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Measuring Ka, Buffers and the pH of Ionic Solutions

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1 Measuring Ka, Buffers and the pH of Ionic Solutions
Stuff we need to know for the Weak Acid Lab in Chem V01BL

2 Anions as Weak Bases every anion can be thought of as the conjugate base of an acid therefore, every anion can potentially be a base A−(aq) + H2O(l) ⇋ HA(aq) + OH−(aq) the stronger the acid HA is, the weaker the conjugate base A- is an anion that is the conjugate base of a strong acid is pH neutral Cl−(aq) + H2O(l)  HCl(aq) + OH−(aq) an anion that is the conjugate base of a weak acid is basic F−(aq) + H2O(l) ⇋ HF(aq) + OH−(aq) since HF is a weak acid, the position of this equilibrium favors the right

3 Use the Table to Determine if the Given Anion Is Basic or Neutral
NO3− the conjugate base of a strong acid, therefore neutral HCO3− the conjugate base of a weak acid, therefore basic PO43−

4 Polyatomic Cations as Weak Acids
some polyatomic cations with a H in them can be thought of as the conjugate acid of a base (:B) BH+(aq) + H2O(l) ⇋ :B(aq) + H3O+(aq) the stronger the base :B(aq) is, the weaker the conjugate acid BH+ is a cation that is the counterion of a strong base (Na+, K+ etc) is pH neutral a cation that is the conjugate acid of a weak base is acidic NH4+(aq) + H2O(l) ⇋ :NH3(aq) + H3O+(aq) since :NH3 is a weak base, the position of this equilibrium favors the right

5 Metal Cations as Weak Acids
While alkali metal cations and alkali earth metal cations pH neutral Cations of small, highly charged metals (especially transition metals) are weakly acidic Al(H2O)63+(aq) + H2O(l) Al(H2O)5(OH)2+ (aq) + H3O+(aq)

6 Classifying Salt Solutions as Acidic, Basic, or Neutral
if the salt cation is the conjugate acid of a weak base and the anion is the conjugate base of a weak acid, the pH of the solution depends on the relative strengths of the acid and base NH4F Ka of NH4+ is larger than Kb of the F−; therefore the solution will be acidic

7 Determine whether a solution of the following salts is acidic, basic, or neutral
SrCl2 Sr2+ is the counterion of a strong base, pH neutral Cl− is the conjugate base of a strong acid, pH neutral solution will be pH neutral AlBr3 Al3+ is a small, highly charged metal ion, weak acid Br− is the conjugate base of a strong acid, pH neutral solution will be acidic CH3NH3NO3 CH3NH3+ is the conjugate acid of a weak base, acidic NO3− is the conjugate base of a strong acid, pH neutral

8 NH4+(aq) + H2O(l) ⇋ NH3(aq) + H3O+(aq)
Determine whether a solution of the following salts is acidic, basic, or neutral and write out any hydrolysis reaction that happens if it is basic or acidic NH4Cl NH4+ is the conjugate acid of the weak base (NH3), so is acidic Cl− is the conjugate base of a strong acid (HCl), pH neutral Overall the solution will be acidic. Since the NH4+ is acidic it reacts with water (undergoes hydrolysis) NH4+(aq) + H2O(l) ⇋ NH3(aq) + H3O+(aq) Have a go completing the first page on today’s handout

9 Measuring pKa of a weak acid by titration
CH3COOH(aq) + NaOH(aq)  NaCH3COO(aq) + H2O(l)

10 Measuring pKb of a weak base by titration
𝐾 𝑏 = 𝑁𝐻 𝑂𝐻 − 𝑁𝐻 3 NH3(aq) + HCl(aq)  NH4Cl(aq) + H2O(l) −𝑙𝑜𝑔 𝐾 𝑏 =−𝑙𝑜𝑔 𝑁𝐻 𝑂𝐻 − 𝑁𝐻 3 Half equivalence point [NH3] = [NH4+] 𝑝𝐾 𝑏 =−𝑙𝑜𝑔 𝑂𝐻 − −𝑙𝑜𝑔 𝑁𝐻 𝑁𝐻 3 𝑝𝐾 𝑏 =𝑝𝑂𝐻 −𝑙𝑜𝑔 𝑁𝐻 𝑁𝐻 3 But we can only measure pH 14−𝑝𝐾 𝑏 =14−𝑝𝑂𝐻 −𝑙𝑜𝑔 𝑁𝐻 𝑁𝐻 3 𝑝𝐾 𝑎 =𝑝𝐻 −𝑙𝑜𝑔 𝑁𝐻 𝑁𝐻 3 At the ½ equivalence point 𝑝𝐾 𝑎 =𝑝𝐻 𝑝𝐾 𝑏 =14− 𝑝𝐾 𝑎

11 Solutions close to the 1/2 equivalence point: Buffers
Aqueous Solution pH Δ pH Bottled Water (30 mL) 5.6 0.7 Bottled Water + 1 drop of 0.1M HNO3 4.9 Deionized Water (30 mL) 6.0 2.2 Deionized Water + 1 drop of 0.1M HNO3 3.8 pH Buffer 7.8 0.0 pH Buffer + 1 drop of 0.1M HNO3 What should the pH be when we add 1 drop of 0.1M HNO3 to 30mL of deionized water ? Assume 1 drop = 0.05mL When this 1 drop is dissolved in 30 mL of H2O

12 How Acid Buffers Work HA(aq) + H2O(l) ⇋ A−(aq) + H3O+(aq)
buffers work by applying Le Châtelier’s Principle to weak acid equilibrium – buffers are solutions that resist change in pH Adding OH- to the buffer: the OH- reacts with the H3O+ to make 2H2O(l) so it removes H3O+ so drives the equilibrium to the right effectively doing the following Effectively 𝐻𝐴 (𝑎𝑞) + 𝑂𝐻 (𝑎𝑞) − → 𝐴 𝑎𝑞 − + 𝐻 2 𝑂 (𝑙) By Le Châtelier it drives the equilibrium to the right causing more HA to make A- and maintaining [H3O+] Adding H3O+ to the buffer: By Le Châtelier it drives the equilibrium to the left (because we are adding more product) causing A- to react with the H3O+ to make more HA maintaining [H3O+] Effectively 𝐴 𝑎𝑞 − + 𝐻 3 𝑂 (𝑎𝑞) + ⇢ 𝐻𝐴 (𝑎𝑞) + 𝐻 2 𝑂 (𝑙)

13 Calculating the pH of Buffers
What is the pH of a buffer that is M HC2H3O2 and M NaC2H3O2 given Ka for HC2H3O2 = 1.8 x 10-5? First let us try this using an ICE table

14 Henderson–Hasselbalch Equation
Earlier we showed that 𝑝𝐾 𝑎 =𝑝𝐻−𝑙𝑜𝑔 𝐴 − 𝐻𝐴 Or 𝑝𝐻 = 𝑝𝐾 𝑎 +𝑙𝑜𝑔 𝐴 − 𝐻𝐴 This is really useful for buffer solutions it is called the Henderson – Hasselbalch equation when we replace the equlibrium values with initial concentrations 𝑝𝐻 = 𝑝𝐾 𝑎 +𝑙𝑜𝑔 𝐴 − 𝐻𝐴 0 This approximation works whenever x is small works with an ICE table


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