Unit 2 Acids and Bases http://www.cdli.ca/courses/ http://www.cbhs.k12.nf.ca/adrianyoung/ 1 Topics Properties / Operational Definitions Acid-Base Theories pH & pOH calculations Equilibria (Kw, Ka, Kb) Indicators Titrations STSE: Acids Around Us 2 Operational Definitions An Operational Definition is a list of properties, or operations that can be performed, to identify a substance. See p. 550 for operational definitions of acids and bases 3 Operational Definitions (Properties – see p. 550) Acids pH < 7 taste sour react with active metals (Mg, Zn) to produce hydrogen gas Bases pH > 7 taste bitter no reaction with active metals feel slippery 4 Operational Definitions Acids blue litmus turns red react with carbonates to produce CO2 gas Bases red litmus turns blue no reaction with carbonates 5 Operational Definitions Acids conduct electric current neutralize bases to produce water and a “salt” any ionic compound Bases conduct electric current neutralize acids to produce water and a “salt” any ionic compound 6 7 8 Acid-Base Theories 1. Arrhenius Theory (p. 549 ) acid – any substance that dissociates in water to produce H+ ions ie. an acid must contain H+ ions 9 Arrhenius Theory eg. HCl(aq) → H2SO4(aq) → HSO4-(aq) → 10 Arrhenius Theory base – any substance that dissociates in water to produce OH- ions ie. a base must contain OH- ions 11 Arrhenius Theory eg. NaOH(aq) Ca(OH)2(aq) 12 Arrhenius Theory Which Arrheniusbase? acid? Which is is an a Arrhenius a) KOH c) CH4 b) HCN d) CH3OH 13 Limitations of Arrhenius theory (p.551) 1. H+ cannot exist as an ion in water. The positive H+ ions are attracted to the polar water molecules forming + HYDRONIUM ions or H3O (aq) H+(aq) + H2O(l) → H3O+(aq) 14 Limitations of Arrhenius theory 2. CO2 dissolves in water to produce an acid. NH3 dissolves in water to produce a base. Neither of these observations can be explained by Arrhenius theory 15 Limitations of Arrhenius theory 3. Some acid-base reactions can occur in solvents other than water. Arrhenius theory can explain only aqueous acids or bases. 16 Limitations of Arrhenius theory Arrhenius theory is not able to predict whether certain species are acids or bases. eg. NaHSO4 H2PO4- HCO34. Arrhenius theory needs some work 17 Acid-Base Theories To be used when Arrhenius is inadequate 2. Modified Arrhenius Theory (p. 552) acid – any substance that reacts with water to produce H3O+ ions eg. HCl(g) + H2O(l) → H3O+(aq) + Cl-(aq) 18 Modified Arrhenius Theory base – any substance that reacts with water to produce OH- ions eg. O(l) - → NH3(aq) + HH+2-OH pp. 558, 559 #’s 1, 3, 8, & 9 19 20 21 Acid-Base Theories 3. Brønsted-Lowry Theory (p. 553) acid – any substance from which a proton (H+) may be removed ie. an acid is a substance that loses a proton (H+) 22 Brønsted-Lowry Theory base – any substance that can remove a proton (H+) from an acid. ie. a base is a substance that gains a proton (H+) In BLT , an acid-base reaction requires the transfer of a proton (H+) from an acid to a base. 23 Brønsted-Lowry Theory base eg. conjugate acid HCN(aq) + NH3(aq) ← → CN-(aq) + NH4+(aq) acid conjugate base 24 Brønsted-Lowry Theory What is a conjugate acid-base pair?? (p. 554) Two particles (molecules or ions) that differ by one proton are called a conjugate acid-base pair. The conjugate base forms when an acid loses a proton. The conjugate acid forms when a base gains a proton (H+). 25 conjugate Brønsted-Lowry Theory acid base acid conjugate base 26 conjugate Brønsted-Lowry Theory base acid eg. NH3(aq) + H2O(l) ← → NH4+(aq) + OH-(aq) acid conjugate base ← H2O(l) + H2O(l) → 27 Brønsted-Lowry Theory - an amphoteric substance can be either an acid or a base - usually these are negative ions that contain at least one hydrogen atom eg. H2O, HCO3-(aq), H2PO4-(aq) 28 Brønsted-Lowry Theory p.557 #’s 1 – 7 p. 558 #’s 8, 9 p. 559 #’s 2, 4-7, 10,11 29 Strength of Acids and Bases A strong acid is an acid that ionizes or dissociates 100% in water eg. HCl(aq)→ H+(aq) + Cl-(aq) Strong acids react 100% with water (BLT) eg. HCl(aq) + H2O(l) → H3O+(aq) + Cl-(aq) 30 Strength of Acids and Bases Strong acids produce more H+ ions OR more H3O+ ions than weak acids with the same molar concentration NOTE: The equilibrium symbol, , is NOT used for strong acids because there is NO REVERSE REACTION. 