Chapter 12: Principles of Neutralization Titrations Solutions and Indicators Used Standard Solutions: strong acids or strong bases

s because they will react completely o Acids: hydrochloric (HCl), perchloric (HClO4), and sulfuric (H2SO4) o Bases: sodium hydroxide (NaOH), potassium hydroxide (KOH) Acid/Base Indicators: a weak organic acid or weak organic base whose undissociated form differs in color from its conjugate form (In would be indicator): HIn + H2O (acid color) or In + H2O In- + H3O (base color) (base color) Ka = [H3O+][In-] [HIn] [H3O+] = Ka[HIn] [In-] o HIn pure acid color: [HIn]/[In-] 10, HIn pure base color: [HIn]/[In-] 0.1. ~The ratios change from indicator to indicator~ o Substitute the ratios into the rearranged Ka: [H3O+] = 10Ka (acid color) o pH range for indicator = pKa 1 [H3O+] = 0.1Ka (base color) HIn+ + OH(acid color)

acid color pH = -log(10Ka) = pKa + 1 base color pH = -log(0.1Ka) = pKa 1 Variables: temperature, ionic strength of medium and presence of organic solvents or colloidal particles Common Acid/Base Indicators Indicator Thymol Blue Thymol blue Methyl yellow pH Range Acid 1.2-2.8 red 8.0-9.6 yellow 2.9-4.0 red Base yellow blue yellow

Methyl orange Bromcresol green Methyl red Bromcresol purple Bromothymol Blue Phenol red Cresol purple Phenolphthalein Thymolphthalein Alizarin yellow GG

3.1-4.4 4.0-5.6 4.4-6.2 5.2-6.8 6.2-7.8 6.4-8.0 7.6-9.2 8.0-10.0 9.4-10.6 10.0-12.0

red yellow red yellow yellow yellow yellow colorless colorless colorless

orange blue yellow purple blue red purple red blue yellow

Calculating pH in Titrations of Strong Acids and Strong Bases In a solution of a strong acid that is more concentrated than about 1x10-6, we can assume that [H3O+] = [acid] same is true for [base] = [OH-] Titrating a Strong Acid with a Strong Base (hypothetical titration curves of pH versus volume of titrant) 1. Preequivalence: calculate the concentration of the acid from is starting concentration and the amount of base that has been added, the concentration of the acid is equal to the concentration of the hydroxide ion and you can calculate pH from the concentration 2. Equivalence: the hydronium and hydroxide ions are present in equal concentrations 3. Postequivalence: the concentration of the excess base is calculated and the hydroxide ion concentration is assumed to be equal to or a multiple of the analytical concentration, the pH can be calculated from the pOH Ex.: Do the calculations needed to generate the hypothetical titration curve for the titration of 50.00 mL of 0.0500 M HCl with 0.1000 M NaOH 1. Initial Point: the solution is 0.0500 M in H3O+, so pH = -log(.0500) = 1.30 2. Preequivalence Point (after addition of 10 mL reagent) CHCl = mmol remaining (original mmol HCl mmol NaOH added)

total volume (mL) = (50.0 mL x 0.0500 M) (10.00 mL x 0.1000 M) 50.0 mL + 10.00 mL = 2.500 x 10 -2 M pH = -log(2.500 x 10-2) = 1.602 3. Equivalence Point [OH-] = [H3O+], pH = 7 4. Postequivalence Point (after addition of 25.10 mL reagent) CHCl = mmol NaOH added original mmol HCl total volume solution = (21.10 mL x 0.1000 M) (50.00 mL x 0.0500 M) 50.0 mL + 25.10 mL = 1.33 x 10-4 M pOH = -log(1.33 x 10-4) = 3.88 pH = 14 pOH = 10.12 o Concentrations: with a higher concentration titrant (0.1 M NaOH versus 0.001 M NaOH), the change in pH equivalence-point region is large o Choosing an indicator: you need to choose an indicator that has a color change in the same range as your equivalence point Titrating a Strong Base with a Strong Acid (hypothetical titration curves): similar to those for strong acids, but opposite Preequivalence: calculate the concentration of the base from is starting concentration and the amount of acid that has been added, the concentration of the base is equal to the concentration of the hydronium ion and you can calculate pOH from the concentration, and then the pH Equivalence: the hydronium and hydroxide ions are present in equal concentrations, so the pH is 7 Postequivalence: the concentration of the excess acid is calculated and the hydronium ion concentration is the same as the concentration of the acid, and the pH can be calculated

