Applying Acid-Base Dissociation Constants A.

Strong Acids and Bases - Equilibrium expressions are not part of the calculations involved with the ionization of strong acids and strong bases because the equilibrium constant are either very large or undefined - There is no significant difference between the analytical concentration and the equilibrium concentration of the ionization products - Common strong acids and bases ACIDS Hydrochloric Acid Hydrobromic Acid Hydriodic Acid Perchloric Acid Nitric Acid Sulfuric Acid BASES Lithium hydroxide Sodium Hydroxide Potassium Hydroxide Barium Hydroxide

HCl HBr HI HClO4 HNO3 H2SO4

LiOH NaOH KOH Ba(OH)2

B. Weak Acids and Bases - When a weak acid or weak base is dissolved in water, partial dissociation occurs

HA + H2O H3O+ + AHA = weak acid; Ka = acid dissociation Ka = [H3O+] [A-]/ [HA] For weak base, Kb = base dissociation constant
+ -

B + H2O BH+ + OH-

Kb = [BH ] [OH ]/ [B] Polyprotic Acids = acids that can donate more than one proton Ka1 = [H3O+] [H2PO4-] [H3PO4] H2PO4- + H2O H3O+ + HPO42Ka2 = [H3O+] [ HPO42-] [H2PO4- ] 2+ 3HPO4 + H2O H3O + PO4 ka3 = [H3O+] [ PO43-] [HPO42- ] Polyequivalent Base =bases that can accept more than one proton Ex. H3PO4 + H2O Ex. Kb1 = [HCO3-] [ OH-] [CO32-] HCO3 + H2O H2CO3 + OH Kb2 = [H2CO3] [ OH-] [HCO3-] The subscripts are used to identify the individual ionization steps and K1>K2>K3 CO32- + H2O HCO3- + OHH3O+ + H2PO4-

Relation Between Ka and Kb for Conjugate Pairs - The Ka and Kb values are used to measure acid and base strength Ka Kb = Kw C. Calculation of pH pH = - log [H3O+] - When an acid HA dissolves in water, both acid and water are suppliers of H3O+: HA + H2O H3O+ + A(a) H2O + H2O H3O+ + OH(b) - When a base B dissolves in water, both the base and water are suppliers of OH-: B + H2O BH+ + OH(c) H2O + H2O H3O+ + OH(d) - Calculation of pH depends on three cases

For Acids Case 1. The acid is the major supplier of H3O+ o This means that the determination of hydronium ion concentration is based on the equilibrium expression for reaction (a) Case 2. Water is the major supplier of H3O+ o The hydronium ion concentration can be determined by solving the equilibrium expression for reaction (b) Case 3. Both the acid and the water are major suppliers of H3O+ o Both reactions mustbe considered For Bases Case 1. The base is the major supplier of OHo This means that the determination of hydroxide ion concentration is based on the equilibrium expression for reaction (c) Case 2. Water is the major supplier of OHo The hydroxide ion concentration can be determined by solving the equilibrium expression for reaction (d) Case 3. Both the base and the water are major suppliers of OHo Both reactions (c) and (d) must be considered Calculation of pH of strong acids and bases Identify which of the above cases applies. For acids Case Major Supplier of H3O+ 1 Strong acid 2 Water 3 Both Case 1. The acid is the major supplier of H3O+. [H3O+] = CHX Case 2. The water is the major supplier of H3O+. [H3O+] = Kw Case 3. Both acid and water are the major supplier of H3O+. [H3O+] - CHX [H3O+] - Kw = 0 For bases Case Major Supplier of OH1 Strong base 2 Water 3 Both Case 1. The base is the major supplier of OH[OH-] = CB Case 2. The water is the major supplier of OH-. [OH-] = Kw Case 3. Both acid and water is the major supplier of OH-. [OH-]- CB [OH-] - Kw = 0 To solve for pH, use the equation below pH + pOH = pKw where pOH = - log [OH-]

Necessary condition CHX >> 10-7 CHX << 10-7 CHX = 10-7

Necessary condition CB >> 10-7 CB << 10-7 CB = 10-7

Calculation of pH of weak acids and bases For weak acids: Case Major Supplier of H3O+ Necessary condition 1 Weak acid Ka x CHA >> 10-7 2 Water Ka x CHA << 10-7 3 Both Ka x CHA = 10-7 + Case 1. The weak acid is the major supplier of the H3O . [H3O+]2 + Ka[H3O+] - KaCHA = 0 If CHA/Ka 10-3, [H3O+] = Ka CHA For weak bases o techniques used on weak acids are the same ones that are used to calculate hydroxide ion concentration in solutions of weak bases. Case Major Supplier of OHNecessary condition 1 Weak base Ka x CHA >> 10-7 2 Water Ka x CHA << 10-7 3 Both Ka x CHA = 10-7 o Case 1. The weak base is the major supplier of the OH-. [OH-]2 + Kb[OH-] KbCB = 0 -3 If CB/Kb 10 , [OH-] = Kb CB Calculation of pH of conjugate acid-base pairs o There are two equilibria involved: HA + H2O H3O+ + A(e) A + H2O HA + OH (f ) o The ionization of water is neglected, and [H3O+] is taken from reaction (e) Ka = [H3O+][A-] [HA] Where: [HA] = CHA - [H3O+] + [OH-] [A-] = CNaA + [H3O+] - [OH-] Ka =[H3O+]( CNaA + [H3O+] - [OH-]) CHA - [H3O+] + [OH-] Solving for [H3O+], [H3O+]3 + (CNaA + Ka) [H3O+]2 - (KaCHA + Kw) [H3O+] - KaKw = 0 o If CHA & CNaA 10-3 and Ka & Kb 10-3, then CHA and CNaA are larger compared to the difference between [H3O+] and [OH-], therefore [HA] = CHA [A-] = CNaA Ka becomes, Ka =[H3O+]CNaA CHA Note also that conjugate acid-base do not react with each other

pH buffers - a mixture of weak acid or base and its conjugate - resists changes in pH upon dilution or addition of acids or base o effect of dilution: pH = pKa - log [HA]/[A-] pH depends on the ratio of the concentrations of acids and conjugate bases rather than their absolute value

effect of addition of acids and bases

Buffer Capacity, depends on both the concentration of components and the concentration ratio - Defined as the quantity of strong acid or strong base needed to cause 1.0 L of buffer to undergo a pH change of 1.0 unit - To determine the useful pH range of a buffer use the previous equation [HA] / [A-] pH from the equation 1 / 10 pHmax = pKa - log 1/10 = pKa + 1 10 / 1 pH min = pKa - log 10/1 = pKa - 1 Therefore the useful pH range is pKa 1. In selecting a buffer for a given application there are two considerations to be considered: 1. The desired pH and 2. The chemical compatibility of the buffer components with the sample Preparing a buffer: o By combining the calculated quantities of an acid-base conjugate pair o In cases one of the conjugate pair is unavailable, combining of excess of the available weak acid or baser with an appropriate amount of strong base or acid can be done. o Preparation of buffers uses the aid of pH meter

Prepared by: Raissa E. Dycoco Instructor