Reading: from chapter 18 of Petrucci, Harwood and Herring
(8th edition): Required: Sections 18-2 through 18-6. Recommended: Section 18-1. Examples: 18-3 through 18-9. Problem Set: Chapter 18 questions: 5, 6, 7, 8, 9, 26, 27a-e, 32. Additional problems from Chapter 18: 54, 55.
York University CHEM 1001 3.0 Acids and Bases - 48
Adding Base to a Weak Acid Solution HF is a weak acid; it partially ionizes in water: HF + H2O W H3O+ + F- pKa = 3.18 What effect does adding NaOH have on this equilibrium? NaOH 6 Na+ + OH- complete ionization H3O+ + OH- 6 H2O neutralization Consequences: C Adding NaOH consumes H 3O+. C The HF equilibrium shifts to the right to partially offset the change (replaces some H3O+). C The increase in pH is less than if the same amount of NaOH was added to pure water. York University CHEM 1001 3.0 Acids and Bases - 49 Adding Acid to a Salt of a Weak Acid NaF is a salt of a weak acid (HF). It hydrolyzes in water: F- + H2O W OH- + HF pKb = 10.82 What effect does adding HCl have on this equilibrium? HCl + H2O 6 H3O+ + Cl- complete ionization H3O+ + OH- 6 H2O neutralization Consequences: C Adding HCl consumes OH-. C The hydrolysis equilibrium shifts to the right to partially offset the change (replaces some OH-). C The decrease in pH is less than if the same amount of HCl was added to pure water. York University CHEM 1001 3.0 Acids and Bases - 50 Solution of a Weak Acid and its Salt Example: Solution of HF and NaF in water. HF + H2O W H3O+ + F- pKa = 3.18 C Adding acid shifts the equilibrium to the left. This partially offsets the reduction in pH. C Adding base shifts the equilibrium to the right. This partially offsets the reduction in pH. C Significant amounts of acid or base can be neutralized since the solution contains substantial [HF] and [F -]. C The pH is kept nearly constant. This solution is a buffer.
York University CHEM 1001 3.0 Acids and Bases - 51
Applications of Buffer Solutions Many chemical processes require control of pH. C The rates and mechanisms of many chemical reactions are sensitive to pH. C pH affects the structure of and charges on proteins. C The activity of enzymes is very sensitive to pH. C Human blood is buffered to a pH of 7.4 C Many industrial chemical processes require a controlled pH.
York University CHEM 1001 3.0 Acids and Bases - 52
Acid-Base Buffers An acid-base buffer is a solution that is resistant to changes in pH. In other words, when an acid or base is added to a buffer, the pH changes only slightly. For a solution to be a buffer, it must contain: C comparable concentrations of a weak acid its conjugate base: 0.1×[acid] < [conjugate base] < 10×[acid] C a concentration of the conjugate base at least 100 times the value of Ka for the acid: [conjugate base] > 100 Ka
York University CHEM 1001 3.0 Acids and Bases - 53
pH of a Buffer Solution Reaction HA + H 2O W H 3O + + A- Initial [HA]0 - 0 [A-]0 M Change -x - x x M Equil. [HA]0-x - x [A-]0+x M Simplifying assumptions: x n [HA]0 and x n [A-]0 Y Ka = [H3O+][A-]/[HA] . x [A-]0 / [HA]0 Y [H3O+] = x = Ka [HA]0 / [A-]0 Check that the assumptions are valid: C Since [A-]0 > 100Ka, x < 0.01[HA]0. C Since [A-]0 > 100Ka and [HA]0 < 10[A-]0, x < 0.1[A-]0. York University CHEM 1001 3.0 Acids and Bases - 54 pH of a Buffer Solution - continued In a buffer, we have: [H3O+] = Ka [HA] / [A-] Take the negative logarithm of both sides: -log[H3O+] = -logKa - log([HA]/[A-]) pHbuffer = pKa + log([A-]/[HA]) This is called the Henderson-Hasselbalch equation. C Relates the pH of a buffer to its composition. C Uses initial concentrations of acid and conjugate base. C Don't memorize - it is easy to mess up but easy to derive.
