ACID-BASE NEUTRALIZATION REACTIONS AND BUFFERS Welcome to the pinnacle chapter of AP Chem.

After this one, its downhill, but you still have to get through this one! In this chapter, careful problem reading and attention to methodology will carry you far. Step 1: CAREFULLY read the problem and note the information given Step 2: Decide if any reaction takes place and construct an appropriate ICE box. If not, go on to step 3. Step 3: Analyze results of ICE box, if needed and then see what you have. Use that information to correctly calculate the pH. a. If you have a strong acid (A) only, the pH is found by log[A]. Remember to use molar concentration, not just moles. b. If you have a strong base (B) only, the pOH is found by log[B]. Remember to use molar concentration, not just moles. c. If the result is a strong acid plus a weak acid, the effect of the strong acid usually predominates and the effect of the weak acid can be ignored. The same is true for a strong base plus a weak base. d. If the result is a weak acid (A) only, the pH is found by using the method we learned in chapter 14. That is: Ka = x2/[A]. The x then represents the [H 3 O+]. The denominator is the molar concentration of weak acid, not just moles. e. If the result is a weak base (B) only, the pOH is found by using the method we learned in chapter 14. That is: Kb = x2/[B]. The x then represents the [OH-]. The denominator is the molar concentration of weak base, not just moles. f. If the result is a weak acid and its conjugate weak base, this is a buffer. You can use either the Ka or Kb equation. In this special case, you can use moles or molarity of the weak acid and its conjugate base (as the volume cancels out when you plug in mol/L). You can also use the Henderson-Hasselbalch equation found in your book for buffers only. For buffers only, you truly have your choice of whether to use the Ka equation or the Kb equation; they both will give the same result. g. As always, [H 3 O+][OH1] = 1.00 x 10-14 and pH + pOH = 14.00. Ka = [H 3 O+][A1-] [HA] Kb = [OH1][HA] [A1- ] [H 3 O+] = Ka x moles HA moles A1[OH-] = Kb x molesAmoles HA

pH = pKa + log ([base]/[acid] ) Henderson-Hasselbalch

PART I: General buffer problems. Example 1: A buffer is made by adding together 0.350 moles of HC 2 H 3 O 2 (acetic acid Ka = 1.8 x 10-5) and added to 0.250 moles of NaC 2 H 3 O 2 and adding water to volume of 2.00 L. Calculate the pH of the buffer. Solution: You just have the weak acid, conjugate base pair HC 2 H 3 O 2 / C 2 H 3 O 2 1-. No reaction takes place, just buffer interaction. There are several ways to solve this problem. Strategy A: Ka = [H 3 O+][A1-] 1.8 x 10-5 = [H 3 O+] x 0.250 mol/2.00L [HA] 0.350 mol/2.00L Notice that the volume 2.00 L cancels out so: [H 3 O+] = 1.8 x 10-5 x 0.350 mol = 2.5 x 10-5 M pH = 4.60 0.250 mol Strategy B: Use the Henderson-Hasselbalch equation. pH = pKa + log ([base]/[acid] ) Henderson-Hasselbalch Ka = 1.8 x 10-5 so pKa = -log Ka = 4.75 pH = 4.75 + log (0.250/0.350) = 4.60. (The volumes in the ratio cancel out.) Strategy C: Since this is a buffer, you can also use the Kb equation to solve for [OH 1-], then pOH and pH. Kb (for C 2 H 3 O 2 1-) = 5.6 x 10-10 [OH-1] = 5.6 x 10-10 x 0.250 = 4.0 x 10-10 , so pOH = 9.40 and pH = 4.60. 0.350 Note you have a lot of choices with buffer problems. This is not the case when you dont have a buffer! Example 2: You add 0.100 moles of HCl to the buffer prepared in example 1. Calculate the pH. Solution: You must construct an ICE box to show the reaction of the strong acid to the buffer. Once you find the moles of HC 2 H 3 O 2 and C 2 H 3 O 2 1- left after the reaction with HCl, you can use any of the strategies from example 1. I will only show one strategy (B). All quantities in mol C 2 H 3 O 2 1- + H+ I 0.250 C -0.100 E 0.150 0.100 -0.100 0 HC 2 H 3 O 2 0.350 +0.100 0.450 The limiting reactant (in this case H+) determines the x in the Change line.

