1 Acids and Bases Chapter 14 © 2009 Brooks/Cole - Cengage Objectives • • • • • • • • • • Review acids and bases (Chem I & Ch. 4) Bronstead acids and bases Define autoionization of water, Kw and pH Define Keq for acids (Ka) and bases (Kb) Types of reactions (qualitative) Calculations w/Keq’s (Ka, Kb and Kw) Polyprotic acids Acid/base properties of salts Lewis acids and bases Molecular structure and acid strength © 2009 Brooks/Cole - Cengage 2 Ch. 14.1 – The Nature of Acids and Bases © 2009 Brooks/Cole - Cengage 3 4 Acid and Bases © 2009 Brooks/Cole - Cengage 5 Acid and Bases © 2009 Brooks/Cole - Cengage Some Definitions • Arrhenius acids and bases – Acid: Substance that, when dissolved in water, increases the concentration of hydrogen ions (protons, H+). HCl(aq) H+(aq) + Cl-(aq) – Base: Substance that, when dissolved in water, increases the concentration of hydroxide ions. NaOH(aq) Na+(aq) + OH-(aq) © 2009 Brooks/Cole - Cengage 6 7 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 © 2009 Brooks/Cole - Cengage ACID-BASE THEORIES The Brønsted definition means NH3 is a BASE in water — and water is itself an ACID NH3 Base © 2009 Brooks/Cole - Cengage + H2O Acid NH4+ + OHAcid Base 8 9 ACID-BASE THEORIES NH3 is a BASE in water — and water is itself an ACID NH3 / NH4+ is a conjugate by the gain or loss of H+ pair — related Every acid has a conjugate base - and vice-versa. © 2009 Brooks/Cole - Cengage Conjugate Pairs © 2009 Brooks/Cole - Cengage 10 11 Acid/Base Conjugate Pair Practice • Write the formula for the conjugate acid of each of the following bases: Base Conj. Acid HSO3H2SO3 FHF PO43HPO42CO HCO+ © 2009 Brooks/Cole - Cengage 12 Conjugate Acid-Base Pair Examples • H2S + NH3 NH4+ + HS• NH3 + HCO31- NH4+ + CO32• H3PO4 + H2O H2PO4- + H3O+ © 2009 Brooks/Cole - Cengage 13 Ch. 14.2 – Acid Strength • Generally divide acids and bases into STRONG or WEAK ones. STRONG ACID: HNO3(aq) + H2O(liq) H3O+(aq) + NO3-(aq) HNO3 is about 100% dissociated in water. © 2009 Brooks/Cole - Cengage Strong and Weak Acids HNO3, HCl, HI, HBr, H2SO4, HClO3 and HClO4 are the strong acids. © 2009 Brooks/Cole - Cengage 14 Strong and Weak Acids • Weak acids are much less than 100% ionized in water. One of the best known is acetic acid = CH3CO2H Also written as HC2H3O2 or HOAc © 2009 Brooks/Cole - Cengage 15 Water as an Acid and a Base H2O can function as both an ACID and a BASE. In pure water there can be AUTOIONIZATION Dissociation Constant for Water= Kw Kw = [H3O+] [OH-] = 1.00 x 10-14 at 25 oC © 2009 Brooks/Cole - Cengage 16 Water as an Acid and as a Base Kw = [H3O+] [OH-] = 1.00 x 10-14 at 25 oC In a neutral solution [H3O+] = [OH-] so Kw = [H3O+]2 = [OH-]2 and so [H3O+] = [OH-] = 1.00 x 10-7 M © 2009 Brooks/Cole - Cengage 17 Calculating [H3O+] & [OH-] You add 0.0010 mol of NaOH to 1.0 L of pure water. Calculate [H3O+] and [OH-]. Solution 2 H2O(liq) H3O+(aq) + OH-(aq) Le Chatelier predicts equilibrium shifts to the __left____. [H3O+] < 10-7 at equilibrium. Set up a ICE table. © 2009 Brooks/Cole - Cengage 18 Calculating [H3O+] & [OH-] You add 0.0010 mol of NaOH to 1.0 L of pure water. Calculate [H3O+] and [OH-]. Solution 2 H2O(liq) H3O+(aq) + OH-(aq) initial 0 0.0010 change +x +x equilib x 0.0010 + x Kw = (x) (0.0010 + x) Because x << 0.0010 M, assume [OH-] = 0.0010 M [H3O+] = x = Kw / 0.0010 = 1.0 x 10-11 M © 2009 Brooks/Cole - Cengage 19 Calculating [H3O+] & [OH-] You add 0.0010 mol of NaOH to 1.0 L of pure water. Calculate [H3O+] and [OH-]. Solution 2 H2O(liq) H3O+(aq) + OH-(aq) [H3O+] = Kw / 0.0010 = 1.0 x 10-11 M This solution is _________ because [H3O+] < [OH-] © 2009 Brooks/Cole - Cengage 20 Ch. 14.3 – The pH Scale A common way to express acidity and basicity is with pH pH = - log [H3O+] In a neutral solution, [H3O+] = [OH-] = 1.00 x 10-7 at 25 oC pH = -log (1.00 x 10-7) = - (-7) = 7 © 2009 Brooks/Cole - Cengage 21 The pH Scale What is the pH of the 0.0010 M NaOH solution? [H3O+] = 1.0 x 10-11 M pH = - log (1.0 x 10-11) = 11.00 General conclusion — Basic solution Neutral Acidic solution © 2009 Brooks/Cole - Cengage pH > 7 pH = 7 pH < 7 22 23 The pH Scale See Active Figure 17.1 © 2009 Brooks/Cole - Cengage pH Calculations If the pH of Coke is 3.12, it is _acidic__. Because pH = - log [H3O+] then log [H3O+] = - pH Take antilog and get [H3O+] = 10-pH [H3O+] = 10-3.12 = 7.6 x 10-4 M © 2009 Brooks/Cole - Cengage 24 pH of Common Substances © 2009 Brooks/Cole - Cengage 25 Other pX Scales In general pX = -log X and so pOH = - log [OH-] Kw = [H3O+] [OH-] = 1.00 x 10-14 at 25 oC Take the log of both sides -log (10-14) = - log [H3O+] + (-log [OH-]) pKw = 14 = pH + pOH So if you know one, you can determine the others. © 2009 Brooks/Cole - Cengage 26 pH, pOH, [H+], [OH-] Practice 27 pH pOH [H+] [OH-] Acidic/Basic? 6.21 7.79 6.2 x 10-7 1.6 x 10-8 acidic 3.87 10.13 1.3 x 10-4 7.4 x 10-11 acidic 2.46 11.54 3.5 x 10-3 2.9 x 10-12 acidic 10.75 3.25 1.8 x 10-11 5.6 x 10-4 basic © 2009 Brooks/Cole - Cengage Ch. 14.4 – Calculating the pH of Strong Acid Solutions • What are the major species in solution? • What is the dominant reaction that will take place? – Is it an equilibrium reaction or a reaction that will go essentially to completion? – React all major species until you are left with an equilibrium reaction. • Solve for the pH if needed. © 2009 Brooks/Cole - Cengage 28 29 pH of Strong Acid Solutions Consider an aqueous solution of 2.0 × 10–3 M HCl. What are the major species in solution? H+, Cl–, H2O What is the pH? pH = 2.70 © 2009 Brooks/Cole - Cengage 30 pH of Strong Acid Solutions Calculate the pH of a 1.5 × 10–11 M solution of HCl. pH = 7.00 © 2009 Brooks/Cole - Cengage pH of Strong Acid Solutions Calculate the pH of a 1.5 × 10–2 