Chemistry 205 Acid - Base Titration purpose • To learn the concept and technique of titration. • To standardize a sodium hydroxide (NaOH) solution against a primary standard acid. • To determine the concentration of an unknown acid by titration with the standardized base solution. Titration In titration a solution of accurately known concentration, called a standard solution, is added gradually to another solution of unknown concentration (or vice versa) until the chemical reaction between the two solutions is complete. Equivalence point – the point at which the reaction is complete. Indicator – substance that changes color at (or near) the equivalence point Slowly add base to unknown acid UNTIL the indicator changes color Titration (Cont’d) • End Point: the point in the titration at which the indicator changes color (visually determined). • Conditions for a good titration o Rapid and complete reaction. o Reaction of known stoichiometry (no side products). o End point easily detected (use proper indicator). Acid – Base Titration Involves a neutralization reaction which is the complete reaction between an acid and a base. Acid + base HCl(aq) + NaOH(aq) H+(aq) + OH (aq) Salt + water NaCl(aq) + H2O(l) H2O(l) Net ionic equation What volume of a 1.420 M NaOH solution is Required to titrate 25.00 mL of a 4.50 M H2SO4 solution? WRITE THE CHEMICAL EQUATION! H2SO4 + 2NaOH 2H2O + Na2SO4 n NaOH = 2 n H2SO4 (M x V) NaOH = 2 (M x V) H2SO4 1.420 mol/L x VNaOH = 2 (4.50 mol/L x 25.00 x 10-3L) V NaOH = 0.158 L = 158 mL Standard Solution • Is a solution of accurately known concentration. • prepared by dissolving an exact amount of the solute, followed by dilution, to form a definite volume of solution. Standard solution (cont’d) • Properties of a good primary standard o High molar mass o Stable o Not hygroscopic (do not absorb water readily) o Highly pure, cheap, and available • Example: potassium hydrogen phthalate, KHC8H4O4, molar mass = 204.23 g / mol. O abbreviated as KHP, C OH Structure: OK C O Standard solution (cont’d) • Sodium hydroxide is not a good primary standard solution. Solid NaOH absorbs water from air (hygroscopic), and its solution reacts with carbon dioxide. • In this experiment a sodium hydroxide (NaOH) solution will be standardized by titration with a primary standard acid (KHP) as follows: KHC8H4O4(aq) + NaOH(aq) → KNaC8H4O4(aq) + H2O(l) or KHP(aq) + NaOH(aq) → KNaP(aq) + H2O(l) or HP-(aq) + OH-(aq) → P2-(aq) + H2O(l) net ionic equation The Ion Product of Water H2O (l) H+ (aq) + OH- (aq) [H+][OH-] Kc = [H2O] [H2O] = constant Kc[H2O] = Kw = [H+][OH-] The ion-product constant (Kw) is the product of the molar concentrations of H+ and OH- ions at a particular temperature. At 250C Kw = [H+][OH-] = 1.0 x 10-14 [H+] = [OH-] Solution Is neutral [H+] > [OH-] acidic [H+] < [OH-] basic pH – A Measure of Acidity pH = -log [H+] Solution Is neutral [H+] = [OH-] At 250C [H+] = 1.0 x 10-7 pH = 7.00 acidic [H+] > [OH-] [H+] > 1.0 x 10-7 pH < 7.00 basic [H+] < [OH-] [H+] < 1.0 x 10-7 pH > 7.00 pH pOH = -log [OH-] [H+][OH-] = Kw = 1.0 x 10-14 -log [H+] – log [OH-] = 14.00 [H+] pH + pOH = 14.00 The pH of rainwater collected in a certain region of the northeastern United States on a particular day was 4.82. What is the H+ ion concentration of the rainwater? pH = -log [H+] [H+] = 10-pH = 10-4.82 = 1.5 x 10-5 M The OH- ion concentration of a blood sample is 2.5 x 10-7 M. What is the pH of the blood? pH + pOH = 14.00 pOH = -log [OH-] = -log (2.5 x 10-7) = 6.60 pH = 14.00 – pOH = 14.00 – 6.60 = 7.40 Strong Acid-Strong Base Titrations Example: Addition of 0.100 M NaOH solution (from a buret ) to an erlenmeyer containing 25.0 mL of 0.100 M HCl. NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq) Indicators • Indicators are used to detect the end point. • They are substances that have distinctly different colors in acidic and basic media, they are weak organic acids or bases that change their color at the equivalence point: H3O+ + In HIn + H2O (acidic) (Basic) + − Ka = [ H 3 O ][ In ] [HIn ] Ka= Acid dissociation constant Indicators (continued) [ HIn] • Rearranging the above equation [H3O+] = Ka − [ In ] • Taking the -log of both sides - log [H3O+] = - log Ka - log [HIn] pH = pKa + log If If [In ] − [In− ] [HIn] [In ] ≤ [In ] ≥ 10 The color of the base ( In ) predominates − [HIn] − [HIn] 1 The color of the acid (HIn) predominates 10 Therefore pH range of indicator is: pH = pKa ± 1 Indicators (continued) • Example: If pKa of the indicator = 6.2, then the indicator pH range = 5.2 – 7.2 Indicators (continued) choose the indicator whose color range includes the equivalence pH or that lies on the steep part of the titration curve. Experimental Four steps are involved: 1- Preparation of a primary standard potassium hydrogen phthalate (KHP) solution. 2- Standardization of 0.1 M sodium hydroxide solution with KHP. 3- Titration of an unknown monoprotic acid with the standardized sodium hydroxide solution. 4- Blank Titration 1- Preparation of KHP Primary Standard • Weigh KHP bottle using the analytical balance. • Transfer the KHP to a 250 mL volumetric flask using a funnel. • Add some water, dissolve ,dilute and shake, make up to the mark and homogenize. • Weigh the empty bottle • Calculate molarity of KHP n mass M= = V Molar mass x volume mass ( g ) M= 204.23 ( g / mol ) x 250.0 x10 −3 mL 2- Standardization of 0.1M NaOH • Rinse the buret with NaOH. • Fill it to the mark, make sure that there are no air bubbles in the tip. • Pipet 25.00 mL of KHP into an Erlenmeyer flask and add two drops of phenolphthalein indicator. • Add 20mL of distilled water. • Titrate against KHP to the end point (light pink color). • Repeat the titration 3 times. • Calculate M of NaOH. (MxV) of NaOH = (MxV) of KHP 3- Titration of an Unknown Acid • Proceed as in part 2. • Use the unknown instead of KHP • Titrate against the standardized NaOH solution using phenolphthalein as an indicator. • Repeat three times. • Calculate the molarity of the unknown. Note: The unknown is monoprotic acid. 4- Blank Titration • Blank titrarion is done to correct for possible acids other than the acid being titrated. (Distilled water and phenolphthalein are acidic). • Proceed as in part 2, use distilled water instead of the KHP. • Subtact the volume of NaOH needed for the blank titration from the average volume of NaOH used in each of parts 1 and 2 before you start your calculations. Practice exercises 1. What is the concentration of OH- ions in a HCl solution whose hydrogen ion concentration is 1.3 M? Answer: 7.7 x 10-15 M 2. A 0.2668 g sample of a monoprotic acid neutralizes 16.4 mL of 0.08133 M KOH solution. Calculate the molar mass of the acid. Answer: 202 g/mol
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