31 Strength of Acids and Bases A weak acid is an acid that ionizes or dissociates LESS THAN 100% eg. HF(aq) H+(aq) + F-(aq) Weak acids react less than 100% with water eg. HF(aq) + H2O(l) H3O+(aq) + F32 Strength of Acids and Bases Weak acids produce fewer H+ ions OR fewer H3O+ ions than strong acids with the same molar concentration For weak acids, an equilibrium is established between the original acid molecule and the ions formed. DO NOT confuse the terms strong and weak with concentrated and dilute. 33 Strength of Acids and Bases eg. Classify the following acids: 0.00100 mol/L HCl(aq) strong and dilute 12.4 mol/L HCl(aq) strong and concentrated 10.5 mol/L CH3COOH(aq) weak and concentrated 34 Strength of Acids and Bases monoprotic – acids that contain or lose one proton diprotic – acids that contain or lose two protons polyprotic – 35 Strength of Acids and Bases A strong base is a base that dissociates 100% in water, or reacts 100% with water, to produce OH- ion. The only strong bases are hydroxide compounds of most Group 1 and Group 2 elements eg. NaOH(s) → Na+(aq) + OH-(aq) Ca(OH)2(s) → Ca2+(aq) + 2 OH-(aq) 36 Strength of Acids and Bases A weak base is a base that reacts less than 100% in water to produce OH- ion. eg. S2-(aq) + H2O(l) HS-(aq) + OH-(aq) 37 Writing Acid-Base Equations (BLT) Step 1: List all the molecules/ions present in the solution ionic compounds form cations and anions strong acids exist as hydronium ion and the anion (conjugate base) for weak acids use full formula of the compound (i.e. un-ionized molecule) always include water in the list. 38 Writing Acid-Base Equations (BLT) Step 2: Identify the strongEST acid and the strongEST base from Step 1. Step 3: Write the equation for the reaction by transferring a proton from the strongest acid to the strongest base. 39 Writing Acid-Base Equations (BLT) Step 4: Determine the type of reaction arrow to use in the equation. Stoichiometric (100%) reactions occur between: Hydronium (H3O+) and bases stronger than nitrite (NO2-) hydroxide (OH-)and acids stronger than hypochlorous acid (HOCl) 40 Writing Acid-Base Equations (BLT) Step 5: Determine the position of the equilibrium by comparing the strengths of both acids in the equation. The favoured side is the side with the weaker acid! 41 Writing Acid-Base Equations (BLT) Sample problems: Write the net ionic equation for the acidbase reaction between: - aqueous sodium hydroxide (NaOH(aq)) and hydrochloric acid (HCl(aq)). 42 species present Na+(aq) OH-(aq) H3O+(aq) Cl-(aq) H2O(l) strongest acid strongest base H3O+(aq) + OH-(aq) H2O(l) + H2O(l) OR H3O+(aq) + OH-(aq) → 2 H2O(l) 43 Writing Acid-Base Equations (BLT) Sample problems: Write an equation for the acid-base reaction between nitrous acid (HNO2(aq)) and aqueous sodium sulfite (Na2SO3(aq)). 44 species present HNO2(aq) Na+(aq) SO32-(aq) SA H2O(l) SB HNO2(aq) + SO32-(aq) NO2-(aq) + HSO3 - (aq) Weaker Acid Stronger Acid Products favored 45 Write the Net Ionic Equation for each aqueous reaction below: 1. Na2CO3(aq) and CH3COOH(aq) 2. NH3(aq) and HNO2(aq) 3. HNO3(aq) and RbOH 4. H2SO4(aq) and K3PO4(aq) 5. HF(aq) and NH4CH3COO(aq) 6. CaCl2(aq) and PbSO4(aq) p. 564 #’s 10 &11 46 species present Na+(aq) CO32-(aq) CH3COOH(aq) H2O(l) SB CH3COOH(aq) + CO32-(aq) Stronger Acid SA CH3COO-(aq) + HCO3-(aq) Weaker Acid Products Favoured 47 species present NH3(aq) HNO2(aq) SB HNO2(aq) + NH3(aq) Stronger Acid H2O(l) SA -(aq) + NH4 + (aq) NO 2 Weaker Acid Products favored 48 species present H3O+(aq) NO3-(aq) Rb+(aq) OH-(aq) H2O(l) strongest acid strongest