Acid-Base Equilibria The reaction of weak acids with water, OR the reaction of weak bases with water, always results in an equilibrium!! The equilibrium constant for the reaction of a weak acid with water is Ka Acid-Base Equilibria eg. HF(aq) + H2O(l) H3O+(aq) + F-(aq) Keq = ? -] [H O+] [F 3 Ka = [HF] Acid-Base Equilibria For any weak acid Ka = Why [H3O+] [conjugate base] [weak acid] is H2O(l) omitted from the Ka expression? Acid-Base Equilibria the equilibrium constant for the reaction of a weak base with water is Kb HS- (aq) + H2O(l) Kb = H S + OH 2 (aq) (aq) Acid-Base Equilibria For any weak base Kb = [OH-] [conjugate acid] [weak base] eg. Write the expression for Kb for S2-(aq) ANSWER: S2- (aq) HS + OH + H2O(l) (aq) (aq) Kb = [OH-] [HS-] [S2-] 5.a) Use Ka to find [H3O+] for 0.100 mol/L HF(aq) HF(aq) + H2O(l) H3O+(aq) + F-(aq) Ka = 6.6 x 10-4 Ka - [ H 3 O ] [F ] [HF] 1st try - Ignore x 6.6 x 10 -4 [x] [x] [0.100 - x] x 2 = (0.100)(6.6 x 10-4) x 2 = 6.6 x 10-5 x = 8.1 x 10-3 mol/L 2nd try– Include x 6.6 x 10 -4 [x] [x] [0.100 - 0.0081] x 2 = (0.0919)(6.6 x 10-4) x 2 = 6.0654 x 10-5 x = 7.8 x 10-3 mol/L 3rd try– Include new x 6.6 x 10 -4 [x] [x] [0.100 - 0.0078] x 2 = (0.0922)(6.6 x 10-4) x 2 = 6.0852 x 10-5 x = 7.8 x 10-3 mol/L [H3O+] = 7.8 x 10-3 mol/L 5.b) find [H3O+] for 0.250 mol/L CH3COOH(aq CH3COOH(aq) + H2O(l) H3O+(aq) + CH3COO-(aq) Ka = 1.8 x 10-5 Ka - [H 3 O ] [CH 3 COO ] [CH 3 COOH] 1st try - Ignore x 1.8 x 10 -5 [x] [x] [0.250 - x] x 2 = (0.250)(1.8 x 10-5) x 2 = 4.5 x 10-6 x = 2.1 x 10-3 mol/L 2nd try– Include x 1.8 x 10 -5 [x] [x] [0.250 - 0.0021] x 2 = (0.2479)(1.8 x 10-5) x 2 = 4.462 x 10-6 x = 2.1 x 10-3 mol/L [H3O+] = 2.1 x 10-3 mol/L pH of a weak acid (pp. 587 – 592) Step #1: Write a balanced equation Step #2: ICE table OR assign variables Step #3: Write the Ka expression Step #4: Check (can we ignore dissociation) Step #5: Substitute into Ka expression pH of a weak acid eg. Find pH of 0.100 mol/L HF(aq). Step #1: Write a balanced equation HF(aq) + H2O(l) H3O+(aq) + F-(aq) Step #2: Equilibrium Concentrations Let x = [H3O+] at equilibrium [F-] = x [HF] = 0.100 - x Step #3: Ka expression Ka = [H3O+] [F-] [HF] Step #4: Check (can we ignore dissociation) If [weak acid] > 500 Ka dissociation (- x) may be IGNORED (0.100) = 151 6.6 x 10-4 Acid dissociation CANNOT be IGNORED in this question. Step #5: Substitute into Ka expression 6.6 x 10 -4 [x] [x] [0.100 - x] x2 = 6.6 x 10-5 - 6.6 x 10-4 x x2 + 6.6 x 10-4 x - 6.6 x 10-5 = 0 a=1 b = 6.6 x 10-4 c = -6.6 x 10-5 b x b 4ac 2 2a x 6.6 x 10 -4 (6.6 x 10 -4 ) 4(1)(-6.6 2 2(1) x 6.6 x 10 -4 0.000264 2 Ignore negative roots x 0.0078 mol/L x 10 -5 ) Try these: a) Find the [H3O+] in 0.250 mol/L HCN(aq) Check: 4.0 x 108 x = 1.24 x 10-5 [H3O+] = 1.24 x 10-5 b) Calculate the pH of 0.0300 mol/L HCOOH(aq) Check: 167 x = 2.24 x 10-3 pH = 2.651 Practice 1. Formic acid, HCOOH, is present in the sting of certain ants. What is the [H3O+] of a 0.025 mol/L solution of formic acid? (0.00203 mol/L) 2. Calculate the pH of a sample of vinegar that contains 0.83 mol/L acetic acid. ( [H3O+] = 3.87 x 10-3 3. pH = 2.413 ) What is the percent dissociation of the vinegar in 2.? % diss = 0.466 % 22 Practice 4. A solution of hydrofluoric acid has a molar concentration of 0.0100 mol/L. What is the pH of this solution? ( [H3O+] = 0.00226 5. pH = 2.646 ) The word “butter” comes from the Greek butyros. Butanoic acid gives rancid butter its distinctive odour. Calculate the [H3O+] of a 1.0 × 10−2 mol/L solution of butanoic acid. (Ka = 1.51 × 10−5 ) (3.89 