AP Chemistry Mr. Markic Chapter 15 - Acids and Bases Acids Have a sour taste. Vinegar owes its taste to acetic acid. Citrus fruits contain citric acid. React with certain metals to produce hydrogen gas. React with carbonates and bicarbonates to produce carbon dioxide gas. Bases Have a bitter taste. Feel slippery. Many soaps contain bases. A Brønsted acid is a proton donor A Brønsted base is a proton acceptor NH3(g) + H2O(l) NH4+ OH- + Sample Exercise Identify the conjugate acid-base pairs in the reaction between ammonia and hydrofluoric acid in aqueous solution NH3(aq) + HF(aq) NH4+ (aq) + F-(aq) CN- + H2O HCN + OH- Review of Concepts Which of the following does not constitute a conjugate acid-base pair? (a) HNO2 - NO1− 2 (b) H2CO3 - CO2− 3 (c) CH3NH3+1 - CH3NH2 Acid-Base Properties of Water H2O (l) H+ (aq) + OH- (aq) autoionization of water H O + [ O H H H + H ] + H O - H H H2O O + H2O H3O+ + OH- The Ion Product of Water H2O (l) H+ (aq) + OH- (aq) Kc = [H+ ][OH− ] [H2 O] [H2O] = constant Kc[H2O] = Kw = [H+][OH-] Page 1 of 12 AP Chemistry The ion-product constant (Kw) is the product of the molar concentrations of H+ and OH- ions at a particular temperature. At 250C Kw = [H+][OH-] = 1.0 x 10-14 [H+] = [OH-] [H+] > [OH-] [H+] < [OH-] Mr. Markic Solution Is neutral acidic basic Sample Exercise The concentration of OH- ions in a certain household ammonia cleaning solution is 0.0025 M. Calculate the concentration of H+ ions. What is the concentration of OH- ions in a HCl solution whose hydrogen ion concentration is 1.3 M? pH – A Measure of Acidity Solution Is neutral acidic basic + - [H ] = [OH ] [H+] > [OH-] [H+] < [OH-] pH = -log [H+] At 250C [H+] = 1.0 x 10-7 [H+] > 1.0 x 10-7 [H+] < 1.0 x 10-7 pH = 7 pH < 7 pH > 7 pH [H+] Other important relationships pOH = -log [OH-] [H+][OH-] = Kw = 1.0 x 10-14 -log [H+] – log [OH-] = 14.00 pH + pOH = 14.00 Sample Exercise The concentration of H+ ions in a bottle of table wine was 3.2 x 10-4 M right after the cork was removed. Only half of the wine was consumed. The other half, after it had been standing open to the air for a month, was found to have a hydrogen ion concentration equal to 1.0 x 10-3 M. Calculate the pH of the wine on these two occasions. Nitric acid (HNO3) is used for the production of fertilizer, dyes, drugs, and explosives. Calculate the pH of a HNO3 solution having a hydrogen ion concentration of 0.76 M Page 2 of 12 AP Chemistry Mr. Markic The pH of rainwater collected in a certain region of the northeastern United States on a particular day was 4.82. Calculate the H+ ion concentration of the rainwater. The pH of a certain orange juice is 3.33. Calculate the H+ ion. In a NaOH solution [OH-] is 2.9 x 10-4 M. Calculate the pH of the solution. The OH- ion concentration of a blood sample is 2.5 x 10-7 M. What is the pH of the blood? Strong Electrolyte – 100% dissociation H2 O NaCl (s) → Na+ (aq) + Cl- (aq) Weak Electrolyte – not completely dissociated CH3COOH CH3COO- (aq) + H+ (aq) Strong Acids are strong electrolytes HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq) HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq) HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4- (aq) H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq) Weak Acids are weak electrolytes HF (aq) + H2O (l) H3O+ (aq) + F- (aq) HNO2 (aq) + H2O (l) H3O+ (aq) + NO2- (aq) HSO4- (aq) + H2O (l) H3O+ (aq) + SO42- (aq) H2O (l) + H2O (l) H3O+ (aq) + OH- (aq) Strong Bases are strong electrolytes Weak Bases are weak electrolytes H2 O + NaOH (s) → H2 O KOH (s) → Na (aq) + OH (aq) K+ (aq) + OH- (aq) H2 O Ba(OH)2 (s) → - F- (aq) + H2O (l) OH- (aq) + HF (aq) NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq) Ba2+ (aq) + 2OH- (aq) Conjugate acid-base pairs: • The conjugate base of a strong acid has no measurable strength. • H3O+ is the strongest acid that can exist in aqueous solution. • The OH- ion is the strongest base that can exist in aqueous solution. Page 3 of 12 AP Chemistry Strong Acid (HCl) Mr. Markic Weak Acid (HF) Sample Exercise Calculate the pH of a (a) 1.0 x 10-3 M HCl solution (b) 0.020 M Ba(OH)2 solution What is the pH of a 1.8 x 10-2 M Ba(OH)2 solution? Predict the direction of the following