M solution of HNO3. When HNO3 is added to water, a reaction takes place immediately: HNO3 + H2O H3O+ + NO3– The reaction controlling the pH is: H2O + H2O H3O+(aq) + OH-(aq) © 2009 Brooks/Cole - Cengage 31 pH of Strong Acid Solutions 32 Let’s Think About It… • What reaction controls the pH? • H2O(l) + H2O(l) H3O+(aq) + OH–(aq) • In aqueous solutions, this reaction is always taking place. • But is water the major contributor of H+ (H3O+)? pH = - log (1.5x10-2) = 1.82 © 2009 Brooks/Cole - Cengage Ch. 14.5 – Calculating pH of Weak Acid Solutions Aspirin is a good example of a weak acid, where most of the species exist as the neutral molecule and not as ions. © 2009 Brooks/Cole - Cengage 33 Calculating pH of Weak Acid Solutions 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%). © 2009 Brooks/Cole - Cengage 34 35 Calculating pH of Weak Acid Solutions Consider acetic acid, CH3CO2H (HOAc) HOAc + H2O H3O+ + OAcAcid Conj. base Ka = [H3O+ ][OAc - ] [HOAc] = 1.8 x 10-5 (K is designated Ka for ACID) Because [H3O+] and [OAc-] are SMALL, Ka << 1. © 2009 Brooks/Cole - Cengage Equilibrium Constants for Weak Acids Weak acid has Ka < 1 Leads to small [H3O+] and a pH of 2 - 7 pKa = -log Ka © 2009 Brooks/Cole - Cengage 36 Ionization Constants for Acids/Bases Acids Conjugate Bases Increase strength Increase strength © 2009 Brooks/Cole - Cengage 37 Calculating pH of Weak Acid Solutions You have 1.00 M HOAc. Calculate the equilibrium concentrations of HOAc, H3O+, OAc-, and the pH. Step 1. Define equilibrium concs. in ICE table. [HOAc] initial change equilib © 2009 Brooks/Cole - Cengage [H3O+] [OAc-] 38 Calculating pH of Weak Acid Solutions You have 1.00 M HOAc. Calc. the equilibrium concs. of HOAc, H3O+, OAc-, and the pH. Step 1. Define equilibrium concs. in ICE table. HOAC(aq) + H2O OAC- + H3O+ [HOAc] [H3O+] [OAc-] initial 1.00 0 0 change -x +x +x equilib 1.00-x x x Note that we neglect [H3O+] from H2O. © 2009 Brooks/Cole - Cengage 39 Calculating pH of Weak Acid Solutions You have 1.00 M HOAc. Calc. the equilibrium concs. of HOAc, H3O+, OAc-, and the pH. Step 2. Write Ka expression K a = 1.8 x 10-5 = [H3O+ ][OAc - ] [HOAc] x2 = 1.00 - x This is a quadratic. However… © 2009 Brooks/Cole - Cengage 40 Calculating pH of Weak Acid Solutions You have 1.00 M HOAc. Calc. the equilibrium concs. of HOAc, H3O+, OAc-, and the pH. Step 3. Solve Ka expression K a = 1.8 x 10-5 = [H3O+ ][OAc - ] [HOAc] x2 = 1.00 - x First assume x is very small because Ka is so small. Therefore, Ka = 1.8 x 10-5 x2 = 1.00 Now we can more easily solve this approximate expression. © 2009 Brooks/Cole - Cengage 41 Calculating pH of Weak Acid Solutions You have 1.00 M HOAc. Calc. the equilibrium concs. of HOAc, H3O+, OAc-, and the pH. Step 3. Solve Ka approximate expression Ka = 1.8 x 10-5 x2 = 1.00 x = [H3O+] = [OAc-] = [Ka • 1.00]1/2 x = [H3O+] = [OAc-] = 