York University CHEM 1001 3.0 Acids and Bases - 55
Buffer Range To have a buffer, we must have: 0.1 < [A-] / [HA] < 10 Taking logarithms: -1.0 < log([A-]/[HA]) < 1.0 Substitute into the Henderson-Hasselbalch equation: pHbuffer = pKa + log([A-]/[HA]) pHbuffer = pKa ± 1.0 Conclusion: A particular weak acid can used to prepare buffers with pH values within 1 unit of the acid's pKa.
York University CHEM 1001 3.0 Acids and Bases - 56
Preparing Buffer Solutions Chemists and biologists often need to prepare solutions with a specific, constant pH. To make a buffer with a specific pH: C Find an acid with a pKa within 1 unit of the required pH. C Use the acid ionization constant to determine the required ratio of acid to conjugate base. C Make the buffer solution. C Use a pH meter to check the pH. Add acid or base as needed to get the correct pH.
York University CHEM 1001 3.0 Acids and Bases - 57
Preparing a Buffer - Example To prepare a buffer with pH = 3.50: Acid pKa Citric Acid 3.13 » Closest to desired pH. Benzoic acid 4.20 Find ratio of acid to base: Acetic acid 4.77 [HA]/[A-] = [H3O+]/Ka = 10pKA-pH Carbonic acid 6.36 [HA]/[A-] = 103.13-3.50 = 0.43 Ammonium ion 9.25 if [A-] = 0.10 M (>100Ka) Phenol 9.89 then [HA] = 0.043 M. For one liter, use 0.143 mol H3C6H5O7 plus 0.100 mol NaOH.
York University CHEM 1001 3.0 Acids and Bases - 58
Adding Acids or Bases to a Buffer Henderson-Hasselbalch equation: pH = pKa + log([A-]/[HA]) C Adding an acid decreases [A -] and increases [HA]. So it lowers the pH. C Adding a base decreases [A -] and increases [HA]. So it raises the pH. C Qualitatively, this is just like any other solution. But in a buffer, the pH changes are much smaller. Q: How much does the pH change when acid or base is added? A: Calculate the changes in [HA] and [A-].
York University CHEM 1001 3.0 Acids and Bases - 59
pH Change in a Buffer Given a citric acid-citrate buffer with [A -]0 = 0.100 M, [HA]0 = 0.043 M, and pH = 3.50 ([H3O+] = 3.16×10-4 M). Find the pH after adding 3.0×10-3 mol HCl to 1.0 liter of this buffer. Solution: Calculate the changes in [HA] and [A-]. [A-] = [A-]0 - 3.0×10-3 M = (0.100-0.003) M = 0.097 M [HA] = [HA]0 + 3.0×10-3 M = (0.043+0.003) M = 0.046 M pH = pKa + log([A-]/[HA]) = 3.13 + log(0.097/0.046) pH = 3.45 Y [H3O+] = 3.55×10-4 M The change in [H3O+] equals 1.3% of the added HCl. York University CHEM 1001 3.0 Acids and Bases - 60 Effect of Buffer Concentration Given a citric acid-citrate buffer with [A -]0 = 0.100 M, [HA]0 = 0.043 M, and pH = 3.50. What happens to the pH if we double both [A-]0 and [HA]0? Answer: No change since pH = pKa + log([A-]/[HA]). (Only approximately true since we really should be using activities instead of concentrations.) However, the buffer capacity will increase, therefore: C The effect of added acid or base will be smaller. C More acid or base could be added before the buffer stops working.
