CHAPTER 9 Acids & Bases General, Organic, & Biological Chemistry Janice Gorzynski Smith CHAPTER 9: Acids & Bases Learning Objectives: Define Acids & Bases: Bronsted-Lowry Understand the difference between strong & weak acids Hydronium ion formation Identify conjugate acids & bases Define & calculate Ka, Kb, Kw Water is both an acid & a base Titrations to calculate analyte concentration Buffers Weak acid + conjugate base Weak base + conjugate acid 2 Smith. General Organic & Biologicial Chemistry 2nd Ed. Acid/Base Brønsted-Lowry Definition The Brønsted–Lowry definition is more widely used: •A Brønsted–Lowry acid is a proton (H+) donor. •A Brønsted–Lowry base is a proton (H+) acceptor. This proton is donated. HCl(g) + H2O(l) H3O+(aq) + Cl−(aq) •HCl is a Brønsted–Lowry acid because it donates a proton to the solvent water. •H2O is a Brønsted–Lowry base because it accepts a proton from HCl. Smith. General Organic & Biologicial Chemistry 2nd Ed. 3 Acid/Base Brønsted-Lowry Definition A Brønsted–Lowry acid must contain a hydrogen atom. •A monoprotic acid contains one acidic proton. HCl •A diprotic acid contains two acidic protons. H2SO4 •A triprotic acid contains three acidic protons. H3PO4 •A Brønsted–Lowry acid may be neutral or it may carry a net positive or negative charge. HCl, H3O+, HSO4− Smith. General Organic & Biologicial Chemistry 2nd Ed. 4 Brønsted-Lowry Definition Acid/Base A base must contain a lone pair of electrons that can be used to form a new bond to the proton. This e− pair forms a new bond to a H from H2O. H N H + H2O(l) H H N H + OH− (aq) H Lone pairs make these neutral compounds bases. NH3 ammonia + H H2O water Smith. General Organic & Biologicial Chemistry 2nd Ed. The OH− is the base in each metal salt. NaOH sodium hydroxide KOH potassium hydroxide 5 Acid/Base This e− pair stays on A. H A acid Brønsted-Lowry Definition This e− pair forms a new bond to H+. gain of H+ + B base A − + H B+ loss of H+ Smith. General Organic & Biologicial Chemistry 2nd Ed. 6 Conjugate Acids & Bases Acid/Base gain of H+ H A acid + B base A − + H B+ conjugate conjugate acid base loss of H+ •The product formed by loss of a proton from an acid is called its conjugate base. •The product formed by gain of a proton by a base is called its conjugate acid. H Br acid + H2O base Smith. General Organic & Biologicial Chemistry 2nd Ed. Br− + H3O+ conjugate conjugate acid base 7 Water: An Acid & Base Acid/Base Amphoteric compound: A compound that contains both a hydrogen atom and a lone pair of e−; it can be either an acid or a base. + H H O H add H+ H2O as a base H O H H2O as an acid Smith. General Organic & Biologicial Chemistry 2nd Ed. H O H conjugate acid remove H+ − H O conjugate base 8 Acid/Base Strong Acids •When a covalent acid dissolves in water, the proton transfer that forms H3O+ is called dissociation. •When a strong acid dissolves in water, 100% of the acid dissociates into ions. HCl(g) + H2O(l) H3O+(aq) + Cl−(aq) •A single reaction arrow is used, because the product is greatly favored at equilibrium. •Common strong acids are HI, HBr, HCl, H2SO4, and HNO3. Smith. General Organic & Biologicial Chemistry 2nd Ed. 9 Acid/Base Weak Acids •When a weak acid dissolves in water, only a small fraction of the acid dissociates into ions. •Unequal reaction arrows are used, because the reactants are usually favored at equilibrium. CH3COOH(l) + H2O(l) H3O+(aq) + CH3COO−(aq) •Common weak acids are H3PO4, HF, H2CO3, and HCN. Smith. General Organic & Biologicial Chemistry 2nd Ed. 10 Acid/Base Strong & Weak Bases •When a strong base dissolves in water, 100% of the base dissociates into ions. NaOH(s) + H2O(l) Na+(aq) + −OH(aq) •Common strong bases are NaOH and KOH. •When a weak base dissolves in water, only a small fraction of the base dissociates into ions. NH3(g) + H2O(l) Smith. General Organic & Biologicial Chemistry 2nd Ed. NH4+(aq) + −OH(aq) 11 Acid/Base Strong/Weak Acids/Bases •A strong acid readily donates a proton, forming a weak conjugate base. HCl strong acid Cl− weak conjugate base •A strong base readily accepts a proton, forming a weak conjugate acid. OH− strong base Smith. General Organic & Biologicial Chemistry 2nd Ed. H2O weak conjugate acid 12 Acid/Base Strong/Weak Acids/Bases Smith. General Organic & Biologicial Chemistry 2nd Ed. 13 Ka & Kb Acid/Base •A Brønsted–Lowry acid–base reaction represents an equilibrium. H A acid + B base A − + H B+ conjugate conjugate acid base •The position of the equilibrium depends upon the strengths of the acids and bases. •The stronger acid reacts with the stronger base to form the weaker acid and the weaker base. Smith. General Organic & Biologicial Chemistry 2nd Ed. 14 Acid/Base Ka & Kb HA(g) + H2O(l) H3O+(aq) + A − (aq) [H3O+][ A −] Ka = [HA] acid dissociation constant •The stronger the acid, the larger the Ka value. •Equilibrium favors formation of the weaker acid, the