4.2 x 10-3 M pH = - log [H3O+] = -log (4.2 x 10-3) = 2.37 © 2009 Brooks/Cole - Cengage 42 Calculating pH of Weak Acid Solutions Consider the approximate expression Ka = 1.8 x 10-5 x2 = 1.00 x = [H3O+ ] = [Ka 1/2 1.00] For many weak acids [H3O+] = [conj. base] = [Ka • Co]1/2 where C0 = initial conc. of acid Useful Rule of Thumb: If Co > 100*Ka then [H3O+] = [Ka•Co]1/2 In other words, the amount of ionization is small relative to the initial amount. © 2009 Brooks/Cole - Cengage 43 Calculating pH of Weak Acid Solutions Calculate the pH of a 0.0010 M solution of formic acid, HCO2H. HCO2H + H2O HCO2- + H3O+ Ka = 1.8 x 10-4 Approximate solution [H3O+] = [Ka • Co]1/2 = 4.2 x 10-4 M, pH = 3.37 Exact Solution [H3O+] = [HCO2-] = 3.4 x 10-4 M [HCO2H] = 0.0010 - 3.4 x 10-4 = 0.0007 M pH = 3.47 © 2009 Brooks/Cole - Cengage 44 45 Calculating pH of Weak Acid Solutions Calculate the pH of a 0.50 M aqueous solution of HF. (Ka = 7.2 x 10-4) What are the major species in solution? HF, H2O Why aren’t H+ and F– major species? Only a few are formed from the dissociation of HF. © 2009 Brooks/Cole - Cengage 46 Calculating pH of Weak Acid Solutions What are the possibilities for the dominant reaction? HF(aq) + H2O(l) H3O+(aq) + F–(aq) Ka=7.2 × 10-4 H2O(l) + H2O(l) H3O+(aq) + OH–(aq) Kw=1.0 × 10-14 Which reaction controls the pH? Why? © 2009 Brooks/Cole - Cengage 47 Calculating pH of Weak Acid Solutions Steps Toward Solving for pH Initial Change Equilibrium H3O+(aq) + F–(aq) 0.50 M ~0 ~0 –x +x +x 0.50–x x x HF(aq) + H2O Ka = 7.2 × 10–4 [H3O+] =(Ka*Co)1/2= (7.2x10-4*0.05)1/2=0.0190 pH = -log(0.0190) = 1.72 © 2009 Brooks/Cole - Cengage Using Ka Example A 0.10 M aqueous solution of lactic acid, CH3CHOHCOOH, has a pH of 2.43. What is the Ka of lactic acid? 1. Write the equilibrium expression: HLac(aq) + H2O(l) ⇌ H3O+(aq) + Lac-(aq) 0.10 – x x x + − 𝑯𝟑𝑶 [𝑳𝒂𝒄 ] 2. Know Ka = [𝑯𝑳𝒂𝒄] 3. Also know [H3O+] = [Lac-] = 10-2.43 =0.00372 and [HLac] = 0.10 – 0.00372 = 0.0963 4. Substitute: [0.00372][0.00372] = 1.4 x 10-4 [0.0963] © 2009 Brooks/Cole - Cengage 48 Using Ka Practice 49 A solution prepared from 0.55 mol of butanoic acid is dissolved in water to give 1.0 L of solution with a pH of 2.21. Determine the Ka for butanoic acid. The acid ionizes according to the equation below. CH3(CH2)2COOH(aq) + H2O(l) H3O+(aq) + CH3(CH2)2COO- © 2009 Brooks/Cole - Cengage 50 a pH meter 0.0001 M Percent Dissociation 0.003 M 0.06 M pH of an acetic acid solution. What are your observations? 2.0 M © 2009 Brooks/Cole - Cengage 51 Percent Dissociation (Ionization) amount dissociated (mol/L) Percent dissociation = 100% initial concentration (mol/L) • For a given weak acid, the percent dissociation increases as the acid becomes more dilute. © 2009 Brooks/Cole - Cengage Percent Dissociation Example A solution of 8.00 M formic acid (HCHO2) is 0.47% ionized in water. Calculate the Ka value for formic acid. Determine the pH of the solution. If 8.00 M of the acid is 0.47% ionized, then 0.038 M dissociates. I C E HCHO2(aq) + H2O H3O+(aq) + CHO2-(aq) 8.00 0 0 -0.038 +0.038 +0.038 7.96 0.038 0.038 𝑲𝒂 = (𝟎.