York University CHEM 1001 3.0 Acids and Bases - 61
Buffer Solutions - Summary C A buffer solution contains a weak acid and the conjugate base of that acid in comparable amounts. C The acid neutralizes added base and the conjugate base neutralizes added acid. C A buffer dramatically reduces the pH changes produced by adding an acid or base. C The pH of a buffer is close to the pKa of the weak acid. C The pH of a buffer solution is readily calculated from the equilibrium condition Ka [HA] = [H3O+][A-]
York University CHEM 1001 3.0 Acids and Bases - 62
Determining pH Two widely used methods: C A pH meter uses an electrode that produces a voltage that is a linear in pH. C Acid-base indicators change color depending on pH. An indicator is a weak acid that has a different color than its conjugate base. HIn + H2O W H3O+ + In- acid color base color Acid color dominates for pH < pKa - 1. Base color dominates for pH > pKa + 1. Easy to use, but results are less precise. York University CHEM 1001 3.0 Acids and Bases - 63 Acid-Base Indicator Examples pH = Phenolphthalein pKa = 9.1
pH = Bromthymol blue pKa = 7.1
York University CHEM 1001 3.0 Acids and Bases - 64
Acid-Base Titrations Acid-base titrations are used to analyze the quantity of acid or base in an unknown sample. Acid + Base W H2O + salt At the equivalence point: moles of acid = moles of base Y CAVA = CBVB VA = volume of acid of unknown concentration CA CB = known concentration of the base VB = volume of base added at equivalence. Y CA = CBVB / VA
York University CHEM 1001 3.0 Acids and Bases - 65
Acid-Base Titrations - continued C The titrant is the strong acid or strong base solution that is added in a measured volume. C The equivalence point can be detected by using a pH meter. C The end point is an experimental approximation of the equivalence point, identified with an acid-base indicator. C The titration error is the difference between the equivalence point and the end point. How close is the end point to the equivalence point? What indicator should be used?
York University CHEM 1001 3.0 Acids and Bases - 66
Titration Curve of a Strong Acid
Titration of 25.00 ml of 0.100 M HCl with 0.100 M NaOH.
York University CHEM 1001 3.0 Acids and Bases - 67 pH during Titration of a Strong Acid During the titration of a strong acid with a strong base: C Initial pH is determined by the concentration of the acid. C During the titration, the acid is gradually neutralized. Before the equivalence point: nA = CAVA, nB = CBVB, [H3O+] = (nA-nB) / (VA+VB) C At the equivalence point: pH = 7. C Beyond the equivalence point: [OH-] = (nA-nB) / (VA+VB) C What about near the equivalence point?
York University CHEM 1001 3.0 Acids and Bases - 68
pH near the Equivalence Point Titration of 25.00 ml of 0.100 M HCl with 0.100 M NaOH. At the equivalence point: VB = 25.00 ml and pH = 7. Find the pH at VB = 24.95 ml (1 drop short of equivalence). Solution: nA = (25.00 ml)(0.100 M) = 25.00 mmol nB = (24.95 ml)(0.100 M) = 24.95 mmol [H3O+] = (0.05 mmol) / (49.95 ml) = 0.0001 M Y pH = 4 By same method, one drop past equivalence, pH = 10. Conclusion: Near equivalence, pH changes very rapidly. York University CHEM 1001 3.0 Acids and Bases - 69 Titration of a Weak Acid C The titrant must be a strong base. C The initial pH is determined by the concentration and pKa of the acid. C During the titration, the acid is gradually converted to its conjugate base. The solution is a buffer. C At the equivalence point, the solution contains only a salt of the conjugate base, so pH >7. C There is a less dramatic pH change near the equivalence point. Indicators must be chosen with care.
York University CHEM 1001 3.0 Acids and Bases - 70
Titration Curve of a Weak Acid
25.0 ml of 0.100 M HC2H3O2 titrated with 0.100 M NaOH.