reaction in aqueous solution: HNO2(aq) + CN-(aq) HCN(aq) + NO2- (aq) Predict whether the equilibrium constant for the following reaction is greater than or smaller than 1: CH3COOH(aq) + HCOO-(aq) CH3COO-(aq) + HCOOH(aq) Review of Concepts (a) List in order of decreasing concentration of all the ionic and molecular species in the following acid solutions: (i) HNO3 (ii) HF (b) List in order of decreasing concentration of all the ionic and molecular species in the following base solutions: (i) NH3 (ii) KOH Page 4 of 12 AP Chemistry Weak Acids (HA) and Acid Ionization Constants Mr. Markic [H+ ][A− ] HA (aq) + H2O (l) H3O+ (aq) + A- (aq) Ka = = HA (aq) H+ (aq) + A- (aq) Ka is the acid ionization constant [HA] Ka weak acid strength Solving weak acid ionization problems: 1. Identify the major species that can affect the pH. • In most cases, you can ignore the autoionization of water. • Ignore [OH-] because it is determined by [H+]. 2. Use ICE to express the equilibrium concentrations in terms of single unknown x. 3. Write Ka in terms of equilibrium concentrations. Solve for x by the approximation method. If approximation is not valid, solve for x exactly. 4. Calculate concentrations of all species and/or pH of the solution. Sample Exercise A 0.0560-g quantity of acetic acid is dissolved in enough water to make 50.0 mL of solution. Calculate the concentrations of H+, CH3COO-1, and CH3COOH (60 g/mol) at equilibrium. (Ka for acetic acid = 1.8 x 10-5.) Practice Exercise Calculate the percent ionization and pH of 0.20 M benzoic acid: Page 5 of 12 AP Chemistry The pH of a 0.10 M solution of formic acid (HCOOH) is 2.39. What is the Ka of the acid? Mr. Markic The pH of a 0.060 M weak monoprotic acid is 3.44. Calculate the Ka of the acid. percent ionization = ionized acid concentration at equilibrium initial concentration of acid x 100% For a monoprotic acid HA, Percent ionization = [𝐻 + ] [𝐻𝐴]0 x 100% [HA]0 = initial concentration Weak Bases and Base Ionization Constants NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq) Kb = − [NH+ 4 ][OH ] [NH3 ] Kb weak base strength Solve weak base problems like weak acids except solve for [OH-] instead of [H+]. Kb is the base ionization constant Sample Exercise What is the pH of a 0.40 M ammonia solution? Page 6 of 12 AP Chemistry Calculate the pH of a 0.26 M methylamine solution (see Table 15.4) Mr. Markic Ionization Constants of Conjugate Acid-Base Pairs HA (aq) H+ (aq) + A- (aq) Weak Acid and Its Conjugate Base Ka Ka = 𝐾𝑤 𝐾𝑏 Kb = 𝐾𝑤 𝐾𝑎 A- (aq) + H2O (l) OH- (aq) + HA (aq) Kb H2O (l) H+ (aq) + OH- (aq) Kw KaKb = Kw Review of Concepts Consider the following two acids and their ionization constants: HCOOH HCN Ka = 1.7 x 10-4 Ka = 4.9 x 10-10 Which conjugate base (HCOO- or CN-) is stronger? Diprotic and Triprotic Acids • May yield more than one hydrogen ion per molecule. • Ionize in a stepwise manner; that is, they lose one proton at a time. • An ionization constant expression can be written for each ionization stage. • Consequently, two or more equilibrium constant expressions must often be used to calculate the concentrations of species in the acid solution. H2CO3(aq) H+(aq) + HCO3-(aq) Ka1 = [𝐻 + ][𝐻𝐶𝑂3− ] [𝐻2 𝐶𝑂3 ] HCO3-(aq) H+(aq) + CO3-2(aq) Ka2 = [𝐻 + ][𝐶𝑂3−2 ] [𝐻𝐶𝑂3− ] H2CO3 HCO3- CO3-2 Sample Exercise Calculate the concentrations of H+, HCO3-, and CO32- in a 0.025 M H2CO3 Page 7 of 12 AP Chemistry Calculate the concentrations of all species in a 0.100 M H3PO4 Mr. Markic Review of Concepts Which of the following diagrams shown here represents a solution of sulfuric acid? Water molecules have been omitted for clarity. Molecular Structure and Acid Strength The stronger the bond The weaker the acid Acidity Increases H – X H+ + X HF << HCl < HBr < HI Page 8 of 12 AP Chemistry Molecular Structure and Oxoacid Strength Z – Oδ- – Hδ+ Mr. Markic Z – O- + H+ The O-H bond will be more polar and easier to break if: • Z is very electronegative or • Z is in a high oxidation state 1. Oxoacids having different central atoms (Z) that are from the same group and that have the same oxidation number. Acid strength increases with increasing electronegativity of Z O Cl is more electronegative than Br •• •• •• •• •• O •• •• H O Br