Transcript Slide 1
1 2 Arrhenius Theory Acids release hydrogen ions + (H ) + HCl → H + Cl Bases release hydroxide ions (OH ) + NaOH → Na + OH 6 ACID-BASE THEORIES • The most general theory for common aqueous acids and bases is the BRØNSTED - LOWRY theory • ACIDS DONATE H+ IONS • BASES ACCEPT H+ IONS Why is Water Neutral? [H3O+ ] = [OH-] When one water gains, another loses a H+ Relative ion concentrations pH is a relative measure of the hydrogen ion concentration pH is a rating; ranges from 0 – 14 0 = most, 7 equal, 14 = least Any pX Scales In general pX = -log X pOH = - log pH = - log [OH ] + [H ] Determining pOH pH + pOH = 14 If know one can determine the other. If pH = 13, what is the pOH? 13 + pOH = 14 pOH = 14 – 13 = 1 Why at a pH = 7 ? Determined by concentration [ X ] of each ion [H+ ]= [OH-] = 10-7M [H+ ]= 10-pHM [OH-] = 10-pOHM Water AUTOIONIZATION H2O can function as both an ACID and a BASE. Equilibrium constant for water = Kw Kw = [H3O+] [OH-] = 1.00 x 10-14 at 25 oC 18 Water 19 OH- H3O+ Autoionization Kw = [H3O+] [OH-] = 1.00 x 10-14 at 25 oC In a neutral solution [H3O+] = [OH-] so [H3O+] = [OH-] = 1.00 x 10-7 M Acid-Base Reactions Chapter 17 20 ACIDS Nonmetal oxides can be acids CO2(aq) + H2O(liq) ---> H2CO3(aq) SO3(aq) + H2O(liq) ---> H2SO4(aq) and can come from burning coal and oil. 21 BASES 22 Metal oxides are bases CaO(s) + H2O(liq) --> Ca(OH)2(aq) CaO in water. Indicator shows solution is basic. Hydrolysis 23 24 Acid-Base Reactions • sometimes called NEUTRALIZATIONS because the solution is neither acidic nor basic at the end. • The other product of the A-B reaction is a SALT, MX. HX + MOH ---> MX + H2O Mn+ comes from base & Xn- comes from acid This is one way to make compounds! 25 Acid-Base Reactions The “driving force” is the formation of water. NaOH(aq) + HCl(aq) ---> NaCl(aq) + H2O(liq) Net ionic equation OH-(aq) + H+(aq) ---> H2O(liq) This applies to ALL reactions of STRONG acids and bases. 26 28 Weak Acids and Bases Acid acetic, CH3CO2H ammonium, NH4+ bicarbonate, HCO3- Conjugate Base CH3CO2-, acetate NH3, ammonia CO32-, carbonate A weak acid (or base) is one that ionizes to a VERY small extent (< 5%). Equilibrium Constants for Weak Acids 30 Weak acid has Ka < 1 Leads to small [H3O+] and a pH of 2 - 7 Equilibrium Constants for Weak Bases 31 Weak base has Kb < 1 Leads to small [OH-] and a pH of 12 - 7 Kw = Ka* Kb 32 Acids Conjugate Bases Weak Acids and Bases 34 acetic acid, CH3CO2H (HOAc) HOAc + H2O D H3O+ + OAcAcid Conj. base + - [H3O ][OAc ] -5 Ka 1.8 x 10 [HOAc] (K is designated Ka for ACID) [H3O+] and [OAc-] are SMALL, Ka << 1. Equilibria Involving A Weak Acid You have 1.00 M HOAc. Calc. the pH. And the equilibrium concs. of EACH Step 1. ICE table. [HOAc] I C E [H3O+] [OAc-] 35 Equilibria Involving A Weak Acid [HOAc] I 1.00 C -x E 1.00-x [H3O+] [OAc-] 0 0 +x +x x x Note that we neglect [H3O+] from H2O. 36 Equilibria Involving A Weak Acid Assume x is very small because Ka is so small. + - [H3O ][OAc ] -5 Ka 1.8 x 10 = [HOAc] -5 Ka 1.8 x 10 = 2 x 1.00 - x 2 x 1.00 Now we can more easily solve this approximate expression. 37 38 Equilibria Involving A Weak Acid Step 3. Solve Ka approximate expression -5 Ka 1.8 x 10 = 2 x 1.00 x = [H3O+] = [OAc-] = [Ka • 1.00]1/2 x = [H3O+] = [OAc-] = 4.2 x 10-3 M pH = -log (4.2 x 10-3) = 2.37 Chapter 17 – Acids and Bases What is the [H+] of a 1.0 M acetic acid if Ka = 1.8 x 10-5 for the solution: A. B. C. D. 1.0 M 0.3 M 0.0042 M 1.8 x 10-5 M © 2011 Pearson Education, Inc. Chapter 17 – Acids and Bases A 0.100 M solution of HX has a pH of is 4.5 Determine the Ka for the acid, HX. A. B. C. D. 1.0 x 10-8 3.0 x 10-7 2.5 x 10-8 4.5 x 10-9 © 2011 Pearson Education, Inc. Weak Bases Equilibria Involving A Weak Base You have 0.010 M NH3. Calc. the pH. NH3 + H2O D NH4+ + OH- Kb = 1.8 x 10-5 Step 1; ICE table [NH3] I C E [NH4+] [OH-] 42 Weak Base 43 Step 1. ICE table [NH3] [NH4+] [OH-] 0 0 I 0.010 C -x +x +x E 0.010 - x x x Weak Base 44 Step 2. Solve the equilibrium expression 2 + ][OH- ] [NH x -5 4 Kb 1.8 x 10 = = [NH3 ] 0.010 - x Assume x is small (100•Kb < Co), so x = [OH-] = [NH4+] = 4.2 x 10-4 M [NH3] = 0.010 - 4.2 x 10-4 ≈ 0.010 M The approximation