Buffer Solutions Buffer: a mixture of a weak acid and its conjugate base or a weak base and its conjugate acid that resists changes in pH of a solution Calculating pH of Buffer Solutions Ka = [H3O+][A-] [HA] Kb = [OH-][HA]
+

HA + H2O H3O+ + AA + H2O OH + HA

-

[A-] Mass-Balance Equation for [HA]: [HA]=cHA [H3O ] + [OH-] Mass-Balance Equation for [A-]: [A-] = cNaA + [H3O+] [OH-] [HA] cHA [A-] cNaA *we can eliminate the rest of the mass-balance equations because of the inverse relationship between the hydronium and the hydroxide ion, as well as because the difference in concentration is so small relative to the concentrations of the acid and conjugate base* If we substitute the concentration equations for [HA] & [A-] into the dissociation constant expression, we get [H3O+] = Ka cHA cNaA *the hydronium ion concentration is dependent only on the ratio of the molar concentrations of the weak acid and its conjugate base, and is independent of dilution because the molar concentrations change proportionately*

o Buffers Formed from a Weak Acid and Its Conjugate Base Ex.: What is the pH of a solution that is 0.400 M in formic acid and 1.00 M in sodium formate? HCOOH + H2O H3O+ + HCOOHCOO- + H2O HCOOH + OHKa = 1.80 x 10-4 Kb = Kw/Ka = 5.56 x 10-11 [HCOO-] cHCOO- = 1.00 M [HCOOH] cHCOOH = 0.400 M [H3O+] = (1.80 x 10-4) (0.400) = 7.20 x 10-5 (1.00) pH = -log(7.20 x 10-5) = 4.14 o Buffers Formed from a Weak Base and its Conjugate Acid Ex.: Calculate the pH of a solution that is 0.200 M in NH3 and 0.300 M in NH4Cl. NH4+ + H2O NH3 + H3O+ NH3 + H2O NH4+ + OHKa = 5.70 x 10-10 Kb = Kw/Ka = 1.75 x 10-5 [NH4+] cNH4Cl = 0.300 M [NH3] cNH3 = 0.200 M [H3O+] = (5.70 x 10-10) (0.300) = 8.55 x 10-10 (0.200) pH = -log(8.55 x 10-10) = 9.07 What are the unique properties of buffer solutions?

o Dilution: the pH of a buffer solution is essentially independent of dilution until the concentrations of the species are decreased to the point so that we cannot assume that the differences between the hydronium and hydroxide ion concentrations is negligible when calculating the concentration of the species o Added Acids and Bases: buffers are resistant to pH change after addition of small amounts of strong acids or bases o Buffer Capacity: The number of moles of strong acid or strong base that causes one liter of the buffer to change pH by one unit The higher the buffer concentration, the smaller the change in pH when an acid or base is added Ex.: Calculate the pH change that takes place when a 100 mL portion of 0.0500 M NaOH is added to a 400 mL buffer consisting of 0.2 M NH3 and 0.3 M NH4Cl (see example for Buffers Formed from a Weak Base and its Conjugate Acid). An addition of a base converts NH4+ to NH3: NH4+ + OH- NH3 + H2O The concentration of the NH3 and NH4Cl change: cNH3 = original mol base + mol base added total volume cNH3 = (400 x 0.200) + (100 x 0.300) = 0.170 M 500 cNH4Cl = original mol acid mol base added total volume cNH3 = (400 x 0.300) + (100 x 0.300) = 0.230 M 500 [H3O+] = (5.70 x 10-10) (0.230) =7.71 x 10-10 (0.170) pH = -log(7.71 x 10-10) = 9.11 pH = 9.11 9.07 = 0.04