Now, plug the equilibrium moles of weak acid and conjugate base into the equation. [H 3 O+] = 1.8 x 10-5 x 0.450 mol = 5.4 x 10-5 M pH = 4.27 0.150 mol

Example 3: You add 0.100 moles of NaOH to the buffer prepared in example 1. Calculate the pH. Solution: You must construct an ICE box to show the reaction of the strong acid to the buffer. Once you find the moles of HC 2 H 3 O 2 and C 2 H 3 O 2 1- left after the reaction with NaOH, you can use any of the strategies from example 1. I will only show one strategy (B). All quantities in mol HC 2 H 3 O 2 + OH- I 0.350 C -0.100 E 0.250 0.100 -0.100 0 C 2 H 3 O 2 10.250 +0.100 0.350 The limiting reactant (in this case OH-) determines the x in the Change line.

Now, plug the equilibrium moles of weak acid and conjugate base into the equation. [H 3 O+] = 1.8 x 10-5 x 0.250 mol = 1.3 x 10-5 M pH = 4.89 0.350 mol Now, you prove that you would get the same result when using concentrations instead of moles, or when using Henderson-Hasselbalch or when using Kb instead of Ka! PART II: Acid-base neutralization: Strong acid-strong base titrations. Example 4: You titrate a 50.00 mL solution of 0.2400 M HCl with 0.4000 M NaOH. What is the pH before any NaOH is added? Solution: -log (0.2400 M) = pH = 0.620 Example 5: You add 10.00 mL 0.4000 M NaOH to the 50.00 mL of 0.2400 M HCl. What is the pH now? Solution: 0.0100 L x 0.4000 M NaOH = 0.00400 mol NaOH 0.05000 L x 0.2400 M HCl = 0.01200 mol HCl All quantities in mol H+ + OH- I 0.01200 0.004 C -0.00400 -0.004 E 0.00800 0 H2O 0 + 0.00400 + 0.00400 The limiting reactant (in this case OH-) determines the x in the Change line.

Excess is H 3 O+ and [H 3 O+] = 0.00800 mol/(.0100 + .0500)L = 0.133 M H 3 O+ and -log (0.133 M) = pH = 0.876

Example 6: What volume of 0.400 M NaOH is needed to react with the 50.0 mL of 0.240 M HCl to get to the equivalence point? Determine the pH at the equivalence point. Solution: We need an equivalent number of moles of NaOH added to the HCl solution. So: initial mol HCl = mol NaOH added. As long as the two react in a 1:1 mole ratio, MAV A = MBVB. (0.05000 L) (0.2400 M HCl) = (x L) (0.4000 M NaOH) x = 0.03000 L NaOH(30.00 mL) All quantities in mol H+ + OH- I 0.01200 0.01200 C -0.01200 -0.0.1200 E 0 0 H2O 0 + 0.01200 0.01200 At the equivalence point, we have added an equivalent number of moles of H+ and OHso all of the reactants have been converted to products.

Since the real reaction that we have done is the formation of H 2 O (and spectator ions) the pH is 7.000. (This is only true for the reaction of strong acids with strong bases.) Example 7: You add 50.00 mL 0.4000 M NaOH to the 50.00 mL of 0.2400 M HCl. What is the pH now? Solution: 0.05000 L x 0.4000 M NaOH = 0.02000 mol NaOH 0.05000 L x 0.2400 M HCl = 0.01200 mol HCl H+ + I 0.01200 C -0.01200 E 0 OH- 0.02000 -0.01200 0.00800 H2O 0 + 0.01200 + 0.01200 The limiting reactant (in this case H+) determines the x in the Change line.

Excess is OH- and [OH-] = 0.00800 mol/(.0500 + .0500)L = 0.0800 M OH- and -log (0.0800 M) = 1.097 pH = 14.00-1.097 = 12.903 PART III: Acid-base neutralization: Weak acid-strong base titrations. Example 8: You titrate a 50.00 mL solution of 0.2400 M HC 2 H 3 O 2 (Ka = 1.8 x 10-5) with 0.4000 M NaOH. What is the pH before any NaOH is added? Solution: This is simply the pH of a 0.240 M HC 2 H 3 O 2 , weak acid as was solved in chapter 14. Ka = [H 3 O+][A1-] [HA] 1.8 x 10-5 = x2 . 0.240 M x = [H 3 O+] = 0.0021 M: pH = 2.67

Example 9: You add 10.00 mL 0.4000 M NaOH to the 50.00 mL of 0.2400 M HC 2 H 3 O 2 . What is the pH now? Solution: 0.01000 L x 0.4000 M NaOH = 0.00400 mol NaOH 0.05000 L x 0.2400 M HC 2 H 3 O 2 = 0.01200 mol HC 2 H 3 O 2 All quantities in mol HC 2 H 3 O 2 + OH- I 0.01200 0.00400 C -0.00400 -0.00400 E 0.00800 0 C 2 H 3 O 2 10 + 0.00400 + 0.00400 + H2O The limiting reactant (in this case OH-) determines the x in the Change line.