𝟎𝟑𝟖)(𝟎.𝟎𝟑𝟖) 𝟕.𝟗𝟔 = 1.8 x 10-4 [H+]=0.038 so pH = -log(0.038) = 1.42 © 2009 Brooks/Cole - Cengage 52 53 Percent Dissociation The value of Ka for a 4.00 M formic acid solution should be: higher than lower than the same as the value of Ka of an 8.00 M formic acid solution. Explain. © 2009 Brooks/Cole - Cengage 54 Percent Dissociation However, the % Dissociation and the pH are higher!! Dominant rxn: HCHO2(aq) + H2O H3O+(aq) + CHO2-(aq) HCHO2(aq) + H2O H3O+(aq) + CHO2-(aq) I 4.00 0 0 C -x +x +x E 4.00-x x x Ka = 1.8 x 10-4 = (x)2/(4.00-x) x = 0.027; (0.027/4.00) x 100 = 0.67% pH=-log(0.027) = 1.57 © 2009 Brooks/Cole - Cengage Ch. 14.6 - Bases • Strong Base: 100% dissociated in water. NaOH(aq) Na+(aq) + OH-(aq) Other common strong bases include KOH and Ca(OH)2. CaO (lime) + H2O CaO © 2009 Brooks/Cole - Cengage Ca(OH)2 (slaked lime) 55 56 Bases • Weak base: less than 100% ionized in water One of the best known weak bases is ammonia NH3(aq) + H2O(liq) NH4+(aq) + OH-(aq) © 2009 Brooks/Cole - Cengage 57 Weak Bases Weak base has Kb < 1 Leads to small [OH-] and a pH of 12 - 7 pKb = -log Kb © 2009 Brooks/Cole - Cengage 58 Weak Bases © 2009 Brooks/Cole - Cengage Equilibria Involving A Weak Base You have 0.010 M NH3. Calc. the pH. NH3 + H2O NH4+ + OH- Kb = 1.8 x 10-5 Step 1. Define equilibrium concs. in ICE table [NH3] initial change equilib © 2009 Brooks/Cole - Cengage [NH4+] [OH-] 59 Equilibria Involving A Weak Base You have 0.010 M NH3. Calc. the pH. NH3 + H2O NH4+ + OH- Kb = 1.8 x 10-5 Step 1. Define equilibrium concs. in ICE table [NH3] [NH4+] [OH-] initial 0.010 0 0 change -x +x +x equilib 0.010 - x x x © 2009 Brooks/Cole - Cengage 60 Equilibria Involving A Weak Base You have 0.010 M NH3. Calc. the pH. NH3 + H2O NH4+ + OH- Kb = 1.8 x 10-5 Step 2. Solve the equilibrium expression -5 Kb = 1.8 x 10 = [NH4+ ][OH- ] [NH3 ] x2 = 0.010 - x Assume x is small (Co>100•Kb), so x = [OH-] = [NH4+] = 4.2 x 10-4 M and [NH3] = 0.010 - 4.2 x 10-4 ≈ 0.010 M The approximation is valid ! © 2009 Brooks/Cole - Cengage 61 Equilibria Involving A Weak Base You have 0.010 M NH3. Calc. the pH. NH3 + H2O NH4+ + OH- Kb = 1.8 x 10-5 Step 3. Calculate pH [OH-] = 4.2 x 10-4 M so pOH = - log [OH-] = 3.37 Because pH + pOH = 14, pH = 10.63 © 2009 Brooks/Cole - Cengage 62 63 Relationship between Ka and Kb Ka and Kb are linked: Combined reaction = ? © 2009 Brooks/Cole - Cengage 64 Relationship between Ka and Kb Ka and Kb are related in this way: Ka Kb = Kw Therefore, if you know one of them, you can calculate the other. 