is valid ! Neutralization Reactions NaOH + HCl → NaCl + H20 REACT a base with an acid. forms salt and water 19.4 Neutralization Reactions > Acid-Base Reactions A reaction between an acid and a base will go to completion when the solutions contain equal moles of hydrogen ions and hydroxide ions. • The balanced equation provides the correct ratio of acid to base. 46 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > Titration Neutralization occurs when the number of moles of hydrogen ions is EQUAL to the number of moles of hydroxide ions. 47 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > Acid-Base Reactions For hydrochloric acid and sodium hydroxide, the mole ratio is 1:1. HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l) 1 mol 48 1 mol 1 mol 1 mol Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > Acid-Base Reactions For sulfuric acid and sodium hydroxide, the ratio is 1:2. • Two moles of the base are required to neutralize one mole of the acid. H2SO4(aq) + 2NaOH(aq) → Na2SO4(aq) + 2H2O(l) 1 mol 49 2 mol 1 mol 2 mol Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > Acid-Base Reactions Similarly, hydrochloric acid and calcium hydroxide react in a 2:1 ratio. 2HCl(aq) + Ca(OH)2(aq) → CaCl2(aq) + 2H2O(l) 2 mol 50 1 mol 1 mol 2 mol Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > Sample Problem 19.7 Finding the Moles Needed for Neutralization How many moles of sulfuric acid are required to neutralize 0.50 mol of sodium hydroxide? The equation for the reaction is H2SO4(aq) + 2NaOH(aq) → Na2SO4(aq) + 2H2O. 51 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > 1 Analyze Sample Problem 19.7 List the knowns and the unknown. To determine the number of moles of acid, you need to know the number of moles of base and the mole ratio of acid to base. KNOWNS UNKNOWN mol NaOH = 0.50 mol mol H2SO4 = ? mol 1 mol H2SO4/2 mol NaOH (from balanced equation) 52 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > 2 Sample Problem 19.7 Calculate Solve for the unknown. Use the mole ratio of acid to base to determine the number of moles of acid. 0.50 mol NaOH × 53 1 mol H2SO4 2 mol NaOH = 0.25 mol H2SO4 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > 3 Sample Problem 19.7 Evaluate Does the result make sense? Because the mole ratio of H2SO4 to NaOH is 1:2, the number of moles of H2SO4 should be half the number of the moles of NaOH. 54 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > Titration You can use a neutralization reaction to determine the concentration of an acid or base. • The process of adding a measured amount of a solution of known concentration to a solution of unknown concentration is called a titration. 55 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > 56 A flask with a known volume of acids (and an indicator) is placed beneath a buret that is filled with a base of known concentration. Titration The base is slowly added from the buret to the acid. A change in the color of the solution is the signal that neutralization has occurred. Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > 57 19.4 Neutralization Reactions > Titration The indicator that is chosen for a titration must change color at or near the pH of the equivalence point. • The point at which the indicator changes color is the end point of the titration. 58 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.2 Hydrogen IonsIndicators and Acidity > Acid-Base An indicator (HIn) is a weak acid or base that dissociates in a known pH range. • Indicators work because their acid form and base form have different colors in solution. • The acid form of the indicator (HIn) is dominant at low pH and high [H+]. • The base form (In−) is dominant at high pH and high [OH−]. 59 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > The pH change of a solution during the titration of a strong acid (HCl) with a strong base (NaOH). • The equivalence point for this reaction occurs at a pH of 7. • As the titration nears the equivalence point, the pH rises dramatically because hydrogen ions are being used up. 60 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > Sample Problem 19.8 Determining Concentration by Titration H2SO4(aq) + 2NaOH(aq) → Na2SO4(aq) + 2H2O(l). A 25-mL solution of H2SO4 is neutralized by 18 mL of 1.0M NaOH. What is the concentration of the H2SO4 solution? 