaction controls the ph? CN (aq) + H 2 O(l) H 2 O(l) + H 2 O(l) HCN(aq) + OH (aq) H 3 O + (aq) + OH (aq) Copyright Cengage Learning. All rights reserved 81
82 Section 14.8 Acid-Base Properties of Salts Steps Toward Solving for ph CN (aq) + H 2 O HCN(aq) + OH (aq) Initial 0.75 M 0 ~ 0 Change x +x +x Equilibrium 0.75 x x x K b = ph = 11.54
83 Section 14.9 The Effect of Structure on Acid-Base Properties Models of Acids and Bases Two factors for acidity in binary compounds: Bond Polarity (high is good) Bond Strength (low is good) Copyright Cengage Learning. All rights reserved 83
84 Section 14.9 The Effect of Structure on Acid-Base Properties Bond Strengths and Acid Strengths for Hydrogen Halides Copyright Cengage Learning. All rights reserved 84
85 Section 14.9 The Effect of Structure on Acid-Base Properties Oxyacids Contains the group H O X. For a given series the acid strength increases with an increase in the number of oxygen atoms attached to the central atom. The greater the ability of X to draw electrons toward itself, the greater the acidity of the molecule. Copyright Cengage Learning. All rights reserved 85
86 Section 14.9 The Effect of Structure on Acid-Base Properties Several Series of Oxyacids and Their K a Values Copyright Cengage Learning. All rights reserved 86
87 Section 14.9 The Effect of Structure on Acid-Base Properties Comparison of Electronegativity of X and K a Value Copyright Cengage Learning. All rights reserved 87
88 Section Acid-Base Properties of Oxides Oxides Acidic Oxides (Acid Anhydrides): O X bond is strong and covalent. SO 2, NO 2, CO 2 When H O X grouping is dissolved in water, the O X bond will remain intact. It will be the polar and relatively weak H O bond that will tend to break, releasing a proton. Copyright Cengage Learning. All rights reserved 88
89 Section Acid-Base Properties of Oxides Oxides Basic Oxides (Basic Anhydrides): O X bond is ionic. K 2 O, CaO If X has a very low electronegativity, the O X bond will be ionic and subject to being broken in polar water, producing a basic solution. Copyright Cengage Learning. All rights reserved 89
90 Section The Lewis Acid-Base Model Lewis Acids and Bases Lewis acid: electron pair acceptor Lewis base: electron pair donor Al O H H Al O H H 6 3+ Lewis acid Lewis base Copyright Cengage Learning. All rights reserved 90
91 Section The Lewis Acid-Base Model Three Models for Acids and Bases Copyright Cengage Learning. All rights reserved 91
92 Section Strategy for Solving Acid-Base Problems: A Summary When analyzing an acid-base equilibrium problem: Ask this question: What are the major species in the solution and what is their chemical behavior? What major species are present? Does a reaction occur that can be assumed to go to completion? What equilibrium dominates the solution? Let the problem guide you. Be patient. Copyright Cengage Learning. All rights reserved 92
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