64 © 2009 Brooks/Cole - Cengage 65 Relationship between Ka and Kb Ka and Kb are linked: Combined reaction = ? © 2009 Brooks/Cole - Cengage Ka and Kb Comparison Several acids are listed here with their respective Ka’s. C6H6OH(aq) + H2O(l) H3O+(aq) + C6H5O-(aq) Ka = 1.3 x 10-10 HCO2H(aq) + H2O(l) H3O+(aq) + HCO2-(aq) Ka = 1.8 x 10-4 HC2O4-(aq) + H2O(l) H3O+(aq) + C2O42-(aq) Ka = 6.4 x 10-5 a) Which acid is the strongest? Weakest? b) Which acid has the weakest conjugate base? Strongest? c) What are the pKa values of each acid? © 2009 Brooks/Cole - Cengage 66 67 Ch. 14.7 - Polyprotic Acids Have more than one acidic proton. If the difference between the Ka for the first dissociation and subsequent Ka values is 103 or more, the pH generally depends only on the first dissociation. 67 © 2009 Brooks/Cole - Cengage 68 Polyprotic Acids • Acids that can furnish more than one proton. • Always dissociates in a stepwise manner, one proton at a time. • The conjugate base of the first dissociation equilibrium becomes the acid in the second step. Example: Citric Acid Dissociation: H3C6H5O7 + H2O H2C6H5O7- + H3O+ Ka1 = 7.4x10-4 H2C6H5O7- + H2O HC6H5O72- + H3O+ Ka2 = 1.7x10-5 HC6H5O72- + H2O C6H5O73- + H3O+ Ka3 = 4.0x10-7 68 © 2009 Brooks/Cole - Cengage 69 Polyprotic Acids • For a typical weak polyprotic acid: Ka1 > Ka2 > Ka3 • For a typical polyprotic acid in water, only the first dissociation step is important to pH, especially if Ka1 >1000Ka2 and so on. • Example Ascorbic Acid: H2C6H6O6 + H2O HC6H6O6- + H3O+ Ka1 = 8.0 x10-5 HC6H6O6- + H2O C6H6O62- + H3O+ Ka2 = 1.6x10-12 • In other words, the amount of H3O+ that HC6H6O6- is contributing to the solution is negligible compared to the H2C6H6O6. (It’s negligible compared to water too!) 69 © 2009 Brooks/Cole - Cengage Ch. 14.8 - Acid-Base Properties of Salts • Salts are ionic compounds. • Salts of the cation of strong bases and the anion of strong acids are neutral. For example: NaCl, KNO3 • There is no equilibrium for strong acids and bases. • We ignore the reverse reaction. • So… © 2009 Brooks/Cole - Cengage 70 71 Acid-Base Properties of Salts MX + H2O acidic or basic solution? Consider NH4Cl NH4Cl(aq) NH4+(aq) + Cl-(aq) (a) Reaction of Cl- with H2O Cl- + H2O HCl + OHbase acid acid base Cl- ion is a VERY weak base because its conjugate acid is strong. Therefore, [Cl-] does not affect pH and above reaction lies completely to the left. © 2009 Brooks/Cole - Cengage 72 Acid-Base Properties of Salts NH4Cl(aq) NH4+(aq) + Cl-(aq) (b) Reaction of NH4+ with H2O NH4+ + H2O NH3 + H3O+ acid base base acid NH4+ ion is a moderate acid because its conjugate base is weak. Therefore, NH4+ is an acidic solution See TABLE 14.6 for a summary of acid-base properties of ions. © 2009 Brooks/Cole - Cengage Acid-Base Properties of Salts Cation neutral neutral Anion neutral conjugate base of weak acid neutral Acidic or Basic neutral basic conjugate acidic acid of weak base conjugate