York University CHEM 1001 3.0 Acids and Bases - 71 pH during Titration of a Weak Acid Titrating 25.00 ml of 0.100 M acetic acid (HC2H3O2, pKa = 4.74) with 0.100 M NaOH. C Initial pH: HA + H2O W H3O+ + A- [H3O+] = [A-] = x [HA] . CA = 0.100 M x2 = Ka [HA] Y x = 1.35×10-3 M Y pH = 2.87 C Buffer region (10% to 90% neutralized): pH = pKa + log([A-]/[HA]) = pKa + log(nB/(nA-nB)) where nA = CAVA, nB = CBVB C At the half-equivalence point: pH = pKa = 4.74
York University CHEM 1001 3.0 Acids and Bases - 72
Titration of a Weak Acid - continued C At the equivalence point: The solution is that of a salt of the conjugate base. This hydrolyzes: A- + H2O W HA + OH- Kb = KW/Ka = [HA][OH-]/[A-] = x2/[A-] [A-] . nA/(VA+VB) = CACB/(CA+CB) = 0.0500 M x2 = Kb[A-] Y x = 5.24×10-6 M Y pOH = 5.28 Y pH = 8.72 Suitable indicators: thymol blue (pKa=8.8) phenolphthalein (pKa=9.1) C Beyond the equivalence point, the pH is determined by the amount of excess base.
York University CHEM 1001 3.0 Acids and Bases - 73
Titration Curve of a Weak Polyprotic Acid
Titrating 10.0 ml of 0.100 M H3PO4 with 0.100 M NaOH.
York University CHEM 1001 3.0 Acids and Bases - 74 pH during Titration of a Polyprotic Acid C Initial pH: Same as for a monoprotic acid. C Buffer regions: There are two or more, with pH.pKa1, pH.pKa2, etc. C Last equivalence point: Same as for a monoprotic acid. C Earlier equivalence points: Not so simple. Example: For H3PO4 at its first equivalence point, there are significant amounts of H 3PO4, H2PO4-, and HPO42-. H3PO4 + H2O W H3O+ + H2PO4- pKa1 = 2.15 H2PO4- + H2O W H3O+ + HPO42- pKa2 = 7.20 Expect pKa1 < pH < pKa1 (small [H 3O+] and [OH-])
York University CHEM 1001 3.0 Acids and Bases - 75
Equivalence Point of a Polyprotic Acid Find the pH at the first equivalence point of H3PO4. Solution: Two equilibria - use the general method. Significant species: H3PO4, H2PO4-, HPO42-, H3O+ (pH<6) Material balance: [H3PO4] + [H2PO4-] + [HPO42-] / M Equilibrium constants: [H2PO4-] = Ka1[H3PO4]/[H3O+] [HPO42-] = Ka2[H2PO4-]/[H3O+] = Ka1Ka2[H3PO4]/[H3O+]2 Electroneutrality: [Na+] + [H3O+] = [H2PO4-] + 2[HPO42-] At equivalence: M = [Na+] . [H2PO4-] + 2[HPO42-] Four equations, four unknowns. York University CHEM 1001 3.0 Acids and Bases - 76 Polyprotic Acid - continued Substitute into material balance: M = [H3PO4]( 1 + Ka1/[H3O+] + Ka1Ka2/[H3O+]2 ) Substitute into electroneutrality: M = [H3PO4]( Ka1/[H3O+] + 2Ka1Ka2/[H3O+]2 ) Subtract electroneutrality from material balance: 0 = 1 - Ka1Ka2/[H3O+]2 Y [H3O+] = (Ka1Ka2)½ Y pH = (pKa1+pKa2)/2 = (2.15+7.20)/2 pH = 4.68
York University CHEM 1001 3.0 Acids and Bases - 77
Acid-Base Titrations - Summary C Acid-base titrations can be used to measure the concentrations of acid or base in solution. C The pH changes rapidly at the equivalence point. C The equivalence point can be determined by using a pH meter or estimated by using an acid-base indicator. C The appropriate indicator to use depends on the pKa (or pKb) of the acid (or base) being titrated. C A titration curve can be used to determine the pKa of a weak acid (or pKb of a weak base).
