Focus: Energetics & Equilibria in Biological Systems
Key Topics:
Weak acids and bases
Dissociation constants (Ka, Kb)
Relationship between acid/base strengths
pH calculations for weak acids/bases
Transition metal complex ions as weak acids
Write Ka and Kb expressions for weak acids and weak bases.
Understand the relationship between Ka and Kb, pKa and pKb.
Calculate the pH of weak acid and base solutions.
Assess transition metal complex ions' behavior as weak acids.
Majority of acids are weak (incomplete dissociation, equilibrium favoring reactants).
Example Comparison:
Strong: HCl -> [H3O+] = 0.10 mol/L
Weak: HNO2 -> [H3O+] = 0.0084 mol/L, [HNO2] = 0.0916 mol/L
Defined by the expression: [ K_a = \frac{[H_3O^+][A^-]}{[HA]} ]
Indicates strength; larger Ka means stronger acid.
pKa relation: [ pK_a = -\log(K_a) ]
For weak bases: [ K_b = \frac{[BH^+][OH^-]}{[B]} ]
Stronger base = larger Kb.
pKb relation: [ pK_b = -\log(K_b) ]
Example values:
CH3COOH: Ka = 1.8×10-5, pKa = 4.74
NH3: Kb = 1.8×10-5, pKb = 4.74
[ K_a K_b = K_w = 1.0\times10^{-14} ]
At 25°C, [ pK_a + pK_b = pK_w = 14.00 ]
Strong acid -> weak conjugate base.
General rule: strong acids have very weak conjugate bases, and vice versa.
Weak acids and their conjugate bases do not have predictable strengths.
Given: [CH3-CH(OH)-COOH] = 1×10-3 mol/L, pKa = 3.86
Use Ka for calculations:
[ K_a = 10^{-pK_a} = 1.38\times10^{-4} ]
Assumptions for calculation:
[CH3-CH(OH)-COO-]e = [H3O+]e
[CH3-CH(OH)-COOH]e ≈ [CH3-CH(OH)-COOH]initial
Final pH calculation yields 3.43.
Kb = 4.1×10-4 for caffeine.
To find pH of 0.025 mol/L solution:
Assume [OH-]e based on Kb and caffeine concentration.
pOH calculation gives pH of 11.51.
Complex ions with water ligands can act as weak acids.
Example: [Ni(H2O)6]2+ dissociates, forming [Ni(H2O)5(OH)]+ and H3O+.
Acid strength increases with positive charge on metal ion.
Problems from Brown (15th): 16.81, 16.86, 16.91, 16.92
Answers are available on Blackboard.