Chapter 21: Acid-Base Equilibria, Buffers,
Solubility, and Partition
Conjugate Acid-Base Pairs
differs by a single hydrogen ion (H⁺). For example, in HA ⇌ H⁺ + A⁻, HA (acid) and
Conjugate Pair: An acid-base pair on each side of an acid-base equilibrium equation that
A⁻ (base) are conjugates.
Ionic Product of Water
H₂O ⇌ H⁺ + OH⁻. Kw = [H⁺][OH⁻] At 298 K, Kw = 1 × 10⁻¹⁴ mol² dm⁻⁶. It increases
Kw (Ionic Product of Water): The equilibrium constant for the ionization of water:
with temperature as ionization is endothermic.
pH Calculations
pH: A measure of hydrogen ion concentration. pH = -log₁₀[H⁺]
Inverse Calculation: [H⁺] = 10^(-pH) mol dm⁻³
For strong acids/bases: Fully dissociated, so [H⁺] = concentration of acid (for monoprotic
acids).
For neutral solutions: pH = 7 ([H⁺] = [OH⁻] = 10⁻⁷ mol dm⁻³).
For alkaline solutions: pH > 7; calculate [H⁺] from Kw / [OH⁻].
Acid Dissociation Constant
weak acid: HA ⇌ H⁺ + A⁻. Ka = ([H⁺][A⁻]) / [HA] (units: mol dm⁻³)
Ka (Acid Dissociation Constant): The equilibrium constant for the dissociation of a
pKa: pKa = -log₁₀ Ka Lower pKa means stronger acid (greater dissociation).
Buffer Solutions
Buffer Solution: A solution that minimizes changes in pH when moderate amounts of
acid or base are added. Typically consists of a weak acid and its conjugate base (e.g.,
CH₃COOH and CH₃COO⁻) or a weak base and its conjugate acid.
How a Buffer Solution Maintains pH (Explanation): Buffers work via equilibrium and
A⁻): HA ⇌ H⁺ + A⁻
Le Chatelier's principle. For an acidic buffer (weak acid HA and salt of conjugate base
o The buffer has high [HA] and [A⁻], so small additions of H⁺ or OH⁻ shift the
equilibrium without significantly changing [H⁺].
o If acid (H⁺) is added: Equilibrium shifts right (A⁻ + H⁺ → HA), removing
excess H⁺.
o If base (OH⁻) is added: OH⁻ reacts with H⁺ (from HA dissociation) to form
water; equilibrium shifts left (HA → H⁺ + A⁻) to replace H⁺.
o Result: pH change is minimal as long as buffer capacity (reservoir of HA and A⁻)
isn't exceeded. For basic buffers (e.g., NH₃ and NH₄⁺), the process is analogous
but focuses on OH⁻ control.
Henderson-Hasselbalch Equation (for Acidic Buffer): pH = pKa + log₁₀([A⁻] / [HA])
Or rearranged: [H⁺] = Ka × ([HA] / [A⁻]) (Note: The provided note "[H+]=Ka*
[base]/[acid]" appears inverted; it's acid over base for acidic buffers, where "base" is
conjugate base [A⁻] and "acid" is [HA].)
Solubility Product
Ksp (Solubility Product): For a sparingly soluble salt (e.g., AB₂ ⇌ A²⁺ + 2B⁻), Ksp is
the product of ion concentrations in a saturated solution at 298 K, raised to their
stoichiometric powers: Ksp = [A²⁺][B⁻]² (units vary by salt).
Interpretation:
o Smaller Ksp value indicates lower solubility (less dissociation into ions).
o If ion product > Ksp, precipitation occurs; if < Ksp, solution is unsaturated.
Common Ion Effect
Common Ion Effect: The reduction in solubility of a sparingly soluble salt when a
compound sharing a common ion is added.
⇌ Ag⁺ + Cl⁻ left (Le Chatelier), decreasing [Ag⁺] and thus solubility.
o Example: Adding NaCl to saturated AgCl solution (common Cl⁻ ion) shifts AgCl
Partition Coefficient
Kpc (Partition Coefficient): The ratio of a solute's concentrations in two immiscible
solvents at equilibrium. Kpc = [X(solvent A)] / [X(solvent B)] (dimensionless).
Applications: Used in extraction processes (e.g., solvent extraction in organic
chemistry). Higher Kpc means more solute partitions into solvent A. Equilibrium
depends on solute solubility in each phase.