CHAPTER 14: ACIDS & BASES Chem 1212 Dr. Aimée Tomlinson Section 14.1 Acid-Base Concepts: The Brønsted-Lowry Theory Three Theories for Acids & Bases Arrhenius acids & bases acid: an H + donor base: an O H - donor H A ( aq ) M O H ( aq ) H ( aq ) A ( aq ) M ( aq ) O H ( aq ) Brønsted-Lowry acids & bases H ( aq ) A ( aq ) acid: an H + donor H A ( aq ) base: H + acceptor H ( aq ) B ( aq ) B H ( aq ) Lewis acids & bases W e w ill see this type at the end of the chapter Conjugate Acid-Base Pairs conjugate acid: the acid that is created after the Brønsted-Lowry base has accepted the proton, BH+ conjugate base: the base that is created after the Brønsted-Lowry acid has donated the proton, A- Examples basic : N H 3 ( g ) H 2 O ( l ) base base conj acid acid acidic : H C l H 2 O acid N H 4 ( aq ) O H ( aq ) Cl conj base H 3O K b 1.76 10 conj base conj acid K a 1 5 Section 14.2 Acid & Base Strength Strong Acids A strong acid will completely dissociate/ionize: All the reactant goes to product/single-headed arrow The product is a very weak conjugate acid/base pair List of Strong acids: HCl, HBr, H2SO4, HI, HClO4, HClO3, HNO3 Strong Bases A strong base will completely dissociate/ionize: List of Strong bases: MOH (M=alkali metal), NH2-, H- Weak Acids Only partially dissociate H N O 2 ( aq ) H ( aq ) N O 2 ( aq ) K a 4.0 10 4 The eq constant is called Ka where “a” for acid There is always some reactant still present at eq unlike the strong acid case The larger the Ka the stronger the acid E.g. Ka >> 1 for HNO3 We will come back to this in a little bit Section 14.3 Hydrated Protons & Hydronium Ions Meet Hydronium H3O+ is acidified water or what truly happens when H+ is in H2O We call this ion hydronium We use H+ and H3O+ interchangeably Amphoterism Defn: A species that may act as both an acid and a base Water as a base: H A ( aq ) H 2 O ( l ) H 3 O ( aq ) A ( aq ) Water as an acid: B ( aq ) H 2 O ( l ) B H ( aq ) O H ( aq ) Section 14.4 Dissociation of Water What’s in Water & What it Means 2𝐻2 𝑂 𝑙 ⇌ 𝑂𝐻−𝑎𝑞 + 𝐻3 𝑂+𝑎𝑞 𝐾𝑐 = [𝑂𝐻−𝑎𝑞 ][𝐻3 𝑂+𝑎𝑞 = 𝐾𝑤 NOTE H2O(l) as always is not in the equilibrium expression Relationship between [OH-(aq)] and [H3O+(aq)]: [ H 3 O ( aq ) ] [ O H ( aq ) ] [ H 3 O ( aq ) ] [ O H ( aq ) ] [ H 3 O ( aq ) ] [ O H ( aq ) ] acidic neutral basic For both ions their concentrations at 298 K is 1.0 x 10-7M making the Kw = 1.0 x 10-14 K w (1.0 10 7 )(1.0 10 7 ) 1.0 10 14 Example Determine the hydroxide concentration in a solution with 𝐻3 𝑂+𝑎𝑞 =1.89 x 10-4 M. Section 14.5 The pH Scale Power of Hydrogen aka pH pH log H 3 O aq pH < 7.0 acidic pH = 7.0 neutral pH > 7.0 basic Power of Hydroxide aka pOH pH log O H aq pH > 7.0 acidic pH = 7.0 neutral pH < 7.0 basic Relationship for pH, pOH & Kw Section 14.6 Measuring pH pH Indicators More relevant in Chapter 15 so we will address it more fully there Section 14.7 pH in Solutions of Strong Acids & Strong Bases The Strong Completely Dissociate H3O+/OH- concentrations will become whatever those of the strong acids or bases were Example I EXAMPLE: Write the balanced equation for each of the following and determine the pH. 1.) 0.5000 M HClO4(aq) 2.) 