x 10-4 mol/L) 23 pH of a weak base same method as acids calculate Kb Ka x Kb K w Kb Kw Ka ignore dissociation if 24 pH of a weak base Calculate the pH of 0.0100mol/L Na2CO3(aq) 25 pH of a weak base Calculate the pH of 0.500 mol/L NaNO2(aq) 26 Calculating Ka from [weak acid] and pH eg. The pH of a 0.072 mol/L solution of benzoic acid, C6H5COOH, is 2.68. Calculate the numerical value of the Ka for this acid. - Equation - Find [H3O+] from pH - Subtract from [weak acid] - Substitute to find Ka See p. 591 #6 & 8 27 C6H5COOH(aq) + H2O(l) H3O+(aq) + C6H5COO-(aq) [H3O+] = 10-2.68 = 0.00209 mol/L [C6H5COO-] = 0.00209 mol/L Find Ka Ka = [C6H5COOH] = 0.072 – 0.00209 = 0.06991 mol/L (0.00209)(0.00209) = 6.2 x 10-5 (0.06991) 28 Calculating Ka from [weak acid] and pH eg. The pH of a 0.072 mol/L solution of benzoic acid, C6H5COOH, is 2.68. Calculate the % dissociation for this acid. [H3O+] = 10-2.68 = 0.00209 mol/L See p. 591 #’s 5 & 6 % diss [H 3 O ] x 100% [weak acid] 0.00209 0.072 x 100% = 2.9 % 29 Calculate the acid dissociation constant, Ka , and the percent dissociation for each acid: a) 0.250 mol/L chlorous acid, HClO2(aq); pH = 1.31 0.012 19.5% b) 0.150 mol/L cyanic acid, HCNO(aq); pH = 2.15 0.00035 4.7% c) 0.100 mol/L arsenic acid, H3AsO4(aq); pH = 1.70 0.0050 20% d) 0.500 mol/L iodic acid, HIO3(aq); pH = 0.670 0.160 42.8% 30 More Practice: Weak Acids: pp. 591, 592 #’s 6 -8 Weak Bases: p. 595 #’s 11 - 16 (Kb’s on p. 592) 1.a) b) 2.a) b) 1.4 x 10-10 0.0014 % 2.5 x 10-9 0.0080 % 3.a) b) 4.a) b) 1.6 x 10-9 0.0080 % 2.7 x 10-9 0.042 % 31 Acid-Base Stoichiometry Solution Stoichiometry (Review) 1. Write a balanced equation m 2. Calculate moles given ( n OR n = CV) M 3. Mole ratios 4. Calculate required quantity n OR n OR m = nM V C C V 32 eg. 25.0 mL of 0.100 mol/L H2SO4(aq) was used to neutralize 36.5 mL of NaOH(aq). Calculate the molar concentration of the NaOH solution. H2SO4(aq) + 2 NaOH(aq) → 2 H2O(l) + Na2SO4(aq) nH SO = 2 4 nNaOH = CNaOH = 33 Acid-Base Stoichiometry pp. 600, 601 – Sample Problems p. 602 #’s 17 - 20 34 Dilution Given 3 of the four variables Only one solution CiVi = CfVf Stoichiometry Given 3 of the four variables Two different solutions 4 step method 35 Excess Acid or Base To calculate the pH of a solution produced by mixing an acid with a base: write the B-L equation (NIE) calculate the moles of H3O+ and OH subtract to determine the moles of excess H3O+ or OH divide by total volume to get concentration calculate pH 36 eg. 20.0 mL of 0.0100 M Ca(OH)2(aq) is mixed with 10.0 mL of 0.00500 M HCl(aq). Determine the pH of the resulting solution. ANSWER: Species present: Ca2+ OHH3O+ Cl- H2O SB SA 37 NIE: OH- + H3O+ → 2 H2O 0.0200 mol/L 0.0200 L 0.00500 mol/L 0.0100 L n = CV 4.00 x 10-4 mol OH- 5.0 x 10-5 mol H3O+ 3.5 x 10-4 mol excess OH38 C n V total 3.5 x 10 4 mol 0.0300 L = 0.01167 mol/L [OH-] = 0.01167 mol/L pOH = 1.933 pH = 12.067 39 Indicators An indicator is a weak acid that changes color with changes in pH To choose an indicator for a titration, the pH of the endpoint must be within the pH range over which the indicator changes color 40 HIn(aq) + H2O(l) Colour #1 H3O+(aq) + In-(aq) Colour #2 HIn is the acid form of the indicator. Adding H3O+ causes colour 1 (LCP) Adding OH- removes the H3O+ & causes colour #2 41 methyl orange HMo(aq) + H2O(l) red H3O+(aq) + Mo-(aq) yellow bromothymol blue HBb(aq) + H2O(l) yellow H3O+(aq) + Bb-(aq) blue 42 Acid-Base Titration (p. 603 → ) A titration is a lab technique used to determine an unknown solution concentration. A standard