conjugate depends acid of base of on Ka & Kb weak base weak acid values © 2009 Brooks/Cole - Cengage Example NaCl NaF NH4Cl Al2(SO4)3 73 Acid-Base Properties of Salts Example What is the pH of a 0.015 M solution of sodium acetate? C2H3O2-(aq) + H2O(l) C2H3O2H(aq) + OH-(aq) I 0.015 C -x E 0.015-x 0 +x x 0 +x +x Since the acetate ion is the conjugate base of a weak acid, it’s going to act as a base and take H+ away from the ‘acid’ water. © 2009 Brooks/Cole - Cengage 74 Acid-Base Properties of Salts Example © 2009 Brooks/Cole - Cengage 75 Acid-Base Properties of Salts Example pH = 14 – 5.54 = 8.46 © 2009 Brooks/Cole - Cengage 76 Acid-Base Properties of Salts Practice Sodium hypochlorite, NaClO, is used as a disinfectant in swimming pools and water treatment plants. What are the concentrations of HClO and OH- and the pH of a 0.025 M solution of NaClO? ClO-(aq) + H2O(l) ⇌ HClO(aq) + OH-(aq) I 0.025 0 0 C -x +x +x E 0.025-x x x Kb = X2 0.025−x = 2.9 x 10-7 x = 0.025 ∗ 2.9 𝑥10−7 = 8.51x10-5 = [OH-] pOH = -log(8.51x10-5) = 4.07 So, the pH = 14.00 – 4.07 = 9.93 © 2009 Brooks/Cole - Cengage 77 Acid-Base Example of a Polyprotic Salt Calculate the pH of a 0.10 M solution of Na2CO3. Na+ + H2O neutral CO32- + H2O HCO3- + OHbase acid acid base Kb = 2.1 x 10-4 Step 1. Set up ICE table [CO32-] initial 0.10 change -x equilib 0.10 - x © 2009 Brooks/Cole - Cengage [HCO3-] [OH-] 0 +x x 0 +x x 78 Acid-Base Example of a Polyprotic Salt Calculate the pH of a 0.10 M solution of Na2CO3. Na+ + H2O is neutral CO32- + H2O HCO3- + OHbase acid acid base Kb = 2.1 x 10-4 Step 2. Solve the equilibrium expression Kb = 2.1 x 10-4 = [HCO3- ][OH- ] [CO3 2- ] x2 = 0.10 - x Assume 0.10 - x ≈ 0.10, because 100•Kb < Co x = [HCO3-] = [OH-] = 0.0046 M © 2009 Brooks/Cole - Cengage 79 Acid-Base Example of a Polyprotic Salt Calculate the pH of a 0.10 M solution of Na2CO3. Na+ + H2O is neutral CO32- + H2O HCO3- + OHbase acid acid base Kb = 2.1 x 10-4 Step 3. Calculate the pH [OH-] = 0.0046 M pOH = - log [OH-] = 2.34 pH + pOH = 14, so pH = 11.66, and the solution is ___basic_. © 2009 Brooks/Cole - Cengage 80 Acid-Base Example of a Polyprotic Salt • Notice now that HCO3- can act as a base as well. Does the Kb for this base affect pH? HCO3- + H2O H2CO3 + OHbase Step 1. initial change equilib © 2009 Brooks/Cole - Cengage acid acid base Kb = 2.4 x 10-8 Set up ICE table as before only… [HCO31-] [H2CO3] [OH-] 0.0046 -x 0.0046 - x 0 +x x 0.0046 +x 0.0046 + x 81 Acid-Base Example of a Polyprotic Salt HCO3- + H2O H2CO3 + 82 OH- base acid acid base Kb = 2.4 x 10-8 Step 2. Solve the equilibrium expression Kb = [𝐱][𝟎.𝟎𝟎𝟒𝟔+𝐱] [𝟎.𝟎𝟎𝟒𝟔 −𝐱] = 𝟐. 