0.0256 M LiOH(aq) Example II Determine the hydronium ion concentration for a 0.01500 M Ca(OH)2 assuming complete dissociation. Section 14.8 Equilibria of Weak Acids Weak Acids & Equilibrium Unlike the strong they only partially dissociate in water hence HA is still present at eq: H A( aq ) H 2 O ( l ) H 3 O ( aq ) A( aq ) or H A( aq ) H ( aq ) A( aq ) H 3 O (aq ) A(aq ) H (aq ) A(aq ) Ka HA HA Ka & Acid Strength The larger the Ka: More strongly the eq will lie toward product More likely the acid is to dissociate The larger the [H3O+] The lower the pH The stronger the acid Ka is large for strong acid HCl but very small for weak acid CH3OH Section 14.9 Calculating the Equilibria of Weak Acids Weak Acids & Equilibrium Calculate [H+] and the pOH of 0.050M of benzoic acid. Ka = 6.5 x 10-5 Weak Acid Flowchart Section 14.10 Percent Dissociation of Weak Acids Percent Dissocation Degree of ionization/dissociation: percentage that an acid ionizes H A( aq ) H ( aq ) A ( aq ) [H ] 100% [ H A] Example: Determine the percent dissociation of 0.050M of benzoic acid. Section 14.11 Polyprotic Acids Polyprotic Acids Acids which possess more than one proton Polyprotic Acid Example Calculate the [H+] of 0.050M of sulfuric acid. H 2 SO 4 ( aq ) H ( aq ) H SO 4 ( aq ) H SO 4 ( aq ) 2 H ( aq ) SO 4 ( aq ) K a 1 K a 1.2 10 2 Polyprotic Acid Flowchart Why Ka1 > Ka2 H 2 SO 4 ( aq ) H ( aq ) H SO 4 ( aq ) H SO 4 ( aq ) 2 H ( aq ) SO 4 ( aq ) K a 1 K a 1.2 10 2 Electrostatically it is more difficult to remove H+ from SO42- than from HSO4- Hence Ka2 is always smaller than Ka1 and so on Section 14.12 Equilibria of Weak Bases Weak Base Equilibria Calculate pH of 0.050M of ammonia. Kb = 1.8 x 10-5 Weak Base Flowchart Section 14.13 The Relationship Between K a & Kb The Link Between Ka & Kb is Kw HCN H 2O CN CN H 2O 2 H 2O H 3O HCN OH H 3O OH Ka Kb Kw Ka Kb Kw Example Determine the Kb of HCN if Ka = 4.9 x 10-10. Section 14.14 Acid/Base Properties of Salts Stronger Partner Dominates Strong acid + weak base = acidic solution Weak acid + strong base = basic solution Strong acid + strong base = neutral solution Example: Classify each of the following as acidic, basic, or neutral. 1.) KBr 2.) NaNO2 3.) NH4Cl What if both are weak? Example II: Classify NH4CN as acidic, basic, or neutral. Finding pH/pOH of a Salt Solution Calculate the pH of a 0.25M NaC2H3O2, Ka = 1.76x10-5 Salt Flowchart Section 14.15 Factors that Affect Acid Strength Recall Electronegativity Trend EN Trend I Increasing acid strength going down the table: As we go down a column we decrease EN We thereby weaken the H-X bond Allows H+ to more readily go into solution Acid strength: HF < HCl < HBr < HI EN Trend II Increasing acid strength from left to right in the table: As we go across we increase EN We make the H-X bond polar This eventually gives an EN difference which leads to H+ Acid strength: CH4 < NH3 < H2O < HF Oxoacids Trend I – more EN An oxoacid is any acid with acidic proton connected to an O-atom – they have the form HnXOm As increase the EN of the halogen X we weaken the O-H bond This is done by pulling electron density from the Oatom This will allow the H+ to break-away more eqsily and go into solution Acid strength: HOI < HOBr < HOCl < HOF Oxoacids Trend II Increasing the number of O-atoms increases acid strength As increase the number of O-atoms weakens the O-H bond Again this is done by pulling electron density from the O-atom This will allow the H+ to break-away more easily and go into solution Acid strength: HOCl < HO2Cl < HO3Cl < HO4Cl Acid Oxidiation State of Cl Ka HClO HClO2 HClO3 HClO4 +1 +3 +5 +7 2.9 x 10-8 1.1 x 10-2 1 1 x 108 Amine Base Trends Increasing the number of electro-donating groups will increase base strength N H 3 N H 2 C H 3 N H C H 3 2 N C H 3 3 Increasing the number of electron-withdrawing/EN groups will decrease base strength N H 3 N H 2 C l N H C l 2 N C l3 Section 14.16 Lewis Acids and Bases Definitions Lewis Acid Electron-pair acceptor N H 3 B F3 H 3 N B F 3 Lewis Base Electron-pair donor