acid with the smaller Ka value. Smith. General Organic & Biologicial Chemistry 2nd Ed. 15 Acid/Base Ka & Kb Smith. General Organic & Biologicial Chemistry 2nd Ed. 16 Acid/Base Ka & Kb OH- (aq) + BH+ (aq) B (g) + H2O(l) Kb = [OH- ][BH+] [ B] Base dissociation constant •The stronger the base, the larger the Kb value. Smith. General Organic & Biologicial Chemistry 2nd Ed. 17 Kw Acid/Base loss of H+ H O H + H acid O H base + H − O H + conjugate base H O H conjugate acid gain of H+ ion-product constant Kw = [H3O+][OH−] Kw is a constant for all aqueous solutions at 25 oC. Kw = (1.0 x 10−7) x (1.0 x 10−7) Kw = 1.0 x 10−14 18 Smith. General Organic & Biologicial Chemistry 2nd Ed. Acid/Base pH The lower the pH, the higher the concentration of H3O+: •Acidic solution: pH < 7 [H3O+] > 1 x 10−7 •Neutral solution: pH = 7 [H3O+] = 1 x 10−7 •Basic solution: pH > 7 [H3O+] < 1 x 10−7 Smith. General Organic & Biologicial Chemistry 2nd Ed. 19 Acid/Base pH Smith. General Organic & Biologicial Chemistry 2nd Ed. 20 Acid/Base Common Acid/Base Reactions Neutralization reaction: An acid-base reaction that produces a salt and water as products. HA(aq) + MOH(aq) base acid H OH(l) + MA(aq) water salt •The acid HA donates a proton (H+) to the OH− base to form H2O. •The anion A− from the acid combines with the cation M+ from the base to form the salt MA. Smith. General Organic & Biologicial Chemistry 2nd Ed. 21 Acid/Base Common Acid/Base Reactions A net ionic equation contains only the species involved in a reaction. HCl(aq) + NaOH(aq) H—OH(l) + NaCl(aq) •Written as individual ions: H+(aq) + Cl−(aq) + Na+(aq) + OH− (aq) H—OH(l) + Na+(aq) + Cl−(aq) •Omit the spectator ions, Na+ and Cl–. •What remains is the net ionic equation: H+(aq) + OH− (aq) H—OH(l) 22 Smith. General Organic & Biologicial Chemistry 2nd Ed. Acid/Base Common Acid/Base Reactions •A bicarbonate base, HCO3−, reacts with one H+ to form carbonic acid, H2CO3. H+(aq) + HCO3−(aq) H2CO3(aq) H2O(l) + CO2(g) •Carbonic acid then decomposes into H2O and CO2. •For example: HCl(aq) + NaHCO3(aq) NaCl(aq) + H2CO3(aq) H2O(l) + CO2(g) Smith. General Organic & Biologicial Chemistry 2nd Ed. 23 Acid/Base Common Acid/Base Reactions •A carbonate base, CO32–, reacts with two H+ to form carbonic acid, H2CO3. 2 H+(aq) + CO32–(aq) H2CO3(aq) H2O(l) + CO2(g) •For example: 2 HCl(aq) + Na2CO3(aq) 2 NaCl(aq) + H2CO3(aq) H2O(l) + CO2(g) Smith. General Organic & Biologicial Chemistry 2nd Ed. 24 Acid/Base Titration Initial Midway Final AH + B A- + BH+ Acid + Base Conjugate Base + Conjugate Acid HCl + NaOH NaCl + H2O H+ (acid) + OH- (base) H2O (neutral water) Calculations: Know: the concentration of Base & the Volume of Base added. 1. VBase (L) x MBase (moles/L) = moles Base added to the acid 2. Mole : Mole ratio of Acid : Base is 1:1 (if monoprotic), therefore moles Base added = moles of Acid reacted 3. Determine the Molarity of the Acid solution initially by dividing the # moles that reacted with the initial volume of the solution (L). Smith. General Organic & Biologicial Chemistry 2nd Ed. 25 Acid/Base Titration Caclulations mole–mole conversion factor Moles of base M (mol/L) conversion factor [1] Volume of base Smith. General Organic & Biologicial Chemistry 2nd Ed. [2] Moles of acid [3] M (mol/L) conversion factor Volume of acid 26 Acid/Base Buffers A buffer is a solution whose pH changes very little when acid or base is added. Most buffers are solutions composed of roughly equal amounts of: •A weak acid •The salt of its conjugate base The buffer resists change in pH because •Added base, OH−, reacts with the weak acid •Added acid, H3O+, reacts with the conjugate base Smith. General Organic & Biologicial Chemistry 2nd Ed. 27 Acid/Base Buffers If an acid is added to the following buffer equilibrium, then the excess acid reacts with the conjugate base, so the overall pH does not change much. Smith. General Organic & Biologicial Chemistry 2nd Ed. 28 Acid/Base Buffers If a base is added to the following buffer equilibrium, then the excess base reacts with the conjugate acid, so the overall pH does not change much. Smith. General Organic & Biologicial Chemistry 2nd Ed. 29 Acid/Base Buffers Smith. General Organic & Biologicial Chemistry 2nd Ed. 30 Acid/Base Buffers The effective pH range of a buffer depends on its Ka. H3O+(aq) + A −(aq) HA(aq) + H2O(l) [H3O+][ A −] [HA] Ka = Rearranging this expression to solve for [H3O+]: [H3 O+] = Ka x [HA] [ A −] determines the buffer pH Smith. General Organic & Biologicial Chemistry 2nd Ed. 31 Acid/Base Buffers •Normal blood pH is between 7.35 and 7.45. •The principle buffer in the blood is carbonic acid/ bicarbonate (H2CO3/HCO3−). CO2(g) + H2O(l) H2CO3(aq) H2O H3O+(aq) + HCO3−(aq) •CO2 is constantly produced by metabolic processes in the body. •The amount of CO2 is related to the pH of the blood. Smith. General Organic & Biologicial Chemistry 2nd Ed. 32