solution is added to a known volume of solution until the endpoint of the titration is reached. Acid-Base Titration The endpoint occurs when there is a sharp change in colour The equivalence point occurs when the moles of hydronium equals the moles of hydroxide The colour change is caused by the indicator added to the titration flask. Acid-Base Titration An indicator is a chemical that changes colour over a given pH range (See indicator table) A buret is used to deliver the standard solution Acid-Base Titration standard solution - solution of known concentration primary standard - a standard solution which can be made by direct weighing of a stable chemical. Titration Lab – pp. 606, 607 46 Multi-Step Titrations (p. 609 - 611) Polyprotic acids donate their protons one at a time when reacted with a base. eg. Write the equations for the steps that occur when H3PO4(aq) is titrated with NaOH(aq) H3PO4(aq) + OH-(aq) H2PO4-(aq) + OH-(aq) HPO42-(aq) + OH-(aq) 47 Multi-Step Titrations H3PO4(aq) + OH-(aq) → H2PO4-(aq) + H2O(l) H2PO4-(aq) + OH-(aq) → HPO42-(aq) + H2O(l) HPO42-(aq) + OH-(aq) PO43-(aq) + H2O(l) H3PO4(aq) + 3 OH-(aq) PO43-(aq) + 3 H2O(l) 48 Multi-Step Titrations Write the balanced net ionic equations, and the overall equation, for the titration of Na2S(aq) with HCl(aq). p. 611 #’s 21.b), 22, & 23 LAST TOPIC!! Titration Curves 49 Acids and Bases Properties / Operational Definitions Acid-Base Theories and Limitations Arrhenius – H-X and X-OH Modified – react with water → hydronium BLT – proton donor/acceptor (CA and CB) Writing Net Ionic Equations (BLT) Strong vs. Weak pH & pOH calculations Equilibria (Kw, Ka, Kb) Titrations/Indicators/Titration Curves Dilutions and Excess Reagent questions Step #2: ICE table [HF] [H3O+] [F-] I 0.100 mol/L 0 0 C -x +x +x E 0.100 - x x x 0.0100mol/L CO23-(aq) CO32-(aq) + H2O(l) HCO3-(aq) + OH(aq) I C E [PO43-] 0.0100 mol/L -x 0.0100 - x [HPO42-] [OH-] 0 0 +x +x x x eg. 20.0 mL of 0.0100 M Ca(OH)2(aq) is mixed with 10.0 mL of 0.00500 M HCl(aq). Determine the pH of the resulting solution. Excess reactant ANSWER: Ca(OH)2(aq) + 2 HCl(aq) → 2 H2O(l) + CaCl2(aq) nbase = 0.0002 mol → needs 0.004 mol HCl nacid = 0.00005 mol → needs 0.000025 mol Ca(OH)2 Limiting reactant Acid-Base Stoichiometry Solution stoichiometry (4 question sheet) Excess reagent problems (use NIE) Titrations Titration curves Indicators STSE: Acids Around Us WorkSheet #9 answers: 1. 0.210 mol/L 2. a) 22.5 mL b) 24.7 mL c) 4.8 mL 3. 31.5 mL 4. a) 0.0992 mol/L b) 0.269 mol/L c) 0.552 mol/L WorkSheet #10 answers: 1. pH = 13.000 2. [H3O+] = 4.12 x 10-2 mol/L -13 [OH ] = 2.43 x 10 mol/L 3. pH = 13.125 4. pH = 7 p. 586 #’s 1 – 4 A primary standard is a pure substance that is stable enough to be stored indefinitely without decomposition, can be weighed accurately without special precautions when exposed to air, and will undergo an accurate stoichiometric reaction in a titration. 15. pH of 0.297 mol/L HOCl HOCl(aq) + H2O(l) H3O+(aq) + OCl-(aq) Let x = [H3O+] at equilibrium [OCl-] = x [HOCl] = 0.297 - x Ka = [H3O+] [OCl-] [HOCl] Check: (0.297) 7 = 1.02 x 10 2.9 x 10-8 dissociation (- x) may be IGNORED 2.9 x 10 -8 [x] [x] [0.297] X = 9.28 x 10-5 pH = 4.03 16. NIE: OH- + H3O+ → 2 H2O 0.484 mol/L 0.07000 L 0.03388 mol OH- 0.125 mol/L 0.02500 L 0.003125 mol H3O+ 0.030755 mol excess OH[OH-] = 0.3237 mol/L pOH = 0.490 pH = 13.510 17. Ignore dissociation [OH-] = 0.0146 mol/L % diss = 2.92 % Vave = 10.975 mL nNaOH = 0.001262 mol nH2SO4 = 0.000631 mol C = 0.0252 mol/L 19. Kb = 3.93 x 10-4 % diss = 6.27 18.