base H3O+(aq) + OH-(aq) H2O(l) + H2O(l) OR H3O+(aq) + OH-(aq) → 2 H2O(l) 49 species present + 3+ HSO K PO H3O (aq) 4 (aq) (aq) 4 (aq) SA H3O+(aq) + PO43-(aq) H2O(l) SB H2O(l) + HPO42-(aq) 50 species present + NH HF(aq) CH COO 4 (aq) 3 (aq) SA HF(aq) + CH3COO-(aq) Stronger Acid H2O(l) SB F-(aq) + CH3COOH(aq) Weaker Acid Products favored 51 strongest acid species present Ca2+(aq) Cl-(aq) Pb2+(aq) SO42-(aq) H2O(l) strongest base H2O(l) + SO42-(aq) Weaker Acid Reactants favored HSO4-(aq) + OH-(l) Stronger Acid 52 NO!! Products are NOT always favoured Try these: CH3COOH(aq) + NH4F(aq) HCN(aq) + NaHS(aq) 53 Acid-Base Calculations Kw Ka Kb [H3O+] pH [OH-] pOH 54 Kw (Ionization Constant for water) With very sensitive conductivity testers, pure water shows slight electrical conductivity. PURE WATER MUST HAVE A SMALL CONCENTRATION OF DISSOLVED IONS 55 Kw Auto-Ionization of water H2O(l) + H2O(l) Kw == H3O+(aq) + OH-(aq) [H3O+] [OH-] [H2O] [H2O] 56 Kw In pure water at 25 °C; [H3O+] = 1.00 x 10-7 mol/L [OH-] = 1.00 x 10-7 mol/L Calculate Kw at 25 °C. 57 H2O(l) + H2O(l) H3O+(aq) + OH- What happens if we add OHions (NaOH(aq)) to water? shift to the left [H3O+] ? [OH-] ? Does Kw change? LCP: GET REAL!! 58 Kw = [H3O+] [OH-] 1.00 x 10-14 = [H3O+] [OH-] [H3O+] 0.00357 M 2.04 x 10-12 8.00 x 10-16 1.50 mol/L [OH-] 2.80 x 10-12 4.89 x 10-3 mol/L 12.5 M 6.67 x 10-15 59 Calculations with Kw (p. 564 – 566) For strong acids and strong bases, the [H3O+] and [OH-] may be calculated using the solute concentration. eg. What is the [H3O+] in a 2.00 mol/L solution of HNO3(aq)? Ans: 2.00 mol/L [OH-] = ??? 60 Calculations with Kw eg. What is the [OH-] in a 2.00 mol/L solution of NaOH(aq)? Ans: 2.00 mol/L eg. What is the [OH-] in a 2.00 mol/L solution of Ca(OH)2(aq)? Ans: 4.00 mol/L [H3O+] = ??? 61 Calculations with Kw eg. What molar concentration of Al(OH)3(aq) is needed to obtain a [OH-] = 0.450 mol/L? Ans: 0.150 mol/L 62 What is the [H3O+] and [OH-] in: [H3O+] [OH-] 1.0 x 10-8 1.0 x 10-6 5.00 x 10-14 0.200 1.50 6.67 x 10-15 1.0 x 10-2 1.0 x 10-12 63 solute [H3O+] [OH-] 0.680 mol/L HCl(aq) 0.680 1.47 x 10-14 1.50 M NaOH 6.67 x 10-15 1.50 0.0500 M Ca(OH)2(aq) 1.00 x 10-13 0.100 0.450 mol/L HClO4(aq) _____ 0.450 M 2.22 x 10-14 ____ mol/L Mg(OH)2(aq) 2.00 x 10-14 0.500 mol/L 0.250 p. 566 #’s 12 - 15 64 what factor does thep. 568) pH By and pOH (See + [H3O ] change when the pH value changes by 1? by 2? 65 pH The [H3O+] changes by a and pOH p. 568) factor of 10 (10X)(See for each pH changes of 1. 66 pH and pOH FORMULAS pH = -log [H3O+] pOH = -log [OH-] [H3O+] = 10-pH [OH-] = 10-pOH 67 pH and pOH eg. What is the pH of a 0.0250 mol/L solution of HCl(aq)? What is the pOH of a 0.00087 mol/L solution of NaOH(aq)? What is the pH of a 1.25 mol/L solution of KOH(aq)? 68 Significant digits in pH values? The number of significant digits in a concentration should be the same as the number of digits to the right of the decimal point in the pH value. eg. In a sample of OJ the [H3O+] = 2.5 × 10−4 mol/L pH = 3.60 (See p. 568) 69 [H3O+] [OH-] pH pOH 0.0035 1.2 x 10-5 4.68 9.15 8.33 x 10-15 -1.10 70 [H3O+] [OH-] pH 0.0035 2.9 x 10-12 2.46 1.2 x 10-5 9.08 2.1 x 10-5 4.8 x 10-10 4.68 1.4 x 10-5 7.1 x 10-10 4.85 1.20 8.33 x 10-15 13 7.9 x 10-16 -0.079 -1.10 8.3 x 10-10 pOH 11.54 4.92 9.32 9.15 14.079 15.10 71 pH, pOH and Kw p. 569 #’s 16 – 19 p. 572 #’s 20 – 25 Examine #23. Where is the energy term in this equation? H2O(l) + H2O(l) H3O+(aq) + OH-(aq) 72 Dilutions When a solution is diluted the number of moles does not change. OR ninitial = nfinal CiVi = CfVf 73 eg. 400.0 mL of water was added to 25.0 mL of HCl(aq) that had a pH of 3.563. Calculate the pH of the resulting solution. [H3O+] dilution formula calculate pH calculate 74 Before dilution: [H3O+] = 10-3.563 = 2.735 x 10-4 mol/L After dilution: (2.735 x 10-4) (25.0 mL) = (Cf)(425.0 mL) [H3O+] = 1.609 x 10-5 pH = -log (1.609 x 10-5) = 4.793 p.574 #’s 26 - 29 75