A buffer is created, because we have a weak acid and its conjugate weak base. We can plug the amounts from the equilibrium line into the Ka expression, solve for[H 3 O+] and pH. [H 3 O+] = 1.8 x 10-5 x 0.00800 mol = 3.6 x 10-5 M pH = 4.44 0.00400 mol Example 10: You add 15.00 mL 0.4000 M NaOH to the 50.00 mL of 0.2400 M HC 2 H 3 O 2 . What is the pH now? Solution: 0.01500 L x 0.4000 M NaOH = 0.00600 mol NaOH 0.05000 L x 0.2400 M HC 2 H 3 O 2 = 0.01200 mol HC 2 H 3 O 2 All quantities in mol HC 2 H 3 O 2 + OH- C 2 H 3 O 2 1I 0.01200 0.00600 0 C -0.00600 -0.00600 + 0.00600 E 0.00600 0 + 0.00600 + H2O

A buffer is created, because we have a weak acid and its conjugate weak base. We can plug the amounts from the equilibrium line into the Ka expression, solve for[H 3 O+] and pH. [H 3 O+] = 1.8 x 10-5 x 0.00600 mol = 1.8 x 10-5 M pH = 4.74 0.00600 mol In this case, we have an equal number of moles of weak acid and conjugate base in the buffer. So [H 3 O+] = Ka and pH = pKa.

Example 11: What volume of 0.400 M NaOH is needed to react with the 50.0 mL of 0.240 M HC 2 H 3 O 2 to get to the equivalence point? Determine the pH at the equivalence point. Solution: We need an equivalent number of moles of NaOH added to the HC 2 H 3 O 2 solution. So: initial mol HC 2 H 3 O 2 = mol NaOH added. As long as the two react in a 1:1 mole ratio, M AV A = MBVB. (0.05000 L) (0.2400 M HC 2 H 3 O 2 ) = (x L) (0.4000 M NaOH) x = 0.03000 L NaOH(30.00 mL) All quantities in mol HC 2 H 3 O 2 + OH- I 0.01200 0.01200 C -0.01200 -0.01200 E 0 0 C 2 H 3 O 2 10 + 0.01200 + 0.01200 + H2O

All of the HC 2 H 3 O 2 is neutralized away and converted to its conjugate base, C 2 H 3 O 2 1-. So the pH is determined by the molarity of conjugate base. [C 2 H 3 O 2 1-] = 0.01200 mol/(.03000 + 0.05000)L = 0.150 M Kb = 1.0 x 10-14 /Ka = 1.0 x 10-14 /1.8 x 10-5 = 5.6 x 10-10. Kb = [OH1][HA] = 5.6 x 10-10 =. x2 . [A1- ] 0.150 M x = 9.2 x 10-6 M = [OH-]. pH = 8.96

Example 12: You add 50.00 mL 0.4000 M NaOH to the 50.00 mL of 0.2400 M HC 2 H 3 O 2 . What is the pH now? Solution: 0.05000 L x 0.4000 M NaOH = 0.02000 mol NaOH 0.05000 L x 0.2400 M HCl = 0.01200 mol HC 2 H 3 O 2 HC 2 H 3 O 2 + OH- C 2 H 3 O 2 1I 0.01200 0.02000 0 C -0.01200 -0.01200 + 0.01200 E 0 0.00800 + 0.01200 + H2O

We have excess OH-and excess C 2 H 3 O 2 1-. In this case, the pH is determined by the excess OH-. [OH-] = 0.00800 mol/(.0500 + .0500)L = 0.0800 M OH-log (0.0800 M) = 1.097 pH = 14.00-1.097 = 12.903: Note that this is identical to the pH of strong acid and strong base, example 7. Both have identical [OH-].