𝟒 𝐱 𝟏𝟎−𝟖 Step 3. Solve. Again assume x is small relative to 0.0046. Then x = 2.4 x 10-8, which really doesn’t add any measurable difference. Since the Ka’s for the two acids differ by >103, all of the OH- are made by CO32-. © 2009 Brooks/Cole - Cengage Ch. 14.9 – Effect of Structure on Acid/Base Properties • Why are some compounds acids? • Why are some compounds bases? • Why do acids and bases vary in strength? • Can we predict variations in acidity or basicity? © 2009 Brooks/Cole - Cengage 83 84 Why is CH3CO2H an Acid? +0.12 +0.24 See Figure 17.12 –0.32 1. The electronegativity of the O atoms causes the H attached to O to be highly positive. 2. The O—H bond is highly polar. 3. The H atom of O—H is readily attracted to polar H2O. © 2009 Brooks/Cole - Cengage 85 Acetic acid Ka = 1.8 x 10-5 Trichloroacetic acid Ka = 0.3 • Trichloroacetic acid is a much stronger acid owing to the high electronegativity of Cl. • Cl withdraws electrons from the rest of the molecule. • This makes the O—H bond highly polar. The H of O—H is very positive. © 2009 Brooks/Cole - Cengage 86 Factors Affecting Acid Strength For a series of oxyacids, acidity increases with the number of oxygens. 86 © 2009 Brooks/Cole - Cengage 87 Basicity of Oxoanions NO3- CO32- PO43- These ions are BASES. They become more and more basic as the negative charge increases. As the charge goes up, they interact more strongly with polar water molecules. © 2009 Brooks/Cole - Cengage Acid Properties of Metal Ion Solutions Electron withdrawing explains why water solutions of Fe3+, Al3+, Cu2+, Pb2+, etc. are acidic. This interaction weakens this bond Another H2O pulls this H away as H+ © 2009 Brooks/Cole - Cengage 88 89 Ch. 14.10 - Acid/Base Properties of Oxides • Acidic Oxides (Acid Anhydrides): – O—X bond is strong and covalent. SO2, NO2, CO2 • When H—O—X grouping is dissolved in water, the O—X bond will remain intact. It will be the polar and relatively weak H—O bond that will tend to break, releasing a proton. © 2009 Brooks/Cole - Cengage 90 Acid/Base Properties of Oxides • Basic Oxides (Basic Anhydrides): – O—X bond is ionic. K2O, CaO • If X has a very low electronegativity (i.e. metal), the O—X bond will be ionic and subject to being broken in polar water, producing a basic solution. © 2009 Brooks/Cole - Cengage Ch. 14.11 - Lewis Acid-Base Model 91 Lewis acid a substance that accepts an electron pair Lewis base a substance that donates an electron pair © 2009 Brooks/Cole - Cengage 92 Reaction of a Lewis Acid and Lewis Base • New bond formed using electron pair from the Lewis base. • Coordinate covalent bond • Notice geometry change on reaction. © 2009 Brooks/Cole - Cengage Lewis Acids & Bases Formation of hydronium ion is also an excellent example. H + ACID •• •• O—H H BASE •• H O—H H •Electron pair of the new O-H bond originates on the Lewis base. © 2009 Brooks/Cole - Cengage 93 94 Lewis Acid/Base Reaction © 2009 Brooks/Cole - Cengage AP Exam Practice • 2009B AP Exam #1 • 2009 AP Exam #1 • 2007 AP Exam #1 • 2005 AP Exam #1(a,b,d,e) © 2009 Brooks/Cole - Cengage 95