Preparing Buffers (in principle the calculations work, but there are uncertainties in numerical values of dissociation constants & simplifications used in calculations) Making up a solution of approximately the desired pH and then adjust by adding acid or conjugate base until the required pH is indicated by a pH meter Empirically derived recipes are available in chemical handbooks and reference works Biological supply houses

Calculating pH in Weak Acid (or Base) Titrations o Steps a. At the beginning: pH is calculated from the concentration of that solute and its dissociation constant b. After various increments of titrant has been added: pH is calculated by the analytical concentrations of the conjugate base or acid and the residual concentrations of the weak acid or base c. At the equivalence point: the pH is calculated from the concentration of the conjugate of the weak acid or base ~ a salt d. Beyond the equivalence point: pH is determined by the concentration of the excess titrant o The Effect of Concentration: the change in pH in the equivalence-point region becomes smaller with lower analyte and reagent concentrations o The Effect of Reaction Completeness: pH change in the equivalence-point region becomes smaller as the acid become weaker (the reaction between the acid and the base becomes less complete) o Choosing an Indicator: the color change must occur in the equivalence-point region Ex.: Determine the pH for the titration of 50.00 mL of 0.1000 M acetic acid after adding 0.00, 5.00, 50.00, and 50.01 mL of 0.100 M sodium hydroxide

HOAc + H2O H3O+ + OAcOAc- + H2O HOAc + OHKa = 1.75 x 10 -5 1) Starting Point: [H3O+] = 1.32 x 10-3 pH = -log(1.32 x 10-3) = 2.88 2) After Titrant Has Been Added (5.00 mL NaOH): *the buffer solution now has NaOAc & HOAc* cHOAc = mol original acid mol base added total volume cHOAc = (50.00 x 0.100) (5.00 x 0.100) = 0.075 60.0 cNaOAc = mol base added total volume cNaOAc = (5.00 x 0.100) = 0.008333 60.0 *we can then substitute these concentrations into the dissociation-constant expression for acetic acid* Ka = [H3O+][OAc-] [HOAc] Ka = 1.75 x 10-5 = [H3O+][0.008333] [0.075] [H3O+] = 1.58 x 10-4 pH = -log(1.58 x 10-4) = 3.80 3) Equivalence Point (50.00 mL NaOH):

*all the acetic acid has been converted to sodium acetate* [NaOAc]= 0.0500 M *we can substitute this in to the base-dissociation constant for OAc-* Kb = [OH-][HOAc] = Kw [OAc-] [HOAc] = [OH-] [OH-]2 = 1.00 x 10-14 0.0500 1.75 x 10-5 [OH-] = 5.34 x 10-6 pH = 14.00 (-log(5.34 x 10-6)) pH = 8.73 4) Beyond the Equivalence Point (50.01 mL NaOH): *the excess base and acetate ion are sources of the hydroxide ion, but the acetate ion concentration is so small it is negligible* [OH-] = cNaOH = mol base added original mol acid total volume [OH-] = (50.01 x 0.100) (50.00 x 0.100) 100.01 [OH-] = 1.00 x 10-5 pH = 14.00 (-log(1.00 x 10-5)) pH = 9.00 How Do Buffer Solutions Change as a Function of pH? o Alpha values: the relative equilibrium concentration of the weak acid/base and its conjugate base/acid (titrating with HOAc with NaOH): *at any point in a titration, cT = cHOAc + cNaOAc* 0 = [HOAc] Ka

cT 1 = [OAc-] cT *alpha values are unitless and are equal to one* 0 + 1 = 1 Derivations *alpha values depend only on [H3O+] and Ka, not cT* *mass-balance requires that cT = [HOAc] + [OAc-]* o For 0, we rearrange the dissociation-constant expression to: [OAc-] = Ka[HOAc] [H3O+] *substitute mass-balance into the dissociation-constant expression* 0 = [HOAc] = [H3O+] cT [H3O+] + Ka o For 1, we rearrange the dissociation-constant expression to: [HOAc] = [H3O+] [OAc-] Ka *substitute mass-balance into the dissociation-constant expression* 1 = [OAc-] = _____Ka________ cT [H3O+] + Ka