61 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > 1 Analyze Sample Problem 19.8 List the knowns and the unknown. The conversion steps are as follows: L NaOH → mol NaOH → mol H2SO4 → M H2SO4. KNOWNS UNKNOWN [NaOH] = 1.0M [H2SO4] = ?M VNaOH = 18 mL = 0.018 L VH SO 2 62 4 = 18 mL = 0.018 L Convert volume to liters because molarity is in moles per liter. Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > 2 Sample Problem 19.8 Calculate Solve for the unknown. Use the molarity to convert the volume of base to moles of base. 0.018 L NaOH × 63 1.0 mol NaOH 1 L NaOH = 0.018 mol NaOH Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > 2 Sample Problem 19.8 Calculate Solve for the unknown. Use the mole ratio to find the moles of acid. 0.018 mol NaOH × 64 1.0 mol H2SO4 = 0.0090 mol H2SO4 2 mol NaOH Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.4 Neutralization Reactions > 2 Sample Problem 19.8 Calculate Solve for the unknown. Calculate the molarity by dividing moles of acid by liters of solution. 0.0090 mol mol of solute molarity = = L of solution 0.025 L = 0.36M H2SO4 65 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. 19.5 Salts in Solution > Interpret Graphs • One curve is for the addition of sodium hydroxide, a strong base, to ethanoic acid, a weak acid. • An aqueous solution of sodium ethanoate exists at the equivalence point. CH3COOH(aq) + NaOH(aq) → CH3COONa(aq) + H2O(l) 66 Copyright © Pearson Education, Inc., or its affiliates. All Rights Reserved. Acetic acid titrated with NaOH Weak acid titrated with a strong base Figure 18.5 67 Acid-Base Titration Section 18.3 You titrate 100. mL of a 0.025 M solution of benzoic acid with 0.100 M NaOH to the equivalence point. What is the pH of the final solution? HBz + NaOH ---> Na+ + Bz- + H2O Kb = 1.6 x 10-10 C6H5CO2H = HBz Benzoate ion = Bz- 68 69 QUESTION: You titrate 100. mL of a 0.025 M solution of benzoic acid with 0.100 M NaOH to the equivalence point. pH at half-way point? Benzoic acid + NaOH pH at equivalence point? pH of solution of benzoic acid, a weak acid Acid-Base Reactions QUESTION: You titrate 100. mL of a 0.025 M solution of benzoic acid with 0.100 M NaOH to the equivalence point. What is the pH of the final solution? Strategy — find the conc. of the conjugate base Bz- in the solution AFTER the titration, then calculate pH. This is a two-step problem 1. 2. stoichiometry of acid-base reaction equilibrium calculation 70 STOICHIOMETRY PORTION M * V = mol 1. Calc. moles of NaOH req’d (0.100 L)(0.025 M) = 0.0025 mol HBz This requires 0.0025 mol NaOH 2.Calc. volume of NaOH req’d 0.0025 mol (1 L / 0.100 mol) = 0.025 L 25 mL of NaOH req’d 71 STOICHIOMETRY PORTION 3. Moles Bz- produced = moles HBz = 0.0025 mol 4. Calc. conc. of BzThere are 0.0025 mol of Bz- in a TOTAL SOLUTION VOLUME of 125 mL [Bz-] = 0.0025 mol / 0.125 L = 0.020 M 72 Equivalence Point 73 Most important species in solution is benzoate ion, Bz-. It will react to form the weak conjugate base, benzoic acid, HBz. Bz- + H2O D HBz + OH- Kb = 1.6 x 10-10 I [Bz-] 0.020 [HBz] 0 [OH-] 0 C -x +x +x E 0.020 - x x x 74 Acid-Base Reactions -10 Kb 1.6 x 10 x= [OH ] 2 x = 0.020 - x = 1.8 x -6 10 pOH = 5.75 -----> pH = 8.25 75 QUESTION: You titrate 100. mL of a 0.025 M solution of benzoic acid with 0.100 M NaOH to the equivalence point. What is the pH at half-way point? pH at half-way point? Equivalence point pH = 8.25 Acid-Base Reactions 76 You titrate 100. mL of a 0.025 M solution of benzoic acid with 0.100 M NaOH. What is the pH at the half-way point? Both HBz and Bzare present. This is a BUFFER! [H 3 O ] = [HBz] - [Bz ] • Ka At the half-way point, [HBz] = [Bz-] Therefore, [H3O+] = Ka = 6.3 x 10-5 pH = 4.20 = pKa of the acid 80 Weak base (NH3) titrated with a strong acid (HCl) Figure 18.7 Acid-Base Reactions • Strong acid + strong base HCl + NaOH ----> SALT WATER • Strong acid + weak base HCl + NH3 ---> ACID • Weak acid + strong base HOAc + NaOH ---> BASIC • Weak acid + weak base HOAc + NH3 ---> Ka / Kb 81