York University CHEM 1001 3.0 Acids and Bases - 78
CO2 in the Atmosphere and Oceans The partial pressure of CO2 in the atmosphere is increasing. C Pre-industrial: 2.8×10-4 atm C Present: 3.7×10-4 atm C Future: doubled? tripled? more? CO2 can dissolve in water and act as an acid: CO2(g) W CO2(aq) Keq = 0.046 CO2(aq) + 2H2O(l) W H3O+ + HCO3- pKa1 = 6.05 HCO3- + H2O(l) W H3O+ + CO32- pKa2 = 9.23 These equilibrium constants are for seawater at 15 °C. What is the impact of increased CO2 on the oceans?
York University CHEM 1001 3.0 Acids and Bases - 79
Why the Sea is Salt Rainwater is slightly acidic, pH - 5. Rainwater gradually dissolves rocks (mostly as ions). Dissolved material is washed into the oceans. Water evaporates from the oceans, dissolved material is left behind along with primordial Na+ and volcanic Cl-. Composition of seawater: C Major cations: Na+, K+, Mg2+, Ca2+ C Major anions: Cl-, SO42-, HCO3-, Br-, CO32- C The atmosphere directly influences HCO3- and CO32- in seawater. pH is a key factor.
York University CHEM 1001 3.0 Acids and Bases - 80
pH of Seawater Significant species: CO2(aq), HCO3-, CO32-, H3O+ Electroneutrality: sum of '+' charges = sum of '-' charges [Na+] + [K+] + ... = [Cl-] + ... + [HCO3-] + 2[CO32-] [Na+], [K+], [Cl-], etc. are constant, so [HCO3-]+2[CO32-] is a constant called the alkalinity: [Alk] / [HCO3-] + 2[CO32-] Equilibrium conditions: [CO2(aq)] = Keq PCO2 [HCO3-] = Ka1[CO2(aq)][H 3O+]-1 = Ka1KeqPCO2[H3O+]-1 [CO32-] = Ka2[HCO3-][H3O+]-1 = Ka1Ka2KeqPCO2[H3O+]-2 Four equations, four unknowns (PCO2 is assumed known). York University CHEM 1001 3.0 Acids and Bases - 81 pH of Seawater - continued Substitute into expression for alkalinity: [Alk] = Ka1KeqPCO2[H3O+]-1 + 2Ka1Ka2KeqPCO2[H3O+]-2 [H3O+] = Ka1KeqPCO2 (1 + 2Ka2/[H3O+]) / [Alk] For seawater: [Alk] . 2.0×10-3 M. Constants given earlier. Simplifying assumption: [H3O+] o 2Ka2 = 1.2×10-9 Y [H3O+]approx = Ka1KeqPCO2 / [Alk] = (2.05×10-5 atm-1)PCO2 Results PCO2 (atm) [H3O+]approx [H3O+]iterate pH pre-industrial 2.8×10-4 5.7×10-9 M 6.7×10-9 M 8.17 doubled CO2 5.6×10-4 1.1×10-8 M 1.3×10-8 M 7.90
York University CHEM 1001 3.0 Acids and Bases - 82
Acidification of the Oceans Does it matter? Yes, especially if you are a coral. Shells and skeletons are made largely of CaCO3, which is slightly soluble: CaCO3(s) W Ca2+ + CO32- In seawater, Q > K, so organisms can extract CaCO3. If CO32- decreases, this become more difficult. We have [CO32-] = Ka1Ka2KeqPCO2 / [H3O+]2 and [H3O+] . Ka1KeqPCO2 / [Alk] so [CO32-] . Ka2[Alk]2 / (Ka1KeqPCO2) Conclusion: More CO2 in the atmosphere means lower [CO32-] in the oceans. Possible problem for marine life. York University CHEM 1001 3.0 Acids and Bases - 83