O •• •• HClO3 > HBrO3 •• •• •• •• H O Cl O •• •• •• 2. Oxoacids having the same central atom (Z) but different numbers of attached groups. Acid strength increases as the oxidation number of Z increases. HClO4 > HClO3 > HClO2 > HClO Sample Exericse Predict the relative strengths of the oxoacids in each of the following groups: (a) HClO, HBrO, and HIO (b) HNO3 and HNO2 Which of the following acids is weaker: HClO2 or HClO3? Page 9 of 12 AP Chemistry Mr. Markic Acid-Base Properties of Salts Neutral Solutions: Salts containing an alkali metal or alkaline earth metal ion (except Be2+) and the conjugate base of a strong acid (e.g. Cl-, Br-, and NO3-). H2 O NaCl (s) → Na+ (aq) + Cl- (aq) Basic Solutions: Salts derived from a strong base and a weak acid. H2 O CH3COONa (s) → Na+ (aq) + CH3COO- (aq) CH3COO- (aq) + H2O (l) CH3COOH (aq) + OH- (aq) Sample Exericse Calculate the pH of a 0.15 M solution of sodium acetate (CH3COONa). What is the percent hydrolysis? Calculate the pH of a 0.24 M sodium formate solution (HCOONa). Acid-Base Properties of Salts Acid Solutions: Salts derived from a strong acid and a weak base. H2 O NH4Cl (s) → NH4+ (aq) + Cl- (aq) NH4+ (aq) NH3 (aq) + H+ (aq) Acid-Base Properties of Salts Solutions in which both the cation and the anion hydrolyze: • Kb for the anion > Ka for the cation, solution will be basic • Kb for the anion < Ka for the cation, solution will be acidic • Kb for the anion Ka for the cation, solution will be neutral Page 10 of 12 AP Chemistry Sample Exercise Predict whether the following solutions will be acidic, basic, or nearly neutral: (a) NH4I (c) FeCl3 (b) NaNO2 (d) NH4F Mr. Markic Predict whether the following solutions will be acidic, basic, or nearly neutral: (a) LiClO4 (c) Bi(NO3)2 (b) Na3PO4 (d) NH4CN Review of Concepts The diagrams shown here represent solutions of three salts NaX (X = A, B, or C). (a) Which X- has the weakest conjugate acid? (b) Arrange the three X- anions in order of increasing base strength. The Na+ ion and water molecules have been omitted for clarity. Oxides of the Representative Elements in Their Highest Oxidation States Na2O (s) + H2O (l) 2NaOH (aq) CO2 (g) + H2O (l) H2CO3 (aq) N2O5 (g) + H2O (l) 2HNO3 (aq) Page 11 of 12 AP Chemistry Mr. Markic Big Idea 6: Any bond or intermolecular attraction that can be formed can be broken. These two processes are in dynamic competition, sensitive to initial conditions and external perturbations. Learning Objectives: 1.20, 3.7, 6.11, 6.12, 6.13, 6.14, 6.15, 6.16, 6.17, 6.18, 6.19, 6.20 Duration: Middle March/Early April Textbook Chapter: 15 Enduring Understanding Essential Knowledge 6.C: Chemical equilibrium plays an 6.C.1: Chemical equilibrium reasoning can be used to describe the important role in acid-base chemistry and proton-transfer reactions of acid-base chemistry. in solubility. 6.C.2: The pH is an important characteristic of aqueous solutions that can be controlled with buffers. Comparing pH to pKa allows one to determine the protonation state of a molecule with a labile proton. Learning Objectives 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. 3.7 The student is able to identify compounds as Bronsted-Lowry acids, bases, and/or conjugate acid-base pairs, using proton-transfer reactions to justify the identification. 6.11 The student can generate or use a particulate representation of an acid (strong or weak or polyprotic) and a strong base to explain the species that will have large versus small concentrations at equilibrium. 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. 6.14 The student can, based on the dependence of Kw on temperature, reason that neutrality requires [H+] = [OH–] as opposed to requiring pH = 7, including especially the applications to biological systems. 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. 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. 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 concentrations at equilibrium. 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. 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 pKa associated with the labile proton. 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. 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